(Green Energy and Technology) Ayhan Demirbas - Waste Energy For Life Cycle Assessment (2016, Springer)

Green Energy and Technology
Ayhan Demirbas
Waste Energy
for Life Cycle
Assessment
More information about this series at http://www.springer.com/series/8059
Ayhan Demirbas
Waste Energy for Life

Cycle Assessment
123
Ayhan Demirbas
Faculty of Engineering
King Abdulaziz University
Jeddah
Saudi Arabia
ISSN 1865-3529 ISSN 1865-3537 (electronic)

ISBN 978-3-319-40550-6 ISBN 978-3-319-40551-3 (eBook)
DOI 10.1007/978-3-319-40551-3
Library of Congress Control Number: 2016943318
© Springer International Publishing Switzerland 2016

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Preface
This book is prepared with the expectation of achieving the comprehensive methods
to produce more convenient and economical primary energy from non-conventional
energy sources and to improve the energy conversion processes.
Approaches to finding new sources of energy, evaluation of unused waste
energy, inactive and unconventional energy sources to be put into operation
recently has become inevitable. Production of energy from these sources and
optimization of the new systems is becoming increasingly important.
Unconventional energy sources cover unusually unconventional energy, with
little or no unused, inactive cases and the energy resources available in waste form.
Waste energy covers unused or used with low efficient energy resources.
This text material was prepared for postgraduates, fuel engineers, scientists,
energy researches, industrialists, policy makers and agricultural engineers. Energy
demand, energy production and cost have always been a concern for researchers as
well as policy makers.
The first chapter on “Introduction” already comprises one tenth of the book; in
these pages emphasis is laid in detail on energy concept, global energy sources,
especially renewables, i.e. biomass, hydro, wind, solar, geothermal and world’s
present energy situation. The second chapter is entitled “Future Energy Sources”
including main renewable energy scenarios, research and development of biomass
energy, water energy and power; hydrogen energy, biogas energy, algae energy and
the next generation of hybrid transportation vehicles are addressed in detail. The
third chapter already comprises 50 % of the book; in these pages emphasis is laid in
detail on “Unconventional Energy Sources” covers the waste energy, energy use,
shaking energy, squeezing energy, water energy, inactive energy sources and
promising energy systems. The fourth chapter covers wind power generation using
shaking energy, compressed air energy, water forces and water energy, gas hydrates
as a potential future energy resource, biofuels from high quality microalgae, ther-
mochemical conversion processes of biomass to hydrogen-rich gas mixtures, bio-
fuels from sewage sludge, biodiesel and bioethanol from unconventional resources,
gasoline-like products from plastic and tire wastes, conversion of oil shale to liquid
v
vi Preface
fuels, conversion of used oils to gasoline-like products, conversion of heavy oil to

light products, upgrading of crude oil and heavy oil and gasoline and diesel range
hydrocarbons from waste vegetable oils. Furthermore, processing conditions are
discussed briefly as well as alternative applications of unconventional energy
sources. The fifth chapter covers optimization of energy conversion processes,
waste heat utilization facilities, importance of unconventional energy sources and
energy economics and energy policy and barriers.
Experts suggest that current oil and gas reserves would suffice to last only a few
more decades. To exceed the rising energy demand and reducing petroleum
reserves, unconventional energy sources, are in the forefront of the alternative
technologies. It is well known that transport is almost totally dependent on fossil
particularly petroleum-based fuels such as gasoline, diesel fuel, liquefied petroleum
gas and natural gas. An alternative energy sources must be technically feasible,
economically competitive, environmentally acceptable and easily available.
Jeddah, Saudi Arabia Ayhan Demirbas

April 2016
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........... 1
1.1 Energy and Force Concepts. . . . . . . . . . . . . . . . ........... 1
1.1.1 Electric and Magnetic Fields and Forces
in Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.2 Geometric Energy Concept . . . . . . . . . . . . . . . . . . . . . 7
1.1.3 Nano-Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2 Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.2.1 Fossil Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2.2 Renewable Energy Sources . . . . . . . . . . . . . . . . . . . . . 22
1.2.3 Nuclear Energy Sources . . . . . . . . . . . . . . . . . . . . . . . 25
1.3 World’s Present Energy Situation. . . . . . . . . . . . . . . . . . . . . . . 28
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2 Future Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.2 Renewable Energy Scenarios. . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.3 Research and Development of Biomass Energy . . . . . . . . . . . . . 38
2.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3.2 Transportation Biofuels from Biomass . . . . . . . . . . . . . 40
2.4 Water Energy and Power . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.5 Hydrogen Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.6 Biogas Energy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.7 Algae Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2.7.1 Biodiesel Production from Algal Oil . . . . . . . . . . . . . . 58
2.7.2 Glycerol from Vegetable Oil for a Promising
Carbon Source. . . . . . . . . . . . . . . . . . . . . . . . ...... 63
2.8 The Next Generation of Hybrid Transportation Vehicles . ...... 65
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 67
3 Unconventional Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.2 Waste Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
vii
viii Contents
3.2.1 Waste Heat Recovery by Cogeneration

(COGEN or CHP) . . . . . . . . . . . . . . . . . . . . . ...... 76
3.2.2 Waste Heat Recovery by Trigeneration
or Combined Cooling, Heat and Power (CCHP) ...... 77
3.3 Energy Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 79
3.3.1 Energy Use in Buildings, Transportation
and Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.3.2 Energy Use in Energy and Power Systems . . . . . . . . . . 83
3.4 Shaking Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.5 Squeezing Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.5.2 Energy Storage Systems . . . . . . . . . . . . . . . . . . . . . . . 93
3.6 Water Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.7 Inactive Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.7.2 Geothermal Energy . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3.7.3 Natural Gas Hydrates . . . . . . . . . . . . . . . . . . . . . . . . . 107
3.8 Promising Energy Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.8.2 Hydrogen as a Future Promising Fuel. . . . . . . . . . . . . . 109
3.8.3 Future Transportation Vehicles . . . . . . . . . . . . . . . . . . 113
3.8.4 Energy from Boron . . . . . . . . . . . . . . . . . . . . . . . . . . 115
3.8.5 Energy from Non-nuclear Metallic Fuels. . . . . . . . . . . . 117
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4 Energy from Waste Materials and Unconventional Sources . . . . . . . 123
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.2 Wind Power Generation Using Shaking Energy . . . . . . . . . . . . . 125
4.3 Compressed Air Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.3.2 Compressed Air Powered Vehicles. . . . . . . . . . . . . . . . 128
4.4 Water Forces and Water Energy . . . . . . . . . . . . . . . . . . . . . . . 130
4.5 Gas Hydrates as a Potential Future Energy Resource . . . . . . . . . 133
4.6 Biofuels from High Quality Microalgae . . . . . . . . . . . . . . . . . . 138
4.7 Thermochemical Conversion Processes of Biomass to
Hydrogen-Rich Gas Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . 146
4.8 Biofuels from Sewage Sludge . . . . . . . . . . . . . . . . . . . . . . . . . 154
4.8.1 Biodiesel from Sewage Sludge . . . . . . . . . . . . . . . . . . 154
4.8.2 Biogas from Sewage Sludge . . . . . . . . . . . . . . . . . . . . 157
4.9 Biodiesel and Bioethanol from Unconventional Resources . . . . . 162
4.9.1 Biodiesel from Unconventional Resources. . . . . . . . . . . 162
4.9.2 Bioethanol from Unconventional Resources. . . . . . . . . . 171
4.10 Gasoline-like Products from Plastic and Tire Wastes . . . . . . . . . 183
4.10.1 Gasoline-like Products from Plastic Wastes . . . . . . . . . . 183
4.10.2 Gasoline-like Products from Tire Wastes. . . . . . . . . . . . 188
Contents ix
4.11 Conversion of Oil Shale to Liquid Fuels. . . . . . . . . . . . . . . . . . 193

4.12 Conversion of Used Oils to Gasoline-like Products . . . . . . . . . . 196
4.13 Conversion of Heavy Oil to Light Products. . . . . . . . . . . . . . . . 204
4.14 Upgrading of Crude Oil and Heavy Oil . . . . . . . . . . . . . . . . . . 211
4.14.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
4.14.2 Deposition and Flocculation of Asphaltenes
from Petroleum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
4.14.3 Removing of Resins from Petroleum . . . . . . . . . . . . . . 221
4.14.4 Dewaxing Processes of Petroleum . . . . . . . . . . . . . . . . 223
4.14.5 Sulfur Removal from Petroleum. . . . . . . . . . . . . . . . . . 227
4.15 Gasoline and Diesel Range Hydrocarbons from Waste
Vegetable Oils. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
5 Optimization of Energy Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . 257
5.1 Optimization of Energy Conversion Processes . . . . . . . . . . . . . . 257
5.2 Waste Heat Utilization Facilities . . . . . . . . . . . . . . . . . . . . . . . 259
5.3 Importance of Unconventional Energy Sources . . . . . . . . . . . . . 263
5.4 Energy Economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
5.5 Energy Policy and Barriers . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
Chapter 1
Introduction
Energy plays a vital role in our everyday lives. The standard of living of the people
of any country is considered to be proportional to the energy consumption by the
people of that country. Energy is one of the vital inputs to socio-economic
development of any country. There are different ways in which the abundance of
energy around us can be stored, converted and amplified for our use. Energy
production has been always a concern for researchers as well as policy makers.
The demand for energy is increasing at an exponential rate due to the expo-
nential growth of world population. Experts suggest that current oil and gas
reserves would suffice to last only a few more decades. It is well known that
transport is almost totally dependent on fossil fuels, particularly petroleum-based
fuels such as gasoline, diesel fuel, liquefied petroleum gas, and natural gas. Of
special concern are the liquid fuels used in automobiles. Hence, there has been
widespread recent interest in learning more about obtaining liquid fuels from
non-fossil sources. The combination of rising oil prices, issues of security, climate
instability, and pollution, and deepening poverty in rural and agricultural areas, is
propelling governments to enact powerful incentives for the use of these fuels,
which is in turn sparking investment.
Approaches to finding new sources of energy, evaluation of unused waste
energy, inactive and unconventional energy sources to be put into operation
recently has become inevitable. Production of energy from these sources and
optimization of the new systems is becoming increasingly important.
1.1 Energy and Force Concepts
Energy is defined as the ability to do work of a system or an object. However, the

energy and the work is the same concept, that work is the equivalent of the
mechanical energy. Therefore, this definition is not sufficient and satisfactory
explanation.
© Springer International Publishing Switzerland 2016 1
A. Demirbas, Waste Energy for Life Cycle Assessment,
Green Energy and Technology, DOI 10.1007/978-3-319-40551-3_1
2 1 Introduction
What is force? Force is a factor acting alone an influence on an object or a

system that causes movement of the object or the system to change. If a system or
object at rest is subjected to a non-zero force it will start to move. Energy cannot be
achieved without affecting the force on a system or an object.
What is energy? Force acting on a system or energy of an object depends on the
distance and speed of the object of change with the contact time.
Substance capable such a change is called the potential energetic material.
Substances of methane, benzene, ethyl alcohol and biodiesel are energetic
materials.
Energy comes in various forms, such as motion, heat, light, electrical, chemical,
nuclear energy, and gravitational. Total energy is the sum of all forms of the energy
a system possesses. In the absence of magnetic, electrical and surface tension
effects, the total energy of a system consists of the kinetic, potential, and internal
energies. The internal energy of a system is made up of sensible, latent, chemical,
and nuclear energies. The sensible internal energy is due to translational, rotational,
and vibration effects of atoms and molecules. Thermal energy is the sensible and
latent forms of internal energy. The classification of energy into different ‘‘types’’
often follows the boundaries of the fields of study in the natural sciences. For
example, chemical energy is the kind of potential energy stored in chemical bonds,
and nuclear energy is the energy stored in interactions between the particles in the
atomic nucleus. Microscopic forms of energy are related to the molecular structure
of a system and they are independent of outside reference frames.
1.1.1 Electric and Magnetic Fields and Forces

in Nanotechnology
It was believed that if a concentration of positive electric charge exists in one place
and a concentration of negative electric charge exists in another place, an electric
potential is set up between the two. Under the driving force of this electric potential
a current of electricity flows from one point of concentration to the other, this
current tending to equalize the concentration.
Aqueous salt solutions conduct electric currents quite easily as the first experi-
menters learned early in their studies.
Towards 1830, Faraday discovered the laws of electrolysis, and measured the
electric charges given up by bodies at the poles of the battery when they are
decomposed by the electric current. He noted that when an electric current is passed
through the solution of a salt, the latter is decomposed into two elements charged
with contrary electricity, which are found at the two poles. This operation, the result
of which is to resolve compound bodies into their elements, is called, as we know,
electrolysis. The bodies capable of undergoing such an operation are called
electrolytes.
1.1 Energy and Force Concepts 3
According to Arrhenius theory, which is evidently very hypothetical, but which

has been admitted because it much facilitates explanations, the dilute solution of a
metallic salt would contain something quite other than the salt itself. The products
of the decomposition constitute ions. Simple bodies, considered as such to be
indecomposable, evidently could not be electrolytes and consequently produce ions.
This last was a fundamental point. The electricity determines the equivalent number
because it determines the forces of combination.
All these theories and the experiments whence they are derived show us that
electricity is every day more and more considered as the essential factor in the
properties of bodies. It must be solely from their electrical charge that these
properties are derived. All chemical forces would have an electrical origin. Since
electricity in motion represents energy, it may be said that the transformation of a
body into electricity realizes a change of matter into energy (Le Bon 1908).
The idea that we might separate particles of electricity from their material
support was not imaginable before the recent discoveries. It was even so contrary to
the early experiments, which seem to show that electricity could not be transported
without material support, that for a long time the cathode rays were considered to be
formed by the projection of material particles. The studies such as of the cathode
rays, or of the conductivity of gases, of radioactive emissions, and the universality
of the dissociation of matter, have bolstered the existence of electrons.
All the experiments, many of which showed us particles of electricity freed from
their material support, have naturally given great force to the theory of atomic
electricity, otherwise called the electronic theory. The electricity composed of
discontinuous particles; but there does not seem to be any necessity whatever for
considering matter as composed of electrons. Electricity is, like heat and the other
forces, one of the forms of intra-atomic energy.
All the explanations can be summarized in the three following principles:
(1) Matter contains an enormous reservoir of energy; (2) it can be dissociated; (3) in
dissociation it liberates, in various forms, but especially as electricity, a part of the
intra-atomic energy accumulated within it at the moment of its formation.
Electricity, heat, and all the energies of the universe represent unstable forms of
matter.
The forces caused by electric and magnetic fields are mostly what we can
actually measure in electromagnetism. These vector quantities are related to the
scalar and vector potentials as follows:
E ¼ fð@u=@xÞ; ð@u=@yÞ; ð@u=@zÞg ð@A=@tÞ ðelectric fieldÞ ð1:1Þ

B fð@Az=@yÞ @Ay =@z g fð@Ax=@zÞ ð@Az =@xÞg fð@Ay=@xÞ
ð@Ax =@yÞg ðmagnetic fieldÞ ð1:2Þ
By comparison of Eqs. (1.1) and (1.2) with the general expression for force in
gauge theory, we find that the electromagnetic force (Fem) on a particle with charge
q is
4 1 Introduction
Fem ¼ fð@U=@xÞ; ð@U=@yÞ; ð@U=@zÞg ð@Q=@tÞ þ v P
Fem ¼ qfð@u=@xÞ; ð@u=@yÞ; ð@u=@zÞg qð@A=@tÞ þ qv B
Fem ¼ qE þ qv B ðElectromagnetic force or Lorentz forceÞ ð1:3Þ
where v in Eq. (1.3) is the velocity of the particle.

The forces on quantified particles due to electromagnetic fields are introduced
and related to the general case of force on a particle by a gauge field. The principles
of electric motors and generators are then addressed as an example of such forces in
action.
The theory of electrons is therefore quite powerless to explain electrification by
influence. It may result from somewhat different mechanisms which prove that
bodies subjected to the same electric influence may, according to circumstances,
acquire charges of contrary sign. The English physicist William Crookes (1832–
1919) had devised, by 1875, a still better evacuated tube (a Crookes tube), in which
the electric current through a vacuum could more easily be studied. It seemed quite
clear that the electric current started at the cathode and traveled to the anode, where
it struck the neighboring glass and created the glow of light.
Crookes demonstrated this by placing a piece of metal in the tube and showing
that it cast a shadow on the glass on the side opposite the cathode.
At the time physicists did not know what an electric current might be and they
could not easily tell just what it was that was moving from the cathode to the anode.
Whatever it was, it traveled in straight lines (as it cast sharp shadows), so without
committing oneself to any decision as to its nature, one could refer to it as a
“radiation”. Indeed, in 1876, the German physicist Eugen Goldstein (1850–1930)
named the flow cathode rays.
Then, in 1897, the English physicist Joseph John Thomson (1856–1940),
working with very highly evacuated tubes, was finally able to show cathode ray
deflection in an electric field that was the final link in the chain of evidence, and it
had to be accepted that the cathode rays were streams of particles carrying a
negative electric charge. The amount by which the cathode ray particle is deflected
in a magnetic field of given strength is determined by its mass and by the size of its
electric charge. Thomson was therefore able to measure the ratio of the mass to the
charge, though he couldn’t measure either separately. On April 30, 1897,
J. J. Thomson (1856–1940) announced that cathode rays were negatively charged
particles which he called ‘corpuscles’ (Thomson 1897).
There were ample reasons for preferring the latter alternative and assuming the
cathode-ray particle to be much smaller than any atom. By 1911 this was proven
definitely by the American physicist Robert Andrews Milikan (1868–1953), who
succeeded in measuring, quite accurately, the minimum electric quantity that could
be carried by a particle.
Ever since the time of Faraday’s laws of electrolysis, it had seemed that elec-
tricity might be carried by particles. In 1891, the Irish physicist George Johnstone
Stoney (1826–1911) had even suggested a name for the fundamental unit of
electricity, whether particle or not.
The photoelectric effect was discovered by Hertz in 1887 (Panarella 1989). He
found that an electric spark had more energy if the electrodes were irradiated with
ultraviolet light. He determined that the spark was initiated at the negative
electrode.
This revolutionary possibility was made the more plausible because of a phe-
nomenon first observed in 1888 by the German physicist Heinrich Rudolf Hertz
(1857–1894) during the course of experiments in which he discovered radio wave.
While sending an electric spark across an air gap from one electrode to another,
Hertz found that when ultraviolet light shone on the cathode, the spark was more
easily emitted. This, together with other electrical phenomena brought about by the
shining of light upon metal, was eventually termed the photoelectric effect.
Since these other rays traveled in the direction opposite to the negatively charged
cathode rays, it seemed that they must be composed of positively charged particles.
This hypothesis was confirmed when the manner in which they were deflected in a
magnetic field was studied. In 1907, J. J. Thomson named them positive rays.
The New Zealand-born physicist Ernest Rutherford (1871–1937) finally decided
to accept the fact that the unit of positive charge was a particle quite different from
the electron, which was the unit of negative charge. He suggested, in 1914, that the
smallest positive ray particle, the one as massive as the hydrogen atom, be accepted
as the fundamental unit of positive charge. He was confirmed in this view by his
later experiments on nuclear reactions when he frequently found himself producing
an identical particle as a hydrogen-nucleus.
In photoelectric emission, light strikes a material, causing electrons to be
emitted. This classical wave model predicted that as the intensity of incident light
was increased, the amplitude and thus the energy of the wave would increase.
In 1905 Einstein propounded his famous photoelectric theory and equation,
based on Planck’s hypothesis. According to Einstein, it required a particle to knock
the atom immediately. However, note that Hull (1949), points out that the atom
cannot absorb all the energy of a photon if energy and momentum are conserved.
Physical properties such as mass and volume of a photon cannot be defined but its
bulky or current properties might be defined. There are need new concepts and new
equations to explain quantitative properties of photon during the light emission,
photon intensity, and others.
Einstein took Planck’s quantum hypothesis a giant step further by proposing that
photons (“particles” of electromagnetic radiation) are not just artifacts of the
emission (or absorption) of radiation by substances, but a fundamental property of
all radiation, everywhere. Thus, radiation-like electric charge and matter itself—is
quantified in discrete units.
Compton (1923) studied the scattering of x-rays by matter. For x-rays of 1 Å or
greater, or less than 0.4 Å wavelength, the scattering followed the classical theory.
That is, electrons were knocked straight out of paraffins or the like, with no
deflection or alteration of the x-rays.
6 1 Introduction
The forces caused by electric and magnetic fields are mostly what we can
actually measure in electromagnetism. The forces on quantified particles due to
electromagnetic fields are introduced and related to the general case of force on a
particle by a gauge field. The principles of electric motors and generators are then
addressed as an example of such forces in action.
The atomic energy levels, the transitions between these levels, and the associated
spectral lines discussed to this point have implicitly assumed that there are no
magnetic fields influencing the atom. If there are magnetic fields present, the atomic
energy levels are split into a larger number of levels and the spectral lines are also
split. This splitting is called the Zeeman Effect (1987). In an earlier paper has given
an account of the discovery, in the fall of 1896, of the Zeeman Effect and of the
developments in the months that followed (Kox 1997).
The shifting and splitting of spectral lines of atoms and molecules due to the
presence of an external static electric field called as the Stark effect. The amount of
splitting and or shifting is called the Stark splitting or Stark shift. In general one
distinguishes first- and second-order Stark effects. The first-order effect is linear in
the applied electric field, while the second-order effect is quadratic in the field.
The Stark effect is the electric analogue of the Zeeman Effect where a spectral
line is split into several components due to the presence of a magnetic.
Table 1.1 depicts the phenomenon related to the type of effect and driving force
for possible modeling. Zeeman and Stark effects occur in magnetic and electric
field, respectively, that these effects do not prove the existence of an electron.
Table 1.1 Phenomenon related to type of effect and driving force

Phenomenon Type of effect Driving force
Cathode rays Occurring of electricity at lower pressures Gas pressure
in Crookes
Campton effect Occurring of electric current and heat Unknown mechanism
Photoelectric Occurring of electric current and heat Unknown mechanism
effect
Zeeman effect Splitting of a spectral or absorption line Static magnetic field
Stark effect Shifting and splitting of spectral lines of atoms and Static electric field
molecules
Electricity by Occurring of static electricity on a ball Geometric factor
influence
Electricity by Occurring of static electricity on a stick Friction energy
friction
Electricity by Occurring of oxidation on iron surface Surface energy
tension
Electricity by Occurring of both the upstroke and down stroke of Kinetic energy
sea waves the float by gravitational effect
Electricity by Linear motion of shaking body Kinetic energy
shaking
Photoelectric effect:
Sunlight wave + K ! K þ þ e ð1:4Þ
Equation (1.4) is less scientific.
Sunlight energy ðlight wave and/or photon, flow or moving energyÞ þ K

! Heat wave + Kwaveactivated þ Electric wave or current ð1:5Þ
Equation (1.5) is more scientific because it is agree with observations. However,

mechanism of photon formation is unknown. This event may be suspected in the
presence of photons. The wave activation may occur in nano size. Possible mod-
eling maybe occurs in “nano-passageway”.
Campton Effect:
Light wave with high energy þ Cu ! Cu þ þ e ðless scientificÞ ð1:6Þ
Light wave with high energy þ Cu ! Heat wave

ð1:7Þ
þ Cuwaveactivated þ Electric wave or current
Friction between stick of ebonite or glass and wool:
Friction energy ðstatic energyÞ ! Heat energy þ Static electric ð1:8Þ
The frictional force Ff between two solid objects in contact obeys an empirical
law. If the two objects are sliding over each other, the frictional force on each object
acts so as to oppose the relative motion of the two objects.
Electrification by Influence occurs via three routes: (1) electricity by influence,
(2) electricity by friction and (3) electricity by surface tension (becoming faster rusty
of bending iron). Influence enables us to obtain, by means of a limited quantity of
positive electricity an indefinite quantity of negative electricity. Electricity is able to
diffuse itself in conducting bodies by conduction, convection, and influence.
I do not believe in the existence of the electron. Electron Theory costed half a
century our scientific life, but it was a beautiful dream. This dream ended in my
brain, but the scientific community has developed some tools such as mobile
phones when dealing with electron.
1.1.2 Geometric Energy Concept
The mechanical energy of a moving object depends on the mass of the body and
takes the path. Heat and light radiation energy, electricity energy and magnetic
energy do not depend on mass. There is a relation between the symmetry of an
object with the energy or the energy depends on the geometry of the object. Energy
8 1 Introduction
is a geometric concept and geometric factor for the energy differences executive.
The energetic potential consists of geometric differences. For example, energy is
inversely proportional to volume. An electromagnetic wave, the wavelength
decreases, energy increases. This is called the frequency factor. Frequency of a
wave is proportional to the energy emitted.
Geometry of energy can be better understood in nanometer-scale, because the
geometric interaction is very effective in nanometric sizes. Affected by nano-sized
precious metals do not interact chemically.
Nanotechnology is the engineering of functional systems at the molecular scale.
This covers both current work and concepts that are more advanced. In its original
sense, nanotechnology refers to the projected ability to construct items from the
bottom up, using techniques and tools being developed today to make complete,
high performance products.
All the explanations can be summarized in the three following principles:
(1) Matter contains an enormous reservoir of energy; (2) it can be dissociated; (3) in
dissociation it liberates, in various forms, but especially as electricity, a part of the
intra-atomic energy accumulated within it at the moment of its formation.
Electricity, heat, and all the energies of the universe represent unstable forms of
matter (Demirbas 2008a).
Chemical shifts of atoms and/or molecules are caused by changes in the geo-
metric configuration. Chemical energy depends on changes in the geometric con-
figuration of the atoms and/or molecules (Demirbas’s Principles). These are:
(1) If the geometry of atoms and/or molecules does not change the chemical
changes or reactions do not occur.
(2) When decreasing of the total volume of atoms and/or molecules, eventually
pulling each other, exothermic chemical changes occur.
(3) If increasing of the total volume of atoms and/or molecules, at the end repels
each other, endothermic chemical changes occur (Demirbas 2008a).
There are four basic types forces (or interactions) in the universe:
1. The Strong Force. This force is responsible for binding of nuclei.
2. The Electromagnetic Force. This is the force which exists between all particles
which have an electric charge.
3. The Weak Force. This force is responsible for nuclear beta decay and other
similar decay processes involving fundamental particles. The range of this force
is smaller than 1 fm and is 10−7 weaker than the strong force.
4. The Gravitational Force. This is the force that holds us onto the Earth. This force
is extremely small, only in the order of 10−38 times that of the strong force.
In our mind, and accumulated a fairly narrow set of specific rules on how to
behave under various conditions effects or forces. These rules are very specific
predictions about behavior to force us to do and will result in the need to provide
observations and make testable predictions. Stage theory of scientific method is an
amazing process to develop a certain type hypotheses.
In fact, “force” is a geometric concept. The definition of a force that covers all
kinds of force is necessary. Then you need to accept that in reality there is only one
force. Force or violence is an effect and is effective no matter how small grows so
much violence in this volume.
Indeed, when we consider the four above-mentioned types of force, the force
applied to the volume decreases, we see that the increase in violence of the force.
This is a new approach to the concept of force.
1.1.3 Nano-Energy
Photosynthesis is an electrochemical event, but rather an event that took place in

nano-scale. Photosynthesis in nano-electrochemical cells formed transformed into
light energy into chemical energy. The origin of all carbon fuels, which constitute
the most important event in the formation of all fuels:
Sunlight
CO2 þ H2 O ! CH2 O þ O2 ð1:9Þ
Nanoelectrochemical cell
In the energy sector, which is the biggest and the most challenging issue facing
us, advances in nanotechnology can solve certain issues successfully; fossil fuels
can become cleaner, safer and cheaper to produce, in a more environmentally
friendly manner. Renewable resources can become cheaper to produce and easier to
implement. In the domain of nuclear energy, Uranium-based reactors would be
safer, smaller in size, and more cost effective, while their radioactive byproducts
can be recycled. More importantly, nanostructured material and new laser devices
can be developed that will allow us to extract nuclear energy without resorting to
brute-force methods and radioactive byproducts.
It is believe that nanotechnology provides our best hope for a new, cleaner and more
efficient energy system, one that will form the backbone of our future energy industry.
Nanotechnology has the greatest potential impact in the energy field. It offers
some unprecedented opportunities in the creation of sustainable energy forms and
greatly increasing the efficiency of transmission and generation of power. Nano
energy technology covers all aspects of basic and applied research on nano-scale
phenomena for energy production, conversion, storage, transmission and conser-
vation; nanotechnology applied to energy and power topics including solar cells,
fuel cells, batteries, capacitors, energy and power storage systems; planning, design,
and implementation to achieve improved energy efficiency and sustainability (green
energy and bio-refinery); mitigation of safety issues of conventional and uncon-
ventional energy/power sources (Shrair 2013).
Conventional batteries have low energy density and long recharge times.
Investment in nanotechnology should concentrate on new materials that can have
profound and ramifying effects on energy efficiency, such as catalysts for energy
generation or emissions scrubbing, membranes for fuel cells or huge storage
10 1 Introduction
capacitors, or new materials for strong, lightweight transmission lines and new
kinds of lighting. Nanotechnology such as nanotubes, nanowires, and nanocom-
posites for batteries, will bring orders of magnitude improvements. Nanostructured
membranes, nanohorn electrodes, and nanocatalysts will make fuel cells smaller
and more affordable (Demirbas 2008b).
Nanotechnology is science at the smallest scale, and allows us to manipulate the
fundamental building blocks of all matter–atoms. By designing and tweaking mate-
rials at this level scientists can create super materials with incredible new chemical,
electrical and physical properties—properties never before thought possible.
Nanotechnology is already being used to produce stain-resistant fabrics,
odor-eating socks even fire-resistant paints, but its real potential is in the field of
energy. By re-engineering the way we generate, store, transmit and use energy at
the nano-scale, we will be able to create energy technologies that are far cleaner,
more efficient and therefore cheaper, than any of the fossil fuel or alternative energy
technologies around today.
Nanotechnology is a relatively new science—the first major breakthroughs took
place in the mid 1980s and since then work has focused on developing the tools and
equipment needed to work at the nano-scale. But now industrial applications are
starting to multiply and the industry is set to explode over the next few years.
Nano-energy in particular has received little attention to-date but is increasingly
talked about as the most significant area for development. We believe that over the
next 4–5 years, the sort of comprehensive nano-energy portfolio we are developing
will prove to be exceptionally valuable.
Breakthroughs in nanotechnology open up the possibility of moving beyond our
current alternatives for energy supply by introducing technologies that are more
efficient, inexpensive, and environmentally sound.
A solution to the global energy problem will require revolutionary new technology,
as well as conservation and evolutionary improvements in existing technologies.
Efficiencies in the use of energy will come from many advances, but particularly from
revolutionary new materials that are inexpensive, environmentally safe, and both
stronger and lighter than steel. Transmission and storage of energy, particularly
electrical power and hydrogen, is a major societal need, and holds the most promise in
solutions with new nanotechnologies (Demirbas 2008b; Shrair 2013).
Nanotechnology involves areas of biotechnology/bio-refinery, automobile
industry, electronic/semiconductor industry, optoelectronics, medical fields; phar-
maceuticals including drug delivery, cosmetics, among others; material science
including textiles, polymers, packaging, among other, environmental monitoring
and control, food science/quality and packaging, aerospace industry, sports
equipment, national security, and military.
Scientists have been dreaming for decades about long-distance wireless power
transmission from space. Nikola Tesla was one of these scientists. In 1882 he said
“Throughout space there is energy. If static, then our hopes are in vain, if kinetic—
and this we know it is for certain—then it is a mere question of time when men will
succeed in attaching their machinery to the very wheel work of nature.” Recent
technological breakthroughs, particularly in nanomaterials and computing, will
open the door wide for the realization of this space energy dream. NASA is working
on a revolutionary model for a “power satellite system.” The satellite will be
designed to either employ large thin film structures or mirrors to redirect incoming
photons to the PV and transmitting arrays (Shrair 2013; Jarvis and Richmond 2011;
Zhang et al. 2014).
The origin of all carbon fuels, which constitute the most important event in the
formation of all fuels. Nano-energy facilities are promised great opportunities on
area of the space technology and nuclear energy for the future. In the future,
nanotechnological know-how may play a key role for the required innovation in the
energy sector. Using nanostructured catalyst is provided new liquid fuels from
fossil and bio-renewable materials.
1.2 Energy Sources
Well known energy sources are mainly classified into three groups fossil, fissile and
renewable. Primary energy sources can be divided into non-renewables and
renewables. Figure 1.1 shows the basic classification of energy sources.
Non-renewable energy sources include coal, petrol, gas, gas hydrate and fissile
material, while renewable energy sources are biomass, hydro, geothermal, solar and
wind energy. The main fissile energy sources are uranium and thorium.
The energy source can be also classified according to its depletion rate. Whilst
the biomass energy can be depleted, solar and wind energy are non-depletable. The
reality shows that the energy availability from the non-renewable sources is limited,
and beyond that, the exploration, the processing and the use of energy impose
considerable impacts on the environment. Today, fossil fuels have been the prime
sources of energy for the purpose of transportation, power generation, and agri-
culture, commercial, domestic and industrial activity for more than a century. The
world’s energy requirements are currently satisfied by fossil fuels, which serve as
the primary energy source.
Because of increase in petroleum prices especially after petrol crisis in 1973 and
then gulf war in 1991, geographically reduced availability of petroleum and more
stringent governmental regulations on exhaust emissions, researchers have studied
on alternative fuels and alternative solution methods.
Fig. 1.1 Basic classification Energy Sources

of energy sources
Non-renewables Fissile Renewables
Conventional Non-conventional Conventional Non-conventional

12 1 Introduction
The world is presently confronted with twin crises of fossil fuel depletion and
environmental degradation. To overcome these problems, recently renewable
energy has been receiving increasing attention due to its environmental benefits and
the fact that it is derived from renewable sources such as virgin or cooked vegetable
oils (both edible and non-edible). The world’s over-demand of energy, oil crisis and
the continuous increase in oil prices led countries to investigate on new and
renewable fuel alternatives. Hence, the energy sources, like sun, wind, geothermal,
hydraulic, nuclear, hydrogen and biomass were taken into consideration.
Interestingly, the renewable energy resources are more evenly distributed than
fossil or nuclear resources. Today’s energy system is unsustainable because of
equity issues as well as environmental, economic, and geopolitical concerns that
will have implications far into the future. Hence, sustainable renewable energy
sources such as biomass, hydro, wind, solar (both thermal and photovoltaic),
geothermal, and marine energy sources will play an important role in the world’s
future energy supply.
Developing renewable sources of energy has become necessary due to limited
supply of fossil fuels. Global environmental concerns and decreasing resources of
crude oil have prompted demand for alternative fuels. Global climate change is also
the major environmental issue of current times. Global Warming, the Kyoto
Protocol, the emission of greenhouse gases and the depletion of fossil fuels are the
topics of environmental pleadings worldwide. Increasing rapidly energy require-
ments parallel to technological development in the world, research and develop-
ment activities force to study new and renewable energy investigations.
The major sources of alternative energy are biorenewables, hydro, solar, wind,
geothermal and other energies, each of them having their own advantages and
disadvantages, including political, economical and practical issues. Renewable
energy is a promising alternative solution because it is clean and environmentally
safe. They also produce lower or negligible levels of greenhouse gases and other
pollutants when compared with the fossil energy sources they replace.
1.2.1 Fossil Energy Sources
The term fossil refers to an earlier geologic age. Fossil fuels were formed a great
many years ago and are not renewable. The fossil energy sources are petroleum
(crude oil), coal, bitumens, natural gas, oil shales, and tar sands. About 98 % of
carbon emissions result from fossil fuel combustion. In fact today, over 80 % of the
energy we use comes from three fossil fuels: petroleum, coal, and natural gas. The
current consumed global energy consists of oil (36 %), natural gas (24 %), coal
(28 %), renewable energy (7 %) such as hydro, wind and solar, and nuclear (6 %).
Petroleum reserves distribute as uneven in the world; for example, the Middle
East has 63 % of the global reserves and is the dominant supplier of petroleum.
Petroleum is the largest single source of energy consumed by the world’s pop-
ulation, exceeding coal, natural gas, nuclear, hydro and renewables. Unfortunately
1.2 Energy Sources 13
the petroleum oil is in danger of becoming short in supply. Hence, the future trend is
towards using alternate energy sources. Fortunately, the technological development
is making the transition possible (Kirtay 2009).
The word “petroleum” comes from the Greek word petra, or rock, and Latin
word oleum, oil. Oil is a thick, dark brown or greenish liquid found in reservoirs in
sedimentary rock. Tiny pores in the rock allowed the petroleum to seep in. These
“reservoir rocks” hold the oil like a sponge, confined by other, non-porous layers
that form a “trap.” It is used to describe a broad range of hydrocarbons that are
found as gases, liquids, or solids beneath the surface of the Earth. The two most
common forms are natural gas and crude oil. Petroleum consists of a complex
mixture of various hydrocarbons, largely of the alkane and aromatic compounds.
The color ranges from pale yellow through red and brown to black or greenish,
while by reflected light it is, in the majority of cases, of a green hue. Petroleum is a
fossil fuel because it was formed from the remains of tiny sea plants and animals
that died millions of years ago, and sank to the bottom of the oceans.
Table 1.2 shows crude oil production data for various regions (IEA 2007). The
Middle East produces 32 % of the world’s oil, but more importantly it has 64 % of
the total proven oil reserves in the world. Oil fields follow a size distribution
consisting of a very few large fields and a great many smaller ones. This distri-
bution is illustrated by the fact that 60 % of the world’s oil supply is extracted from
only 1 % of the world’s active oil fields. As one of these very large fields plays out
it can require the development of hundreds of small fields to replace its production.
Some definitions will be useful. ‘Petroleum’ and ‘oil’ are used synonymously to
include crude oil, shale oil, oil sands and natural gas liquids. The word petroleum
generally refers to crude oil or the refined products obtained from the processing of
crude oil (gasoline, diesel fuel, heating oil, etc.). Crude oil (raw petroleum) is
separated into fractions by fractional distillation. The fractions at the top are lower
than the fractions at the bottom. The heavy bottom fractions are often cracked into
lighter, more useful products.
Crude oil (raw petroleum) is separated into fractions by fractional distillation in
the refinery. The fractions at the top are lower than the fractions at the bottom. The
heavy bottom fractions are often cracked into lighter, more useful products. All of
the fractions are processed further in other refining units.
Table 1.2 1973 and 2012 Region 1973 2012

regional shares of crude oil
production Middle East (%) 37.0 31.5
OECD (%) 23.6 23.2
Former USSR (%) 15.0 14.9
Africa (%) 10.0 11.8
Latin America (%) 8.6 8.9
Asia excludes China (%) 3.2 4.6
China (%) 1.9 4.9
Non-OECD Europe (%) 0.7 0.2
Total (Million tons) 2867 3992
14 1 Introduction
An oil refinery cleans and separates the crude oil into various fuels and
byproducts. The most important one is gasoline. Some other petroleum products are
diesel fuel, heating oil, and jet fuel. Refineries use many different methods to make
these products. One method is a heating process called distillation. Since oil
products have different boiling points, the end products can be distilled or sepa-
rated. For example, asphalts have a higher boiling point than gasolines, allowing the
two to be separated. A refinery removes sulfur from gasoline, for example, to
increase its efficiency and to reduce air pollution.
When a mixture of two liquids of different boiling points is heated to its boiling
point, the vapor contains a higher mole fraction of the liquid with the lower boiling
point than the original liquid; i.e. the vapor is enriched in the more volatile com-
ponent. If this vapor is now condensed, the resultant liquid has also been enriched
in the more volatile component. This is the principle of batch fractional distillation,
and in a distillation column many, many such cycles are performed continuously,
allowing almost complete separation of liquid components. A generalized distil-
lation column is shown in Fig. 1.2 (Demirbas 2010). The first step in the refining of
crude oil, whether in a simple or a complex refinery, is the separation of the crude
oil into fractions (fractionation or fractional distillation). These fractions are mix-
tures containing hydrocarbon compounds whose boiling points lie within a speci-
fied range.
Uncondensed gases
Condensor Separator
Reflux
Furnace for Multi-stage

Feed partial Fractional
vaporization Distillation
column
Reboil
Heat
exhanger
Bottom products
Fig. 1.2 A generalized fractional distillation column

Industrial distillation is typically performed in large, vertical, steel cylindrical

columns known as “distillation towers” or “distillation columns” with diameters
ranging from about 65 cm–11 m and heights ranging from about 6–60 m or more. To
improve the separation, the tower is normally provided inside with horizontal plates or
trays, or the column is packed with a packing material. To provide the heat required
for the vaporization is most often added to the bottom of the column by a reboiler.
Large-scale industrial fractionation towers use reflux to achieve more efficient
separation of products. Reflux refers to the portion of the condensed overhead
liquid product from a distillation tower that is returned to the upper part of the
tower. Inside the tower, the downflowing reflux liquid provides cooling and partial
condensation of the upflowing vapors, thereby increasing the efficacy of the dis-
tillation tower. There are generally 25–45 plates or trays in a distillation tower. Each
of the plates or trays is at a different temperature and pressure. The stage at the
tower bottom has the highest pressure and temperature. Progressing upwards in the
tower, the pressure and temperature decreases for each succeeding stage. Another
way of improving the separation in a distillation column is to use a packing material
instead of trays.
Crude oil is a complex mixture that is between 50 and 95 % hydrocarbon by
weight. The first step in refining crude oil involves separating the oil into different
hydrocarbon fractions by distillation. An oil refinery cleans and separates the crude
oil into various fuels and byproducts, including gasoline, diesel fuel, heating oil,
and jet fuel. Since various components boil at different temperatures, refineries use
a heating process called distillation to separate the components. For example,
gasoline has a lower boiling point than kerosene, allowing the two to be separated
by heating to different temperatures. Another important job of the refineries is to
remove contaminants from the oil. For example, sulfur from gasoline or diesel to
reduce air pollution from the automobile exhausts. After processing at the refinery,
gasoline and other liquid products are usually shipped out through pipelines, which
are the safest and cheapest way to move large quantities of petroleum across land.
Three major refinery processes change crude oil into finished products:
(1) Separation,
(2) Conversion,
(3) Purification.
The first step is to separate the crude oil into its naturally occurring components.
This is known as separation and is accomplished by applying heat through a process
called distillation. Separation is performed in a series of distillation towers. The
conversion processes have focused on reducing the length of some hydrocarbon
chains. Primary purpose of conversion processes is to convert low valued heavy oil
into high valued petrol. For example, Catalytic Reforming is a conversion process.
The purpose of the reformer is to increase the octane number of petrol blend
components. Once crude oil has been through separation and conversion, the
resulting products are ready for purification, which is principally sulfur removal.
Common process units found in an oil refinery are presented in Table 1.3.
16 1 Introduction
Table 1.3 Common process units found in an oil refinery

Unit Treatment
1 Desalter It washes out salt from the crude oil before it enters the
atmospheric distillation unit
2 Atmospheric It distills crude oil into fractions
distillation
3 Vacuum distillation It further distills residual bottoms after atmospheric distillation
4 Naphtha hydrotreater It uses hydrogen to desulfurize naphtha from atmospheric
distillation
5 Catalytic reformer It is used to convert the naphtha-boiling range molecules into
higher octane reformer product (reformate)
6 Distillate hydrotreater It desulfurizes distillates (such as diesel) after atmospheric
distillation
7 Fluid catalytic cracker FCC upgrades heavier fractions into lighter, more valuable
(FCC) products
8 Hydrocracker It uses hydrogen to upgrade heavier fractions into lighter,
more valuable products
9 Visbreaking It upgrades heavy residual oils by thermally cracking them
into lighter, more valuable reduced viscosity products
10 Merox It treats LPG, kerosene or jet fuel by oxidizing mercaptans to
organic disulfides
11 Coking It converts very heavy residual oils into gasoline and diesel
fuel, leaving petroleum coke as a residual product
12 Alkylation It produces high-octane component for gasoline blending
13 Dimerization It converts olefins into higher-octane gasoline blending
components
14 Isomerization It converts linear molecules to higher-octane branched
molecules for blending into gasoline
15 Steam reforming It produces hydrogen for the hydrotreaters or hydrocracker
16 Liquefied gas storage For propane and similar gaseous fuels at pressure sufficient to
maintain in liquid form
17 Storage tanks For crude oil and finished products, usually cylindrical, with
some sort of vapor emission control
18 Amine gas and tail For converting hydrogen sulfide from hydrodesulfurization
gas treatment into elemental sulfur
19 Utility units Such as cooling towers for circulating cooling water, boiler
plants for steam generation
20 Wastewater collection It converts wastewater to water suitable for reuse or for
and treating disposal
21 Solvent refining It use solvent such as cresol or furfural to remove unwanted,
mainly asphaltenic materials from lubricating oil stock
22 Solvent dewaxing For removing the heavy waxy constituents petroleum from
vacuum distillation products
(continued)
Table 1.3 (continued)

Unit Treatment
23 Deasphalting Precipitation of asphaltenes from raw petroleum provides a
huge problem for the oil industry. Maltenes can be removed
from crude oil by n-hexane filtration and asphaltenes remain
as residue and subsequently recovered by aromatic washing
24 Resins removing The resins are soluble in light alkanes and they are adsorbed
on a solid such as alumina, clay, or silica, and subsequently
recovered by use of a more polar solvent
The refining of heavy oil requires exacting and thorough chemical, engineering,
and computing processes. Before the actual refining begins, the stored heavy crude
oil is cleaned of contaminants such as sand and water.
Petrochemicals are chemical products made from raw materials of petroleum or
other hydrocarbon origin. Although some of the chemical compounds that originate
from petroleum may also be derived from other sources such as coal or natural gas,
petroleum is a major source of many.
The two main classes of petrochemical raw materials are olefins (including
ethylene and propylene) and aromatics (including benzene and xylene isomers),
both of which are produced in very large quantities. At oil refineries, olefins are
produced mainly from hydrocarbons by chemical cracking such as steam cracking
and by catalytic. At oil refineries, aromatic hydrocarbons are mainly produced by
catalytic reforming or similar processes. From these basic building blocks is made a
very wide range of chemicals and other materials used in industry—monomers,
solvents, and adhesives. From the monomers, polymers or oligomers are produced
for plastics, resins, fibers, elastomers, certain lubricants, and gels.
World production of ethylene is around 110 million tons per annum, of
propylene 65 million tons, and of aromatic raw materials 70 million tons. The
largest petrochemical industries are to be found in the USA and Western Europe,
though the major growth in new production capacity is in the Middle East and Asia.
There is a substantial inter-regional trade in petrochemicals of all kinds.
After processing at the refinery, gasoline and other petroleum products are
usually shipped out through pipelines. There are about 230,000 miles of pipeline in
the United States. Pipelines are the safest and cheapest way to move large quantities
of petroleum across land. Pump stations, which are spaced 20–100 miles apart
along the underground pipelines, keep the petroleum products moving at around
five miles per hour. At this rate, it takes 15 days to move a shipment of gasoline
from Houston, Texas to New York City.
Americans use almost 17 million barrels of oil every day of the year. Texas
produces more oil than any other state. The other top producing states are Alaska,
California, Louisiana, and Oklahoma in that order. In all, 31 states produce
petroleum.
18 1 Introduction
The United States has become increasingly dependent upon other countries for
petroleum. In 1994 the US purchased 45 % of our petroleum from other countries.
Americans know this dependence can be dangerous.
The oil industry classifies “crude” by the location of its origin (e.g., “West Texas
Intermediate, WTI” or “Brent”) and often by its relative weight (API gravity) or
viscosity (“light”, “intermediate” or “heavy”); refiners may also refer to it as
“sweet”, which means it contains relatively little sulfur, or as “sour”, which means
it contains substantial amounts of sulfur and requires more refining in order to meet
current product specifications.
There are different classification schemes: based on economic and/or geological
criteria. There generally are main oil classes: Conventional oil and Non-
conventional oil. The conventional oil is oil which can be produced with current
technology under present economic conditions.
The crude oil is separated by boiling points into six main grades of hydrocar-
bons: refinery gas (used for refinery fuel), gasoline (naphthas), kerosene, light oils
(diesel oil or diesel fuel) and heavy gas oils (fuel oil) and long residue. This initial
separation is done by distillation. The first step in the refining of crude oil, whether
in a simple or a complex refinery, is the separation of the crude oil into fractions
(fractionation or distillation). These fractions are mixtures containing hydrocarbon
compounds whose boiling points lie within a specified range.
Gasoline is a petroleum-derived liquid mixture, primarily used as fuel in internal
combustion engines, specifically in spark-ignition engines. In the Otto cycle engine
a mixture of gasoline and air is compressed and is then ignited by a spark plug.
The Otto Cycle Engine was invented by Dr. Nikolaus August Otto in 1876 it is
also commonly known as a four-stroke cycle Engine because of the four strokes
involved in an internal combustion engine.
Gasoline is a complex mixture of over 500 hydrocarbons that may have between
5 and 12 carbons. Gasoline is a blend of hydrocarbons with some contaminants,
including sulfur, nitrogen, oxygen and certain metals. The four major constituent
groups of gasoline are olefins, aromatics, paraffins, and naphthenes. It consists
mostly of aliphatic hydrocarbons, enhanced with iso-octane or the aromatic
hydrocarbons toluene and benzene to increase its octane rating.
The important characteristics of gasoline are density, vapor pressure, distillation
range, octane number, and chemical composition. To be attractive, a motor gasoline
must have (a) desirable volatility, (b) anti-knock resistance (related to octane rat-
ing), (c) good fuel economy, (d) minimal deposition on engine component surfaces,
and (e) complete combustion and low pollutant emissions.
An important characteristic of gasoline is its octane number or octane rating,
which is a measure of how resistant gasoline is to the abnormal combustion phe-
nomenon known as pre-detonation (also known as knocking, pinging, spark knock,
and other names). Octane number is measured relative to a mixture of
2,2,4-trimethylpentane and n-heptane. Octane number a measure of the gasoline
quality for prevention of early ignition which leads to cylinder knocks. Higher
octane numbers are preferred in internal combustion engines. For gasoline
production, aromatics, naphthenes and isoalkanes are highly desirable, whereas

olefins and n-paraffins are less desired.
The density of gasoline is 0.71–0.77 kg/L. Gasoline is more volatile than diesel
oil, Jet-A or kerosene, not only because of the base constituents, but because of the
additives that are put into it. The final control of volatility is often achieved by
blending with butane. The desired volatility depends on the ambient temperature: in
hotter climates, gasoline components of higher molecular weight and thus lower
volatility are used. In cold climates, too little volatility results in cars failing to start.
In hot climates, excessive volatility results in what is known as “vapor lock” where
combustion fails to occur, because the liquid fuel has changed to a gaseous fuel in
the fuel lines, rendering the fuel pump ineffective and starving the engine of fuel.
The typical composition of gasoline hydrocarbons (% volume) is as follows:
4–8 % alkanes; 2–5 % alkenes; 25–40 % isoalkanes; 3–7 % cycloalkanes; l–4 %
cycloalkenes; and 20–50 % total aromatics (0.5–2.5 % benzene). Additives and
blending agents are added to the hydrocarbon mixture to improve the performance
and stability of gasoline. These compounds include anti-knock agents, anti-
oxidants, metal deactivators, lead scavengers, anti-rust agents, anti-icing agents,
upper-cylinder lubricants, detergents, and dyes.
Diesel is produced by distilling raw oil which is extracted from bedrock. Diesel
is a fossil fuel. Diesel consists of hydrocarbons with between 9 and 27 carbon atoms
in a chain as well as a smaller amount of sulfur, nitrogen, oxygen and metal
compounds. It is a general property of hydrocarbons that the auto-ignition tem-
perature is higher for more volatile hydrocarbons. The hydrocarbons present in the
diesel fuels include alkanes, naphthenes, olefins and aromatics. In addition other
substances are added to improve the characteristics of diesel fuel. Its boiling point is
between 445 and 640 K. A good diesel fuel is characterized by low sulfur and
aromatic content, good ignition quality, the right cold weather properties, low
content of pollutants and also the right density, viscosity and boiling point.
The diesel engine burns fuel oil rather than gasoline and differs from the gasoline
engine in that it uses compressed air in the cylinder rather than a spark to ignite the
fuel. Diesel or diesel fuel in general is any fuel used in diesel engines. The diesel
engine is used mainly for heavy vehicles. The main advantage of the diesel engine
is that the level of efficiency is greater than in the Otto cycle engine. This means
that a greater part of the energy content of the fuel is exploited. The efficiency of a
diesel engine is at best 45 %, compared to 30 % for the Otto engine.
Diesel fuel comes in several different grades, depending upon its intended use.
Like gasoline, diesel fuel is not a single substance, but a mixture of various
petroleum-derived components, including paraffins, isoparaffins, napthenes, olefins
and aromatic hydrocarbons, each with their own physical and chemical properties.
Unlike spark-ignition engines, the power and economy of diesel engines are
comparatively insensitive to fuel volatility. There is some indirect impact in that
less volatile fuels have higher heating values (HHVs). Conversely fuels with higher
front-end volatility tend to improve starting and warm-up performance and reduce
smoke. Ideal fuel volatility requirements will vary based on engine size and design,
speed and load conditions, and atmospheric conditions. As an example, more
20 1 Introduction
volatile fuels may provide better performance for fluctuating loads and speeds such
as those experienced by trucks and buses.
The viscosity of diesel fuel is an important property which impacts the perfor-
mance of fuel injection systems. Some injection pumps can experience excessive
wear and power loss due to injector or pump leakage if viscosity is too low. If fuel
viscosity is too high, it may cause too much pump resistance, filter damage and
adversely affect fuel spray patterns. High fuel viscosity can cause an injector spray
pattern with poor fuel dispersion.
Coal can be defined as a sedimentary rock that burns. It was formed by the
decomposition of plant matter, and it is a complex substance that can be found in
many forms. Coal is divided into four classes: lignite, bituminous, sub-bituminous,
and anthracite.
The worldwide coal production is roughly equal to the gas production and only
second to that of oil. Coal is produced in deep mines (hard coal) and in surface
mines (lignite). Coal has played a key role as a primary source of organic chemicals
as well as a primary energy source. Coal may become more important both as an
energy source and as the source of carbon-based materials, especially aromatic
chemicals in the 21st century (Schobert and Song 2002).
First known and the oldest fossil fuel is coal. Coal has played a key role as a
primary energy source as well as a primary source of organic chemicals. It is a
complex, heterogeneous combustible material, made up of portions which are either
useful (carbon and hydrogen), or useless (diluents such as moisture, ash and oxy-
gen, or contaminants such as sulfur and heavy metals). Coal can be defined as a
sedimentary rock that burns. It was formed by the decomposition of plant matter,
and it is a complex substance that can be found in many forms. Coal is divided into
four classes: anthracite, bituminous, sub-bituminous, and lignite. Elemental analysis
gives empirical formulas such as C137H97O9NS for bituminous coal and
C240H90O4NS for high-grade anthracite.
Coal accounted for 26 % of the world’s primary energy consumption and 37 % of
the energy consumed worldwide for electricity generation. For coal to remain com-
petitive with other sources of energy in the industrialized countries of the world,
continuing technological improvements in all aspects of coal extraction are necessary.
Nearly all the different forms of coal are used in some way or other. For instance, peat
has been used for burning in furnaces; lignite is used in power station and home
stoves, whereas bituminous coal is used extensively for the generation of electricity.
Coal is formed from plant remains that have been compacted, hardened,
chemically altered, and metamorphosed underground by heat and pressure over
millions of years. When plants die in a low-oxygen swamp environment, instead of
decaying by bacteria and oxidation, their organic matter is preserved. Over time,
heat and pressure remove the water and transform the matter into coal. The first step
in coal formation yields peat, compressed plant matter which still contains leaves
and twigs. The second step is the formation of brown coal or lignite. Lignite has
already lost most of the original moisture, oxygen, and nitrogen. It is widely used as
a heating fuel but is of little chemical interest. The third stage, bituminous coal, is
also widely utilized as a fuel for heating. Bituminous is the most abundant form of
Table 1.4 World’s recoverable coal reserves

Country Bituminous including anthracite Sub-bituminous Lignite
United States of America 115891 101021 33082
China 62200 33700 18600
India 82396 – 2000
South Africa 49520 – –
Kazakhstan 31100 – 3000
Brazil – 11929 –
Colombia 6267 381 –
Canada 3471 871 2236
Indonesia 790 1430 3150
Botswana 4300 – –
Uzbekistan 1000 – 3000
Turkey 278 761 2650
Pakistan – 2265 –
Thailand – – 1268
Chile 31 1150 –
Mexico 860 300 51
Peru 960 – 100
Kyrgyzstan – – 812
Japan 773 – –
Korea (Democ. People’s Rep.) 300 300 –
Zimbabwe 502 – –
Venezuela 479 – –
Philippines – 232 100
Mozambique 212 – –
Swaziland 208 – –
Tanzania 200 – –
Others 449 379 27
coal and is the source of coke for smelting, coal tar, and many forms of chemically
modified fuels. Table 1.4 shows world’s recoverable coal reserves (IEA 2007).
The role of natural gas (NG) in the world’s energy supply is growing rapidly.
NG is the fastest growing primary energy source in the world. The reserves and
resources of conventional NG are comparable in size to those of conventional oil,
but global gas consumption is still considerably lower than that of oil. The proved
gas reserves are not evenly distributed around the globe: 41 % of them are in the
Middle East and 27 % in Russia. A peak in conventional gas production may occur
between 2020 and 2050. NG accounts today for 25 % of world primary energy
production (Jean-Baptiste and Ducroux 2003). Because it is cleaner fuel than oil or
coal and not as controversial as nuclear power, gas is expected to be the fuel of
choice for many countries in the future. Increasing demand for NG is expected in all
22 1 Introduction
Table 1.5 World natural gas Country Percent of world total

reserves by country
Russian Federation 33.0
Iran 16.2
Qatr 5.8
United Arab Emirates 4.1
Suudi Arabia 4.0
United States 3.3
Venezuela 2.8
Algeria 2.5
Nigeria 2.4
Iraq 2.1
Turkmenistan 2.0
Top 20 countries 89.0
Rest of world 10.7
sectors of the world, as resource availability, rate, and environmental considerations

all favor its use. World natural NG reserves by country are given in Table 1.5
1.2.2 Renewable Energy Sources
Renewable energy is the source of energy that can be replenished in a short while
by nature. Renewable energy sources that use indigenous resources have the
potential to provide energy services with zero or almost zero emissions of both air
pollutants and greenhouse gases. Currently, renewable energy sources supply 14 %
of the total world energy demand. Large-scale hydropower supplies 20 % of global
electricity. Renewable resources are more evenly distributed than fossil and nuclear
resources. Renewable energy scenarios depend on environmental protection which
is an essential characteristic of sustainable developments.
For biomass resources, several potentials may be used. Biomass resources are
agricultural and forest residues, algae and grasses, animal manure, organic wastes
and biomaterials. The supply is dominated by traditional biomass used for cooking
and heating, especially in rural areas of developing countries. Worldwide biomass
ranks fourth as an energy resource, providing approximately 14 % of the world’s
energy needs (Hall et al. 1992).
Biomass, mainly now represent only 3 % of primary energy consumption in
industrialized countries. However, much of the rural population in developing
countries, which represents about 50 % of the world’s population, is reliant on
biomass, mainly in the form of wood, for fuel. In Europe, North America and the
Middle East, the share of biomass averages 2–3 % of total final energy con-
sumption, whereas in Africa, Asia and Latin America, which together account for
three-quarters of the world’s population, biomass provides a substantial share of the
energy needs: a third on average, but as much as 80–90 % in some of the poorest
countries of Africa and Asia (e.g. Angola, Ethiopia, Mozambique, Tanzania,
Democratic Republic of Congo, Nepal and Myanmar). Large scale hydro power
provide about one-quarter of the world’s total electricity supply, virtually all of
Norway’s electricity and more than 40 % of the electricity used in developing
countries. The technically usable world potential of large-scale hydro is estimated
to be over 2200 GW.
There are two small-scale hydropower systems: micro hydropower systems
(MHP) with capacities below 100 kW and small hydropower systems (SHP) with
capacity between 101 kW and 1 MW. Large-scale hydropower supplies 20 % of
global electricity. In the developing countries, considerable potential still exists, but
large hydropower projects may face financial, environmental, and social constraints
(UNDP 2000).
Geothermal energy for electricity generation has been produced commercially
since 1913 and for four decades on the scale of hundreds of MW both for electricity
generation and direct use. The utilization has increased rapidly during the last three
decades. In 2000, geothermal resources have been identified in over 80 countries
and there are quantified records of geothermal utilization in 58 countries in the
world. Table 1.6 shows the status of geothermal energy (Fridleifsson 2001).
Geothermal energy is clean, cheap and renewable, and can be utilized in various
forms such as space heating and domestic hot water supply, CO2 and dry-ice
production process, heat pumps, greenhouse heating, swimming and balneology
(therapeutic baths), industrial processes and electricity generation. The main types
of direct use are bathing, swimming and balneology (42 %), space heating (35 %),
greenhouses (9 %), fish farming (6 %), and industry (6 %) (Fridleifsson 2001).
Table 1.6 World’s top Country Installed MWt Production (GWh/a)

countries using geothermal
energy in direct uses China 2282 10531
Japan 1167 7482
USA 3766 5640
Iceland 1469 5603
Turkey 820 4377
New Zealand 308 1967
Georgia 250 1752
Russia 308 1707
France 326 1360
Sweden 377 1147
Hungary 473 1135
Mexico 164 1089
Italy 326 1048
Romania 152 797
Switzerland 547 663
24 1 Introduction
One of the most abundant energy resources on the surface of the earth is sun-
light. Today, solar energy has a tiny contribution in the world total primary energy
supply of less than 1.0 (Ramachandra 2007). The potential of solar energy—passive
solar heat, collectors for e.g. hot water, and photovoltaic (PV) power—is
tremendous.
Following the oil crises of the 1970s, energy experts began to explore whether
solar-based power generation held potential as an alternative petroleum-based fuels.
Development of solar power has progressed considerably since then, yet its record
of performance has been mixed, and it has not come into widespread use in either
industrialized or developing countries.
PV systems, other than solar home heating systems, are used for communication,
water pumping for drinking and irrigation, and electricity generation. The total
installed capacity of such systems is estimated at about 1000 kW. A solar home
heating system is a solar PV system with a maximum capacity of 40 W. These
systems are installed and managed by a household or a small community (Garg and
Datta 1998).
Like wind power markets, PV markets have seen rapid growth and costs have
fallen dramatically. The total installed capacity of such systems is estimated at
about 1000 kW. Solar PV is growing fast, the PV and grid-connected wind installed
capacities are growing at a rate of 30 % a year (Demirbas 2005a).
Wind energy is a significant resource; it is safe, clean, and abundant. Wind
energy is an indigenous supply permanently available in virtually every nation in
the world. Using the wind to produce electricity by turning blades on a wind turbine
is called as wind energy or wind power. More recently large wind turbines have
been designed that are used to generate electricity. Wind source of energy is
non-polluting and freely available in many areas. As wind turbines are becoming
more efficient, the cost of the electricity they generate is falling.
Wind power in coastal and other windy regions is promising as well. Today there
are wind farms around the world. Production of wind-generated electricity has risen
from practically zero in the early 1980s to more than 7.5 TWh per year in 1995.
Cumulative generating capacity worldwide has topped 6500 MW in late 1997
(Demirbas 2005a). Globally, wind power generation more than quadrupled between
1999 and 2005.
Wind energy is abundant, renewable, widely distributed, clean, and mitigates the
greenhouse effect if it is used to replace fossil-fuel-derived electricity. Wind energy
has limitations based on geography and meteorology, plus there may be political or
environmental problems (e.g. dead birds) with putting turbines in (Garg and Datta
1998). On the other hand, wind can cause to air pollution by degradation and
distribution of pieces of pollutants such as waste paper, straw etc.
The world developments in the field of energy supply, after the oil crisis of the
70s and the oil crisis of 2004, are showing the way to more serious decisions
towards sustainability in strategic energy planning, the improvement of energy
efficiency and the rational use of energy. Renewable energy sources are increas-
ingly becoming a key factor in this line of thought.
1.2.3 Nuclear Energy Sources
Atoms are two types, non-radioactive (stable) and radioactive (including unstable or
unbalanced nucleus). Unstable (i.e. radioactive) lost mass of an atomic nucleus
called a nuclear fission or other smaller nuclear reaction into nuclear. A radioactive
element or a substance contained in the radioactive atom emits spontaneously
energetic particles or waves. There are several types of particles or waves that may
shoot out of a radioactive nucleus: Alpha particles, beta particles, gamma rays, and
neutrons.
Nuclear energy can also be freed in two other ways: nuclear fission and nuclear
fusion. Nuclear fission is the splitting of an atom and nuclear fusion is the com-
bining of two atoms into one. Both ways make big amounts of energy. Fusion is the
source of heat in the sun. Fission is also used in nuclear power plants to produce
electricity. Both fusion and fission can be used in nuclear weapons.
When more than a certain critical mass of radioactive material is combined
decomposition and uncontrollable nuclear explosion took place. Placing radioactive
rods with a specific mass to the heart of a nuclear reactor is controlled energy
production. There have been only two serious accidents in the commercial
exploitation of nuclear power: Three Mile Island in 1979 (in Pennsylvania, USA)
and Chernobyl in 1986 (in the Soviet Union, Ukraine).
Nuclear power is a sustainable source of energy. Nuclear energy is clean, safe,
reliable and competitive source of energy. When it used a significant portion of the
energy source instead of the atmosphere polluting fossil fuels contributes to the
greenhouse effect.
Table 1.7 shows the energy reserves of the world. Only uranium reserves have
260 times more energy than the total energy of other energy sources.
The nuclear energy consumption increased rapidly from 0.1 % in 1970 to 7.4 in
1998 in the world and this increase was especially high in the 1980s.
Thorium discovered by Berzelius in 1828. Thorium occurs in thorite and in
thorianite. Large deposits of thorium minerals have been reported in New England
and elsewhere, but these have not yet been exploited. Thorium is now thought to be
about three times as abundant as uranium and about as abundant as lead or
molybdenum. The metal is a source of nuclear power. There is probably more
energy available for use from thorium in the minerals of the earth’s crust than from
both uranium and fossil fuels. Thorium might serve as a matrix for fissioning or
transmuting minor actinides if this should be required. The necessity and case for
this objective, or for preferring thorium to other matrices, both remain to be
established (Demirbas 2001; 2005b).
Table 1.7 Energy reserves of the world

Deuterium Uranium Coal Shale oil Crude oil Natural gas Tar sands
7.5 109
1.2 10 5
320.0 79.0 37.0 19.6 6.1
Each unit = 1 1015 MJ = 1.67 1011 Bbl crude oil
26 1 Introduction
The essence of a conventional nuclear reactor is the controlled fission chain

reaction of U-235 and Pu-239. This produces heat which is used to make steam
which drives a turbine. The chain reaction depends on having a surplus of neutrons
to keep it going.
Work has been done in developing thorium cycle converter-reactor systems.
Several prototypes, including the high-temperature gas-cooled reactor (HTGR) and
molten salt converter reactor experiment (MSRE), have operated. While the HTGR
reactors are efficient, they are not expected to become important commercially for
many years because of certain operating difficulties. Thorium is recovered com-
mercially from the mineral monazite, which contains from 3 to 9 % ThO2 along
with rare-earth minerals. Much of the internal heat the earth produces has been
attributed to thorium and uranium.
In the long term thorium may well provide a means of resource extension, in
parallel with fast-reactor developments rather than as a substitute for them.
Meanwhile the most valuable contribution to industry that it can make appears
likely to be in extending fuel irradiation where recycling of recovered fissile and
fertile values is considered impracticable or undesirable.
Thorium has long been recognized as a possible nuclear fuel, since although the
natural element consists almost entirely of the non-fissile Th-232, it is fertile in being
capable of transmutation by a neutron flux into the fissile uranium-233. In favorable
circumstances, given a start with some other neutron source such as U-235, pluto-
nium or an accelerator-driven generator, it can sustain a thermal breeding cycle in
which as much fissile material is generated as consumed. This cycle has been
adequately demonstrated in principle. Thorium, particularly with breeding, could
therefore add to the available nuclear fuel currently dependent on the established
uranium cycle. For neutronic reasons, thorium is also somewhat more suited than
uranium to HTGRs which are capable of better thermodynamic efficiencies than the
currently dominant water-cooled types, or of serving as sources of process heat.
However, uranium is still plentiful, HTRs have never been commercially deployed,
and the thorium cycle has not been widely adopted (Thorn et al. 1983).
The technology to utilize thorium in nuclear reactors was thought to be similar to
that of uranium. Thorium resources are larger than those of uranium and neutron
yields of U-233 in the thermal and epithermal regions are higher than for Pu-239 in
the uranium/plutonium fuel cycle. The introduction of the thorium-based nuclear
fuel cycle would therefore vastly enlarge the fissile resources by breeding U-233.
Other reasons identified in past studies are the potential for fuel cycle cost reduc-
tion, the reduction in U-235 enrichment requirements, safer reactor operation
because of lower core excess reactivity requirements, and safer and more reliable
operation of ThO2 fuel as compared to UO2 fuel at high burnup due to the former’s
higher irradiation and corrosion resistance (IAEA 2002).
For many years there has been interest in utilizing thorium (Th-232) as a nuclear
fuel since it is three times as abundant in the earth’s crust as uranium. Also, all of
the mined thorium is potentially useable in a reactor, compared with the 0.7 % of
natural uranium, so some 40 times the amount of energy per unit mass might be
available. A thorium reactor would work by having Th-232 capture a neutron to
become Th-233 which decays to uranium-233, which fissions. The problem is that
insufficient neutrons are generated to keep the reaction going (Demirbas 2005b).
It is an alpha emitter. Th-232 goes through six alpha and four beta decay steps
before becoming the stable isotope Pb-208. Th-232 is sufficiently radioactive to
expose a photographic plate in a few hours. Thorium disintegrates with the production
of “thoron” (Rn-220), which is an alpha emitter and presents a radiation hazard. Good
ventilation of areas where thorium is stored or handled is therefore essential.
Several methods are available for producing thorium metal; it can be obtained by
reducing thorium oxide with calcium, by electrolysis of anhydrous thorium chloride
in a fused mixture of sodium and potassium chlorides, by calcium reduction of
thorium tetrachloride mixed with anhydrous zinc chloride, and by reduction of
thorium tetrachloride with an alkali metal (Demirbas 2005b).
Is thorium the better nuclear fuel?
• Weapons-grade fissionable material (U-233) is harder to retrieve safely and
clandestinely from the thorium reactor than plutonium is from the uranium
breeder reactor.
• Thorium produces 10 to 10,000 times less long-lived radioactive waste than
uranium or plutonium reactors.
• Thorium comes out of the ground as a 100 % pure, usable isotope, which does
not require enrichment, whereas natural uranium contains only 0.7 % fissionable
U-235.
• Because thorium does not sustain chain reaction, fission stops by default if we
stop priming it, and a runaway chain reaction accident is improbable.
232 233
A neutron is captured by 90Th , which makes it 90Th :
90 Th
232
þ 0 n1 ! 90 Th233 ð1:10Þ
Th-233 spontaneously emits a beta particle, leaving behind one additional pro-
ton, and one fewer neutron. This is called beta decay.
90 Th
233
! 91 Pa233 þ b ð1:11Þ
233
The element with 91 protons is Protactinium (Pa). The isotope 91PA also
undergoes beta decay,
91 Pa
233
! 92 U233 þ b ð1:12Þ
The U-233 isotope that is produced in step (3) is fissionable, but has fewer
neutrons than its heavier cousin, U-235, and its fission releases only 2 neutrons,
not 3.
92 U
233
þ 0 n1 ! fission fragments þ 20 n1 ð1:13Þ
28 1 Introduction
The priming neutrons are emitted in a process called spallation, which is the
induced splitting of an otherwise non-fissionable large nucleus. The capability of
high-current, high-energy accelerators to produce neutrons by spallation from
heavy elements has been used in the structural research of such materials. In this
process a beam of high-energy protons (usually >500 meV) is directed at a
high-atomic number target such as tungsten, tantalum, depleted uranium, thorium,
zirconium, lead, lead-bismuth, mercury and up to one neutron can be produced per
25 meV of the incident proton beam.
The idea is to use a particle accelerator producing neutrons by spallation (in-
teraction of particles with a target) to feed a fuel/moderator assembly where the
neutrons multiply by fission chain reactions. If the energy liberated becomes sub-
stantially greater than that needed to drive the accelerator, the process has a net gain
and becomes self supporting. Hence this is called as Energy Amplifier (EA). In the
energy amplifier (EA), a proton beam impinges on lead, the high energy protons
splitting lead nuclei, leading to release of neutrons.
If the spallation target is surrounded by a blanket assembly of nuclear fuel, such
as fissile isotopes of uranium or plutonium, there is a possibility of sustaining a
fission reaction. This is described as an Accelerator-Driven System (ADS). In this,
up to ten percent of the neutrons could come from the spallation, though it would
normally be less, even where actinide incineration is the main objective.
1.3 World’s Present Energy Situation
Today the energy world is facing five major challenges:

(1) High fuel prices
(2) Reduce energy consumption
(3) Reduce climatic changes
(4) Investigate alternative energy sources
(5) Utilization of non-conventional (unusual, inactive and waste) energy sources
Growing global energy demand, mostly driven by developing countries, and the
increasing scarcity of resources inevitably cause a rise in energy prices. Growing
environmental concerns and ecological awareness push for an overhaul of existing
energy production systems. The recession puts a burden on household, business and
public budgets and is an incentive to reduce energy consumption. The world’s
over-demand of energy, oil crisis and the continuous increase in oil prices led
countries to investigate on new and renewable fuel alternatives. Hence, the energy
sources, like sun, wind, geothermal, hydraulic, nuclear, hydrogen and biomass were
taken into consideration (Karaosmanoglu and Aksoy 1988).
The world energy consumption pattern is also increasing as shown in the
Table 1.8. The energy consumption has been increasing and it will triple in a period
of 50 years by 2025. Mainly the population increase and also the need to increase
the standard of living are the factors forcing to see new and alternate energy
1.3 World’s Present Energy Situation 29
Table 1.8 World’s energy Years World’s energy consumption

consumption by years
1970 208
1975 243
1980 282
1985 313
1990 339
1995 367
2000 405
1005 234
2010 487 (10,549 Mtoe)
2015 548 (11,870 Mtoe)
2020 607 (13,148 Mtoe)
2025 650 (14,079 Mtoe)
2030 710 (15,379 Mtoe)
Mtoe: Million tons oil equivalent
options. The world population will increase from 6 billion to 11 billion this century
and the life expectancy has increased 2 times in the last two centuries and the
energy requirement has increased 35 times in the same period. The main drivers of
the alternate energy search are the population growth, economy, technology, and
agriculture.
The world’s energy consumption according to resources is given in Table 1.9.
Fossil fuels still represent over 80 % of total energy supplies in the world today,
in 2020, but the trend towards new energy sources is clear in the future thanks to the
new technological developments.
Oil is the fossil fuel that is most in danger to become short in supply. The Middle
East is the world’s dominant oil provinces, covering 63 % of global reserves.
Table 1.10 shows global oil production scenarios based on today’s production.
A peak in global oil production may occur between 2015 and 2030. Countries in the
Middle East and the Russian Federation hold 70 % of the world’s dwindling
reserves of oil and gas. Geographical distribution of energy reserves and resources
is important.
Natural gas (NG) accounts today for 24 % of world primary energy production.
Natural gas is the fastest growing primary energy source in the world, because it is
cleaner fuel than oil or coal. Growing demand for natural gas is expected in all
Table 1.9 The world’s Resources of energy consumption %

energy consumption
according to resources Oil 37
Coal 25
Natural gas 24
Nuclear power 6
Biomass 4
Hydroelectricity 3
30 1 Introduction
Table 1.10 Global oil Years Percent of today’s production

production scenarios based
on today’s production 2000 88.2
2007 93.5
2015 100.0
2025 93.4
2035 86.8
2045 63.4
2055 52.8
2065 44.2
2075 38.5
regions of the world, as resource availability, cost, and environmental considera-

tions all favor its use.
The peak of world NG gas production may not occur until 2025, but two things
are sure: we will have even less warning than we had for Peak Oil, and the
subsequent decline rates may be shockingly high. For the NG model shows the
peak a plateau from 2025 to 2030. This is followed by a rapid increase in decline to
8 % per year by 2050, remaining at a constant 8 % per year for the following
50 years (Kirtay 2009).
Coal is the ugly stepsister of fossil fuels. Most coal today is used to generate
electricity. As economies grow, so does their demand for electricity, and if elec-
tricity is used to replace some of the energy lost due to the decline of oil and natural
gas, this will put yet more upward pressure on the demand for coal. Just as we saw
with oil and gas, coal will exhibit an energy peak and decline. One factor in this is
that we have in the past concentrated on finding and using the highest grade of coal,
anthracite. Much of what remains consists of lower grade bituminous and lignite.
These grades of coal produce less energy when burned, and require the mining of
ever more coal to get the same amount of energy (Kirtay 2009).
Among of non-nuclear energy resources, a coals reserve of the world is the first
one (Table 1.7). Coal is the most abundant and burned fossil fuel. Deposits of oil
shale exist in many locations around the globe, and many oil shales can be burned
directly without processing. Tar sands are another possible source of vast quantities
of oil. Oil is the fossil fuel that is most in danger to become short in supply. A peak
in global oil production may occur between 2015 and 2030. Tar sands are sand
deposits which are impregnated with dense, viscous petroleum.
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Chapter 2
Future Energy Sources
2.1 Introduction
Energy affects all aspects of modern life. Energy sources will play an important role
in the world’s future. Because of the exponential growth of the world population,
demand for energy is increasing at an exponential rate. Current examples of these
priorities include: reducing greenhouse gas emissions, improving the energy effi-
ciency of our homes, offices and industries, energy marketing, energy cost, energy
management, energy conservation, energy security, finding practical and affordable
alternate sources of energy, developing cleaner and more efficient transportation
vehicles and systems, energy policy, energy strategy and alternative energy usage.
The world is presently confronted with twin crises of fossil fuel depletion and
environmental degradation. To overcome these problems, recently renewable
energy has been receiving increasing attention due to its environmental benefits.
Competition of renewable liquid fuels to the petroleum liquid fuels is important in
the near future. Renewable energy is a promising alternative solution because it is
clean and environmentally safe. Biomass is the most used renewable energy source
now and in future. Geothermal, hydrogen, wind and solar energies will become the
most important sources in future.
The promising future transportation fuels are liquid biofuels, hydrogen, biogas,
and methane. Biomass will be the most important energy sources. The algae will be
one of the important energy sources in the future. Electricity and hydrogen are
principle energy carriers and can be produced from all primary energy sources.

34 2 Future Energy Sources
2.2 Renewable Energy Scenarios
Renewable energy is a promising alternative solution because it is clean and envi-

ronmentally safe. They also produce lower or negligible levels of greenhouse gases
and other pollutants when compared with the fossil energy sources they replace.
Table 2.1 shows global renewable energy scenario by 2030. Approximately, half of
the global energy supply from renewables in 2030 according to European
Renewable Energy Council (EREC) (2009). The most significant developments in
renewable energy production are observed in photovoltaics (from 0.2 to 221 Mtoe)
and wind energy (from 4.7 to 542 Mtoe) between 2001 and 2030.
Biomass is the most used renewable energy source now and in future. The
potential of sustainable large hydro is quite limited to some regions in the world.
The potential for small hydro (<10 MW) power is still significant and more sig-
nificant in future. Wind energy is a technology with annual growth rates of more
than 30 % during the last years that will become more significant in future.
Photovoltaics already had impressive annual growth rates of more that 30 % during
the last years that will become more significant in future. Geothermal and solar
thermal sources are more important energy systems in future.
Using fossil fuels as the primary energy source has led to serious energy crisis
and environmental pollution on a global scale. In order to mitigate environmental
problems renewable energy especially wind and solar energies at competitive costs
resulting from the fast technological development. The limitations of solar power
are site-specific, intermittent and, thus, not reliable for instantaneous supply. Using
batteries to store any energy surplus for later consumption can resolve the time
mismatch between energy supply and demand. The shortcomings of battery storage
are low-storage capacity, short equipment life, and considerable solid and chemical
wastes generated. A system consisting of photovoltaic (PV) panels coupled with
electrolyzers is a promising design to produce hydrogen (Ni et al. 2006).
Table 2.1 Global renewable energy scenario by 2040

2001 2010 2020 2030
Total consumption (million ton oil equivalent) 10,038 10,549 13,148 15,379
Biomass 1080 1313 1791 2483
Large hydro 22.7 266 309 341
Geothermal 43.2 86 186 333
Small hydro 9.5 19 49 106
Wind 4.7 44 266 542
Solar thermal 4.1 15 66 244
Photovoltaic 0.2 2 24 221
Solar thermal electricity 0.1 0.4 3 16
Marine (tidal/wave/ocean) 0.05 0.1 0.6 5
Total renewable energy sources 1365.5 1745.5 2694.6 4291
Renewable energy sources contribution (%) 13.6 16.6 20.5 27.9
2.2 Renewable Energy Scenarios 35
Table 2.2 Growth scenarios Years Stagnat Moderata Strong

for global installed wind growth growth growth
power capacity (GW)
2010 63 73 81
2020 132 140 165
2030 166 195 250
The detailed analysis of the technical, economic and regulatory issues of wind
power is scanned in the European Wind Energy Association (EWEA) Report:
“Large scale integration of wind energy in the European power supply: Analysis,
issues and recommendations” published in December 2005. In 2005, worldwide
capacity of wind-powered generators was 58,982 MW; although it currently pro-
duces less than 1 % of world-wide electricity use, it accounts for 23 % of electricity
use in Denmark, 4.3 % in Germany and approximately 8 % in Spain. Globally,
wind power generation more than quadrupled between 1999 and 2005 according to
the EWEA (2005).
Table 2.2 shows the growth scenarios for global installed wind power (IEA
2004). In 2004, the International Energy Agency (IEA) Reference Scenario pro-
jections for wind energy were updated to 66 GW in 2010, 131 GW in 2020 and
170 GW in 2030. The IEA Reference Scenario projections for wind energy were
updated to 75 GW in 2010, 145 GW in 2020 and 202 GW in 2030. The IEA
advanced strong growth scenario projected a wind energy market of 82 GW in
2010, 165 GW in 2020 and 250 GW in 2030. Figure 2.1 shows the scenarios for
global installed wind power.
Stagnat growth Moderate growth Strong growth

260
220
Installed global capacity, GW
180
140
100
60
2010 2020 2030
Years
Fig. 2.1 Scenarios for global installed wind power

Geothermal energy can be utilized in various forms such as electricity genera-

tion, direct use, space heating, heat pumps, greenhouse heating, and industrial. The
electricity generation is improving faster in geothermal energy rich countries. As an
energy source, geothermal energy has come of age. The utilization has increased
rapidly during the last three decades.
As an energy source, geothermal energy has come of age. Geothermal energy for
electricity generation has been produced commercially since 1913, and for four
decades on the scale of hundreds of MW both for electricity generation and direct
use. In Tuscany, Italy, a geothermal plant has been operating since the early 1900s.
There are also geothermal power stations in the USA, New Zealand and Iceland. In
Southampton (UK) there is a district heating scheme based on geothermal energy.
Hot water is pumped up from about 1,800 m below ground. The utilization has
increased rapidly during the last three decades. In 2000, geothermal resources have
been identified in over 80 countries and there are quantified records of geothermal
utilization in 58 countries in the world.
greenhouses (9 %), fish farming (6 %), and industry (6 %). Geothermal energy can
be utilized in various forms such as electricity generation, direct use, space heating,
heat pumps, greenhouse heating, and industrial usage. Electricity is produced with
geothermal steam in 21 countries spread over all continents. Low temperature
geothermal energy is exploited in many countries to generate heat, with an esti-
mated capacity of about 10,000 MW thermal.
World’s total installed geothermal electric capacity was 7304 MWe in 1996. In
much of the world electricity from fossil fuel-burning electricity plants can be
provided at half the cost of new geothermal electricity. A comparison of the
renewable energy sources shows the current electrical energy cost to be 2–10 US¢/
kWh for geothermal and hydro, 5–13 US¢/kWh for wind, 5–15 US¢/kWh for
biomass, 25–125 US¢/kWh for solar photovoltaic and 12–18 US¢/kWh for solar
thermal electricity (Demirbas 2006a).
Solar energy is defined as that radiant energy transmitted by the sun and inter-
cepted by Earth. It is transmitted through space to Earth by electromagnetic radi-
ation with wavelengths ranging between 0.20 and 15 lm. The availability of solar
flux for terrestrial applications varies with season, time of day, location, and col-
lecting surface orientation. In this chapter we shall treat these matters analytically
(Kutz 2007).
One of the most abundant energy resources on the surface of the earth is sunlight.
Today, solar energy has a tiny contribution in the world total primary energy.
Photovoltaic (PV) systems, other than solar home heating systems, are used for
communication, water pumping for drinking and irrigation, and electricity generation.
The total installed capacity of such systems is estimated at about 1000 kW. A solar
2.2 Renewable Energy Scenarios 37
home heating system is a solar PV system with a maximum capacity of 40 W. These

systems are installed and managed by a household or a small community.
Like wind power markets, PV markets have seen rapid growth and costs have
fallen dramatically. The total installed capacity of such systems is estimated at
about 1000 kW. The PV installed capacities are growing at a rate of 30 % a year.
Solar PV system has been found to be a promising energy in future. One of the most
significant developments in renewable energy production is observed in PVs.
The PV will then be the largest renewable electricity source with a production of
25.1 % of global power generation in 2040 (EWEA 2005).
Solar thermal electricity power system is a device by the use of solar radiation
for the generation of electricity through the solar thermal conversion. Solar thermal
electricity may be defined as the result of a process by which directly collected solar
energy is converted to electricity through the use of some sort of heat to electricity
conversion device. The last three decades have witnessed a trend in solar thermal
electricity generation of increasing the concentration of sunlight. There are three
main systems of solar thermal electricity: solar towers, dishes and the parabolic
troughs. Solar thermal power stations based on parabolic and heliostat trough
concentrating collectors can soon become a competitive option on the world’s
electricity market. Table 2.3 shows the economics and emissions of conventional
technologies compared with solar power generation.
PV systems convert sunlight directly to electricity. They work any time the sun
is shining, but more electricity is produced when the sunlight is more intense and
strikes the PV modules directly. The basic building block of PV technology is the
solar “cell.” Multiple PV cells are connected to form a PV “module,” the smallest
PV component sold commercially. Modules range in power output from about
10–300 W. A PV system connected to the utility grid has these components:
(1) One or more PV modules, which are connected to an inverter. (2) The inverter,
which converts the system’s direct-current (DC) electricity to alternating current
(AC). (3) Batteries (optional) to provide energy storage or backup power in case of
a power interruption or outage on the grid.
Small, single-PV-panel systems with built-in inverters that produce about 75 W
may cost around $900 installed, or $12 per watt. A 2-kW system that meets nearly
all the needs of a very energy efficient home could cost $16,000 to $20,000
installed, or $8 to $10 per watt. At the high end, a 5-kW system that completely
Table 2.3 Economics and emissions of conventional technologies compared with solar power
generation
Electricity generation technology Carbon emissions (g C/kWh) Generation costs (US¢/kWh)
Solar thermal and solar PV systems 0 9–40
Pulverized coal–natural gas turbine 100–230 5–7
Air
Oxygen Cathod
Electrolyte
Anod Electrical Current

Fuel
Fig. 2.2 Schematic of a fuel cell
Fig. 2.3 Configuration of PV system with AC appliances
meets the energy needs of many conventional homes can cost $30,000 to $40,000
installed, or $6 to $8 per watt. Figure 2.2 shows the schematic of a fuel cell.
Figure 2.3 shows the configuration of PV system with AC appliances (e.g.,
household lighting, heating, refrigeration, television or video).
2.3 Research and Development of Biomass Energy
2.3.1 Introduction
Biomass energy research should include an interdisciplinary approach and includes

researchers from various professions such as agricultural, environmental,
2.3 Research and Development of Biomass Energy 39
mechanical, chemical, electrical engineering, and biology. The group works on the
biochemical and thermochemical conversion of different biomass sources into
biofuels.
Biomass has historically been a dispersed, labor-intensive, and land-intensive
source of energy. By the year 2050, it is estimated that 90 % of the world popu-
lation will live in developing countries. It is critical therefore that the biomass
processes used in these countries are sustainable. In the future, biomass has the
potential to provide a cost-effective and sustainable supply of energy. The mod-
ernization of biomass technologies, leading to more efficient biomass production
and conversion is one possible direction for biomass use in developing countries.
Biomass provides a clean, renewable energy source that could dramatically
improve our environment, economy and energy security. Biomass energy generates
far less air emissions than fossil fuels, reduces the amount of waste sent to landfills
and decreases our reliance on foreign oil. Biomass energy also creates thousands of
jobs and helps revitalize rural communities.
In Europe, North America and the Middle East, the share of biomass averages
2–3 % of total final energy consumption, whereas in Africa, Asia and Latin America,
which together account for three-quarters of the world’s population, biomass
provides a substantial share of the energy needs: a third on average, but as much as
80–90 % in some of the poorest countries of Africa and Asia (e.g. Angola, Ethiopia,
Mozambique, Tanzania, Democratic Republic of Congo, Nepal and Myanmar).
Indeed, for large portions of the rural populations of developing countries, and for
the poorest sections of urban populations, biomass is often the only available and
affordable source of energy for basic needs such as cooking and heating.
Biomass provides a number of local environmental gains. Energy forestry crops
have a much greater diversity of wildlife and flora than the alternative land use,
which is arable or pasture land. In industrialized countries, the main biomass
processes utilized in the future are expected to be direct combustion of residues and
wastes for electricity generation, bio-ethanol and biodiesel as liquid fuels and
combined heat and power production from energy crops. The future of biomass
electricity generation lies in biomass integrated gasification/gas turbine technology,
which offers high energy conversion efficiencies. Biomass will compete favorably
with fossil mass for niches in the chemical feedstock industry. Biomass is a
renewable, flexible and adaptable resource. Crops can be grown to satisfy changing
end user needs.
In the future, biomass has the potential to provide a cost-effective and sustain-
able supply of energy, while at the same time aiding countries in meeting their
greenhouse gas reduction targets. By the year 2050, it is estimated that 90 % of the
world population will live in developing countries. Figure 2.4 shows the carbon
cycle, photosynthesis, and the steps of biomass fuels formation.
Fig. 2.4 Carbon cycle, photosynthesis, and the steps of biomass fuels formation
2.3.2 Transportation Biofuels from Biomass
The term biofuel is referred to as liquid or gaseous fuels for the transport sector that
are predominantly produced from biomass. The biofuels mainly include bioethanol,
biobutanol, biodiesel, vegetable oils, biomethanol, pyrolysis oils, biogas, and bio-
hydrogen. There are two global biomass based liquid transportation fuels that might
replace gasoline and diesel fuel. These are bioethanol and biodiesel. There are
several reasons for biofuels to be considered as relevant technologies by both
developing and industrialized countries. They include energy security reasons,
environmental concerns, foreign exchange savings, and socioeconomic issues
related to the rural sector.
Biofuels are important because they replace petroleum fuels. Biofuels are gen-
erally considered as offering many priorities, including sustainability, reduction of
greenhouse gas emissions, regional development, social structure and agriculture,
security of supply (Reijnders 2006).
Biofuels appear to be a potential alternative “greener” energy substitute for fossil
fuels. They are renewable and available throughout the world. Biomass can con-
tribute to sustainable development and globally environmental preservation since it
is renewable and carbon neutral. Biofuels are currently expensive than conventional
energy sources. There are different technologies presently being practiced to pro-
duce biofuels economically from biomass. Biofuel technology will play a major
role in future because it can utilize the renewable sources of energy.
The use of liquid biofuels for transport in order to reduce greenhouse gas
emissions and the environmental impact of transport, as well as to increase security
of supply, technological innovation and agricultural diversification has a strategic
important. Biofuels can be burned in such a way as to produce no harmful
emissions.
There are several reasons for biofuels to be considered as relevant technologies
by both developing and industrialized countries. Due to its environmental benefits,
the share of biofuel such as bioethanol and biodiesel in the automotive fuel market
will grow fast in the next decade.
Bioethanol is a petrol additive/substitute. It is possible that wood, straw and even
household wastes may be economically converted to bioethanol. Biodiesel is an
environmentally friendly alternative liquid fuel that can be used in any diesel engine
without modification. Biodiesel is better than diesel fuel in terms of sulfur content,
flash point, aromatic content and biodegradability. Bioethanol is by far the most
widely used bio-fuel for transportation worldwide. Global bioethanol production
more than doubled between 2000 and 2005. About 60 % of global bioethanol
production comes from sugarcane and 40 % from other crops.
According to International Energy Agency (IEA), scenarios developed for the
USA and the EU indicate that near-term targets of up to 6 % displacement of
petroleum fuels with biofuels appear feasible using conventional biofuels, given
available cropland. A 5 % displacement of gasoline in the EU requires about 5 % of
available cropland to produce ethanol while in the USA 8 % is required. A 5 %
displacement of diesel requires 13 % of USA cropland, 15 % in the EU (IEA
2006).
The recent commitment by the USA government to increase bio-energy
three-fold in 10 years has added impetus to the search for viable biofuels. The
advantages of bio-fuels are the following: (a) Bio-fuels are easily available from
common biomass sources, (b) They are represent a carbon dioxide-cycle in com-
bustion, (c) Bio-fuels have a considerable environmentally friendly potential,
(d) There are many benefits the environment, economy and consumers in using
bio-fuels, and (e) They are biodegradable and contribute to sustainability (IEA
2004).
The dwindling fossil fuel sources and the increasing dependency of the USA on
imported crude oil have led to a major interest in expanding the use of bio-energy.
The recent commitment by the USA government to increase bio-energy three-fold
in 10 years has added impetus to the search for viable biofuels. The EU have also
adopted a proposal for a directive on the promotion of the use of bio-fuels with
measures ensuring that bio-fuels account for at least 2 % of the market for gasoline
and diesel sold as transport fuel by the end of 2005, increasing in stages to a
minimum of 5.75 % by the end of 2010 (Puppan 2002). Bioethanol is a fuel derived
from renewable sources of feedstock; typically plants such as wheat, sugar beet,
Table 2.4 Shares of alternative fuels compared to the total automotive fuel consumption in the
world (%)
Fuel 2020 2025 2030 2035 2040 2045 2050
Biofuels 5.0 6.9 9.1 10.2 10.8 11.4 11.8
Natural gas 5.7 9.0 10.2 10.9 9.6 9.3 7.9
Hydrogen 3.4 3.9 10.6 13.2 15.8 17.4 18.5
corn, straw, and wood. Bioethanol is a petrol additive/substitute. Biodiesel is better

than diesel fuel in terms of sulfur content, flash point, aromatic content and
biodegradability.
If the biodiesel valorized efficiently at energy purpose, so would be benefit for
the environment and the local population. Job creations, provision of modern
energy carriers to rural communities avoid urban migration and reduction of CO2
and sulfur levels in the atmosphere. Biofuels include energy security reasons,
environmental concerns, foreign exchange savings, and socioeconomic issues
related to the rural sector.
Table 2.4 shows the shares of alternative fuels compared to the total automotive
fuel consumption in the world as a futuristic view (Demirbas 2006b). Hydrogen is
currently more expensive than conventional energy sources. There are different
technologies presently being practiced to produce hydrogen economically from
biomass. Biohydrogen technology will play a major role in future because it can
utilize the renewable sources of energy (Nath and Das 2003).
Bioethanol is a gasoline additive/substitute. Bioethanol is by far the most widely
used bio-fuel for transportation worldwide. Global bioethanol production more than
doubled between 2000 and 2005. About 60 % of global bioethanol production
comes from sugarcane and 40 % from other crops. Biodiesel refers to a
diesel-equivalent mono alkyl ester based oxygenated fuel. Biodiesel production
using inedible vegetable oil, waste oil and grease has become more attractive
recently. The economic performance of a biodiesel plant can be determined once
certain factors are identified, such as plant capacity, process technology, raw
material cost and chemical costs. Even with today’s high oil prices, biofuels cost
more than conventional fuels. The central policy of biofuel concerns job creation,
greater efficiency in the general business environment, and protection of the
environment.
The biggest difference between biofuels and petroleum feedstocks is oxygen
content. Biofuels have oxygen levels from 10–45 % while petroleum has essen-
tially none making the chemical properties of biofuels very different from petro-
leum. All have very low sulfur levels and many have low nitrogen levels. Biofuels
are non-polluting, locally available, accessible, sustainable and reliable fuel
obtained from renewable sources.
Sustainable biofuel production potential mainly depends on the productivity and
the plantation options. A sustainable use of biomass for bioenergy production is
expected to reduce environmental contamination. Achieving a solution to envi-
ronmental problems requires long-term policies for sustainable development. In this
Table 2.5 Availability of modern transportation fuels

Fuel type Availability
Current Future
Gasoline Excellent Moderate-poor
Bioethanol Moderate Excellent
Biodiesel Moderate Excellent
Compressed natural gas (CNG) Excellent Moderate
Hydrogen for fuel cells Poor Excellent
Vegetable oil for fuel cells Poor Moderate-excellent
Liquefied petroleum gas (LPG) Moderate-excellent Moderate
Liquefied natural gas (LNG) Poor Moderate
Methane Poor Excellent
aspect, renewable energy resources appear to be the one of the most efficient and
effective solutions. Sustainability of renewable energy systems must support both
human and ecosystem health over the long term, goals on tolerable emissions
should look well into the future. The sustainability of biofuels for energy use
requires a high efficiency recycling of energy and low emissions of carbon com-
pounds, NOx, persistent organics and acidifying compounds and heavy metals due
to biomass combustion. Electricity generation from biofuels has been found to be a
promising method in the nearest future. The electricity costs are in the 6–8 c/kWh
range. The future of biomass electricity generation lies in biomass integrated
gasification/gas turbine technology, which offers high-energy conversion
efficiencies.
Liquid biofuels for transportation have recently attracted huge attention in dif-
ferent countries all over the world because of its renewability, sustainability,
common availability, regional development, rural manufacturing jobs, reduction of
greenhouse gas emissions, and its biodegradability. Table 2.5 shows the availability
of modern transportation fuels. The advantage of biofuel in this aspect is that it is a
derivative of natural products. Policy drivers for renewable liquid biofuels have
attracted particularly high levels of assistance in some countries given their promise
of benefits in several areas of interest to governments, including agricultural pro-
duction, greenhouse gas emissions, energy security, trade balances, rural devel-
opment and economic opportunities for developing countries. The European Union
is on the third rank of biofuel production worldwide, behind Brazil and the United
States. In Europe, Germany is the largest, and France the second largest producer of
biofuels. Most biofuels in commercial production in Europe today are based on
sugar beet, wheat and rapeseed, which are converted to bioethanol/ETBE and
biodiesel.
Ethanol has gained huge interest in both industry and research as a plausible
renewable energy source in the future. Bioethanol is a gasoline additive/substitute.
Biomass wastes that have high contents of hydrocarbon, such as sugarcane, sugar
beets, corn and from molasses, can be good sources of bioethanol. Bioethanol is an
alternative fuel that is produced almost entirely from food crops. Bioethanol rep-
resents an important, renewable liquid fuel for motor vehicles. Bioethanol is derived
from alcoholic fermentation of sucrose or simple sugars, which are produced from
biomass by hydrolysis process. In order to produce bioethanol from cellulosic
biomass, a pretreatment process is used to reduce the sample size, break down the
hemicelluloses to sugars, and open up the structure of the cellulose component. The
cellulose portion is hydrolyzed by acids or enzymes into glucose sugar that is
fermented to bioethanol.
The sugars from the hemicelluloses are also fermented bioethanol. Producing
and using bioethanol as a transportation fuel can help reduce carbon dioxide
buildup in two important ways: by displacing the use of fossil fuels, and by
recycling the carbon dioxide that is released when it is combusted as fuel. Using
ethanol-blended fuel for automobiles can significantly reduce petroleum use and
exhaust greenhouse gas emission. An important advantage of crop based ethanol is
its greenhouse benefits. Corn stover consists of the stalks, leaves, cobs, and husk. It
is possible that corn stover may be economically converted to bioethanol.
Ethanol can be produced in a culture medium. For this purpose, an alginate-loofa
matrix was developed as a cell carrier for ethanol fermentation owing to its porous
structure and strong fibrous nature. The matrix was effective for cell immobilization
and had good mechanical strength and stability for long-term use (Phisalaphong
et al. 2007).
Partly due to the oil crises, biomass-derived syngas (bio syngas) has become an
important part of alternative energy since the 1980s. Once clean biosyngas is
available, the known process technology can be used produce biomethanol,
Fischer-Tropsch diesel oil, and hydrogen. Methanol can be produced from
hydrogen-carbon oxide mixtures by means of the catalytic reaction of carbon
monoxide and some carbon dioxide with hydrogen. Biosynthesis gas (bio-syngas)
is a gas rich in CO and H2 obtained by gasification of biomass. Mixture of gases
from organic waste materials is converted to methanol in a conventional
steam-reforming/water-gas shift reaction followed by high-pressure catalytic
methanol synthesis.
Biodiesel is known as monoalkyl, such as methyl and ethyl, esters of fatty acids.
Biodiesel is produced from triglycerides by transesterification process (Demirbas
2003). Environmental and political concerns are generating a growing interest in
alternative engine fuels such as biodiesel. Biodiesel is the best candidate for diesel
fuels in diesel engines. Biodiesel refers to a diesel-equivalent, processed fuel
derived from biological sources. Biodiesel is the name for a variety of ester based
oxygenated fuel from renewable biological sources. It can be made from processed
organic oils and fats. Biodiesel production using inedible vegetable oils, waste oil
and grease has also become more attractive recently. Biodiesels play an important
role in meeting future fuel requirements in view of their nature (less toxic), and
have an edge over conventional diesel as they are obtained from renewable sources
(Sastry et al. 2006).
Cottonseed methyl ester was used in a four-stroke, single cylinder, and
air-cooled diesel engine as alternative fuel. Engine tests carried out at full
load-different speed range, the engine torque and power of cottonseed oil methyl
ester was found to be lower than that of diesel fuel in the range of 3–9 % and
specific fuel consumption was higher than that of diesel fuel by approximately
8–10 %. CO2, CO, and NOx emissions of cottonseed methyl ester were lower than
that of diesel fuel (Yucesu and Ilkilic 2006).
In general, the physical and chemical properties and the performance of the
cotton seed oil methyl ester was comparable to diesel fuel. The effects of cotton
seed oil methyl ester and diesel fuel on a direct-injected, four-stroke,
single-cylinder, air-cooled diesel engine performance and exhaust emissions were
investigated. Test quantities of cottonseed oil methyl ester of renewable fuels were
processed and characterized, and performance and exhaust gas emissions were
tested in various injection pressures. In order to determine emission and perfor-
mance characteristics, the engine were tested with full load varied injection pressure
and constant speed. The results show that engine performance using cottonseed oil
methyl ester fuel differed little from engine performance and torque with diesel fuel.
As to the emissions, there was an approximate 30 % reduction in CO and
approximate 25 % reduction in NOx.
An engine performance test using sunflower methyl esters exhibited character-
istics very similar to regular diesel. The test values obtained from a 2.5 L, 4
cylinder Peugeot XD3p157 engine shows that torque values obtained by the two
types of fuels are 5–10 % in favor of regular diesel. Specific fuel consumption,
however, is better with biodiesel. This means that a better combustion characteristic
is achieved with biodiesel, which compensates for its lower calorific value. Soot
emissions are slightly less with biodiesel, as expected, due to the improvement in
specific fuel consumption (Kaplan et al. 2006). Physical and chemical properties of
methyl ester of waste cooking oil were determined in the laboratory. The methyl
ester was tested in a diesel engine with turbocharged, four cylinders and direct
injection. Obtained results were compared with No. 2 diesel fuel (Utlu 2007).
A new lipase immobilization method, textile cloth immobilization, was devel-
oped for conversion of soybean oil to biodiesel. Immobilized Candida lipase
sp. 99–125 was applied as the enzyme catalyst. The effect of flow rate of reaction
liquid, solvents, reaction time, and water content on the biodiesel yield is investi-
gated. The test results indicate that the maximum yield of biodiesel of 92 % was
obtained at the conditions of hexane being the solvent, water content being 20 wt%,
and reaction time being 24 h (Lv et al. 2008).
The dynamic transesterification reaction of peanut oil in supercritical methanol
media was investigated. The reaction temperature and pressure were in the range of
523–583 K and 10.0–16.0 MPa, respectively. The molar ratio of peanut oil to
methanol was 1:30. It was found that the yield of methyl esters was higher than
90 % under the supercritical methanol. The apparent reaction order and activation
energy of transesterification was 1.5 and 7.472 kJ/mol, respectively. In this method,
the reaction time was shorter and the processing was simpler than that of the
common acid catalysis transesterification (Cheng et al. 2008; Demirbas 2016).
The existing biodiesel production process is neither completely “green” nor

renewable because it utilizes fossil fuels, mainly natural gas as an input for
methanol production. Also the catalysts currently in use are highly caustic and
toxic. To overcome the limitation of the existing process, a new method was
proposed that used waste vegetable oil and non-edible plant oils as biodiesel
feedstock and non-toxic, inexpensive, and natural catalysts. The economic benefit
of the proposed method is also discussed. The new method will render the biodiesel
production process truly green (Chhetri and Islam 2008).
A four-stroke, 3-cylinder, 30 kW TUMOSAN (Turkish Motor Industry and
Trade) diesel engine was used for experimentation of biodiesel. The kinematic
viscosity, density, flash point, cloud point, pour point, freezing point, copper strip
corrosion values of all biodiesel fuels stayed within the limit values described by
DIN-TSE EN 14214. They can readily be used without any need for modifications
of the engine. Even though specific fuel consumption for biodiesel fuels tended to
be higher than that for normal diesel fuel, the exhaust smokiness values of biodiesel
fuels were considerably lower than that for petroleum diesel fuel. On the other
hand, there were no significant differences observed for torque, power and exhaust
smokiness (Oguz et al. 2007).
Problems to be studied include fuel storage stability, fuel solubility, and
oxidative stability of recycled soybean-derived biodiesel was investigated. Unlike
newly manufactured soy oils, it was found that this recycled soy oil was not stable
in fuels. The question was what in the recycled oil led to the observed fuel
degradation (Mushrush et al. 2007).
The oxidative and thermal degradation occurs on the double bonds of unsatu-
rated aliphatic carbons chains in biolipids. Oxidation of biodiesel results in the
formation of hydroperoxides. The oxidative and thermal instability are determined
by the amount and configuration of the olefinic unsaturation on the fatty acid
chains. The viscosity of biodiesel increases with the increase of thermal degradation
degree due to the trans-isomer formation on double bonds. The decomposition of
biodiesel and its corresponding fatty acids linearly increases from 293 to 625 K.
The densities of biodiesel fuels decreased linearly with temperatures from 293 to
575 K. The combustion heat of biodiesel partially decreases with the increase of
thermal degradation degree (Arisoy 2008).
The emission-forming gasses, such as carbon dioxide and carbon monoxide
from combustion of biodiesel, generally are less than diesel fuel. Sulfur emissions
are essentially eliminated with pure biodiesel. The exhaust emissions of sulfur
oxides and sulfates from biodiesel were essentially eliminated compared to diesel.
The smog-forming potential of biodiesel hydrocarbons is less than diesel fuel. The
ozone-forming potential of the speciated hydrocarbon emissions was 50 % less than
that measured for diesel fuel (Dincer 2008).
2.4 Water Energy and Power 47
2.4 Water Energy and Power
Water is used in power generation. Hydroelectricity is electricity obtained from

hydropower. Hydroelectric power comes from water driving a water turbine con-
nected to a generator. Hydroelectricity is a low-cost, non-polluting, renewable
energy source. The energy is supplied by the motion of water. Typically a dam is
constructed on a river, creating an artificial lake behind it. Water flowing out of the
lake is forced through turbines that turn generators.
Adhesive forces are the attractive forces between unlike molecules. They are
caused by forces acting between two substances, such as mechanical forces and
electrostatic forces. In the case of a liquid wetting agent, adhesion causes the liquid
to cling to the surface on which it rests. When water is poured on clean glass, it
tends to spread, forming a thin, uniform film over the glasses surface. This is
because the adhesive forces between water and glass are strong enough to pull the
water molecules out of their spherical formation and hold them against the surface
of the glass, thus avoiding the repulsion between like molecules.
When liquid is placed on a smooth surface, the relative strengths of the cohesive
and adhesive forces acting on that liquid determine the shape it will take. If the
adhesive forces between a liquid and a surface are stronger, they will pull the liquid
down, causing it to wet the surface. However, if they cohesive forces among the
liquid itself are stronger, they will resist such adhesion and cause the liquid to retain
a spherical shape and bead the surface.
According to the second law of Pascal, in a container, pressure acts perpen-
dicular to the boundary. It is dependent the nature of plane or curved surface. If F is
total force, P is hydrostatic pressure and A is total surface:
Hydraulic ram (hydram) pumps are water-lifting or water pumping devices that
are powered by filling water. The hydram pumps have been used for over two
centuries in many parts of the world. The pump works by using the energy of a
large amount of water lifting a small height to lift a small amount of that water to a
much greater height. Wherever a fall of water can be obtained, the ram pump can be
used as a comparatively cheap, simple and reliable means of raising water to
considerable heights. The main and unique advantage of hydram pumps is that with
a continuous flow of water, a hydram pump operates automatically and continu-
ously with no other external energy source—be it electricity or hydrocarbon fuel. It
uses a renewable energy source (stream of water) mid hence ensures low running
cost (Tessama 2000).
Lifting water from the source to a higher location can be carried out usually
through a number of potential water-lifting options, depending on the particular site
conditions. One means for lifting water is the hydraulic ram pump or hydram. The
hydram is a self-actuating pump operated by the same principle of a water hammer. If
correctly installed and properly maintained, it is a dependable and useful device that
can lift water to a great height without the use of any other source of energy or fuel
other than water itself. The hydram can be used for lifting water from a source lying at
a lower elevation to a point of use located at a higher elevation for domestic use,
drinking, cooking and washing, and irrigation of small areas, gardens, and orchards.
Energy that is stored in the gravitational field is called gravitational potential
energy, or potential energy due to gravity. If the object is being lifted at constant
velocity, then it is not accelerating, and the net force on it is zero. When lifting
something at a constant velocity the force that you lift with equals the weight of the
object. So, the work done lifting an object is equal to its mass times the acceleration
due to gravity times the height of the lift. As the object falls it travels faster and
faster, and thus, picks up more and more kinetic energy. This increase in kinetic
energy during the fall is due to the drop in gravitational potential energy during the
fall. The gravitational potential energy becomes the kinetic energy of the falling
object.
Archimedes’ principle may be stated thus in terms of forces: Any object, wholly
or partially immersed in a fluid, is buoyed up by a force equal to the weight of the
fluid displaced by the object. A ship loaded into the sea to the mountain top is
removable by using the system of sequential pools installed.
The water energy is converted into electrical energy. Buoyancy of the water can
be used as a source of infinite energy by using convenient geometric devices. The
“emitting” device can be basically long cylindrical, metallic cavity with a
non-metallic outer layer. The geometric energy field around the emitting device can
be converted the electricity power.
Buoyancy is an upward force exerted by a fluid that opposes the weight of an
immersed object. The buoyancy of the water is a source of infinite energy. Because
numerous ship swim in the ocean does not decrease the force. Buoyancy of the
water can be converted into electrical energy using suitable geometric devices. It
has been operated with OWOAS.
2.5 Hydrogen Energy
Hydrogen is not a primary fuel. It must be manufactured from water with either
fossil or nonfossil energy sources. Widespread use of hydrogen as an energy source
could improve global climate change, energy efficiency, and air quality. The
thermochemical conversion processes, such as pyrolysis, gasification and steam
gasification is available for converting the biomass to a more useful energy. The
yield from steam gasification increases with increasing water-to-sample ratio. The
yields of hydrogen from the pyrolysis and the steam gasification increase with
increasing of temperature. The list of some biomass material used for hydrogen
production is given in Table 2.6. Hydrogen powered fuel cells are an important
enabling technology for the hydrogen future and more-efficient alternatives to the
combustion of gasoline and other fossil fuels. Hydrogen has the potential to solve
two major energy problems: reducing dependence on petroleum and reducing
pollution and greenhouse gas emissions.
2.5 Hydrogen Energy 49
Table 2.6 List of some Biomass species Main conversion process

biomass material used for
hydrogen production Bio-nut shell Steam gasification
Olive husk Pyrolysis
Tea waste Pyrolysis
Crop straw Pyrolysis
Black liquor Steam gasification
Municipal solid waste Supercritical water extraction
Crop grain residue Supercritical fluid extraction
Pulp and paper waste Microbiol fermentation
Petroleum basis plastic waste Supercritical fluid extraction
Manure slurry Microbiol fermentation
Algae Pyrolysis
Municipal sewage sludge Supercritical water extraction
Forest wastes Microbiol fermentation
Tyre waste Supercritical fluid extraction
A fuel cell is a device or an electrochemical engine that converts the energy of a

fuel directly to electricity and heat without combustion. Fuel cells consist of two
electrodes sandwiched around an electrolyte. When oxygen passes over one elec-
trode and hydrogen over the other, electricity is generated. Fuel cells running on
hydrogen derived from a renewable source would emit nothing but water vapor.
Fuel cells are clean, quiet, and efficient.
Hydrogen is currently more expensive than conventional energy sources. There
are different technologies presently being practiced to produce hydrogen econom-
ically from biomass. Hydrogen can be produced by pyrolysis from biomass. It can
be burned to produce heat or passed through a fuel cell to produce electricity.
Biomass represents a large potential feedstock resource for environmentally clean
hydrogen production. It lends itself to both biological and thermal conversion
processes. In the thermal path hydrogen can be produced in two ways: direct
gasification and pyrolysis to produce liquid bio-oil, followed by steam reforming.
Hydrogen can alternately be produced by supercritical water gasification of biomass
(Byrd et al. 2007).
Biological generation of hydrogen (biohydrogen) technologies provide a wide
range of approaches to generate hydrogen, including direct biophotolysis, indirect
biophotolysis, photo-fermentations, and dark-fermentation. Biological hydrogen
production processes are found to be more environmental friendly and less energy
intensive as compared to thermochemical and electrochemical processes.
Researchers have started to investigate hydrogen production with anaerobic bacteria
since 1980s. Biohydrogen technology will play a major role in future because it can
utilize the renewable sources of energy.
There are three types of microorganisms of hydrogen generation: cyano-bacteria,
anaerobic bacteria, and fermentative bacteria. The cyano-bacteria directly decom-
pose water to hydrogen and oxygen in the presence of light energy by
photosynthesis. Photosynthetic bacteria use organic substrates like organic acids.

Anaerobic bacteria use organic substances as the sole source of electrons and
energy, converting them into hydrogen. Biohydrogen can be generated using
bacteria such as Clostridia by temperature, pH control, reactor hydraulic retention
time (HRT) and other factors of the treatment system.
Biological hydrogen can be generated from plants by biophotolysis of water
using microalgae (green algae and cyanobacteria), fermentation of organic com-
pounds, and photodecomposition of organic compounds by photo-synthetic bac-
teria. To produce hydrogen by fermentation of biomass, a continuous process using
a non-sterile substrate with a readily available mixed micro6ora is desirable (Hussy
et al. 2005). A successful biological conversion of biomass to hydrogen depends
strongly on the processing of raw materials to produce feedstock which can be
fermented by the microorganisms.
Hydrogen production from the bacterial fermentation of sugars has been
examined in a variety of reactor systems. Hexose concentration has a greater effect
on H2 yields than the HRT. Flocculation also was an important factor in the
performance of the reactor.
Hydrogen gas is a product of the mixed acid fermentation of Escherichia coli,
the butylene glycol fermentation of Aerobacter, and the butyric acid fermentations
of Clostridium spp. It was conducted to improve hydrogen fermentation of food
waste in a leaching-bed reactor by heat-shocked anaerobic sludge, and also to
investigate the effect of dilution rate on the production of hydrogen and metabolites
in hydrogen fermentation.
The combustion products of hydrogen when it is burned completely with air
consist of water, oxygen, and nitrogen. In the meantime, it has been suggested,
hydrogen is too valuable to burn. Laboratory tests conducted on internal combus-
tion engines burning hydrogen demonstrate good performance (Berry et al. 1996).
In comparison with an engine burning gasoline, the emission of nitrogen oxides is
far less for the engine-fueled hydrogen. The product of hydrogen combustion with
air is water vapor and negligible pollution when the peak temperature is limited.
Some oxides of nitrogen (NOx) are formed at very high combustion temperatures
(<2300 K); fortunately, the auto ignition temperature of hydrogen is only 858 K.
Hydrogen has good properties as a fuel for internal combustion engines in
automobiles. Some of the characteristic properties of a hydrogen–air mixture that
can definitely influence the engine design and performance are low ignition energy,
low density, wide range of ignition limits, high diffusion speed, and high flame
speed (Plass et al. 1990).
The main disadvantages of using hydrogen as a fuel for automobiles are huge
on-board storage tanks, which are required because of hydrogen’s extremely low
density. Hydrogen may be stored on board a vehicle as compressed gas in
ultra-high-pressure vessels, as a liquid in cryogenic containers, or as a gas bound
with certain metals in metal hydrides.
Hydrogen is one of the most promising alternative fuel. Hydrogen can be generated
in a number of ways, such as electrochemical processes, thermochemical processes,
photochemical processes, photocatalytic processes, or photoelectrochemical processes
2.5 Hydrogen Energy 51
(Momirlan and Veziroglu 2002). Bio-hydrogen production by anaerobic fermentation

of from renewable organic waste sources has been found to be a promising method for
the recovery of bio-energy (Han and Shin 2004). In this method, anaerobic bacteria
use organic substances as the sole source of electrons and energy, converting them into
hydrogen.
The use of hydrogen as a fuel for transportation and stationary applications is
receiving much favorable attention as a technical and policy issue (Cherry 2004).
Hydrogen gas is being explored for use in combustion engines and fuel-cell electric
vehicles. It is a gas at normal temperatures and pressures, which presents greater
transportation and storage hurdles than exist for the liquid fuels. Several hydrogen
technologies are under development; the most promising of these is the fuel cell.
Fuel cells use hydrogen, oxygen, catalyst, and electrolytic solution to produce
energy in the form of heat and electricity.
2.6 Biogas Energy
The first methane digester plant was built at a leper colony in Bombay, India in
1859 (Meynell 1976). A methane digester system, commonly referred to as an
anaerobic digester is a device that promotes the decomposition of manure or
digestion of the organics in manure to simple organics and gaseous biogas products.
Anaerobic digestion (AD) is the conversion of organic material directly to a gas,
termed biogas, a mixture of mainly methane and carbon dioxide with small
quantities of other gases such as hydrogen sulfide. Methane is the major component
of the biogas used in many homes for cooking and heating (Kan 2009).
Biogas, a clean and renewable form of energy could very well substitute
(especially in the rural sector) for conventional sources of energy (fossil fuels, oil,
etc.) which are causing ecological–environmental problems and at the same time
depleting at a faster rate. Biogas is a modern form of bioenergy that is derived from
the anaerobic digestion of organic matter, such as manure, sewage sludge,
municipal solid waste, biodegradable waste and agricultural slurry under anaerobic
conditions.
Anaerobic digestion (AD) is a bacterial fermentation process that is sometimes
employed in wastewater treatment for sludge degradation and stabilization. The AD
is known to occur over a wide temperature range from 283 to 344 K. Anaerobic
digestion requires attention to the nutritional needs and the maintenance of rea-
sonable temperatures for the facultative and methanogenic bacteria degrading the
waste substrates. The carbon/nitrogen (C/N) ratio of the feedstock is especially
important. Biogas can be used after appropriate gas cleanup as a fuel for engines,
gas turbines, fuel cells, boilers, industrial heaters, other processes, and the manu-
facturing of chemicals.
For anaerobic systems, methane gas is an important product. Depending on the
type and nature of the biological components, different yields can be obtained for
different biodegradable wastes. For pure cellulose, for example, the biogas product
is 50 % methane and 50 % carbon dioxide. Mixed waste feedstocks yield biogas

with methane concentrations of 40–60 % (by volume). Fats and oils can yield
biogas with 70 % methane content.
For first 3 days, methane yield is almost 0 % and carbon dioxide generation is
almost 100 %. In this period, digestion occurred as fermentation to carbon dioxide.
The yields of methane and carbon dioxide gases are fifty-fifty at 11th day. At the
end of the 20th day, the digestion reaches the stationary phase. The methane content
of the biogas is in the range of 63–79 % for the runs, the remainder being prin-
cipally carbon dioxide. During digestion, the volatile fatty acid concentration is
lower and the pH higher.
Digestion is a term usually applied to anaerobic mixed bacterial culture systems
employed in many wastewater treatment facilities for sludge degradation and sta-
bilization. Anaerobic digestion is also becoming more widely used in on-farm
animal manure management systems, and is the principal process occurring in
landfills that creates landfill gas (LFG). Anaerobic digestion operates without free
oxygen and results in a fuel gas called biogas containing mostly methane (CH4) and
carbon dioxide (CO2), but frequently carrying impurities such as moisture,
hydrogen sulfide (H2S), and particulate matter.
Biogas can be used after appropriate gas cleanup as a fuel for engines, gas
turbines, fuel cells, boilers, industrial heaters, other processes, or for the manu-
facturing of chemicals. Before landfilling, treatment or stabilization of biodegrad-
able materials can be accomplished by a combination of anaerobic digestion
followed by aerobic composting.
Landfill leachate treatment has received significant attention in recent years,
especially in municipal areas. The generation of municipal solid wastes (MSW) has
increased in parallel to rapid industrialization. Approximately 16 % of all discarded
MSW is incinerated; the remainder is disposed of in landfills. Effective manage-
ment of these wastes has become a major social and environmental concern.
Disposal of MSW in sanitary landfills is usually associated with soil, surface water
and groundwater contamination when the landfill is not properly constructed. The
flow rate and composition of leachate vary from site to site, seasonally at each site
and depending on the age of the landfill. Young leachate normally contains high
amounts of volatile fatty acids. MSW statistics and management practices including
waste recovery and recycling initiatives have been evaluated. Anaerobic digestion
of the organic food fraction of MSW, on its own or co-digested with primary
sewage sludge, produces high quality biogas, suitable as renewable energy. The
processing of MSW (i.e. landfill, incineration, aerobic composting) secures many
advantages and limitations. The greenhouse gas emissions can be reduced by the
uncontrolled releasing of methane from improperly disposed organic waste in a
large landfill.
Decomposition in landfills occurs in a series of stages, each of which is char-
acterized by the increase or decrease of specific bacterial populations and the for-
mation and utilization of certain metabolic products. The first stage of
decomposition, which usually lasts less than a week, is characterized by the
removal of oxygen from the waste by aerobic bacteria. In the second stage, which
2.6 Biogas Energy 53
Table 2.7 Production of biogas components with time in landfill (percent of biogas, by volume)
Time, month Methane Carbon dioxide Oxygen Nitrogen Hydrogen
0 0 0 21 78 0
3 0 35.0 0 64.5 0.5
5 0 49.0 0 46.8 4.2
10 0 61.7 0 32.3
15 – 68.9 0 16.6 14.5
20 – 71.5 0 13.1 15.4
25 0.3 76.6 0 6.4 17.0
37 4.5 76.1 0 4.2 15.2
48 12.7 68.6 0 1.2 7.5
60 33.5 66.5 0 0 0
70 38.0 62.0 0 0 0
90 48.0 52.0 0 0 0
100 53.3 46.7 0 0 0
110 56.0 44.0 0 0 0
120 56.8 43.2 0 0 0
has been termed the anaerobic acid stage, a diverse population of hydrolytic and
fermentative bacteria hydrolyzes polymers, such as cellulose, hemicelluloses, pro-
teins, and lipids, into soluble sugars, amino acids, long-chain carboxylic acids, and
glycerol. The main components of landfill gas are by-products of the decomposition
of organic material, usually in the form of domestic waste, by the action of naturally
occurring bacteria under anaerobic conditions. Table 2.7 shows the production of
biogas components with time in landfill (Demirbas 2006b).
Methods developed for treatment of landfill leachates can be classified as
physical, chemical and biological which are usually used in combinations in order
to improve the treatment efficiency. Biological treatment methods used for the
leachate treatment can be classified as aerobic, anaerobic and anoxic processes
which are widely used for the removal of biodegradable compounds. Biological
treatment of landfill leachate usually results in low nutrient removals because of
high chemical oxygen demand (COD), high ammonium-N content and the presence
of toxic compounds such as heavy metals. Landfill leachate obtained from the solid
waste landfill area contained high COD and ammonium ions which resulted in low
COD and ammonium removals by direct biological treatment. Typical analysis
results of raw landfill gas are given in Table 2.8.
Anaerobic digestion of organic compounds is a complex process, involving
several different types of microorganisms. This is the natural breakdown of organic
matter, such as biomass, by bacterial populations in the absence of air into biogas,
i.e., a mixture of methane (40–75 % v/v) and carbon dioxide. The end products of
anaerobic digestion are biogas and digestate, a moist solid which is normally
dewatered to produce a liquid stream and a drier solid. During anaerobic digestion,
Table 2.8 Typical analysis of raw landfill gas

Component Chemical formula Content
Methane CH4 40–60 (% by vol.)
Carbon dioxide CO2 30–50 (% by vol.)
Nitrogen N2 2–15 (% by vol.)
Oxygen O2 <1 (% by vol.)
Heavier hydrocarbons CnH2n+2 <1 (% by vol.)
Hydrogen sulfide H2S 40–100 ppm
Complex organics – 1000–2000 ppm
typically 30–60 % of the input solids are converted to biogas; byproducts consist of
undigested fibre and various water-soluble substances.
The anaerobic digestion process occurs in the following four basic steps:
(1) hydrolysis, (2) acidogenesis, (3) acetogenesis, and (4) methanogenesis.
The first step in anaerobic degradation is the hydrolysis of complex organic
compounds such as carbohydrates, proteins and lipids. Organic compounds are
hydrolyzed into smaller units, such as sugars, amino acids, alcohols and long-chain
fatty acids. During the hydrolysis step both solubilization of insoluble particulate
matter and biological decomposition of organic polymers to monomers or dimers
take place. Thermal, mechanic and chemical treatment have been investigated as a
possible pre-treatment step to accelerate sludge hydrolysis. The aim of the
pre-treatment is disintegrate sludge solids to facilitate the release of cell components
and other organic matter.
In the second step, acidogenesis, another group of microorganisms ferments the
break-down products to acetic acid, hydrogen, carbon dioxide and other lower
weight simple volatile organic acids like propionic acid and butyric acid which are
in turn converted to acetic acid. Acetate, carbon dioxide and molecular hydrogen
can be directly utilised as a substrate by another group of anaerobic microorganisms
called methanogens. These organisms comprise a wide variety of different bacterial
genera representing both obligate and facultative anaerobes.
During acidogenesis, the freshly fed biomass on the top produced a lot of
volatile fatty acids (VFAs) intermediates that accumulated in the bed. A daily
sprinkling of the bed once on one side introduced acidogenic organisms onto the
upper regions of the biomass bed and it also carried down VFA intermediates to
lower regions of the bed. This degradation pathway is often the fastest step and also
gives a high-energy yield for the microorganisms, and the products can be used
directly as substrates by the methanogenic microorganism.
The third step is the biological process of acetogenesis where the products of
acidogenesis are further digested to produce carbon dioxide, hydrogen and mainly
acetic acid, although higher-molecular-weight organic acids (e.g., propionic,
butyric, valeric) are also produced. The products formed during acetogenesis are
due to a number of different microbes, e.g., Syntrophobacter wolinii, a propionate
decomposer and Sytrophomonos wolfei, a butyrate decomposer. Other acid formers
2.6 Biogas Energy 55
are Clostridium spp., Peptococcus anerobus, Lactobacillus, and Actinomyces

(Verma 2002). Acetogens are slow-growing microorganisms that are sensitive to
environmental changes such as changes in the organic loading rate and flow rate.
The microorganisms in the step are usually facultative heterotrophs which function
best in a range of pH from 4.0 to 6.5 (Zhang et al. 2005).
Anaerobic digestion can occur over a wide range of environmental conditions,
although narrower ranges are needed for optimum operation. The key factors to
successfully control the stability and efficiency of the process are reactor configu-
rations, temperature, pH, HRT, OLR, inhibitor concentrations, concentrations of
total volatile fatty acid (TVFA) and substrate composition.
Temperature significantly influences anaerobic digestion process, especially in
methanogenesis wherein the degradation rate is increasing with temperature. It has
been found that the optimum temperature ranges for anaerobic digestion are
mesophilic (303–313 K), and thermophilic (323–333 K) (Braun 2007). Based on
the temperature chosen, the duration of the process and effectiveness in destroying
pathogens will vary. In mesophilic digestion, the digester is heated to 35 °C and the
typical time of retention in the digester is 15–30 days, whereas in thermophilic
digestion the digester is heated to 328 K and the time of retention is typically
12–14 days (Erickson et al. 2004). It has been observed that higher temperatures in
the thermophilic range reduce the required retention time (Verma 2002). However,
anaerobes are most active in the mesophilic and thermophilic temperature range.
The activities of microorganisms increase with the increase of temperature,
reflecting stable degradation of the substrate.
Temperature is a universal process variable. It influences the rate of bacterial
action as well as the quantity of moisture in the biogas. The biogas moisture content
increases exponentially with temperature. Temperature also influences the quantity
of gas and volatile organic substances dissolved in solution as well as the con-
centration of ammonia and hydrogen sulfide gas.
pH is a major variable to be monitored and controlled. The range of acceptable
pH in digestion is theoretically from 5.5 to 8.5. It may be necessary to use a base or
buffer to maintain the pH in the biodigester. In general, the pH has been reported as
one of the most important parameters for the inhibition of the methanogenic activity
in an acid phase reactor, operating in the pH range 4.5–6.5. Maximum propionate
degradation and methane production were observed at pH 7.5 and pH 7.0,
respectively. Efficient methanogenesis from a digester operating in a steady state
should not require pH control, but at other times, for example, during start-up or
with unusually high feed loads, pH control may be necessary. pH can only be used
as a process indicator when treating waste with low buffering capacity, such as
carbohydrate-rich waste (Parawira 2004).
Agricultural residues contain low nitrogen and have carbon-to-nitrogen ratios (C/N)
of around 60–90. The proper C/N ratio for anaerobic digestion is 25–35; therefore,
nitrogen needs to be supplemented to enhance the anaerobic digestion of agricultural
solid residues. Nitrogen can be added in inorganic form such as ammonia or in organic
form such as livestock manure, urea, or food wastes. Once nitrogen is released from
the organic matter, it becomes ammonium which is water soluble. Recycling nitrogen
in the digested liquid reduces the amount of nitrogen needed.
2.7 Algae Energy
Billions of years ago the earth atmosphere was filled with CO2. Thus there was no
life on earth. Life on earth started with Cyanobacterium and algae.
Algae are the fastest-growing plants in the world. Industrial reactors for algal
culture are open ponds, photobioreactors and closed systems. Algae are very
important as a biomass source. Algae will someday be competitive as a source for
biofuel.
Different species of algae may be better suited for different types of fuel. Algae
can be grown almost anywhere, even on sewage or salt water, and does not require
fertile land or food crops, and processing requires less energy than the algae
provides.
Algae can be a replacement for oil based fuels, one that is more effective and has
no disadvantages. Algae are among the fastest growing plants in the world, and
about 50 % of their weight is oil. This lipid oil can be used to make biodiesel for
cars, trucks, and airplanes.
Microalgae have much faster growth-rates than terrestrial crops. the per unit area
yield of oil from algae is estimated to be from between 20,000 and 80,000 L per
acre, per year; this is 7 to 31 times greater than the next best crop, palm oil. The
lipid and fatty acid contents of microalgae vary in accordance with culture condi-
tions. Most current research on oil extraction is focused on microalgae to produce
biodiesel from algal-oil. Algal-oil processes into biodiesel as easily as oil derived
from land-based crops.
Microalgae can be used for bioenergy generation (biodiesel, biomethane, bio-
hydrogen), or combined applications for biofuels production and CO2 mitigation.
Microalgae are veritable miniature biochemical factories, and appear more photo-
synthetically efficient than terrestrial plants (Pirt 1986) and are efficient CO2 fixers
(Brown and Zeiler 1993).
The existing large-scale natural sources are of algae are: bogs, marshes and
swamps—salt marshes and salt lakes. Microalgae contain lipids and fatty acids as
membrane components, storage products, metabolites and sources of energy. Algae
contain anything between 2 and 40 % of lipids/oils by weight. Growth medium
must provide the inorganic elements that constitute the algal cell. Essential elements
include nitrogen (N), phosphorus (P), iron and in some cases silicon (Chisti 2007).
Minimal nutritional requirements can be estimated using the approximate molecular
formula of the microalgal biomass that is CO0.48H1.83N0.11P0.01. This formula is
based on data presented by Grobbelaar (2004).
The production of microalgal biodiesel requires large quantities of algal biomass.
Macro and microalgae are currently mainly used for food, in animal feed, in feed
for aquaculture and as bio-fertilizer. Biomass from microalgae is dried and
2.7 Algae Energy 57
marketed in the human health food market in form of powders or pressed in the
form of tablets Aquatic biomass could also be used as raw material for co-firing to
produce electricity, for liquid fuel (bio-oil) production via pyrolysis, or for bio-
methane generation through fermentation. Bio-methane can be produced from
marine biomass.
Microalgae cultivation using sunlight energy can be carried out in open or
covered ponds or closed photobioreactors, based on tubular, flat plate or other
designs. Closed systems are much more expensive than ponds, and present sig-
nificant operating challenges, and due to gas exchange limitations, among others,
cannot be scaled-up much beyond about a hundred square meters for an individual
growth unit.
The concept of using microalgae as a source of fuel is older than most people
realize. The idea of producing methane gas from algae was proposed in the early
1950s. Industrial reactors for algal culture are at present. There are:
1. Photobioreactors
2. Open ponds
3. Closed and hybrid systems.
Photobioreactors are different types of tanks or closed systems in which algae are
cultivated. Open pond systems are shallow ponds in which algae are cultivated.
Nutrients can be provided through runoff water from nearby land areas or by
channelling the water from sewage/water treatment plants. Technical and biological
limitations of these open systems have given rise to the development of enclosed
photoreactors. Microalgae cultivation using sunlight energy can be carried out in
open or covered ponds or closed photobioreactors, based on tubular, flat plate or
other designs. A few open systems are presented for which particularly reliable
results are available. Emphasis is then put on closed systems, which have been
considered as capital intensive and are justified only when a fine chemical is to be
produced. Microalgae production in closed photobioreactors is highly expensive.
Closed systems are much more expensive than ponds. However, the closed systems
require much less light and agricultural land to grow the algae. High oil species of
microalgae cultured in growth optimized conditions of photobioreactors have the
potential to yield 19,000–57,000 L of microalgal oil per acre per year. The yield of
oil from algae is over 200 times the yield from the best-performing plant/vegetable
oils (Chisti 2007). Figure 2.5 shows the open pond systems or open algae farms.
Large-scale production of microalgal biomass generally uses continuous culture
during daylight. In this method of operation, fresh culture medium is fed at a
constant rate and the same quantity of microalgal broth is withdrawn continuously
(Molina Grima 1999). Feeding ceases during the night, but the mixing of broth
must continue to prevent settling of the biomass (Molina Grima 1999). As much as
25 % of the biomass produced during daylight, may be lost during the night
because of respiration. The extent of this loss depends on the light level under
which the biomass was grown, the growth temperature, and the temperature at night
(Chisti 2007).
Sunligth
Wastewater with Nutrients
Motor
paddle
Algae
Waste CO2
Fig. 2.5 Open pond systems or open algae farms
Algal cultures consist of a single or several specific strains optimized for pro-
ducing the desired product. Water, necessary nutrients and CO2 are provided in a
controlled way, while oxygen has to be removed (Carlsson et al. 2007). Algae
receive sunlight either directly through the transparent container walls or via light
fibers or tubes that channel it from sunlight collectors. A great amount of devel-
opmental work to optimize different photobioreactor systems for algae cultivation
has been carried out and is reviewed in Janssen et al. (2003), Choi et al. (2003),
Carvalho et al. (2006), Hankamer et al. (2007).
Bioreactors are the preferred method for scientific researchers, and recently for
some newer, innovative production designs. These systems are more expensive to
build and operate; however, they allow for a very controlled environment. This
means that gas levels, temperature, pH, mixing, media concentration, and light can
be optimized for maximum production (Chisti 2007). Unlike open ponds, biore-
actors can ensure a single alga species is grown without interference or competition
(Campbell 2008).
Algae can be harvested by centrifugation, flocculation or froth flotation. Alum
and ferric chloride are chemical flocculants used to harvest algae. Water that is
brackish or salty requires additional chemical flocculants to induce flocculation.
Harvesting by chemical is a method that is often too expensive for large operations.
However, interrupting the carbon dioxide supply to an algal system can cause algae
to flocculate on its own, which is called “auto-flocculation”. In froth flotation, the
water and algae are aerated into froth and algae in then removed from the water.
2.7.1 Biodiesel Production from Algal Oil
Microalgae contain lipids and fatty acids as membrane components, storage

products, metabolites and sources of energy. Algae present an exciting possibility
2.7 Algae Energy 59
Table 2.9 Oil contents of Microalga Oil content (wt% of dry basis)
some microalgae
Botryococcus braunii 25–75
Chlorella sp. 28–32
Crypthecodinium cohnii 20
Cylindrotheca sp. 16–37
Dunaliella primolecta 23
Isochrysis sp. 25–33
Monallanthus salina >20
Nannochloris sp. 20–35
Nannochloropsis sp. 31–68
Neochloris oleoabundans 35–54
Nitzschia sp. 45–47
Phaeodactylum 20–30
tricornutum 50–77
Schizochytrium sp. 15–23
Tetraselmis sueica
as a feedstock for biodiesel, and when you realize that oil was originally formed
from algae.
In order to have an optimal yield, these algae need to have carbon dioxide (CO2)
in large quantities in the basins or bioreactors where they grow. Thus, the basins
and bioreactors need to be coupled with traditional thermal power centers pro-
ducing electricity which produce CO2 at an average tenor of 13 % of total flue gas
emissions. The CO2 is put in the basins and is assimilated by the algae. It is thus a
technology which recycles CO2 while also treating used water.
Algae can grow practically anywhere where there is enough sunshine. Some
algae can grow in saline water. All algae contain proteins, carbohydrates, lipids and
nucleic acids in varying proportions. The oil contents of some microalgae are given
in Table 2.9 (Chisti 2007). Microalgae are very efficient solar energy converters and
they can produce a great variety of metabolites (Chaumont 2005). The culture of
algae can yield 30–50 % oil (Dimitrov 2008). Oil supply is based on the theoretical
claims that 47,000–308,000 L/ha/year of oil could be produced using algae. The
calculated cost per barrel would be only $20 (Demirbas 2009a).
Algae are theoretically very promising source of biodiesel. The lipid and fatty
acid contents of microalgae vary in accordance with culture conditions. In some
cases, lipid content can be enhanced by the imposition of nitrogen starvation or other
stress factors. Which is the best species of algae for biodiesel? There is no one strain
or species of algae that can be said to be the best in terms of oil yield for biodiesel.
However diatoms and secondly green algae were the most promising. Scenedesmus
dimorphus is a unicellular alga in the class Chlorophyceae (green algae). While this
is one of the preferred species for oil yield for biodiesel, one of the problems with
Scenedesmus is that it is heavy, and forms thick sediments if not kept in constant
agitation. The strain called as Dunaliella tertiolecta has oil yield of about 37 %
(organic basis). Dunaliella tertiolecta is a fast growing strain and that means it has a
high CO2 sequestration rate as well (Sheehan et al. 1998; Chisti 2007; Ozkurt 2009;
Demirbas 2009a). Table 2.10 shows the yield of various plant oils.
Table 2.10 Yield of various Crop Oil in liters per hectare

plant oils
Algae 100,000
Castor 1413
Coconut 2689
Palm 5950
Safflower 779
Soy 446
Sunflower 952
Certain algae strains also produce polyunsaturated fatty acids (omega-3’s) in the
form of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) generally
found in fish oils. Phototrophic microalgae are used to provide polyunsaturated
fatty acids (omega-3 and omega-6) for aquaculture operations. These additional
products greatly enhance the overall marketability and economics of producing
algae (Volkman et al. 1989; Yaguchi et al. 1997; Vazhappilly and Chen 1998).
The algae that are used in biodiesel production are usually aquatic unicellular
green algae. This type of algae is a photosynthetic eukaryote characterized by high
growth rates and high population densities. Under good conditions, green algae can
double its biomass in less than 24 h. Additionally, green algae can have huge lipid
contents, frequently over 50 % (Schneider 2006; Chisti 2007). This high yield, high
density biomass is ideal for intensive agriculture and may be an excellent source for
biodiesel production.
The annual productivity and oil content of algae is far greater than seed crops.
Soybean can only produce about 450 L of oil per hectare. Canola can produce
1200 L per hectare, and Palm can produce 6000 L. Now, compare that to algae
which can yield 90,000 L per hectare (Schneider 2006; Chisti 2007; Haag 2007). It
is possible that the US demand for liquid fuel could be achieved by cultivating
algae in one tenth of the area currently devoted to soybean cultivation (Scott and
Bryner 2006).
The process for producing microalgal oils consists of a microalgal biomass
production step that requires light, carbon dioxide, water and inorganic nutrients.
The latter are mainly nitrates, phosphates, iron and some trace elements.
Approximately half of the dry weight of the microalgal biomass is carbon, which is
typically derived from carbon dioxide. Therefore, producing 100 tons of algal
biomass fixes roughly 183 tons of carbon dioxide. This carbon dioxide must be fed
continually during daylight hours. This carbon dioxide is often available at little or
no cost (Chisti 2008). Optimal temperature for growing many microalgae is
between 293 and 303 K. A temperature outside this range could kill or otherwise
damage the cells.
There are three well-known methods to extract the oil from algae:
(1) Expeller/Press, (2) Solvent extraction with hexane and (3) Supercritical Fluid
extraction. A simple process is to use a press to extract a large percentage (70–
75 %) of the oils out of algae. Algal oil can be extracted using chemicals. The most
popular chemical for solvent extraction is hexane, which is relatively inexpensive.
2.7 Algae Energy 61
Supercritical fluid extraction is far more efficient than traditional solvent separation
methods. Supercritical fluids are selective, thus providing the high purity and
product concentrations (Paul and Wise 1971). This can extract almost 100 % of the
oils all by itself. In the supercritical fluid carbon dioxide (CO2) extraction, CO2 is
liquefied under pressure and heated to the point that it has the properties of both a
liquid and gas. This liquefied fluid then acts as the solvent in extracting the oil.
The lipid and fatty acid contents of microalgae vary in accordance with culture
conditions. Algal oil contains saturated and monounsaturated fatty acids. The fatty
acids were determined in the algal oil in the following proportions: 36 % oleic
(18:1), 15 % palmitic (16:0), 11 % stearic (18:0), 8.4 % iso-17:0, and 7.4 %
linoleic (18:2). The high proportion of saturated and monounsaturated fatty acids in
this alga is considered optimal from a fuel quality standpoint, in that fuel poly-
merization during combustion would be substantially less than what would occur
with polyunsaturated fatty acid-derived fuel (Sheehan et al. 1998).
After oil extraction from algae, the remaining biomass fraction can be used as a
high protein feed for livestock (Schneider 2006; Haag 2007). This gives further
value to the process and reduces waste.
Most current research on oil extraction is focused on microalgae to produce
biodiesel from algal oil. The biodiesel from algal oil in itself is not significantly
different from biodiesel produced from vegetable oils. Figure 2.6 shows the pro-
duction of biodiesel from algae.
Fig. 2.6 Production of Macro- and Microalgae

biodiesel from algae
Grinding
Oil extraction
Transesterification
Separation of biodiesel and glycerine
Water washing soap and glycerine
Purification of Biodiesel Biodiesel

Oils were obtained by extracting the algae with hexane in a Soxhlet extractor for
18 h. Transesterification of algal oils were performed in a 100-mL cylindrical using
supercritical methanol according to earlier methods (Kusdiana and Saka 2001).
Fatty acids of the algal oils were fractionated into saturated, monounsaturates,
polyunsaturates and free forms by a preparative chromatographic thin layer on a
glass plate coating with a 0.25 lm polyethanol succinate.
Xu et al. (2006) used Chlorella protothecoides (a microalga) for production of
biodiesel. Cells were harvested by centrifugation, washed with distilled water, and
then dried by a freeze dryer. The main chemical components of heterotrophic
C. protothecoides were measured as previous study (Miao et al. 2004). Microalgal
oil was prepared by pulverization of heterotrophic cell powder in a mortar and
extraction with n-hexane.
The optimum process combination was 100 % catalyst quantity (based on oil
weight) with 56:1 molar ratio of methanol to oil at temperature of 303 K, which
reduced product specific gravity from an initial value of 0.912 to a final value of
0.864 in about 4 h of reaction time (Xu et al. 2006).
The technique of metabolic controlling through heterotrophic growth of
C. protothecoides was applied, and the heterotrophic C. protothecoides contained
the crude lipid content of 55.2 %. To increase the biomass and reduce the cost of
alga, corn powder hydrolysate instead of glucose was used as organic carbon source
in heterotrophic culture medium in fermenters. The result showed that cell density
significantly increased under the heterotrophic condition, and the highest cell
concentration reached 15.5 g/L. Large amount of microalgal oil was efficiently
extracted from the heterotrophic cells by using n-hexane, and then transmuted into
biodiesel by acidic transesterification (Xu et al. 2006).
Algae biomass cultivation has four important potentials than other sources. First,
algae biomass can be produced at extremely high volumes and this biomass can
yield a much higher percentage of oil than other sources. Second algae oil has
limited market competition. Third, algae can be cultivated on marginal land, fresh
water, or sea water. Fourth, innovations to algae production allow it to become
more productive while consuming resources that would otherwise be considered
waste (Campbell 2008).
Biodiesel derived from oil crops is a potential renewable and carbon neutral
alternative to petroleum fuels. Unfortunately, biodiesel from oil crops, waste
cooking oil and animal fat cannot realistically satisfy even a small fraction of the
existing demand for transport fuels. Microalgae appear to be the only source of
renewable biodiesel that is capable of meeting the global demand for transport
fuels.
Like plants, microalgae use sunlight to produce oils but they do so more effi-
ciently than crop plants. Oil productivity of many microalgae greatly exceeds the oil
productivity of the best producing oil crops. Approaches for making microalgal
biodiesel economically competitive with petrodiesel are discussed (Chisti 2007).
Biodiesel derived from green algae biomass has the potential for high volume, cost
effective production (Campbell 2008).
2.7 Algae Energy 63
Laboratory studies, exploring methods to maximize both density and oil content,
have demonstrated that there is yet much unrealized potential. Xu et al. (2006)
cultivated the algae Chlorella protothecoids in a light deprived, heterotrophic
environment with inexpensive hydrolyzed corn starch as the sole food source.
Biodiesel from microalgae seems to be the only renewable biofuel that has the
potential to completely displace petroleum-derived transport fuels without
adversely affecting supply of food and other crop products. Most productive oil
crops, such as oil palm, do not come close to microalgae in being able to sus-
tainably provide the necessary amounts of biodiesel. Similarly, bioethanol from
sugarcane is no match for microalgal biodiesel (Chisti 2008).
Algae can grow practically anywhere where there is enough sunshine. Some
algae can grow in saline water. All algae contain proteins, carbohydrates, lipids and
nucleic acids in varying proportions. While the percentages vary with the type of
algae, there are algae types that are comprised up to 40 % of their overall mass by
fatty acids (Becker 1994). The most significant distinguishing characteristic of algal
oil is its yield and hence its biodiesel yield. According to some estimates, the yield
(per acre) of oil from algae is over 200 times the yield from the best-performing
plant/vegetable oils (Sheehan et al. 1998).
2.7.2 Glycerol from Vegetable Oil for a Promising Carbon

Source
Glycerol is present in many applications in the cosmetic, paint, automotive, food,

tobacco, pharmaceutical, pulp and paper, leather and textile industries. Glycerol is a
by-product from biodiesel and soap industries. The principal by–product of bio-
diesel production is the crude glycerol, which is about 10 %wt of vegetable oil.
Triglycerides from vegetable oils and animal fats can be hydrolyzed or split into its
corresponding fatty acids and glycerine. Figure 2.7 shows biodiesel and glycerol
from transesterification process.
Direct addition of glycerol to the fuel is not possible; however, derivatives of
glycerol such as ethers have potential for use as additives with biodiesel, diesel or
biodiesel-diesel blends. Glycerol can be converted into commercially valued
Triglyceride in oil or fat Methanol Glycerol Methyl ester of fatty acid (biodiesel)
Fig. 2.7 Biodiesel and glycerol from transesterification process

oxygenate products using for the diesel fuel blends. Glycerol alkyl ethers (GAEs)
are easily synthesized using glycerol which is reacted with isobutylene in the
presence of an acid catalyst. The ethers of glycerol can be effectively added to
biodiesel fuels, providing a 5 K reduction in cloud point and an 8 % reduction in
viscosity.
The excess glycerol generated may become an environmental problem, since it
cannot be disposed of in the environment. One of the possible applications is its use
as carbon and energy source for microbial growth in industrial microbiology.
Glycerol bioconversion in valuable chemicals, such as 1,3-propanediol, dihydrox-
yacetone, ethanol, succinate etc. is discussed in this review article (da Silva et al.
2009).
Glycerol must be modified to fuel oxygenates derivatives using as additive in
diesel and biodiesel fuel blends. The most obvious derivative of glycerol has an
analogy in gasoline reformulation.
Glycerol alkyl ethers (GAEs) are easily synthesized using glycerol which is
reacted with isobutylene in the presence of an acid catalyst, and the yield is
maximized by carrying out the reaction in a two-phase reaction system, with one
phase being a glycerol-rich polar phase (containing the acidic catalyst) and the other
phase being an olefin-rich hydrocarbon phase from which the product ethers can be
readily separated (Gupta 1995).
The etherification of glycerol with tert-butanol has been studied by Klepacova
et al. (2003) at the presence of catex Amberlyst 15 as catalyst. The maximum
conversion of glycerol near 96 % was reached at the temperature 363 K and at the
molar ratio tert-butanol/glycerol = 4:1 after 180 min (Klepacova et al. 2003).
The preparation of the glycerol alkyl ethers (GAE) by etherification
(o-alkylation) by alkenes, and preferentially by isobutylene is one of the possibil-
ities of the glycerol usage. The GAEs can be also obtained from alkenes with C4-
fraction from pyrolysis and fluid catalytic cracking at the presence of the acid
catalyst. The mixture of mono-, di- and tri- alkyl glycerol ethers can be produced.
These ethers (mainly di- and tri- alkyl glycerols) are the main products of glycerol
etherification reaction and are excellent oxygen additives for diesel fuel (Jamróz
et al. 2007). The addition of these ethers has positive effect on the combustion of
diesel fuel (high cetane number, CN) and preferentially ethers are active by
reduction of fumes and particulate matters, carbon oxides and carbonyl compounds
in exhausts (Klepacova et al. 2003).
Glycerol can be converted to propylene glycol (1,2-propanediol) by dehydration
followed by hydrogenation (hydrogenolysis) reaction. Propylene glycol is used in
an antifreeze mixture (70 % propylene glycol and 30 % glycerol) that can be
produced, refined, and marketed directly by existing biodiesel facilities. The
method is based on hydrogenolysis of glycerol over a copper chromite catalyst at
475 K (Pagliaro et al. 2007). Figure 2.8 shows a simple flow diagram of glycerol
from continuous biodiesel production process with subcritical water and super-
critical methanol stages.
2.8 The Next Generation of Hybrid Transportation Vehicles 65
Fig. 2.8 A simple flow Vegetable oils

diagram of glycerol from a
continuous biodiesel
production process
Water hydrolysis at 545 K
Phase separation
Fatty acids Water phase
Glycerol purification
Methanol Esterification
Biodiesel Glycerol Wastewater
2.8 The Next Generation of Hybrid Transportation

Vehicles
Internal combustion engines (ICEs) will end in near future and their life until 2040
is estimated. A variety of propulsion technologies and fuels have the promise to
reduce petroleum use and greenhouse gas emissions from motor vehicles.
Cars are being developed in many different ways. According to predictions made
a few decades ago, current travel should involve self-driving automobiles, jetpacks
and flying cars, with space transport a common occurrence. Figure 2.9 shows
conventional and future transportation vehicles.
Hybrid electric vehicle (HEV) technology and its various applications, the
subject of this paper, have made significant market gains in recent years and form
an important part of the fuel economy equation. HEVs are powered with a com-
bination of a combustion engine and an electric motor. A hybrid vehicle is a vehicle
that uses two or more distinct power sources to move the vehicle.
Though hybrid cars consume less petroleum than conventional cars, there is still
an issue regarding the environmental damage of the hybrid car battery. Today most
hybrid car batteries are one of two types: (1) nickel metal hydride, or (2) lithium
ion; both are regarded as more environmentally friendly than lead-based batteries
which constitute the bulk of gasoline car starter batteries today.
Plug-in hybrids are an evolution from today’s so-called “full” hybrid vehicles,
such as the Toyota Prius or Ford Escape. A “full” hybrid has the ability to start and
accelerate to low speeds without starting the gasoline engine, but the battery pack is
charged exclusively from the on-board internal combustion engine and regenerative
breaking. A plug-in hybrid operates in the same way but has a larger battery pack
TRANSPORTATION VEHICLES
Conventional Transportation Vehicles Future Transportation Vehicles
Internal Combustion External Combustion Fuel-cell

Hybrid
Engines Engines Vehicles
Vehicles
Otto Engine Diesel Engine Stirling Engine Battery Electric Flying Cars
Vehicles
Fig. 2.9 Conventional and future transportation vehicles
and gives the driver the option of charging the battery from a household outlet and
then running their vehicle on grid electricity instead of petroleum (NRDC 2007).
Today’s popular hybrid vehicles use nickel metal hydride (NiMH) batteries,
which can be engineered for relatively short battery-only driving distances in
plug-in hybrids. Plug-in hybrids have an advantage over pure battery electric
vehicles because drivers don’t have to worry about running out of electricity—
when the battery runs down, plug-ins operate like conventional hybrids and use the
engine and regenerative braking to charge the battery and drive the vehicle.
The purchase price of a hybrid vehicle is higher compared to a conventional
vehicle, both for passenger cars, buses, and trucks. However, given the lower fuel
consumption, the total cost of ownership or life cycle cost of buying and using a
hybrid can be equal to or even lower than buying and using a conventional vehicle
—depending on yearly mileage and fuel prices. The life cycle cost does not only
include the cost of purchasing the vehicle but also the cost of fueling and
maintenance.
Electric vehicles which store electrical energy in a capacitor or battery would not
be able to immediately replace all gasoline cars given the available transportation
infrastructure. For example, while a gasoline car could undertake a road trip which
would require several short (around 5 min) fuel stops to complete, current electric
car technology would not be capable of completing the trip in the same length of
time; in addition to the limited range of current electric cars, they are not as quick or
as practical to recharge.
Proponents of electric cars usually tout an increased efficiency as the primary
advantage of an electric vehicle as compared to one powered by an internal com-
bustion engine. The energy efficiency comparison is difficult to make because the
two vehicles operate on different principles. Vehicles powered by internal com-
bustion engines operate convert energy stored in fossil fuels to mechanical energy
through the use of a heat engine. Heat engines operate with very low efficiencies
because heat cannot be converted directly into mechanical energy. Electric vehicles
2.8 The Next Generation of Hybrid Transportation Vehicles 67
convert stored electric potential into mechanical energy. Electricity can be con-
verted into mechanical energy at very high efficiencies.
A flying car or roadable aircraft is an aircraft that can also travel along roads. All
the working examples have required some manual or automated process of con-
version between the two modes of operation.
Flying cars not imagine today. Ground and air traffic, security, speed, conve-
nience fuel with higher heating value and lower weight and low cost are the most
important problems for flying cars.
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Chapter 3
Unconventional Energy Sources
3.1 Introduction
Unconventional energy sources cover unusually unconventional energy, with little

or no unused, inactive cases and the energy resources available waste form.
Figure 3.1 shows unconventional energy sources. For example; extra heavy oil,
heavy crude oil and no 4–6 fuel oils are unconventional energy sources because
they are used in small amounts or for they not use in the production of diesel fuel
and/or gasoline. Natural gas hydrate is an example to inactive energy source due to
it has not yet been used in the production of methane. Releasing heats from cooking
food in a kitchen or from the flue of a cement factory are waste heats, for examples,
because they can be used to generate electricity.
The unconventional hydrocarbon applications have been growing rapidly in
recent years. Conventional fossil energy will not be enough to meet the continu-
ously increasing need for energy in the future. In this case, renewable energy
sources will become important. Conventional oil sources are currently preferred
because they are less expensive than unconventional sources. New technologies are
being developed to reduce unconventional oil production costs. Unconventional oil
can be produced from oil sands, oil shale, extra heavy oil, gas to liquids and other
liquids.
Primary energy sources can be divided into non-renewable and renewable.
Non-renewable energy resources include fossil and fissile materials, while renew-
able energy sources are biomass, hydro, geothermal, solar and wind energy
(Demirbas 2008a). The fossil energy sources are petroleum (crude oil), coal, natural
gas, oil shales, tar sands, bitumens, and natural gas hydrates. The energy source can
be also classified according to its depletion rate. Whilst the biomass energy can be
depleted, solar and wind energy are non-depletable. Figure 3.2 shows a basic
classification of non-renewable energy sources. Figure 3.3 shows a basic classifi-
cation of renewable energy sources.

72 3 Unconventional Energy Sources
UNCONVENTIONAL
ENERGY SOURCES
UNUSUAL ENERGY INACTIVE ENERGY WASTE ENERGY
Fig. 3.1 Unconventional energy sources
Non-renewable Energy Sources
Conventional Non-conventional
Fossil Energy Sources
Petroleum Coal Natural Gas Fossil Energy Sources Non-Fossil Energy Sources
Oil Shales Tar Sands Bitumens Gas hydrates Earth Minerals Metal Ores
Fig. 3.2 Basic classification of non-renewable energy sources
Because of increase in petroleum prices especially after petrol crisis in 1973 and
then gulf war in 1991, geographically reduced availability of petroleum and more
stringent governmental regulations on exhaust emissions, researchers have studied
on alternative fuels and alternative solution methods (Durgun and Sahin 2007).
Reducing the use of fossil fuels would considerably reduce the amount of carbon
dioxide and other pollutants produced. This can be achieved by either using less
energy altogether or by replacing fossil fuel by renewable fuels. Hence, current
efforts focus on advancing technologies that emit less carbon or no carbon such as
nuclear, hydrogen, hydropower, solar, wind, geothermal, or on using energy more
efficiently and on developing sequestering carbon dioxide emitted during fossil fuel
combustion. Hence, the future trend is towards using alternate energy sources such
as “Unconventional Energy Sources”.
About 98 % of carbon emissions result from fossil fuel combustion. Reducing
the use of fossil fuels would considerably reduce the amount of carbon dioxide and
other pollutants produced. This can be achieved by either using less energy alto-
gether or by replacing fossil fuel by renewable fuels. Hence, current efforts focus on
advancing technologies that emit less carbon (e.g., high efficiency combustion) or
no carbon such as nuclear, hydrogen, solar, wind, geothermal, or on using energy
more efficiently and on developing sequestering carbon dioxide emitted during
fossil fuel combustion (Demirbas 2009). Figure 3.3 shows the fossil energy
3.1 Introduction 73
Renewable Energy Sources
Conventional Non-conventional
Biomass Geothermal
Solar Tidal Power Wave Power
Hydro
Wind
Waste Energy Shaking Energy
Fig. 3.3 Basic classification of renewable energy sources
350
300
250
200
150
100
50
0
Coal Shale oil Crude oil Natural gas Tar sands
Fig. 3.4 Fossil energy reserves of the world (Each unit = 1 × 1015 MJ = 1.67 × 1011 Bbl
crude oil)
reserves of the world. Coal reserves of the world are 3.2 × 1017 MJ. On the other
hand, deuterium and uranium reserves of the world are 7.5 × 1024 and
1.2 × 1020 MJ, respectively (Demirbas 2002a) (Fig. 3.4).
3.2 Waste Energy
Waste energy covers unused or used with low efficient energy resources. Magma is
an unused and inactive energy source. Seismic energy is an energy source that
cannot be controlled. Forestry wastes, municipal solid wastes (MSW) and munic-
ipal sewage sludge (MSS) can be considered as the waste energy sources. The MSS
contains mainly proteins, sugars, detergents, phenols, and lipids. Sewage sludge
also includes toxic and hazardous organic and inorganic pollutants sources.
Most electricity in the world is conventionally generated using coal, oil, natural
gas, nuclear energy, or hydropower. Electricity generation by using gas has
increased due to its lower cost compared to coal. Continued increases in the use of
natural gas for electricity generation are expected worldwide. However, the use of
cheaper unconventional sources in electricity production is carried out researches in
the clipboard (Demirbas 2005a, 2006a; Ozturk and Demirbas 2006).
The role of nuclear power in the world’s electricity markets is projected to lessen
as reactors in industrialized nations reach the end of their life spans. Nuclear
electricity satisfies both economic and environmental protection goals. The con-
trolled fission of small amounts of uranium fuel creates large volumes of electricity
without combusting carbon-based fuel sources. This avoids the release of both
residual carbon gases and other combustion by product emissions such as nitrogen
oxides. Improved production techniques have actually reduced the amounts of used
fuel created while increasing electricity output (Demirbas 2000).
It is known that hydro is the cheapest source of electricity production. Some
production is done with alternative fuels like geothermal energy, wind power,
biomass, solar energy, or fuel. Due to environmental concerns and the fact that
fossil energy sources are non-renewable, there is a growing interest in alternative
energy sources for heat and electricity production (Demirbas 2006a).
The future of biomass electricity generation lies in biomass integrated
gasification/gas turbine technology, which offers high-energy conversion efficien-
cies. The electricity is produced by direct combustion of biomass, advanced gasi-
fication and pyrolysis technologies are almost ready for commercial scale use.
Biomass power plants (BPPs) use technology that is very similar to that used in
coal-fired power plants. For example, biomass plants use similar steam-turbine
generators and fuel delivery systems. BPP efficiencies of is about 25 %. Electricity
costs are in the 6-8 c/kWh range. The average BPP is about 20 MW in size, with a
few dedicated wood-fired plants in the 40–50 MW size range. As the
biomass-to-electricity industry grows, it will be characterized by larger facilities of
50–150 MW capacity, with gas turbine/steam combined cycle. The feasibility of
combining gas and steam expansion in a power cycle has been extensively explored
(Sorensen 1983). Biomass is burned to produce steam, the steam turns a turbine and
drives a generator, producing electricity. Because of potential ash build up, only
certain types of biomass materials are used for direct combustion. Heat is used to
thermochemically convert biomass into a pyrolysis oil. The oil, which is easier to
store and transport than solid biomass material, is then burned like petroleum to
generate electricity (Demirbas 2001).
Biomass can be used as a primary energy source or as a secondary energy source
to power gas turbines. As a secondary energy source, biomass is used to make a
fuel, which can be used to fire a gas turbine. The heat produced from the electricity
generating process is captured and utilized to produce domestic purposes and can be
used in steam turbines to generate additional electricity. Figure 3.5 shows the
comparison between energy inputs to separate heat and power system and cogen-
eration system. Cogeneration is the simultaneous production of electricity and
useful thermal energy from a single source.
3.2 Waste Energy 75
I. SEPARATE HEAT AND POWER SYSTEM
Output (15 units

Fuel Input Electricity Generator electricity)
(50 units) (efficiency 30%)
Fuel Input Overall usable energy: 55 units

(100 units)
Fuel Input Boiler

(50 units) (efficiency 80%) Output (40 units heat)
II. COGENERATION SYSTEM
Fuel Input Heat Transmission Output (56 units heat)

(100 units (efficiency 80%)
Electricity Generator Output (30 units Overall cogeneration

(efficiency 30%) electricity) energy: 86 units
Fig. 3.5 Comparison between energy inputs to separate heat and power system and cogeneration
system
Fig. 3.6 Integrated biomass gas turbine/steam combined cycle power plant
In the last decade, many new biomass power plants have been built and the
development of new technologies for biomass based power generation is pro-
ceeding. Figure 3.6 shows the integrated biomass gas turbine/steam combined cycle
power plant.
3.2.1 Waste Heat Recovery by Cogeneration

(COGEN or CHP)
Cogeneration (COGEN) is the simultaneous production of electricity and useful

thermal energy from a single source. Generating electricity and useful heat from the
same power plant is called “cogeneration” in North America and “combined heat
and power” (CHP) in Europe. The COGEN is considered worldwide as the major
option to achieve considerable energy saving with respect to traditional systems.
The energy saving and the environmental benefits of a small-scale and on-site
COGEN are undisputed, but some obstacles still remain to its large diffusion, also
in a vibrant market in which the liberalization of energy production can play a
major role (Dentice d’Accadia et al. 2003). The main advantage of a cogenerative
application is that less input energy is consumed than would be required to produce
the same thermal and electrical outputs in separate operations. Cogenerative
applications often are reduced CO2 emissions by declining fuel consumption and
provide a decrease in energy cost and more safe operations (June Wu and Rosen
1999).
The COGEN is defined as the combined production of two forms of energy in
one technological process: (1) Electric or mechanical power, (2) Useful thermal
energy. The electric power produced by a cogenerator can be used on site or
distributed through the utility grid, or both. COGEN systems recapture thermal
energy that would otherwise be wasted, usually from a heat engine that produces
electricity (such as a steam turbine, gas turbine, or diesel engine), and use it for
space conditioning, industrial processes, or as an energy source for another energy
component.
A typical COGEN system consists of an engine, steam turbine, or combustion
turbine that drives an electrical generator. These turbines are similar to jet engines
used in aircraft. In this size range, gas turbines are more efficient than any other type
of fossil fuel fired power plants, reaching electrical efficiencies of up to 45 % and
with the addition of waste heat recovery (COGEN), efficiencies of over 80 %.
When used for COGEN, the hot exhaust gases from the gas turbine are passed
through a heat exchanger where the heat is transferred to water in pipes producing
steam. A waste heat exchanger recovers waste heat from the engine and/or exhaust
gas to produce hot water or steam. The COGEN produces a given amount of
electric power and process heat with 15–35 % less fuel than it takes to produce the
electricity and process heat separately.
The opportunities for energy cost savings and emission reductions are very
dependent on the existing design of the process and the energy system. The
potential for enhanced heat recovery, and whether or not the initial energy system
includes COGEN capacity, are internal parameters that have proved to be very
important for the result (Axelsson et al. 2003).
The COGEN is a technique that reduces the primary energy consumption
compared to separate generation of heat and power (Laughton 1996). In other
words, it is one of the effective techniques of efficient energy management
3.2 Waste Energy 77
Table 3.1 Main advantages The main benefit of COGEN is the more efficient use of fossil
of the COGEN System fuels used for the generation of electricity
It reduces the overall costs of producing electricity and heat
because less fuel is consumed. COGEN also reduces some of
the emissions of atmospheric pollutants associated with the
combustion of fossil fuels such as carbon dioxide, a contributor
to global warming, and sulfur dioxide which results in acid rain
COGEN power plants are generally smaller in size than
traditional fossil fuel power plants and designed to emit fewer
pollutants
Table 3.2 Carbon dioxide Carbon dioxide Thermal

emissions and electricity emissions (t/MWh) efficiency (%)
generation efficiencies from
different firing types Brown coal 1.23 30
Black coal 0.92 36
Natural gas 0.48 39
Combined 0.39 48
cycle
Cogeneration 0.27 78
Trigeneration 0.24 87
(Silveira et al. 1997). The savings in primary energy by small scale CHP gas turbine
units can be about 30 % when power generation replaces a conventional power
plant, and about 15 % when power generation replaces natural gas-fired combined
cycles. COGEN, in and of itself, is an example of pollution prevention.
Cogenerators, by using excess heat, may enhance the efficiency of total energy use
by up to 80 % or more from the typical 33–38 % efficiency of electricity-only
generation. Table 3.1 shows main advantages of the COGEN System.
Table 3.2 shows the increasing thermal efficiency from the use of thermal brown
coal to cogeneration and an inverse relationship to carbon dioxide emissions. At a
time when there is increased emphasis on both increased thermal efficiency and the
mitigation of carbon dioxide emissions, electricity generation by COGEN appears
to be a logical choice. An additional advantage of COGEN is that the plant is
usually located near the end user and, as such, no power transmission losses are
suffered.
3.2.2 Waste Heat Recovery by Trigeneration or Combined

Cooling, Heat and Power (CCHP)
Trigeneration or combined cooling, heat and power (CCHP), is a process a portion

of the heat generated by the cogeneration plant is used to produce cold water for air
conditioning and refrigeration. The CCHP refers to the simultaneous generation of

electricity and useful heating and cooling from the combustion of a fuel or a solar
heat collector.
Figure 3.7 shows a basic design of a combined cooling, heat and power (CCHP)
system. Absorption based refrigeration technology offers the most established and
economic solution for reduced emission, air conditioning systems. Table 3.3 shows
main advantages of the CCHP systems. Table 3.4 shows the main challenges and
barriers of the CCHP systems.
Electricity
Fuel Boiler Turbine Generator Grid
Hot
Exhaust Nearby
Gases Buildings or
Facilities
Heat
Recovery Steam or Hot/Cold Water
Water Unit
Fig. 3.7 A basic design of a combined cooling, heat and power (CCHP) system
Table 3.3 Main advantages of the combined cooling, heat and power (CCHP) system
Production of high efficiency production of electricity and heat
Operated with heat, utilizing relatively inexpensive ‘excess energy’
Absorption system has noiseless operation
Reduced fuel and energy costs
No harmful chemical pollutants since water is used as the refrigerant
Low operating costs and lifecycle costs
Significant reductions in greenhouse gas emissions
Using water as a refrigerant replaces the use of ozone damaging substances.
Table 3.4 Main challenges and barriers of the combined cooling, heat and power (CCHP)
systems
Technological barriers Economical barriers Political barriers
Large complex projects involve Higher initial investment Site selection and permits
many actors
Require special equipments and Long recovery period Exit fee
design
Lack information on costs Interconnection and Local red-tape
other costs
Lack information on performance Uncertainties about rates Protective switch and
power grid
3.3 Energy Use 79
3.3 Energy Use
Energy affects all aspects of modern life, because of the exponential growth of the
world population; demand for energy is increasing at an exponential rate. Using
advanced energy and energy efficiency technologies and thus potentially reducing
the environmental and national security costs and increasing reliability. Reducing
the energy consumption is required to provide the technical information about
energy services for heating and cooling, the use of the buildings lighting, power of
industrial processes, food processing, transport fuels, energy and information
communication technologies (Demirbas 2002a).
Energy consumption is increasing rapidly from day-to-day, therefore present
energy sources should be used economically, and engineers and researchers all over
the world are in search of new and renewable energy sources. In response to
increasing electrical energy costs and the desire for better lad management, thermal
storage technology has recently been developed. Applied to refrigeration, thermal
storage usually involves the nearly constant operation of a refrigeration system of a
smaller capacity than would ordinarily be required. Cooling capacity, both in the
form of chilled water or ice, is stored during periods of low demand and subse-
quently used, along with a refrigeration system, during periods of peak demand.
Thermal storage has been characterized as a kind of thermal battery.
Energy efficiency refers to different policies, technologies and strategies that are
aimed at solving issues related to energy use whether at residential, commercial,
industrial and national capacities so as to minimize emission of greenhouse gases
which cause global warming together with reducing financial costs (Ganda and
Ngwakwe 2014).
The concept of sustainable development has been difficult to interpret because
blanketed the very ambiguous meanings and explanations. Sustainable energy
efficiency undertakes the basic functions of institutions and countries take related to
providing equal rights (Ganda and Ngwakwe 2014).
Energy efficiency improvements decrease the amount of energy needed to operate
factories, schools, homes, vehicles, and equipment. Energy efficiency improvements
are similar to economic productivity enhancements in other factors of production
(e.g. capital, labor) and contribute to overall economic productivity; they should
really be called “energy productivity” improvements. Energy conservation is needed
improved energy efficiency, improved insulation and heat recovery, effective energy
usage, process change and improvement, and good maintenance of machinery and
equipments.
Energy efficiency is can be defined as the percentage of energy generated by a
heat source that is converted into usable heat. Efficiency is usually measured as the
ratio of energy output and input. Energy efficient heating and cooling of buildings
are aided through the use of automated controls, ventilation, improved duct sys-
tems, and advanced technologies. The main areas related to energy efficiency are
buildings, transportation, industry and power.
Energy efficiency (EE) can be defined as the percentage of energy generated by a

heat source that is converted into usable heat:
Output Energy
Energy Efficiency ðEEÞ ¼ 100 ð3:1Þ
Input Energy
The EE is considered to be the cheapest energy source. Energy efficiency ratio

(EER) is usually measured as the ratio of energy output and input:
Output Energy
Energy Efficiency Ratio ðEERÞ ¼ ð3:2Þ
Input Energy
Measured this way, EE improvements have already been achieved for almost all
types of energy conversion facilities. Defining EE is a difficult task and measuring
changes in EE is even more difficult.
Some researchers believed that EE indicators could measure some kind of
economic well-being, and suggested that a wide range of indicators would offer
insight into the “ordinary business of life” and the relationships, causes, and
opportunities in observed trends. Another suggested concept of efficiency is a strict
technological equipment-based concept. This concept cannot be strictly measured
by broad intensities, because intensities tend to carry structural and behavioral
components. Alternatively, some researchers believe that differentiating between
intensity and efficiency is senseless.
Most of what is defined as EE is actually energy intensity (EI). The EI is the ratio
of energy consumption to some measure of demand for energy services. However,
EI measures are at best a rough surrogate for EE. This is because EI may mask
structural and behavioral changes that do not represent “true” efficiency improve-
ments such a shift away from energy-intensive industries. The choice of a demand
indicator in efficiency analysis is critical.
Energy storage involves methods and apparatus used to store heating, cooling, or
power. In district energy applications these encompass a wide variety of applica-
tions, but all are designed to be recharged on a cyclical basis and fulfill one or more
of the following purposes:
(1) Increase system generation capacity
(2) Enable dispatch of cogeneration plants
(3) Shift energy purchases to low cost periods
(4) Increase system reliability
(5) Integration with other functions
In general meaning, storage of heat is a temporary operation since perfect
thermal insulators are known; thus heat is temporarily absorbed in solids or liquids
as sensible or latent heat to be released later at designated times and conditions.
Heat storage can reduce the time or rate mismatch between energy supply and
demand, therefore playing a vital role in energy conservation. Energy storage leads
to saving fuels and makes the system more effective by reducing the wastage of
3.3 Energy Use 81
energy. The methods available for storing energy, can be divided generally into
three classes, namely, electrochemical, mechanical, and thermal.
Thermal energy storage (TES) systems are often utilized in applications where
heat demands occur when the economically most favorable heat supply is not
available. Thermal storage systems are an essential element of many energy effi-
ciency programs in industry, commercial building and solar energy utilization, and
many reports on TES applications and studies have been published (Bejan 1982;
Beckman and Gilli 1984; Rosen 1999). A energy storage system must be eco-
nomically and technically acceptable. Capital operating costs are expected to be
reasonable, and the energy conversion should be achieved with low losses and free
of severe operating problems.
During the last 200 years, developed countries have shifted their energy con-
sumption toward fossil fuels. Renewable energies have been the primary energy
source in the history of the human race. Wood was used for cooking, water and
space heating. The first renewable energy technologies were primarily simple
mechanical applications and did not reach high energetic efficiencies.
Industrialization changed the primary energy use from renewable resources to
sources with a much higher energetic value such as coal and oil. The promise of
unlimited fossil fuels was much more attractive and rapid technical progress made
the industrial use of oil and coal economical.
The share of renewable energy sources is expected to increase very significantly.
Hydropower and traditional biomass are already important factors in the world’s
energy mix, contributing about 18 % of the total world energy requirements,
whereas the renewables contribute only about 2 % of the present world primary
energy use. Biomass, wind and geothermal energy are commercially competitive
and are making relatively fast progress (Fridleifsson 2001).
In broad terms, coal, oil, natural gas, biomass, hydropower, uranium, wind, and
other energy resources are extracted, refined or converted into “energy carriers”
such as gasoline, electricity, natural gas, etc., and then consumed by the end-user to
provide energy services such as building heating and cooling, industrial motor
drive, and passenger transport. The power sector consumes about 39 % of total
primary energy as it generates electricity. The remaining 61 % of primary energy is
refined into gasoline, diesel or other petroleum fuels, cleaned for transmission and
use as natural gas, and burned in vehicles, boilers, furnaces, water heaters, and other
combustion equipment.
3.3.1 Energy Use in Buildings, Transportation and Industry
Energy is used in buildings in two basic ways. About 50 % is used to heat and cool
buildings and to provide hot water. The remaining 50 % is used to light the building
and power it’s any appliances and pieces of equipment, such as refrigerators,
commercial freezers, televisions, washing machines, and stoves. About 55 % of
building energy is used in homes, with the remainder consumed in commercial

buildings, such as offices, schools, and hospitals.
In buildings, EE means using less energy for heating, cooling, and lighting. It
also means buying energy-saving appliances and equipment for use in a building.
This section focuses on EE or saving energy in buildings. Two renewable energy
sources that can save energy in buildings are discussed separately: solar energy and
geothermal heat pumps. An important concept for EE in buildings is the building
envelope, which is everything that separates the interior of the building from the
outdoor environment: the doors, windows, walls, foundation, roof, and insulation.
All the components of the building envelope need to work together to keep a
building warm in the winter and cool in the summer. Your home’s insulation, for
instance, will be less effective if the roof, walls, and ceiling allow air to leak in or
allow moisture to collect in the insulation.
Various approaches can help improve the building envelope. Storm windows
and doors can reduce heat loss when temperatures drop. In warm regions, windows
with special glazing can let in daylight without heat gain. Even some simple
weatherization techniques, such as weather stripping doors and windows, can
significantly improve a building’s energy efficiency.
Energy is used in buildings in two basic ways. About 50 % is used to heat and
cool buildings and to provide hot water. The remaining 50 % is used to light the
building and its power any appliances and pieces of equipment, such as refriger-
ators, commercial freezers, televisions, washing machines, and stoves.
About 55 % of building energy is used in homes, with the remainder consumed
in commercial buildings, such as offices, schools, and hospitals.
Heating and cooling systems typically use the most energy in a building. In
homes, the addition of efficient controls, like a programmable thermostat, can
significantly reduce the energy use of these systems. Some homes can also use zone
heating and cooling systems, which reduce heating and cooling in the unused areas
of a home. And in commercial buildings, integrated space and water heating sys-
tems can provide the best approach to energy efficient heating (Demirbas 2002a).
Energy efficient heating and cooling of buildings are aided through the use of
automated controls, ventilation, improved duct systems, and advanced technolo-
gies. Energy efficient water heating combined with water-efficient appliances and
fixtures will save water, energy, and money. The building envelope includes
everything that separates the interior of a building from the outdoor environment,
including the windows, walls, foundation, basement slab, ceiling, roof, and insu-
lation. Compact fluorescent light bulbs and other efficient lighting technologies save
energy and money. Energy efficient options are available for clothes washers and
dryers, refrigerators, freezers, dishwashers, ovens, and stoves (Demirbas 2002a).
The energy used to heat water can be reduced by both heating water more
efficiently and by reducing hot water use. A wide variety of fixtures, such as
low-flow showerheads and faucet aerators, can reduce hot water use. In a home, an
older water heater can be replaced with a newer, more energy efficient one, and the
water heater and hot water pipes can be insulated to minimize heat loss.
3.3 Energy Use 83
Buildings are designed and built to fulfill the demands of users, customers and
society. Many of these demands are expressed as functional requirements through
building codes, standards and local regulations (Jansson et al. 2013). Customer
requirements and local regulations regarding more energy efficient and sustainable
buildings design in the process of put higher demands (Malmqvist et al. 2011).
Until now, energy research has been focused mostly on methods and tools in
evaluation of engineering quantitative data (Attia et al. 2012), while research on the
design process for energy efficient building represent only a small part of the field
(Schweber and Leiringer 2012).
The transportation sector exhibits the least variation in energy sources and uses.
The transportation sector also uses comparatively small amounts of bioenergy,
natural gas, and electricity. The 57 % of transportation energy used by “light-duty
vehicles” includes both cars and light trucks, with the latter now accounting for
47 % of new vehicle sales. Alternative, non-oil transportation energy sources are
increasingly used in urban areas.
The industrial sector is the most diverse sector in terms of both the types of
energy services required and the mix of energy sources used to provide those
services. Several crosscutting types of energy services are particularly important in
this sector:
(1) Motor drive equipment, which accounts for 64 % of industrial electricity use
(2) Steam systems, both to heat products and to drive mechanical processes
(3) Compressed air equipment
Industrial energy use is heavily concentrated in a small number of “heavy”
industries, which generally produce commodity materials that require substantial
energy to move, process, and shape. About 37 % of the sector’s primary energy use
is in the form of electricity, 28 % natural gas, 24 % oil products, 6 % coal, and 5 %
biomass and other energy sources.
3.3.2 Energy Use in Energy and Power Systems
Heat must be generated from a fuel source such as coal, wood, electricity, gas, etc.
It must then be transferred to the objects or areas to be heated. This happens in a
combination of three ways, with one predominating. Conduction heat moves from
warmer to cooler areas through another material, such as glass or metal. Convection
heat moves as part of another substance, such as air or water. Radiation energy is
collected and emitted as heat from one surface to be absorbed by another, such as
from a hot stove surface to a human being.
Cooling a home involves drawing warm air outside and dissipating it. Many
consumers purchase alternate heating appliances which including wood-burning
stoves, kerosene heaters and electric space heaters to supplement their central
heating system. Homeowners may also use zone heating, in which unused portions
of the home are shut off and only the spaces in use are heated.
The development of energy-efficiency indictors, for any country, is limited by

the availability of data. Data are limited for several reasons. As the amount of data
collected increases so do the costs of collecting, processing, and analyzing the data.
The configuration of certain technologies and processes can also limit the possi-
bility of obtaining micro data. As an example, in the manufacturing sector, some
motors are encased in such a way that it is impossible to collect data on the motor
unless records have been maintained for the motor. This leads to another reason
data are limited respondent burden. Care has to be taken so that surveys are not so
long that participation is discouraged or inaccurate answers are given due to the
difficulty and time it takes to obtain the data.
Several country entities are directly or indirectly involved in EE issues and
activities. The main areas related to EE are buildings, transportation, industry and
power. Nearly all of the electricity is produced at central power stations and
delivered through a network of transmission and distribution lines.
Fossil fuels continue to dominate US electricity production, accounting for about
71 % of electricity produced. Bioenergy comprises a large component of the US
renewable energy market, accounting for 50 % of all renewables and 88 % of
non-hydropower renewables. Hydropower is the second-largest contributor to
renewable energy, comprising 44 % of US renewable energy production. Wind
power is one of the fastest growing energy sources in the world, with rapid growth
across both Europe and the United States. Other areas of renewable production
include solar and geothermal power (Demirbas 2001).
Coal’s role in energy use worldwide has shifted substantially over the decades,
from a fuel used extensively in all sectors of the economy to one that is now used
primarily for electricity generation and in a few key industrial sectors, such as steel,
cement, and chemicals. Although coal has lost market share to petroleum products
and natural gas, it continues to be a key source of energy because of the dominant
role it has maintained in its core markets and its success in penetrating markets in
emerging economies. In 1995, coal accounted for 26 % of the world’s primary
energy consumption and 37 % of the energy consumed worldwide for electricity
generation.
Deposits of oil shale exist in many locations around the globe, and the use of
shale oils extracted from oil shale represents a viable alternative to conventional
fossil fuels for many nations (Tucker et al. 2000). Oil shale has been used for
energy for over 150 years around the world, even before the first oil wells were
drilled. Although there are large shale oil reserves in the world, total production of
oil from oil shale is unavailable due to contents of high mineral matter (30–70 %)
and water (5–10 %). Many oil shales can be burned directly without processing.
Traditionally, shale oil has been extracted using retorting process, particularly under
nitrogen sweep gas, that rely heavily on pyrolysis of kerogen and bitumen, the
carbonaceous macromolecule and derivatives contained within the pores of the oil
shale.
Oil is the main source of primary energy consumed (41 % of world energy
consumption). In the future crude oil resources will become scarcer and much more
costly. Many non-oil producing countries are enriched with other sources of energy,
3.3 Energy Use 85
such as coal, oil shale, tar sand, renewable, and uranium, which are not fully
utilized. Tar sands are another possible source of vast quantities of oil. Tar sands are
sand deposits which are impregnated with dense, viscous petroleum. Supercritical
fluid extraction (SFE) of tar sand was carried out in a batch autoclave at different
temperatures. Extracts recovered from SFE were fractionated into oils, asphaltenes,
preasphaltenes and gases via solvent extraction.
Natural gas accounts today for 25 % of world primary energy production
(Demirbas 2001). Natural gas is the fastest growing primary energy source in the
world. Because it is cleaner fuel than oil or coal and not as controversial as nuclear
power, gas is expected to be the fuel of choice for many countries in the future
(Jean-Baptiste and Ducroux 2003). Growing demand for natural gas is expected in all
regions of the world, as resource availability, cost, and environmental considerations
all favor its use. Progress achieved in cost and performance of gas turbines, the present
low prices, and the large world reserves, make natural gas a high growth energy source.
Main new and renewable energy resources are nuclear energy, biomass energy,
geothermal energy, solar energy, and wind energy. Nuclear energy is a clean energy
like hydropower, wind energy, geothermal energy, and hydrogen energy.
Biomass energy (firewood, agricultural residues, animal wastes, charcoal and
other derived fuels) currently represents approximately 14 % of world final energy
consumption, a higher share than that of coal (12 %) and comparable to those of gas
(15 %) and electricity (14 %). Biomass is the main source of energy for many
developing countries and most of it is non-commercial. Hence there is enormous
difficulty in collecting reliable biomass energy data. Yet good data are essential for
analyzing tendencies and consumption patterns, for modeling future trends and for
designing coherent strategies. Data on biomass energy use and production are also
needed to evaluate whether its use enhances or damages the environment, and to
measure its effect on global emissions of carbon dioxide.
Biomass is generally considered as an energy source completely CO2-neutral.
The underlying assumption is that the CO2 released in the atmosphere is matched by
the amount used in its production. Table 3.5 shows the importance of biomass in
different world regions. In OECD regions, Transition Economies and the Middle
East, the share of biomass averages 2–3 % of total final energy consumption,
whereas in Africa, Asia and Latin America, which together account for
three-quarters of the world’s population, biomass provides a substantial share of the
Table 3.5 The importance of Region Share of biomass in final energy

biomass in different world consumption
regions
Africa 60.0
South Asia 56.3
East Asia 25.1
China 23.5
Latin America 18.2
Others 3.3
energy needs: a third on average, but as much as 80–90 % in some of the poorest
countries of Africa and Asia (e.g. Angola, Ethiopia, Mozambique, Tanzania,
Democratic Republic of Congo, Nepal and Myanmar). Indeed, for large portions of
the rural populations of developing countries, and for the poorest sections of urban
populations, biomass is often the only available and affordable source of energy for
basic needs such as cooking and heating.
Wood related industries and homeowners consume the most biomass energy.
The lumber, pulp and paper industries burn their own wood wastes in large furnaces
and boilers to supply 60 % of the energy needed to run the factories. In our homes,
we burn wood in stoves and fireplaces to cook meals and warm our residences. The
energy conversion efficiency of an efficient fuelwood stove (or efficient stove) is
estimated to be 20–30 % compared to about 10 % efficiency of traditional fuelwood
stoves. Therefore, efficient stoves can reduce fuelwood consumption significantly.
Biomass is burned by direct combustion to produce steam, the steam turns a
turbine and the turbine drives a generator, producing electricity. Gasifier are used to
convert biomass into a combustible gas (biogas). The biogas is then used to drive a
high efficiency, combined cycle gas turbine (Yazici and Demirbas 2001; Dogru
et al. 2002).
use. The utilization has increased rapidly during the last three decades. In 2000,
geothermal resources have been identified in over 80 countries and there are
quantified records of geothermal utilization in 58 countries in the world. Table 6
shows the status of geothermal energy.
Direct application of geothermal energy can involve a wide variety of end uses,
such as space heating and cooling, industry, greenhouses, fish farming, and health
spas. It uses mostly existing technology and straight forward engineering. The
technology, reliability, economics, and environmental acceptability of direct use of
geothermal energy has been demonstrated throughout the world. Electricity is
produced with geothermal steam in 21 countries spread over all continents. Low
temperature geothermal energy is exploited in many countries to generate heat, with
an estimated capacity of about 10,000 MW thermal.
Solar energy systems are solar home system, solar photovoltaic (SPV) systems,
solar water heating (SWH) systems, solar dryers, and solar cookers. A solar home
system is a photovoltaic system with a maximum capacity of 40 W. These systems
are installed and managed by a household or a small community.
Photovoltaic systems, other than solar home systems, are used for communi-
cation, water pumping for drinking and irrigation, and electricity generation. The
total installed capacity of such systems is estimated at about 1000 kW.
Solar dryers are used for drying fruits and spices. The three most popular types
of dryers are box type, cabinet type, and tunnel type. Box type uses direct heat for
dehydration. In cabinet type dryers, air heated by the collector dehydrates the food
product, whereas in tunnel type forced air circulation is used to distribute heat for
dehydration. Cabinet and tunnel type dryers yield a high quality of dried products
3.3 Energy Use 87
but they are very bulky and costly compared to the box type dryers. Of about 800
dryers disseminated so far, 760 are of the box type (Demirbas 2002a).
Cookers of both the box and concentric disk design have been disseminated by
various agencies. It is estimated that out of about 100 solar cookers disseminated,
only a few are of the concentric type.
By any measure the power in the wind is no longer an alternative source of
energy. Production of wind-generated electricity has risen from practically zero in
the early 1980s to more than 7.5 TWh per year in 1995. Cumulative generating
capacity worldwide has topped 6500 MW in late 1997 (Dogru et al. 2002).
3.4 Shaking Energy
Driving potential of energy is the force. Force acting on a system or energy of an

object depends on the distance and speed of the object of change with the contact
time. Force, the impact on the acceleration is proportional to the mass of the body
and had it won, but every kind of force cannot be defined as simple as that
(Demirbas 2014).
Energy comes in various forms, such as motion, heat, light, electrical, chemical,
nuclear energy, and gravitational. Total energy is the sum of all forms of the energy
a system possesses. In the absence of magnetic, electrical and surface tension
effects, the total energy of a system consists of the kinetic, potential, and internal
energies. The internal energy of a system is made up of sensible, latent, chemical,
and nuclear energies. The sensible internal energy is due to translational, rotational,
and vibrational effects of atoms and molecules.
Energy may be transformed from one kind into another, but its total magnitude
remains the same. Even when energy seems to explode out of nowhere, as in
lightning or fireworks, the light and heat energy is really being transferred from
other forms of stored energy. Energy comes in many different forms. In addition to
thermal energy (heat) and radiant energy (light), there is also electrical energy,
chemical energy, and physical (kinetic) energy. All energy derives ultimately from
the sun, and it is transferred through many processes. The sun, for example, heats
up the atmosphere to create wind and drive the water cycle.
Production of Electric Power has more than 100 methods. These methods and
inventions are increasing in recent years and it is being renewed the old production
methods day by day. Some of these inventions require tens of millions of dollars
each full advantage thus has radical. Ideally, an energy resource should be
renewable and sustainable, cheap, clean, abundant, a minimal of energy input, it is
not have a negative impact on the environment, reliably, safely and quit.
Nikola Tesla invented wireless transmission of electrical power. Tesla’s ultimate
goal was to power global civilization with a single mammoth wireless power
transmission system. Tesla demonstrated it by wirelessly illuminates’ 200–250 W
electric bulbs at the distance of 25 miles in Colorado Springs in 1899.
There is a relationship between the shaking and the swing energy wind energy,
because the wind often causes shaking in nature. The main wind causes fluctuations
in the sea. The energy of the sailboats was available from the wind. Windmills and
wind turbines are well known to work with the wind energy.
Windmills and wind turbines in the wind-energized to run the crankshaft. The
diverter or router to run with the crankshaft shake a wind energy system is required.
This system just like the drive bevel tool is not enough to run through four bevel
gears. Shake to apply energy directly to the crankshaft can benefit from magnetic
fields.
A windmill sails or blades mill that converts the rotational energy by means of
wind energy called veins. Centuries ago, windmills, often mill grain, pumping
water, or is used for both. So often grist mills, wind pumps, or it was both. There
are two types of windmills: Horizontal windmills and the horizontal-axis or vertical
windmill.
The first practical windmills had returned to sail in a horizontal plane about a
vertical axis. A similar type of horizontal windmill with rectangular blades has used
for irrigation. The horizontal or vertical axis windmill, also called motion relative to
the sail plane.
A type of windmill is used for pumping water. Wind pumps are used to pump
water now since at least 9th century.
A wind turbine, in particular an improved structure, such as a windmill, gen-
erates electricity. These are seen as the next step in the development of the
windmill. The first wind turbines were built at the end of the nineteenth century.
Serial production of wind turbines in modern wind power industry began in
1979. This is the first turbines each with a capacity of 20–30 kW, small by today’s
standards. Wind turbine production is expanded to many countries since then,
commercial turbines, delivering up to 7 MW size has increased dramatically.
The basic equation for power extraction is as follows:
P ¼ Fb v ð3:3Þ
where P is the power, Fb is the blade force, and v is the velocity vector of the
moving wind turbine part.
Interaction with blade force (Fb) created by wind. The primary focus of wind
turbine aerodynamics is the magnitude and distribution of the force. The most
common type of aerodynamic force is drag. The direction of the drag force is
parallel to the relative wind. Typically, alter the flow around the component parts of
the wind turbine is moving.
The release of the reciprocating motion of an object is called, or makes a simple
harmonic motion. The oscillating motion, the movement is a kind of vibration.
Vibrations are mechanical oscillations around an equilibrium point (Den Hartog
1985).
3.4 Shaking Energy 89
The equation of motion for one-dimensional simple harmonic motion:
Fh ¼ kx ð3:4Þ
where Fh is force of harmonic motion, x is displacement of the oscillating body

from the equilibrium position, and k is a constant called the spring constant for a
mass on a spring. The dimension of k is (Force/Length).
d2 x=dt2 ¼ ðk=mÞx ð3:5Þ
where m is the inertial mass of the oscillating body and t is time. Solving the
differential equation above, a solution which is a sinusoidal function is obtained.
xðtÞ ¼ c1 cosðxtÞ þ c2 sinðxtÞ ¼ Acosðxt uÞ ð3:6Þ
where c1 and c2 are two constants determined by the initial conditions, and the
origin is set to be the equilibrium position. A is the amplitude (maximum dis-
placement from the equilibrium position), ω = 2πυ is the angular frequency, and φ
is the phase.
The kinetic energy (KE) of the system at time t is
KE ¼ mv2 =2 ¼ kA2 sin2 ðxt uÞ=2 ð3:7Þ
and the potential energy (PE) is
PE ¼ kx2 =2 ¼ kA2 cos2 ðxt uÞ=2 ð3:8Þ
The total mechanical energy of the system
E ¼ KE þ PE ¼ kA2 =2 ð3:9Þ
According to Balasubramanian and Bagci (1978) the shaking force can be

completely balanced by distributing the masses of the existing links and design
equations are developed by considering the existing links. The shaking force due to
the reciprocating mass is computed by FS = MrAp, where the reciprocating mass is
the summation of the piston mass, the wrist pin mass, and the reciprocating point
mass of the connecting rod. The shaking force due to the reciprocating mass is the
dominant force for only the first two harmonics (Chaudhary and Saha 2008; Dresig
and Dien 2011).
When vigorously shaken a little water in the flask was found to vary temperature
of the water in the flask. The temperature of the water in the shake flask according
to the severity and duration increases of 10–15 °C. In this experiment, potential
energy from muscles converts into kinetic energy, which transfers thermal energy
into the shaking water as a result of the friction of the molecules bumping against
each other and the sides of the flask.
Classic Joule experiment was first proven in the conversion of mechanical

energy to heat energy and energy conversion was equal. Energy conversions of
liquids (flow energy conversion) examine in fluid mechanics. The first law of
thermodynamics states that the total change in energy (ΔE) of a system is the result
of work (W) and heat (Q) transfers to the system (Smits 2014). That is,
DE ¼ Q þ W ð3:10Þ
Control of boundary layer refers to methods of controlling the behavior of fluid

flow boundary layers. So many methods occur due to adverse pressure gradient
boundary layer separation can be used to control. Because the boundary layer
separation is often related to large energy losses, the liquid flow control fluid
separation continues to be extremely important for many technological applications
of fluid mechanics (Chang 1976; Lin 2002; Chaudhary and Saha 2008; Dresig and
Dien 2011; Briot and Arakelian 2012).
Vortex (turbulence) generating affects the boundary layer flow around an airfoil.
Turbulent boundary layer separation is more resistant. In this way it is possible to
fly with a slower attack speed and higher angles. Vortex generators on the control
surface deflections similar stabilizers act to increase the effectiveness of control at
high and low speeds. There are some rudders to improve the efficiency of vortex
generators in several locations the vertical plane of the wing upper surface others
affecting the take-off or otherwise on the engine during landing strip.
A lift force is generated by adding a swirl flow on circular cylinders. Lifting
force is proportional to the vortex of power. Elevator increases, powerful vortex
bound when the power is increased, and thus escape the vortex. The maximum
power trailing vortex occurs whenever the maximum takeoff and landing. To avoid
the danger of all airports it has the minimum time interval between successive
takeoffs and landings (Smits 2014).
In simple terms a vortex generator (VG) is a device that creates a turbulence or
vortex of fluid due to its shape. VGs work by mixing high-energy fluid with the
lower energy fluid found near the skin surface, called the boundary layer. This
process is called re-energizing the boundary layer. A VG means usually containing
a small wing attached to a lifting surface or rotor blade of a wind turbine is the
aerodynamic device. VGs are typically used to delay flow separation. To accom-
plish this, usually is placed on the external surface of the vehicle and the wind
turbine blade. Slow moving quickly in contact with the surface boundary layer of
outside air transport, to form a pointed tip vortex energy have an angle of attack on
the local air flow, so VGs is positioned inclined. Turbulent boundary layers of a
laminar separation are less likely, and the rear edge is desirable to ensure the
effectiveness of the control surfaces (Nehemiah et al. 2012).
VGs are small components deployed on the wings and stabilizers surfaces. They
change the surface boundary layer flow, which affects around. Properly arranged,
improve the performance and controllability of the aircraft, particularly at low flight
speeds, climb, and high angles of attack. The VGs change the boundary layer. In the
boundary layers are significant viscosity and friction forces. The viscosity of the
3.4 Shaking Energy 91
fluid and the friction of the object surfaces create high transverse velocity gradients.
Therefore, the boundary layer is an area of particular importance (Forster and White
2014).
The mass and momentum transfer between the layers occurs only at the
microscopic level; this transfer is not affected in a macroscopic scale. Viscous
forces dominate over inertial forces because here randomly generated disturbances
are suppressed immediately.
In addition to the main motion of liquid particles in turbulent flow also makes
vibration. Layers also move perpendicular to the direction of flow and created are
vortex structures. The leading edge at a certain distance from the boundary layer is
the turbulent nature of a migration has changed. Despite the turbulent nature of this
area, right on the wing surface, there is still a thin laminar layer where there is no
turbulence. Over the years many solutions have been designed to affect and border
control. Very effective but simple solution vortex generators (turbulators) is to use.
Each of these small elements creates a vortex wake that places energy in the
boundary layer of the wing.
3.5 Squeezing Energy
3.5.1 Introduction
The compressed air is air at atmospheric pressure under a pressure which is higher.
Compressed air is used in many household and industrial processes. There are many
industries using compressed air for the variety of applications which is mainly used
in instrumentation systems, industrial processes, and hand tools (Taylan et al.
2016).
Air can be squeezed (compressed) into a much smaller space than it would
normally occupy. Squeezed air is one of the most important industrial inputs after
electricity, water and fuel. The electric energy consumption of compressed air
systems fall in the ranking of third order in energy costs in the production facilities
(Gulec 1999). In European Union, compressed air constitutes almost 10 % of
industrial electricity consumption (Saidur et al. 2010).
Compressed air has a great deal of potential as a clean, inexpensive, and infinitely
renewable energy source. Its use is currently being explored as an alternative to fossil
fuels. In 1991, the first compressed air energy storage (CAES) plant in the United
States opened in McIntosh, Alabama. The CAES when compressed air is another
way to store energy generated at a time for use. Current electrical energy storage
technologies cover pumped storage, compressed air energy storage, flywheel energy
storage, battery energy storage, superconducting magnetic energy, super capacitor
energy storage and so on (Demibas 2002b; Rachel 2010; Ma et al. 2013).
Compression of air creates heat and the air is warmer after compression. If the
heat generated during compression can be stored and used during expansion, the
efficiency of the storage improves considerably. There are three ways in which a
CAES system can deal with the heat. Air storage can be isothermal, adiabatic or
diabetic (Kaya et al. 2002). Energy storage at a later time that captures the energy
generated at a time for use. A device that stores energy is sometimes called an
energy accumulator. The compressed air consumption is the most expensive form
of energy usage in industrial plants (Yang 2009). As Saudi Arabia is a very hot
country, the usage of compressed air is important and is more reliable (Cheong and
Chung 2015).
Compressed air is an environmentally friendly material. Besides the environ-
mental benefits and improving energy efficiency, the optimization of the industrial
systems offers a way for companies to realize productivity and operational benefits.
Compressors and dryers are the main energy consumers in the systems. Dindorf
(2012) stated that when a compressor is installed efficiently, the energy can be
saved in all applications. Sapmaz et al. (2015) explained that about 90 % of the
power used to run the compressors could be recovered as valuable heat energy. On
the other hand, quantification approaches were applied to determine the energy
losses associated with compressed-air systems, and the costs to the manufacturers
using the payback period (Kaya et al. 2002). Similarly, Saidur et al. 2012) identified
energy saving opportunities and cost of current applications of electrical motors.
A compressed air motor is a kind of engine which does mechanical work by
expanding compressed air (Mishra and Sugandh 2014). Compressed air energy has
been used as compressed air power to run the car engine. Figure 3.8 shows a
simplified schematic illustrating of a compressed air system components.
Control Wet
Dry
Receiver
Receiver
Air Cooler Air Filter Pressure Distribution

Compressor Dryer Controller System
End
User
Fig. 3.8 A simplified schematic illustrating of a compressed air system components

3.5 Squeezing Energy 93
3.5.2 Energy Storage Systems
All kinds of energy storage systems play important role in energy conservation. In
processes which are wasteful of energy, energy storage will result in a saving of
premium fuels.
Thermal Energy Storage (TES) deals with the storing of energy by cooling,
heating, melting, solidifying or vaporizing a material, the energy becoming avail-
able as heat when the process is reversed. Figure 3.9 shows energy storage from
solar and industrial sources.
TES systems provide several alternatives for efficient energy use and conser-
vation (Socaciu 2012). TES can take the form of sensible heat storage (SHS) or
latent heat storage (LHS). To store the same amount of energy, significantly larger
quantities of storage medium are required for SHS in comparison to LHS.
When LHS is used to store solar energy it can increase the thermal storage effi-
ciency (Demirbas 2006a).
Upgraded low quality heat can very well be used in heating and cooling systems.
Upgrading can take place using a so-called chemical heat pump, operating in a
continuous or batch-wise mode. Reversible decomposition reactions of organic or
inorganic substances are used to achieve the required temperature lift. Heat Q stored
from a heat source at T1 temperature can be recovered by transformation at a
different temperature T2:
At T1 temperature:
AB þ Q ! A þ B ð3:11Þ
At T2 temperature:
A þ B ! AB þ Q ð3:12Þ
Phase change materials (PCMs) are latent heat thermal storage materials. They
use chemical bonds to store and release heat. The thermal energy transfer occurs
Fig. 3.9 Energy storage from

solar and industrial sources
when a material changes from a solid to a liquid or from a liquid to a solid. This is
called a change in state, or phase. Within the human comfort range of 295–305 K,
latent thermal storage materials are very effective. They store 5–14 times more heat
per unit volume than sensible storage materials such as water, masonry, or rock
(Ghuniem and Klein 1989).
Research underground thermal energy storage systems (UTESS) started in the
late 70s. The purpose was to develop energy storage technology utilizing waste,
renewable or ambient energy sources to supply space heating, space cooling and
process cooling to achieve significantly improved efficiency.
Storage options that can be used in UTESS can be grouped into three types:
(1) heat storage in water, (2) heat storage in aquifers, and (3) heat storage in ground.
Hydrogen may be stored on board a vehicle as compressed gas in
ultra-high-pressure vessels, as a liquid in cryogenic containers or as a gas bound
with certain metals in metal hydrides. Hydrogen gas is stored in a tank as a
“compound” with metal alloy particles. The iron-titanium alloy, FeTi, acts as a
sponge to absorb the hydrogen, thus becoming a metal hydride (FeTiH1.6). Its
physical appearance is like that of a fine silvery powder. The safest method for
hydrogen storage is the “metal hydride” systems (Williamson and Edeskuty 1986;
Veziroğlu 1975).
When hydrogen combines with the metal alloy, an exothermic reaction occurs.
The gas is thus stored in these metal particles until some heat is applied to release
the hydrogen and build up the pressure in the tanks. This heat is obtained from the
engine exhaust, which is ordinarily wasted in a conventional engine (Demirbas
2002b). When a metal hydride absorbs hydrogen, heat is given off. A hydride cold
start heater can be developed that instantly heats an automobile’s catalytic converter
when the car is started to dramatically reduce overall exhaust pollution up to 80 %.
This technology can be used for other quick heat applications such as passenger
compartment heating on cold winter days (Demirbas 2007b).
The two low-temperature hydrides, FeTiH2 and LaNi5H7 hold hydrogen loosely
and evolve it at low temperature. The high-temperature hydrides, MgH and
Mg2NiH4 only release hydrogen at high temperature since they have high binding
entalpies (Dinga 1998).
The metal hydrides provide a safe method for fuel storage in hydrogen-powered
vehicles. Charging and discharging of the hydride tanks is a process that can be
repeated an indefinite number of times provided that the hydride material does not
become contaminated.
3.6 Water Energy
Water energy sources are hydro, tidal and wave technologies. Large scale hydro
power provide about one-quarter of the world’s total electricity supply, virtually all
of Norway’s electricity and more than 40 % of the electricity used in developing
3.6 Water Energy 95
countries. The technically usable world potential of large-scale hydro is estimated

to be over 2200 GW, of which only about 25 % is currently exploited.
The two small-scale hydropower systems are the sites with capacities below
100 kW (referred to as micro hydropower systems) and sites with capacity between
101 kW and 1 MW (referred to as small hydropower systems). Micro hydropower
(MHP) systems which uses cross flow turbines and pelton wheels, can provide both
direct mechanical energy (for crop processing) and electrical energy. However, due
to design constraints, turbines up to a capacity of 30 kW are suitable for extracting
mechanical energy. Of the total installed capacity of about 12 MW of MHP sys-
tems, half is used solely for crop processing. The most popular of the MHP systems
is the peltric set, which is an integrated pelton turbine and electricity generation unit
with an average capacity of 1 kW.
MHP systems are sometimes described as those having capacities below
100 kW, mini hydropower plants are those ranging from 100 to 1000 kW and small
hydropower (SHP) plants are those that produce from 1 to 30 MW.
Hydropower provides unique benefits, rarely found in other sources of energy.
These benefits can be attributed to the electricity itself, or to side-benefits, often
associated with reservoir development. Principles of sustainable development of
particular relevance to energy provision include: Improving the well-being of entire
populations, ensuring that development is people-centered, participatory and
equitable; integrating environmental concerns into decision-making processes; and
taking into account the full range of costs and benefits of development (WCD
2000).
Investment costs for small hydropower (SHP) plants vary according to
site-specific and local characteristics. The most important system and cost elements
are: (1) civil engineering, (2) equipment, and (3) turbine. The electrical generator
represents less than 5 % of the total cost of a power plant and the efficiency of
generators for new plants is already close to 100 %. Yet standardization of gen-
erator equipment for small hydropower could further reduce installation and
maintenance costs.
Despite the recent debates, few would disclaim that the net environmental
benefits of hydropower are far superior to fossil-based generation. Hydroelectricity
is produced for an average of 0.85 cents per kWh. In comparison with hydropower,
thermal plants take less time to design, obtain approval, build and recover
investment.
The remaining economically exploitable potential is about 5400 TWh/year. An
investment of at least USD$1500 billion would be necessary to realize such a
program. The mean level of hydropower plants capacity in the range of 50–
100 MW, some 20,000 plants would need to be built. In order to implement a plant
construction program of this magnitude, a great deal of work (technical, financial
and political) would need to be accomplished by all the investments involved,
particularly in Asia, South America and Africa (WEC 2001).
A water power plant is in general a highly effective energy conversion system.
There is no pollution of the environment, but objections are raised relative to the
flooding of valuable real estate and scenic areas. Whether a particular hydroelectric
installation is economically competitive with a fossil fuel power plant will depend
upon a number of factors, in particular, fuel and construction costs (Demirbas
2006a). As far as non-fossil energy is concerned, hydropower and nuclear power
resources are the principal assets, due to their high production potential and their
economic efficiency.
There are two types of turbines: Reaction turbines and impulse turbines.
Table 3.6 shows main types of water turbines using in hydropower applications. In
reaction turbines, such as Francis and Kaplan turbines, water pressure applies force
onto the face of the runner blades, which decreases as it proceeds through the
turbine. Francis turbines are generally used in a head range of 5–250 m and can be
designed with either a vertical or horizontal shaft. Kaplan turbines are axial-flow
reaction turbines, generally used for low-heads.
In impulse turbines water pressure is converted into kinetic energy in the form of
a high-speed jet that strikes buckets mounted on the periphery of the runner. The
most common impulse type is the Pelton turbine. It is generally used in installations
with a head of fifty to several hundred meters. By adjusting the flow through the
nozzle, a Pelton turbine can operate at high efficiency over wide range of head and
flow conditions.
Typically, larger turbines have higher efficiencies. For example, efficiency is
usually above 90 % for turbines producing several hundred kW or more, whereas
the efficiency of a micro-hydropower turbine of 10 KW is likely to be in the order
of 60–80 % (OECD/IEA 2003).
Two main types of generators are used in the small hydropower industry:
Synchronous and asynchronous generators. Both generator types are very well
known throughout the industry and have been steadily improved to meet the needs
and demands of the hydropower sector.
Table 3.6 Main types of Types of water turbine Simple application image
water turbines
Francis turbine
Kaplan turbine
Pelton turbine
(a) Francis turbine, (b) Kaplan turbine, (c) Pelton turbine

3.6 Water Energy 97
The efficiency of small hydropower depends mainly on the performance of the

turbine. Today, generators commonly have efficiency rates of 98–99 %. As a
general rule, larger and newer plants have higher efficiencies of up to 90 %.
Efficiency can be as low as 60 % for old and smaller plants (OECD/IEA 2003).
Hydropower is the most efficient way to generate electricity. Modern hydro turbines
can convert as much as 90 % of the available energy into electricity. The best fossil
fuel plants are only about 50 % efficient.
Hydraulic ram (hydram) pumps are water lifting or water pumping devices that
are powered by filling water. The hydram pumps have been used for over two
centuries in many parts of the world. It is a useful device that can pump water uphill
from a flowing source of water above the source with no power requirement except
the force of gravity. The hydram pumps have a cyclic pumping action that produces
their characteristic beat during operation.
An excellent work on history of the hydram pump was completed by Krol in
1947. The powerful effect of stopping a flow of water has long been known,
occasionally resulting in burst pipes and broken taps; this is caused by the effect
often called water hammer. It was this effect that caused the tap at the end of a long
pipe delivering water to a basement around 1770 to keep failing. In an attempt to
remedy the situation, John Whitehurst fitted an air vessel, after a time that also
failed; he realized that the pressure causing the air vessel to fail could be used
constructively to pump water to a higher level (Krol 1947). In 1772, he built the
first hydraulic ram apparatus for use by a brewery to deliver water to the top floor; a
child was employed to continually open and close the tap/valve and in 1775 drew
attention to the device in a communication to the Royal Society (Krol 1947;
Maratos 2002).
In 1776 Montgolfier invented a device with an automatic valve; following this a
large number of automatic hydram pumps were designed and used worldwide. The
ram pump is in use today and some made over 100 years ago are still working
(Maratos 2002).
Hydram pump works by using the energy of a large amount of water lifting a
small height to lift a small amount of that water to a much greater height and is
powered by the potential energy of the supply. Hydram pumps are currently of
interest because they make use of a renewable energy resource and are environ-
mentally friendly. Ram pumps are particularly appropriate for use in the developing
world as their construction is basic and robust (Young 1996). Since being super-
seded by pumps using fossil fuel energy nearly a century ago, they are now coming
back into favor in many parts of the developing world (Young 1995). Wherever a
fall of water can be obtained, the hydram pump can be used as a comparatively
cheap, simple and reliable means of raising water to considerable heights. The main
and unique advantage of hydram pumps is that with a continuous flow of water, a
hydram pump operates automatically and continuously with no other external
energy source such as electricity or hydrocarbon fuel. Automatic, continuous
operation requires no supervision or human input. It uses a renewable energy source
hence ensures low running cost (Tessema 2000).
The hydram is a self-actuating pump operated by the same principle of a water

hammer. This extremely simple and durable machine has two moving parts, one is a
valve (typically a poppet type that ‘pops up and down’), and whilst the other is a flat
piece of rubber which acts as a one way valve (Maratos 2002). The hydram can be
used for lifting water from a source lying at a lower elevation to a point of use
located at a higher elevation for domestic use, drinking, cooking and washing, and
irrigation of small areas, gardens, and orchards (Demirbas 2006b). Hydram pumps
are relatively economical to purchase and install. If properly installed, they will give
many trouble-free years of service with no pumping costs.
Energy that is stored in the gravitational field is called gravitational potential
energy, or potential energy due to gravity. At the top water has more gravitational
potential energy than when is at the bottom, because the water at the top is further
from the center of the Earth than at the bottom. So, if the water is allowed to fall
from the top to the bottom, (that is, the Earth’s gravitational force does work on the
water moving it), then the energy stored as potential energy at the top becomes
transformed into the kinetic energy of this water and we can use it to do work.
Potential energy, therefore, is the energy associated with different positions in the
force field. Potential energy is a representation of the position of a system in a field
of force. If the object is being lifted at constant velocity, then it is not accelerating,
and the net force on it is zero. When something is lifted at a constant velocity the
force equals the weight of the object. So, the work done lifting an object is equal to
its mass times the acceleration due to gravity times the height of the lift. As the
object falls it travels faster and faster, and thus, picks up more and more kinetic
energy. This increase in kinetic energy during the fall is due to the drop in gravi-
tational potential energy during the fall. The gravitational potential energy becomes
the kinetic energy of the falling object. The water above receives energy as it falls
down the short waterfall. This energy was stored as potential energy in the gravi-
tational field of the earth and came out of storage as the water dropped. This energy
which came out of the gravitational field ended up being expressed as the kinetic
energy of the water (Demirbas 2006b). Kinetic energy is converted into electricity
energy by generators.
However, the facilities for the thermoelectric power generation and the nuclear
power generation have complex structures, cost a great amount in generating the
electricity due to a large amount of power consumption, and affect an ecosystem.
The hydroelectric power generation is unable to generate sufficient electricity
because of limited water sources. Also, the power generation capacity using wind or
solar energy is considerably influenced by change of weather. Hydroelectric power
causes disturbances in ecosystems from dams and large land use and is criticized
because it does change the environment by affecting natural habitats. It is important
an electricity generating apparatus using gravity and buoyancy can curtail costs of
power generation and prevent environmental pollution and prevent destruction of
an ecosystem.
For these reasons, the hydraulic ram is an attractive solution for electricity
generation where a large gravity flow exists. It is necessary to investigate the
theoretical feasibility of using hydram pump (typically used for pumping relatively
3.6 Water Energy 99
small quantities of river water to a higher level) for this purpose. A major question
is whether the hydram pump can pump the large quantities of water required for
electricity generation.
As described above in detail, the electricity generating apparatus of the present
invention easily generates the electricity by using the gravity and the buoyancy
applied to the buoyant bodies as energy sources for driving the generator. Also,
since the structure of the apparatus is simple, it is convenient to install, operate and
manage the apparatus. In addition, since the apparatus generates the electricity by
using the nonpolluting energy sources, it contributes to the protection of
environment.
A preferred method of obtaining electrical energy from the motion of sea
water-waves is the direct conversion of wave movement to electrical power using
electrical linear generators. In this arrangement, the reciprocating motion of one or
more floats is used to cause relative movement between the stator and armature of
such a generator. The direct generation of power is thereby realized without the
need for any form of intermediary mechanism, as would be necessary for example
when using rotary electrical generators.
Apparatus for converting the motion of sea wave energy to electrical energy
includes one or more float driven linear generators, in which the inertial mass of the
float and any linkage means to the linear generator is minimized. In order to
generate electrical power consistently upon both the upstroke and down stroke of
the float, the moving part of the generator is so sized that its gravitational weight
acting upon the float, together with that of the float itself and any intermediate
linkage means, is substantially equal to half the total buoyancy of the float.
An example of a subsidiary function affecting the performance of many designs
of wave conversion plant using buoyancy chambers is the expenditure of wave
energy necessary to accelerate the mass itself of the buoyancy chamber and any
associated apparatus not directly concerned with the conversion of power. For
example, in the case of buoyant hinged raft type constructions, which are used to
generate power by employing the motion of buoyant chambers to drive hydraulic
pistons, the mass of the raft buoyancy chambers themselves is considerable. As a
result of this, the up thrust resulting from their buoyancy must be expended both in
accelerating them in order to keep up with the speed of ascendancy of the wave
acting upon them, and for driving the hydraulic piston.
The linear generators experience substantially consistent upwards and down-
wards thrust during the passing of a wave, and thus consistent generation of power
during both of these phases is achieved. In addition, because the mass of the floats
and any intermediate linkage mechanism is kept to a minimum, no energy is lost in
accelerating any parasitic weight, other than the necessary mass of the moving
components of the linear generators themselves, which might otherwise impede the
following by the floats of the wave motion.
All of the available force arising from the presence of the float moving upon the
waves, and thus the captured energy, is expended solely in the movement alone of
the generators for doing useful work.
The potential hydropower (HP) and water resources and developments can be
replaced fossil and other conventional world’s energy sources in the near future.
The water in rivers and streams can be captured and turned into hydropower (HP),
also called hydroelectric power. The HP currently provides about 20 % of the
world’s electricity supply, virtually all of Norway’s electricity and more than 40 %
of the electricity used in developing countries. However, the greatest hydropower
potential still exists in worldwide. Norway produces more than 99 % of its elec-
tricity with hydropower. New Zealand uses hydropower for 75 % of its electricity.
HP is the leading source of renewable energy. It provides more than 97 % of all
electricity generated by renewable sources. Other sources are solar, geothermal,
biomass, and wind account for less than 3 % of renewable electricity production.
When the electricity share of total energy consumption is considered, the increase
becomes even more dramatic. The International Energy Outlook 2000 forecasts that
global consumption of electricity will be 76 % higher in 2020 than in 1997.
Consumption will increase from 12,000 TWh in 1997 to 22,000 TWh in 2020
(EIA 2000).
World’s total technically feasible hydro potential is about 14,400 TWh/year, of
which just over 8000 TWh/year is currently considered to be economically feasible
for development. Installed hydro-electric generating capacity is some 692 GW,
with a further 110 GW under construction. The HP provides about 19 %
(2650 TWh/year) of the world’s electricity supply (WEC 2001). Renewable energy
sources (RES) supply 14 % of the total world energy demand. Renewable energy
technology exists in many forms. These are HP, biomass, geothermal, solar, wind
and marine energies. Recent thinking often relates renewable energy to electricity
from either wind energy, solar energy or geothermal energy. Yet the largest source
of renewable energy comes from a proven technology, hydropower. The renew-
ables are the primary, domestic and clean or inexhaustible energy resources. The
technically usable world potential of large-scale hydro is estimated to be over
2200 GW, of which only about 25 % is currently exploited. Hydroelectricity, at
present the most important of the clean, economically feasible, renewable energy
options, can be a major benefit of a water resources development project; however,
it is seldom the only benefit. It is clear, therefore, that hydropower has an important
role to play in the future, both in terms of energy supply and water resources
development (WEC 2001). The total worldwide energy consumption, from all
sources, will grow by 60 % between 1997 and 2020. Consumption is expected to
increase from 111,000 to 178,000 TWh/year.
The definition of micro hydro or small-scale hydro varies in different countries.
The potential for small hydropower (SHP) systems depends on the availability of
water flow where the resource exists. SHP systems allow achieving self-sufficiency
by using the scarce natural water resources. These systems supply low cost of
energy production that is applying in many developing countries in the world
(Romas and Almedia 1999).
There are two small-scale HP systems: micro hydropower systems (MHP) with
capacities below 100 kW and SHP with capacity between 101 kW and 1 MW. In
3.6 Water Energy 101
the case of hydropower, small projects generally require a far greater total reservoir
area than a single large project, to provide the same stored water volume.
The MHP systems which use cross-flow turbines and pelton wheels can provide
both direct mechanical energy and electrical energy. However, due to design
constraints, turbines up to a capacity of 30 kW are suitable for extracting
mechanical energy. Of the total installed capacity of about 12 MW of MHP sys-
tems, half is used solely for crop processing. The most popular of the MHP systems
is the peltric set, which is an integrated pelton turbine and electricity generation unit
with an average capacity of 1 kW. MHP systems are sometimes described as those
having capacities below 100 kW, mini hydropower plants are those ranging from
100 to 1000 kW and the SHP plants are those that produce from 1 to 30 MW.
Table 3.7 shows the regional distribution of installed HP capacity (WEC 2001).
The remaining economically exploitable potential is about 5400 TWh/year. An
investment of at least US$1500 billion would be necessary to realize such a pro-
gram. The mean level of HP plants capacity in the range of 50–100 MW, some
20,000 plants would need to be built. In order to implement a plant construction
program of this magnitude, a great deal of work (technical, financial and political)
would need to be accomplished by all the investments involved, particularly in
Asia, South America and Africa (WEC 2001).
Dams are individually unique structures and dam construction represents the
biggest structures in basic infrastructure within all nations (Novak et al. 1996).
Today, nearly 500,000 km2 of land are inundated by reservoirs in the world,
capable of storing 6000 km3 of water. As a result of this distribution of fresh water
in the reservoirs, small but measurable changes have occurred in the world. The
construction of a dam and power plant, along with the impounding of a reservoir,
creates certain social and physical changes.
The total installed capacity of HP is 640,000 MW (26 % of the theoretical
potential) generating an estimated 2380 TWh/year in the world, producing nearly
20 % of the world’s total supply of electricity. The current and estimated electricity
generation of the world from the HP and 27,900 MW of the total HP are at small
scale sites, generating 115 TWh/year (Gleick 1999; Bakis et al. 2004; Penche 1998).
Main benefits of dams are given in Table 3.8 Hydropower projects have
impacted fish and fisheries in a number of ways. These include changes in habitat
quality and availability, changes in flow regime and fish passage.
Table 3.7 Regional Region Percentage of total capacity

distribution of installed HP
capacity Europe 31.0
Asia 25.1
North America 23.1
South America 15.4
Africa 2.9
Oceania 1.9
Middle East 0.6
Table 3.8 Main benefits of Benefit Percentage of total

dams
Recreation 28
Farm pond 19
Food control 16
Public water supply 14
Irrigation 12
Hydroelectricity 3
Climatic change 2
Environmental protection 2
Other 3
HP is a clean, renewable, energy to the world. Hydropower is renewable because

it draws its essential energy from the sun which drives the hydrological cycle
which, in turn, provides a continuous renewable supply of water.
The most important characteristics of HP can be summarized as follows (WEC
2001). HP resources are widely spread around the world. HP plays a major role in
reducing greenhouse gas emissions in terms of avoided generation by fossil fuels.
HP is a relatively small source of atmospheric emissions compared with fossil-fired
generating options. The production of peak load energy from HP has flexible
electricity sources. HP is a proven and well advanced technology. As hydro plants
are often integrated within multipurpose developments, the projects can help to
meet other fundamental human needs. The investment of HP has the lowest costs
and longest plant life, compared with other large-scale generating options.
Hydropower provides unique benefits, rarely found in other sources of energy.
These benefits can be attributed to the electricity itself, or to side-benefits, often
associated with reservoir development. Principles of sustainable development of
particular relevance to energy provision include: improving the well-being of entire
populations, ensuring that development is people-centered, participatory and
equitable; integrating environmental concerns into decision-making processes; and
taking into account the full range of costs and benefits of development (WCD
2000). The world’s total technical feasible hydro potential is estimated at
14,370 TWh/year, of which about 8082 TWh/year is currently considered eco-
nomically feasible for development.
HP, as an energy supply, also provides unique benefits to an electrical system.
First, when stored in large quantities in the reservoir behind a dam, it is immediately
available for use when required. Second, the energy source can be rapidly adjusted
to meet demand instantaneously.
Despite the recent debates, few would disclaim that the net environmental
benefits of hydropower are far superior to fossil-based generation. HP is produced
for an average of 0.85 cents per kWh. Hydropower is the most efficient way to
generate electricity. Modern hydro turbines can convert as much as 90 % of the
available energy into electricity. The best fossil fuel plants are only about 50 %
efficient. Table 3.9 shows the technically and economically feasible potential of
hydropower in the world (WCD 2000).
3.6 Water Energy 103
Table 3.9 Technically and Region Technically Economically

economically feasible feasible potential feasible potential
potential of hydropower in the (TWh/year) (TWh/year)
world
Africa 1750 1000
Asia 6800 3600
North + Central 1660 1000
America
South America 2665 1600
There is international consensus that greenhouse gas (GHG) emissions will lead
to major climatic changes, and will therefore have consequences on the hydro-
logical system as well as on the sea level. Continued international research confirms
that the GHG emission factor for hydro plants is substantially less than the factors
for fossil fuel generation, taking into account net emissions from reservoirs (Rosa
2001). It is clear that many hydro plants in the world have environmental problems,
but today the profession is well aware of the problems to be addressed, the expertise
exists to mitigate the known impacts to achieve an acceptable balance, and research
is continuing. HP is a clean energy source. It prevents the burning of 22 billion
gallons of oil or 120 million tons of coal each year. HP does not produce green-
house gasses or other air pollution. HP leaves behind no waste. All modern
hydropower projects include a comprehensive environmental impact assessment at
the early stages of investigation. Hydropower thus has a very important role to play
in the future (Demirbas 2007a).
Tidal energy or tidal power is a form of hydropower that converts the energy
obtained from tides into electricity. The world wave, tidal and ocean energy
resources are difficult to estimate. Notice the large proportion of the world resource
available to the UK. The world wave resource is between 200 and 5000 GW mostly
found in offshore locations (Garg and Datta 1998). Wave energy converters fixed to
the shoreline are likely to be the first to be fully developed and deployed, but waves
are typically 2–3 times more powerful in deep offshore waters than at the shoreline.
3.7 Inactive Energy Sources
3.7.1 Introduction
In physics, kinetic, electrical, mechanical and radiant energies are active but
potential energy is an inactive energy. Inactive energy is a resist to a motion and or
deformation. Another name for inactive energy is “potential energy” in physics.
Inactive and passive energy concepts are different. Inactive energy (in the sense
of passive energy) is used for rather than solar energy. Passive energy, a term
usually used in reference to passive solar energy. By contrast, active energy is
energy which is used to generate electricity.
By definition, “inactive energy” cannot be used or unused energy that has a

certain potential. In this sense a radioactive substance found in nature as spread
under the critical mass is an inactive energy source. Such a source is necessary to
enrich the content of radioactive material to activate.
Natural gas hydrates is accepted as the most important inactive energy sources.
Only methane gas hydrate amounts is larger than all carbonaceous fuel reserves
including fossil and renewable energy resources.
There are three types of magmatic volcanoes: active, dormant or inactive and
extinct. This classification is based on the eruption frequency. An erupt volcanoes
regularly called active, those that have erupted in historical times but are now quiet
called dormant or inactive, and those that have not erupted in historical times called
extinct. An extinct volcano is inactive energy sources. As interesting as that might
be, one more practical aspect that comes from drilling into the magma pocket is that
it suggests a potential new source of geothermal energy. Such a potential is an
inactive source.
Magma (molten rock) may come quite close to the surface where the crust has
been thinned, faulted, or fractured by plate tectonics. When this near-surface heat is
transferred to water, a usable form of geothermal energy is created. Most
geothermal energy is produced by merely drilling into warm rock and circulating
water into this rock to produce steam that then drives turbines.
A seismic source generates seismic energy reflection and refraction-controlled
study was used to perform both seismic devices. A good seismic source should be
sufficient energy over suitable frequency range, safe and environmentally accept-
able, repeatable, economical, efficient and convenient.
Available but unused rivers with potential energy are also inactive energy
sources. Sea water is also used inactive is a major source of energy. The lifting
power of sea water is poor utilization.
Municipal solid waste (MSW), forest waste and municipal sewage sludge
(MSS) in the group can be also accepted as active energy resources. Table 3.10
shows some inactive energy sources.
Table 3.10 Some inactive Natural gas hydrates

energy sources
Geothermal energy
Municipal solid waste (MSW)
Forest wastes
Municipal sewage sludge (MSS)
Magmatic energy
Seismic energy
Volcano energy
Sea water lifting power
Unused rivers
Tidal energy
3.7 Inactive Energy Sources 105
3.7.2 Geothermal Energy
Geothermal energy comes from the heat within the earth. Geothermal energy is
called a renewable energy source because the water is replenished by rainfall, and
the heat is continuously produced by the earth. Some visible features of geothermal
energy are volcanoes, hot springs, geysers, and fumaroles. But usually geothermal
energy is deep underground. Geothermal energy is used to produce electricity, to
heat buildings and greenhouses, and for other purposes.
Geologists use many methods to find geothermal resources. They may study
aerial photographs and geological maps. They may analyze the chemistry of local
water sources and the concentration of metals in the soil. They may measure
variations in gravity and magnetic fields. The earth is a hotbed of geothermal
energy. The most active geothermal resources are usually found along major plate
boundaries where earthquakes and volcanoes are concentrated.
Geothermal energy can be utilized in various forms such as electricity genera-
tion, direct use, space heating, heat pumps, greenhouse heating, and industrial. The
electricity generation is improving faster in geothermal energy rich countries.
There are four main kinds of geothermal resources: hydrothermal,
geo-pressured, hot dry rock and magma. Today hydrothermal resources are the only
kind in wide use. The other three resources are still in the infant stages of devel-
opment, in other words inactive energy.
Hydrothermal resources have the common ingredients of water (hydro) and heat
(thermal). These geothermal reservoirs of steam or hot water occur naturally where
magma comes close enough to the surface to heat ground water trapped in fractured
or porous rocks, or where water circulates at great depth along faults. Hydrothermal
resources are used for different energy purposes depending on their temperature and
how deep they are.
use. The utilization has increased rapidly during the last three decades. In 2000,
geothermal resources have been identified in over 80 countries and there are
quantified records of geothermal utilization in 58 countries in the world. World’s
top countries using geothermal energy in direct uses are given in Table 3.11
(Fridleifsson 2001).
Geothermal energy is heat from Earth’s interior. Nearly all of geothermal energy
refers to heat derived from the Earth’s molten core. Some of what is often referred
to as geothermal heat derives from solar heating of the surface of the Earth,
although it amounts to a very small fraction of the energy derived from the Earth’s
core. For centuries, geothermal energy was apparent only through anomalies in the
Earth’s crust that permit the heat from Earth’s molten core to venture close to the
surface. Volcanoes, geysers, fumaroles, and hot springs are the most visible surface
manifestations of these anomalies. Earth’s core temperature is estimated by most
geologists to be around 5000–7000 °C. For reference, that is nearly as hot as the
Table 3.11 World’s top Country Installed MWt Production (GWh/a)

countries using geothermal
energy in direct uses China 2282 10,531
Japan 1167 7482
USA 3766 5640
Iceland 1469 5603
Turkey 820 4377
New Zealand 308 1967
Georgia 250 1752
Russia 308 1707
France 326 1360
Sweden 377 1147
Hungary 473 1135
Mexico 164 1089
Italy 326 1048
Romania 152 797
Switzerland 547 663
surface of the sun (although, substantially cooler than the sun’s interior). And
although the Earth’s core is cooling, it is doing so very slowly in a geologic sense,
since the thermal conductivity of rock is very low and, further, the heat being
radiated from Earth is being substantially offset by radioactive decay and solar
radiation. Some scientists estimate that over the past three billion years, Earth may
have cooled several hundred degrees (Kutz 2007).
greenhouses (9 %), fish farming (6 %), and industry (6 %) (Fridleifsson 2001).
Geothermal energy can be utilized in various forms such as electricity generation,
direct use, space heating, heat pumps, greenhouse heating, and industrial usage.
Electricity is produced with geothermal steam in 21 countries spread over all
continents. Low temperature geothermal energy is exploited in many countries to
generate heat, with an estimated capacity of about 10,000 MW thermal.
Geothermal energy has been used for centuries, where it is accessible, for
aquaculture, greenhouses, industrial process heat, and space heating. It was first
used for production of electricity in 1904 in Lardarello, Tuscany, Italy, with the first
commercial geothermal power plant (250 kWe) developed there in 1913. Since then
geothermal energy has been used for electric power production all over the world,
but most significantly in the United States, the Philippines, Mexico, Italy, Japan,
Indonesia, and New Zealand.
In Tuscany, Italy, a geothermal plant has been operating since the early 1900s.
There are also geothermal power stations in the USA, New Zealand and Iceland.
3.7 Inactive Energy Sources 107
Table 3.12 Production costs of electricity from new plants, in US $ per kWh
Country Geothermal Cheapest fossil fuel Cheapest renewable
US 0.06 0.03, NG 0.06, wind
Japan 0.13 0.07, LNG 0.22, wind
New Zealand 0.06 0.03, various 0.42, wind
(NG Natural gas, LNG Liquefied NG)
In Southampton (UK) there is a district heating scheme based on geothermal

energy. Hot water is pumped up from about 1800 m below ground.
Direct application of geothermal energy can involve a wide variety of end uses,
such as space heating and cooling, industry, greenhouses, fish farming, and health
spas. It uses mostly existing technology and straight forward engineering. The
technology, reliability, economics, and environmental acceptability of direct use of
geothermal energy have been demonstrated throughout the world.
World’s total installed geothermal electric capacity was 7304 MWe in 1996. In
much of the world electricity from fossil fuel-burning electricity plants can be
provided at half the cost of new geothermal electricity. Table 3.12 shows the
production costs of electricity from new plants in US, Japan and New Zealand
(Murphy and Niitsuma 1999). A comparison of the renewable energy sources
shows the current electrical energy cost to be 2–10 US¢/kWh for geothermal and
hydro, 5–13 US¢/kWh for wind, 5–15 US¢/kWh for biomass, 25–125 US¢/kWh
for solar photovoltaic and 12–18 US¢/kWh for solar thermal electricity. Of the total
electricity production from renewables of 2826 TWh in 1998, 92 % came from
hydropower, 5.5 % from biomass, 1.6 % from geothermal and 0.6 % from wind.
Solar electricity contributed 0.05 % and tidal 0.02 %.
Geothermal energy is a power source that produces electricity with minimal
environmental impact. Geothermal energy, with its proven technology and abun-
dant resources, can make a significant contribution towards reducing the emission
of greenhouse gases. There are some advantages and disadvantages of geothermal
energy. Table 3.13 shows advantages and disadvantages of geothermal energy.
3.7.3 Natural Gas Hydrates
Natural gas hydrates, potentially one of the most important energy resources for the
future. Methane gas hydrates are increasingly considered a potential energy
resource. Considerable knowledge has been developed about their occurrence in
nature and properties (Kvenvolden 1993a; Kvenvolden and Lorenson 2000).
However, the issues of technology and economics of natural gas production from
gas hydrates are less well understood. Gas hydrates are increasingly recognized as a
potential future energy resource, based on the vast amounts of methane trapped
within them (Kvenvolden 1993b).
Table 3.13 Advantages and disadvantages of geothermal energy

Advantages of geothermal energy Disadvantages of geothermal energy
It is renewable source. The heat is Geographic distance between source and use.
continuously produced by the earth Not all areas are suitable for geothermal energy
Clean and safe energy: emissions of Extracting geothermal energy can disrupt the
undesirable substances are small surrounding environment
Sustainable energy source: Heat extraction Total generation potential of this source is too
is small compared to the size of heat small
reservoir
Geothermal energy can be use directly There is always a danger of eruption of
volcano. Hot water from geothermal sources
can contain dangerous parts
Maintenance cost of geothermal power Huge initial costs: Installation cost of steam
plants is very less power plant is very high
Diversity in energy sources/conservation of It may release some harmful, poisonous gases
fossil fuels that can escape through the holes drilled during
construction
Unlike hydro, solar and wind energy, it is It is not easily transported
not dependent on the weather conditions
Natural gas hydrates are of considerable interest for their potential as an energy
resource and for their potential role in global climate change. From an energy
resource point of view, the enormous amounts of gas hydrate under the ocean and
beneath arctic permafrost represent an estimated 53 % of all fossil fuel reserves on
earth, about 10,000 gigatons (Lee and Holder 2001). Table 3.14 shows worldwide
amounts of organic carbon resources. The worldwide amounts of organic carbon
bound in gas hydrates is conservatively estimated to total twice the amount of
carbon to be found in all known fossil fuels on Earth (Satoh et al. 1996;
Kvenvolden 1998; Collett 2002).
Methane can be recovered from the gas hydrates by the depressurization, thermal
stimulation and chemical inhibitor injection methods. The thermal stimulation and
chemical inhibitor injection methods are quite expensive. The depressurization
method is considered to be the most economically promising method for the pro-
duction of methane gas from gas hydrates.
Table 3.14 Global amounts of organic carbon resources

Source of organic carbon Amount
(Gigaton)
Gas hydrates (onshore and offshore) 10,000–11,000
Recoverable and non-recoverable fossil fuels (crude oil, coal, natural gas) 5000
Carbonaceous materials (Soil, Dissolved organic matter, Land biota, Peat, 3830
Others)
3.8 Promising Energy Systems 109
3.8 Promising Energy Systems
3.8.1 Introduction
These are only a few alternative energy sources that are available around the world
such as biomass, hydro, solar and wind. Renewable energy is a promising alter-
native solution because it is clean and environmentally safe. Solar photovoltaic
system has been found to be a promising energy in future. One of the most sig-
nificant developments in renewable energy production is observed in photovoltaic
systems (EWEA 2005; Reijnders 2006).
Hydrogen is a fuel for the future promising. Hydrogen is clean and a high energy
content of fuel. Hydrogen is a peaceful energy carrier for all countries. Hydrogen
produced chemically, thermochemically, biologically, biochemically, and biopho-
tolytically from all biomass materials. Hydrogen is an environmentally friendly
alternative automotive fuel that can be used in an internal combustion engine.
One of the promising future energy sources is biomass and biomass derived
resources and fuels such as biogas, biofuels, algae. The futuristic concept of engine
fuel covers the promising fuel resources compete with oil.
Table 3.15 shows some promising energy sources, promising fuels and
promising energy systems.
3.8.2 Hydrogen as a Future Promising Fuel
Hydrogen is a fuel for the future promising. Hydrogen is clean and a high energy
content of fuel. Hydrogen is a peaceful energy carrier for all countries. Biohydrogen
is hydrogen originating from biorenewable sources. Hydrogen can be produced
from biorenewable feedstocks via thermochemical conversion processes such as
pyrolysis, gassification, steam gasification, steam-reforming of bio-oils, and
Table 3.15 Some promising energy sources, promising fuels and promising energy systems
Promising energy Promising fuels Promising energy systems
sources
Water Hydrogen Fuel cells, hybrid cars
Biomass Biogas, Bioethanol, Vehicles, fuel cells
Biodiesel
Algae Biofuels, Biodiesel Vehicles, fuel cells
Compressed air – Compressed air vehicles
Boron mine Boron and Boron Rockets, fuel cells, nuclear
compounds reactors
Electricity – Electric cars and hybrid cars
Natural gas hydrates Methane Electricity generation
supercritical water gasification of biomass. Hydrogen is an environmentally friendly

alternative automotive fuel that can be used in an internal combustion engine.
Comparison of pyrolysis and air-steam gasification, the yield of hydrogen from
biomass is generally higher by air-steam gasification than that of by pyrolysis,
because with interaction of water and char from decomposition of biomass inter-
mediate products occurs which leads to more hydrogen-rich gas yield by the steam
reforming (Nath and Das 2003).
The combustion products of hydrogen when it is burned completely with air
consist of water, oxygen, and nitrogen. Higher heating value (HHV) of hydrogen is
142.3 MJ/kg at standard combustion conditions. Compared to other fuels such as
methane, boron and gasoline, hydrogen has a unique chemical energy. Table 3.16
shows the higher heating value (HHV) of hydrogen and the common fuels. In the
meantime, it has been suggested, hydrogen is too valuable to burn. In comparison
with an engine burning gasoline, the emission of nitrogen oxides is far less for the
engine-fueled hydrogen. Hydrogen has good properties as a fuel for internal
combustion engines in automobiles.
Hydrogen is one of the best fuels in the future. Today in front of it the biggest
obstacle is the high cost of hydrogen. The widespread use of hydrogen as a motor
fuel would be the biggest victory of technology in the 21st century. The most
intelligent solution of the low cost hydrogen is the use of non-conventional energy
of solar and water energy production method more efficiently. The hydrogen energy
will become the principal fuel source of abundant clean energy.
In the future, hydrogen will be the most important and indispensable energy
source. Hydrogen is also the best energy source in the future. Today generation of
hydrogen is unavailable. The widespread use of hydrogen as a motor fuel would be
the biggest victory of technology in the 21st century.
Hydrogen offers a number of technical and environmental benefits over con-
ventional fossil fuels, which make them attractive as alternatives for the transport
sector. Table 3.17 shows major benefits of hydrogen.
Any type of energy can be used to produce hydrogen as direct (electrical,
photovoltaics) and indirect (fossil, biomass, wind, solar, hydropower, geothermal
etc.). In the near future, decrease of cost of electricity, solar energy, wind energy,
nuclear energy, fuel cells, photovoltaic cell, photovoltaic-support fuel cell, even
bioethanol and biodiesel will cause reducing of hydrogen cost.
Table 3.16 Higher heating Fuel Higher heating value (MJ/kg)

value (HHV) of hydrogen and
the common fuels Hydrogen 142.3
Methane 55.6
Boron 54.7
Gasoline 45–47
Biodiesel 39–41
Vegetable oil 36–39
Carbon 33.5
Table 3.17 Major benefits of hydrogen

Economic impacts Resource abundance and prevalence
Sustainability and fuel diversity
Increased number of rural manufacturing jobs
Increased investments in plant and equipment
International competitiveness
Reducing the dependency on imported petroleum
New market opportunities
New job opportunities
Environmental impacts Reducing of greenhouse gas emissions
Reducing of global warning
Reducing of air pollution
Non-carbon fuel
Clean energy carrier
Advanced fuel technology
Energy security Peaceful and domestic targets
Reducing use of fossil fuels
Energy flexibility
Ready availability
Domestic production
Domestic distribution
Renewability
Several hydrogen technologies are under development; the most promising of

these is the fuel cell. A fuel cell produces electricity directly from the electro-
chemical reaction of hydrogen, from a hydrogen-containing fuel, and oxygen from
the air. Hydrogen is the ideal fuel for a fuel cell, the infrastructure for producing and
storing. Fuel cells, photovoltaic cells, hybrid fuels, electric cars and fly cars are
more energetic tools that are already emerging. Developing of flying cars depend on
the development of hydrogen as a motor fuel is used. Hydrogen, clean and a high
energy content of fuel. Hydrogen is a promising fuel for the future with these
characteristics.
Today, in front of it the biggest obstacle is the high cost of hydrogen. The most
intelligent solution of the low cost hydrogen is the use of non-conventional energy
of solar and water energy production method more efficiently. Table 3.18 shows the
main disadvantages and technical challenges of using hydrogen as a fuel for
automobiles.
The cost of hydrogen production from different sources varies widely given
unique capital equipment costs, feedstock cost, availability and transport, and
technology maturity. A hydrogen production economics survey summarized the
results of numerous studies on the estimated cost for hydrogen production, storage,
and transportation technologies near commercialization (Norman 2007). The most
Table 3.18 The main disadvantages and technical challenges of using hydrogen as a fuel for
automobiles
Cost Hydrogen economy include lowering the cost of hydrogen
production
Storage Huge on-board storage tanks are necessary
Density Hydrogen has an extremely low density
Liquid form It can be liquefied on board a vehicle as compressed gas in
ultra-high-pressure vessels
Stored as metal Hydrogen may be stored as a gas bound with certain metals in metal
hydride form hydrides
Delivery It needs special equipment for its distribution
End user applications More information need for transportation applications
Table 3.19 Optimistic Production method US$/GJ US$/kg

estimated cost of hydrogen
production from various Steam methane reforming 6.45 0.78
sources Coal gasification 11.71 1.41
Hydrocarbon partial oxidation 8.23 0.99
Biomass gasification 10.31 1.24
Biomass pyrolysis 10.51 1.26
Electrolysis 23.96 2.88
Solar electrolysis 35.75 4.29
Photobiological production 31.36 3.77
optimistic projected cost of hydrogen production from various sources is given in

Table 3.19.
The conventional methods for hydrogen production covered the science, busi-
ness, economics, and politics of hydrogen and fuel cells, and carried lively opinion
pieces from some of the field’s most respected practitioners and thinkers.
Fuel cell was an online resource that had the mission to promote and advance the
commercialization of fuel cells and hydrogen by supplying accurate, unbiased
information and developing and disseminating summary materials accessible to a
general audience (Lipman 2004; T-Raissi and Block 2004; Chalk and Miller 2006;
Li and Hurley 2007; Kotay and Das 2008).
Fuel cell changes the chemical energy stored in chemical agent into electrical
energy. During the past decade, fuel cells received enormous attention all over the
world as novel electrical energy conversion systems. The higher efficiencies and
lower emissions make the fuel cells a valuable contribution to the power generation
facilities.
A fuel cell is an electrochemical that uses hydrogen (or a hydrogen-rich fuel) and
oxygen to produce electricity, heat and water by an electrochemical reaction
without resorting to a burning process, rather than to heat by a combustion reaction.
The chemical energy of the fuel is released in the form of an electrical energy
instead of heat when the fuel is oxidized in an ideal electrochemical cell.
The hydrogen energy will become the principal fuel source of abundant clean
energy for mankind. The important role of hydrogen energy in the future is an
inexhaustible and clean energy system (Li and Hurley 2007). Hydrogen is con-
sidered in many countries to be an important alternative energy source and a bridge
to a sustainable energy future. The promise of hydrogen as an energy carrier that
can provide pollution-free, carbon-free power and fuels for buildings, industry, and
transport makes it a potentially critical player in our energy future (Balat and Kirtay
2010).
Hydrogen is one of the best rocket fuels for any system. Hydrogen may be stored
as a liquid which will reduces the size of the storage tanks. However, expensive and
complicated cryogenics equipment is necessary to maintain the hydrogen in the
liquid state. Because of the difficulties in handling and storage of pure hydrogen,
most rocket fuels are now hydrogen-containing compounds, particularly hydro-
carbons, which do not have the associated handling difficulties.
3.8.3 Future Transportation Vehicles
The vehicles with Otto and Diesel engines (Internal Combustion Engines), of
course, are not vehicles of the future. Internal combustion engines (ICEs) will end
in near future and their life until 2040 is estimated. The challenge of meeting the
fuel economy targets is defined by both the magnitude and the timing of these
requirements. Doubling the fuel economy by 2030 is also challenging, but more
feasible since the auto industry will have more lead time to respond (Bandivadekar
et al. 2008). Potential future car technologies include varied energy sources and
materials, which are being developed in order to make automobiles more energy
efficient with reduced regulated emissions (Bandivadekar et al. 2008; Cheah et al.
2009; Heywood 2010; Kromer et al. 2010; Cheah and Heywood 2011; Bastani et al.
2012). A variety of propulsion technologies and fuels have the promise to reduce
petroleum use and greenhouse gas emissions from motor vehicles. Future vehicles
must forgo horsepower improvements, become lighter, and a greater number will
use advanced, more fuel efficient powertrains (Bandivadekar et al. 2008).
The cars are being developed in many different ways. According to predictions
made a few decades ago, current travel should involve self-driving automobiles,
jetpacks and flying cars, with space transport a common occurrence. These vehicles
almost surely will become available by the end of the century. Transportation
professionals help creates the future, so it is important that we consider the overall
context of long-term planning decisions. Good planning does not simply extrapo-
late trends; it attempts to understand the factors that cause change. With rising fuel
prices, now the future of cars is leaning towards fuel efficiency, energy-savers,
hybrid vehicles, battery electric vehicles, and fuel-cell vehicles.
One major problem in developing cleaner, energy efficient automobiles is the

source of power to drive the engine. Placing a much greater emphasis on reducing
fuel consumption rather than improving vehicle performance can greatly reduce the
required market penetration rates (Bandivadekar et al. 2008; Cheah and Heywood
2011).
Conventional automobiles operate at about 15 % efficiency. The rest of the
energy is lost to engine and drive-train inefficiencies and idling. Therefore, the
potential to improve fuel efficiency with advanced technologies is enormous.
Various technologies have been developed and utilized to increase the energy
efficiency of conventional cars or supplement them, resulting in energy savings.
Regenerative braking technology saves and stores energy for future use or as
backup power. The most common form of regenerative brake involves using an
electric motor as an electric generator. In electric railways the generated electricity
is fed back into the supply system, whereas in battery electric and hybrid electric
vehicles, the energy is stored in a battery for later use (Wikipedia 2011).
Turbo-steamer concept uses energy from the exhaust gases of the traditional
ICEs to power a steam engine which also contributes power to the automobile
(Hanlon 2005). This can increase energy efficiency by up to 15 %. Compressed air
hybrid reduces fuel consumption by 30 %. By using air instead of oxygen, even
with compressed oxygen for providing of higher combustion efficiency will be
having many more innovations in future vehicles. Oxygen, in especially Stirling
engines, provides the possibility to use solid fuel.
The development of battery-powered, battery-powered electric vehicles to
increase the efficiency and the reduction depends on the weight of the battery. Many
research studies on this subject and these batteries, especially lithium being
intensified on. With battery-powered electric vehicles, no matter how developed is
developed, which produces its own electricity directly from engines cannot take
place (Kim et al. 2012; Hu et al. 2012; Zhou et al. 2012; Han et al. 2012; Stamp
et al. 2012).
That produces electricity directly from a vehicle charging problem is eliminated.
Vehicles driven by electric motors use the motor as a generator when using
regenerative braking: it is operated as a generator during braking and its output is
supplied to an electrical load; the transfer of energy to the load provides the braking
effect.
Regenerative braking is used on hybrid gas/electric automobiles to recoup some
of the energy lost during stopping. This energy is saved in a storage battery and
used later to power the motor whenever the car is in electric mode. Regenerative
braking has been in extensive use on railways for many decades. Many modern
hybrid and electric vehicles use the regenerative braking technique to extend the
range of the battery pack.
The main disadvantage of regenerative brakes when compared with dynamic
brakes is the need to closely match the generated current with the supply charac-
teristics and increased maintenance cost of the lines. With DC supplies, this requires
that the voltage be closely controlled. Only with the development of power
electronics has this been possible with AC supplies, where the supply frequency
must also be matched.
3.8.4 Energy from Boron
Boron fuel is made up of the element boron. Boron as a chemical fuel will be a
promising engine fuel in the future. Cars in which boron fuel simply burns will be
true zero emission vehicles (Balat 2007; Demirbas 2008c).
Elemental boron and its compounds are considered as most promising candi-
dates to be used as hydrogen storage and production material (Ozturk and Demirbas
2006). Boron is a promising engine fuel and engine fuel additive (Demirbas 2005b;
Uslu 2009; Sen et al. 2009).
Boron as a chemical fuel will be promising motor fuel in the future. Cars in
which boron fuel simply burns will be true zero emission vehicles. Boron has a very
high energy density, much better than that of liquid hydrogen and also a lot safer
(Demirbas 1998).
The idea of boron as a better automobile fuel than hydrogen is to use nuclear
energy to split boron oxide, and to use the boron as fuel in suitable automobile
engines.
Boron naturally occurs in borax (Na2B4O75H2O). Boron occurs on the Earth in
compounds known as the borate minerals. There are over 100 different borate
minerals, but the most common are: borax, kernite, ulexite etc. (Muetterties 1967).
Boron minerals are shown an alternative energy source in spite of the danger that
the world is running out of fossil based fuel. Because of that boron based fuel cells
are developed (Kar et al. 2006).
Boron fuel is made up of the element boron. It is mixed with pure oxygen in the
engine. Boron is very safe, because it is hard to ignite. It also contains more energy
than petroleum derivatives fuels (as seen in Table 3.15). Boron has a very high
energy density, much better than that of liquid hydrogen and also a lot safer. So it
seems practical as a fuel for a vehicle. Unfortunately boron is quite a limited
resource and pure oxygen is expensive (Demirbas 2005b).
In air boron may be practically unignitable. If the oxygen is pure, boron burns
better. Unfortunately boron is quite a limited resource and pure oxygen is expen-
sive. Techniques are required for purifying air oxygen on board the vehicle and then
the oxygen must be prevented from burning the motor along with the fuel.
To ignite boron it can be burnt in an environment of pure oxygen, and it has no
other product than solid boron oxide, there are no other harmful pollutants or
emissions. The unique compactness of boron means that it could easily have a
transcontinental range.
It has a huge advantage as a fuel because it is very combustible in pure oxygen.
Boron’s major safety advantage is that it strongly resists ignition. For this reason it
is very safe in cars since many accidents are made more dangerous due to highly
flammable fuel. Boron has a possibility for the fuel of the future for a real zero
emission vehicle. The combustion reaction of boron can be given with Eq. (1):
B þ 0:75O2 ! 0:5B2 O3 þ 2473 kJ ð3:13Þ
The B2H6 very easily burns to the boric oxide:
B2 H6 þ 3O2 ðgÞ ! 2BðOHÞ3 ðsÞ þ 9331 kJ ð3:14Þ
This is a very high combustion heat comparing with the combustion heat of ethane:
C2 H6 þ 3:5O2 ðgÞ ! 2CO2 ðgÞ þ 3H2 OðlÞ þ 6518 kJ ð3:15Þ
The B2H6 also can be converted to hydrogen with water:
B2 H6 þ 6H2 O ! 6H2 þ 2BðOHÞ3 ð3:16Þ
Shortly after the Second World War much work was done to put boron to work
as a military jet fuel by making liquid compounds of it. These compounds were
boron-hydrogen compounds, boranes, and compounds of boron, hydrogen, and
carbon, known as carboranes.
Boron hydrides are the best fuels known. They are pyrophoric, however, and
ignite upon contact with the atmosphere. In addition to being toxic, boron hydrides
also yield high-mass B(OH)3 (s) as exhaust which does not provide good thrust.
Boron hydride (BH3) exists only as a reaction intermediate and easily converts to
the B2H6. The B2H6 is a bridge-bonded compound and it decomposes at 475 K as
B2 H6 ! B4 H10 þ B5 H9 þ B6 H10 þ ð3:17Þ
Boron hydrides are the best fuels known for rockets. They boron hydrides yield
high-mass B(OH)3 as exhaust which does not provide good thrust. Zip fuel, also
known as high energy fuel (HEF), is any member of a family of jet fuels containing
additives in the form of hydro-boron compounds, or boranes. Zip fuels offered
higher energy density than conventional fuels, helping extend the range of jet
aircraft.
Boron as the neutron absorber has another positive property. The reaction
products (after a neutron absorption), helium and lithium, are stable isotopes.
Natural boron includes 10B isotopes, whose nuclei have a large cross-section of
neutron absorption. Therefore there are minimal problems with decay heating of
control rods or burnable absorbers used in the reactor core.
Boron may be used as nuclear fuel. The function in the fusion is a proton is
driven into a boron atom making it a carbon atom in a very highly energized state.
The new carbon atom is proton/neutron unbalanced making it inherently unstable
and so flies apart.
3.8.5 Energy from Non-nuclear Metallic Fuels
The metallic aluminum powder burns to result a strong exothermic reaction in the
presence of the magnesium (Mg) stripe. The burning Mg strips had highly effect on
the mixture.
2Al þ 1:5O2 ! Al2 O3 þ 1687 kJ=at-g ð3:18Þ
The heat of combustion of iron is 5858 J/g. Iron wire can be burned in calorimeter
bomb.
2Fe þ 1:5O2 ! Fe2 O3 þ 328 kJ=at-g ð3:19Þ
Aluminothermy a process of producing high temperatures by causing finely

divided aluminum to react with the oxygen from another metallic oxide:
Fe2 O3 þ 2Al ! Al2 O3 þ 2Fe þ 850 kJ ð3:20Þ
Cr2 O3 þ 2Al ! Al2 O3 þ 2Cr þ 2291 kJ ð3:21Þ
This reaction is supposed to proceed smoothly, producing a blinding white heat

as the reaction moves across the sample mixture. This can be explained through
aluminum metal’s high affinity for metal oxides. The combustion heats of metals
are considerably different. The specific heats of metals are similar each other.
The metal elements use to produce hydrogen from water. The alkali metals,
lithium, sodium, and potassium react violently with water at the ambient temper-
ature, yielding hydrogen. Steam is decomposed when passed over heated magne-
sium, zinc, and iron.
The boron and metal elements such as aluminum, magnesium, and iron and their
specific substances have a strategically important for motor and rockets as fuels.
The metal hydride rocket fuels include aluminum hydrides, lithium hydrides,
beryllium hydrides, and lithium aluminum hydrides. In preferred embodiments, the
metal hydride is selected from the group consisting of AlH3, LiAlH3, BeH2, and
Li3AlH6. The use of Li3AlH6 is particularly preferred.
The metal hydrides commonly use as propellant material. A propellant is a
material that is used to move an object by applying a motive force. This may or may
not involve a chemical reaction. It may be a gas, liquid, plasma, or, before the
chemical reaction, a solid. Common chemical propellants consist of a fuel, like
rocket fuel, jet fuel and gasoline, and an oxidizer. The use of metal hydrides
properly AlH3 and BeH2 as rocket propellants have been briefly explored.
However, because hydrides readily react with moisture and ambient gases, hydrides
must be handled and stored with special care. As a result, despite the physical and
chemical characteristics that show promise as a rocket fuel, the use of metal
hydrides as rocket fuels has not been practical and/or commercially feasible
(Demirbas 2008c).
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Chapter 4
Energy from Waste Materials
and Unconventional Sources
4.1 Introduction
The increasing demand for oil and gas resources more will be needed for uncon-
ventional sources of oil and natural gas. The unconventional hydrocarbon appli-
cations have been growing rapidly in recent years. Unconventional oil can be
produced from oil sands, oil shale, extra heavy oil, and gas to liquids and other
liquids. Conventional fossil energy reserves will not be enough to meet the con-
tinuously increasing need for energy in the future. In this case, renewable energy
sources will become important. Conventional oil sources are currently preferred
because they are less expensive than unconventional sources. New technologies are
being developed to reduce unconventional oil production costs.
New production technologies have contributed significantly to the advanced
development of these unconventional resources. The safe and responsible devel-
opment of unconventional domestic energy resources production creates new job
facilities and provides economic benefits to all domestic production supply benefit
from lower feedstock and energy costs.
In general conventional oil is easier and cheaper to produce than unconventional
oil. Unconventional oil can be produced from hydrocarbon resources using tech-
niques other than the conventional method (Demirbas et al. 2015a).
Oil shale and bituminous materials suitable for obtaining petroleum like prod-
ucts. The process designed study has the ability to control unwanted volatile
materials. Oil sands or tar sands generally consist of extra heavy crude oil or crude
bitumen trapped in unconsolidated sandstone. They cannot be produced by con-
ventional methods, transported without heating or dilution with lighter hydrocar-
bons, or refined by older oil refineries without major modifications.
Tight oil, including light tight oil is crude oil contained in petroleum-bearing
formations of low permeability, often shale or tight sandstone.

124 4 Energy from Waste Materials and Unconventional Sources
Gas hydrates represent one of the world’s largest untapped reservoirs of energy
and, according to some estimates, have the potential to meet global energy needs for
the next thousand years.
Conventional fossil energy will not be enough to meet the continuously
increasing need for energy in the future. In this case, renewable energy sources will
become important. Some electricity production is done with alternative energy
sources like biomass, geothermal, wind, and solar energy.
It is known that hydro is the cheapest source of electricity production. In other
words, the country, which has available water sources for hydro production, has the
advantage to lower generation costs. Some production is done with alternative fuels
like geothermal energy, wind power, biomass, solar energy, or fuel (Demirbas
2006a, b).
Biomass is semi-conventional energy source because it is in the process of
becoming mainstream. Sun, wind and water are considered semi-conventional,
renewable, nonpolluting energy sources because they are continually replenished.
Although the concept of harnessing renewable energy sources has become main-
stream, its full implementation is still taking place, primarily because of cost
considerations (Demirbas 2007).
Most electricity in the world is conventionally generated using coal, oil, natural
gas, nuclear energy, or hydropower. Coal has been used widely in electricity
generation for decades. The future of biomass electricity generation lies in biomass
integrated gasification/gas turbine technology, which offers high-energy conversion
efficiencies.
The wind energy sector is one of the fastest-growing energy sectors in the world
(Garg and Datta 1998). The last three decades have witnessed a trend in solar
thermal electricity generation of increasing the concentration of sunlight (Kribus
2002). There are three main systems of solar thermal electricity: solar towers, dishes
and the parabolic troughs (Zhang et al. 1998).
General research for the development of unconventional sources, development
and deployment strategy and support opportunities regarding the application of
technology should be implemented. For each of the unconventional energy source;
the technical, safety, and environmental challenges should be identified in con-
nection with each of the unconventional resources; and the current status of
research activity, both public and private, focused on these resources.
The emergence of new job opportunities for the unconventional resources will
be positive impacts. Environmental and socioeconomic impacts of development of
unconventional resources on a regional basis should be facilitated and quantifying
the environmental and safety impacts of unconventional resource development and
identifying ways must be evaluated separately.
Sources of unconventional oil will be increasingly relied upon when conven-
tional oil becomes more expensive due to depletion. Conventional oil sources are
currently preferred because they are less expensive than unconventional sources.
New technologies, such as steam injection for oil sands deposits, are being
developed to reduce unconventional oil production costs. Unconventional hydro-
carbons are more difficult and expensive to retrieve than the traditional stuff.
4.1 Introduction 125
Small businesses in particular can be negatively affected by higher energy prices.

Increases in these costs can spur higher prices for the transportation of products and
affect other costs associated with running a company.
4.2 Wind Power Generation Using Shaking Energy
Electric power has more than 100 methods of production. Energy made from the
vibrating wind farms could be much cheaper. Unconventional bladeless wind tur-
bines can be used for power generation by shaking, not spinning.
The vortex producing affects on wind turbines bladeless generating of electricity
by shaking. This system produces wind power by shaking. The magnets used in this
design it is possible to achieve power in all weather conditions. The nonlinear
magnetic-spring configuration is employed for generating sufficient power from
hand shaking of irregular and low-frequency vibrations.
The turbulent flow causes the oscillating frequency of the cylinder to vary,
making it difficult to optimize for energy production. In simple terms a vortex
generator (VG) is a device that creates a swirl or “vortex” of fluid due to its shape.
The VGs come in many shapes and sizes depending on their intended use. Proper
location of vortex generators is very important. They should be positioned precisely
in the transition region of the boundary layer.
Vortex generators (VGs) usually take the form of a plate (See Sect. 3.4). This
vortex flow is basically one of rotating around its own axis. Basically this plate
extracts energy from the flow generating this rotation on the flow. If properly
oriented interacts with the boundary layer over the wing providing further energy to
it. This extra energy to the boundary layer to increase the angle of attack and more
income means more resistant separation obtain a higher coefficient of lift for the
same wing. When wind passes one of the cylindrical turbines, it shears off the
downwind side of the cylinder in a VG turbine. The VG then exerts force on the
cylinder, causing it to vibrate. The kinetic energy of the oscillating cylinder is
converted to electricity through a linear generator. Vibration energy generated from
wind farms could be much cheaper.
The vortex generating affects wind turbines bladeless generating of electricity by
shaking. The magnets used in this design it is possible to achieve power in all
weather conditions (Cottet and Koumoutsakos 2000). The nonlinear
magnetic-spring configuration is employed for generating sufficient power from
hand shaking of irregular and low-frequency vibrations (Liu et al. 2014).
Vortex generators (VGs) usually take the form of a plate. This vortex flow is
basically one of rotating around its own axis. Basically this plate extracts energy
from the flow generating this rotation on the flow. The VG then exerts force on the
cylinder, causing it to vibrate. The kinetic energy of the oscillating cylinder is
converted to electricity through a linear generator. In a bladeless wind turbine,
depending on the wind speed can be achieved quick shaking and vibrations espe-
cially in stormy weather, whirlwind coincided with the structure of the attractive
frequency is vortex frequency, it is then that energy is absorbed reaching a peak due
to aeroelastic coupling. As the sticks vibrate, that movement is converted into
electricity by an alternator (Den Hartog 1985; Cottet and Koumoutsakos 2000;
Nehemiah et al. 2012; Forster and White 2014; Liu et al. 2014).
In a bladeless wind turbine, depending on the wind speed can be achieved quick
shaking and vibrations especially in stormy weather, whirlwind coincided with the
structure of the attractive frequency is vortex frequency, it is then that energy is
absorbed reaching a peak due to aeroelastic coupling. It is a great way of trans-
mitting energy from a fluid source to a structure. The shaking and vibrating
movements of the constructions is converted into energy by an alternator at the
base. Vibration energy generated from wind farms could be much cheaper.
Figure 4.1 shows wind turbines: Conventional (a) and bladeless (b).
If you compare a bladeless wind turbine to a conventional wind turbine with
similar energy generation, the bladeless wind turbine would cost significantly less,
around 45 % less. Motion into electrical energy, available through the system
according to 40 % cheaper alternator converts the swinging propeller system.
Bladeless wind turbines providing a 50 % rate, cheap production and maintenance
costs, is remarkable at low cost. Despite the advantages of the bladeless turbines, VG
turbines constitute about 30 % less electricity than traditional spinning-blade tur-
bines. Designed to reduce the visual and aural impact of traditional spinning-blade
turbines, the bladeless turbine takes advantage of the power contained in swirling
vortices of air.
Fig. 4.1 Wind turbines: Conventional (a) and bladeless (b)

4.2 Wind Power Generation Using Shaking Energy 127
Instead of turning, what the turbine does is oscillate thereby producing move-
ment and displacement. The system is based on the same principles as an elec-
tromagnetic induction generator. The movement and speed of them can be
multiplied that magnetically without the use of ball bearing. When the structure
starts oscillating, an alternator at the base of the device converts the mechanical
movement into electricity. This is a good example how the mechanical energy of
the structure can be turned into electricity.
As compared to the modern wind turbines, bladeless wind turbines operate, only
20 % of maintenance costs, produce and half of the operating predicted to reduce
costs less than 40 % of global power production costs.
Noise is a major factor for wind farms, wind power generators must therefore
operate noiseless as possible. To avoid making any noise of classic wind turbines,
bladeless wind turbines are quiet.
Many opponents of spinning wind turbines point to their supposed danger to
birds and other flying animals. Environmental effects of the bladeless wind turbines
on human, birds and other flying are almost zero.
Scientific degree turbines instead of taking advantage of a phenomenon specific
reason to cling strongly hope that the blades of wind farms reduced the cost of
removing wind energy.
Economic power generations, especially in energy-poor countries are gaining
importance day by day. Bladeless wind turbine method holds promise for the
future. The bladeless turbines will generate electricity for 40 % less than the cost of
power from conventional wind turbines. It can be developed a small 3–5 kW
bladeless wind turbine aimed at supplying small business, distributed energy grids
or individual homes.
Table 4.1 shows the main advantages and disadvantages of bladeless wind
turbines.
Table 4.1 Main advantages and disadvantages of bladeless wind turbines

Advantages Disadvantages
The shaking and vibrating movements of the Requiring quick shaking and vibrations especially in
constructions is converted into energy by an stormy weather, it requires additional motor and
alternator at the base accessory cost, lack of information, lack of skills
If you compare a bladeless wind turbine to a Vortex generation turbines constitute about 30 %
conventional wind turbine with similar energy less electricity than traditional spinning-blade
generation, the bladeless wind turbine would cost turbines, lack of service facilities, lack of
significantly less, around 45 % less information, lack of skills
As compared to the modern wind turbines, bladeless Lack of service facilities, lack of information, lack of
wind turbines operate, only 20 % of maintenance skills, poor market acceptance
costs
As compared to the modern wind turbines, Lack of information, lack of skills, lack of service
establishment costs of bladeless wind turbines is facilities, poor market acceptance
very low
A very small capacity turbine (3–5 kW) may be Lack of information, advanced technology, lack of
manufactured economically for individual homes service facilities, poor market acceptance
As compared to the modern wind turbines, bladeless Lack of information, advanced engineering
wind turbines are higher available technology, lack of service facilities
4.3 Compressed Air Energy
4.3.1 Introduction
Compressed air and electrical power is the most important form of energy used
industry and workshops. Compressed air is the second industrial energy source after
electrical power. It is used in many household and industrial processes. In European
Union, compressed air consumption almost is 10 % of industrial electricity. Air can
be squeezed (compressed) into a much smaller space than it would normally
occupy. Squeezed air is one of the most important industrial inputs after electricity,
water and fuel.
Two main types of compressors are used: reciprocating compressors and screw
compressors.
The compressors and dryers are the main energy consumers in the systems. Most
of the energy used to generate compressed air is rejected in the form of heat. This
heat can be recovered for space heating or for the heating of domestic water. Up to
85 % of the input electrical energy can be recovered. A device that stores energy is
sometimes called an energy accumulator (Fig. 4.2).
4.3.2 Compressed Air Powered Vehicles
Compressed air drives the motor crankshaft and hence, the wheel movement is
obtained. This use of the engine has several technical advantages. There is no
combustion in the engine working temperature is close to ambient temperature. This
helps in reducing the wear of engine parts. There is also the possibility of deto-
nation. Thus compressed air powered car has the capacity to satisfy current demand
and can provide the needs of future vehicles (Baig and Hussain 2015). This engine
has a zero emission and compressed air used this engine is clean, safe, simple and
efficient (Shaw et al. 2013). Compressed air is also used in some vehicles to
increase the first moment (Shetty et al. 2015).
In general, compressed air vehicles have attracted scientists and engineers for
centuries due to different uses and nonpolluting advantages of compressed air.
While developing of pressurized air vehicle, control of pressurized air parameters
such as temperature, energy density, requirement of input power, energy release and
emission control have to be mastered for the development of a safe, light and
cost-effective pressurized air vehicle in the near future (Szabłowskia and Milewskia
2011; Mourya et al. 2014).
Air Cooler Filter Dryer Receiver End

Compressor User
Fig. 4.2 A simplified block diagram of a compressed air system

4.3 Compressed Air Energy 129
A compressed air vehicle (CAV) using compressed air stored in the tank and
powered by the air motor. Instead of pistons with hot expanding gas mixing fuel
with air and combustion engine drive, compressed air tools, use compressed air to
drive their pistons expansion (Lal 2013). The CAV maybe operate with a 90 %
efficient engine design with 70 mph power.
A compressed air vehicle is powered by motor driven by compressed air at
30 MPa. Unlike the driving engine pistons with burned fuel-air mixture, com-
pressed air vehicles use the expansion of compressed air, in a similar manner to the
expansion of steam in a steam engine. The car is designed for filling a high pressure
pump.
The compressed-air propulsion may be included in the battery as hybrid electric
drive systems. This kind of system is called hybrid-pneumatic electric propulsion.
Additionally, regenerative braking can also be used in conjunction with this system.
Compressed air vehicles operate as emission-free. However, a compressed air
car is usually electricity; therefore its total environmental impact depends on how
clean the source of this electricity is.
There are many advantages of compressed air vehicles. The lack of local
combustion is one of their only significant advantages. They are not free of pol-
lution; at least with current technology, they still need lubricants mixed in the air to
keep them from sticking. They need an external power source to run the com-
pressor, making them less efficient. As their range is very limited and the air tank is
drained, significantly reducing power radical cools. Table 4.2 shows main advan-
tages of compressed air vehicles.
Compressed air vehicle (CAV) engine is compressed if the power instead of
letting the air pressure applier lot cheaper than systems used in production and
working costs are reduced. For this purpose founded on the road especially in the
Table 4.2 Main advantages of compressed air vehicles

It use compressed air It uses no gasoline or other bio-carbon based fuel
Easy refueling It is easy to store compressed air in purpose-built tanks
It has simple design The design and operation of pneumatic equipment is very simple.
Compressed air engines reduce the cost of vehicle production, because
there is no need to build a cooling system, spark plugs, starter motor, or
mufflers
Auto-climatic system Expansion of the compressed air lowers its temperature; this may be
exploited for use as air conditioning (Joule-Thomson Principle)
Clean, dry, no emission Compressed air vehicles operate with zero emission
Easily transported Compressed air can be transported over great distances in pipelines
Safe to use Pneumatic systems and components in general wear very little. They
therefore have a long working life
Accident-proof Pneumatic elements are very safe with regard to fire, explosion and
electrical hazards
Fast work medium The very high flow speeds allow rapid completion of work cycles. This
provides short cut-in times and fast conversion of energy into work
Fully adjustable Travel speeds and exerted force are fully and easily adjustable
bridge crossing the bottom of the piston platforms can be used. The pistons in the
bottom of the vehicle on the platform by passing from platform to obtain high
pressure air tight. Between the piston and high-pressure tank check valve system is
located. Such platform can be installed at the bottom of a dam in the deepest water.
To fill the fuel tank on the CAV do not need to go to any station because
compressed air can be fill into the tank using a pump even at home.
4.4 Water Forces and Water Energy
Structural and technical properties of liquids, especially water, are unknown

enough. Water doubt humanity, animals and plants are the biggest source of life.
However, water has also unique technological properties. As with every aspect of
exploitation of natural water sources, not artificially benefits on the basis of the
water technologies and energy facilities.
Currently, even an example of town is not established to supply the entire needs
such as energy (as well as heat and electricity), water roads and water transporta-
tion. Such a water town also fish and other aquatic products will be well suited to
bringing up. A city like “water town” not necessarily is flat, because gradually to
the highest parts can be reached by rising water pools.
Even though the water molecule as a whole is electrically neutral, the distri-
bution of charge in the molecule is not symmetrical and has to a dipole moment.
This leads to a net attraction between such polar molecules which finds expression
in the cohesion of water molecules and contributes to viscosity and surface tension.
Even though the molecules don’t have permanent dipole moments, they can
have instantaneous dipole moments which change or oscillate with time. These
fluctuations of molecular dipole moments lead to a net attraction between molecules
which allow nonpolar substances like carbon tetrachloride to form liquids.
Cohesive and adhesive forces are associated with bulk (or macroscopic) prop-
erties and hence the terms are not applicable to discussion of atomic and molecular
properties. When a liquid comes into contact with a surface, both cohesive and
adhesive forces will act on it. These forces govern the shape which the liquid takes
on. Due to the effects of adhesive forces, liquid on a surface can spread out to form
a thin, relatively uniform film over the surface, a process known as wetting.
Alternatively, in the presence of strong cohesive forces, the liquid can divide into a
number of small, roughly spherical beads which stand on the surface, maintaining
minimal contact with the surface.
Cohesive forces are the intermolecular forces which cause a tendency in liquids
to resist separation. These attractive forces exist between molecules of the same
substance. For instance, rain falls in droplets, rather than a fine mist, because water
has strong cohesion which pulls its molecules tightly together, forming droplets.
Adhesive forces are the attractive forces between unlike molecules. They are
caused by forces acting between two substances, such as mechanical forces
(sticking together) and electrostatic forces (attraction due to opposing charges). In
4.4 Water Forces and Water Energy 131
the case of a liquid wetting agent, adhesion causes the liquid to cling to the surface
on which it rests. When water is poured on clean glass, it tends to spread, forming a
thin, uniform film over the glasses surface. This is because the adhesive forces
between water and glass are strong enough to pull the water molecules out of their
spherical formation and hold them against the surface of the glass, thus avoiding the
repulsion between like molecules.
This section has exhibited the advantage of electricity generation using water
lifting force and how it is effectively used. It is anticipated that the low cost,
environmentally friendly water lifting force for electricity generation will play an
important role in the electricity generation and contribute much to the coming
electricity generation economy. Hence there are a good many reasons that water
lifting force will be used future at many ranges for electricity generation.
An important factor concerning the generation of electricity from any source is
the efficiency of energy conversion. This is particularly important in the case of
capturing renewable energy from water lifting force. Because of the high cost of
installing the power conversion plant, the operator must be absolutely certain that
the commercial returns will be adequate. An electricity generating apparatus using
gravity and buoyancy can curtail costs of power generation and prevent environ-
mental pollution and prevent destruction of an ecosystem. In this way the com-
panies can reduce their costs. This method will gradually become competitive with
traditional methods. It has almost no environmental impact and only limited
maintenance is required.
Figure 4.3 shows a sea wave to electrical energy conversion plant. As seen in
Fig. 4.3 wave energy to electrical energy conversion apparatus is depicted
immersed in the sea. The apparatus comprises a float driven linear generator, the
stator of which comprises a fixed rod 1, which houses a sequence of permanent
1 5
8 6 4
9
2 3 7
Fig. 4.3 A sea wave to electrical energy conversion plant

magnets. The rod is embedded, at its lowest extremity, in a concrete block, 2. The
block itself is anchored to the sea bed-shown generally at 3-to avoid drifting. The
armature of the generator 4 comprises a cylindrical housing in which is embedded a
series of coils. Coaxially surrounding the armature, and affixed thereto, is an
annular flotation chamber 5. The float is made of a construction which is as light as
possible. This is in order to ensure that its weight is negligible in comparison with
that of the armature of the generator, and therefore that the wave energy present is
expended usefully on generating electrical power rather than accelerating any undue
mass of the float itself, and/or restricting the assembly from following the wave
motion. Located at the upper and lower surfaces of the armature are bearing blocks
6 and 7, for guiding the armature coaxially up and down the stator. Annular
paddles, 8, are also affixed to the flotation chamber. The paddles are contoured in
order to offer as much resistance as possible to vertical movements of the sea water.
The size and/or length of the armature of the linear generator, and thus its weight, is
so selected that its weight, combined with that of the float, is such as to counteract
by half the total up thrust afforded by the volume of water that would be displaced
by the float were the float to be submerged (Demirbas 2010a).
The action of the apparatus is as follows. As a wave arrives, the natural buoy-
ancy of the flotation chamber causes the whole assembly to rise. This is assisted by
the pressure of the rising water acting against the paddles 8. Thus relative motion
arises between the armature and stator of the linear generator and alternating current
is generated within the coils of the generator, the amplitude and frequency of which
depend upon the vigor of the wave motion. The current is conducted to a shore
station by a suitably armored and flexible cable, 9. Once the wave has reached its
zenith, and begins to fall, the weight of the assembly causes the same also to fall.
Power again is generated as the armature traverses the stator. Because the up thrust
experienced by the generator is substantially the same as the weight of the
assembly, electricity is generated reasonably consistently both upon the rise and fall
phases of the wave. There is some natural phase lag between the ascending of the
assembly relative to the waves, and its fall, due to the natural damping effect of the
electromotive force generated.
In a feature of the invention, in order to enhance the captivation of wave energy,
the flotation chambers are equipped with one or more paddles immersed in the sea,
the planar axes of the paddles being arranged to be substantially parallel to the sea
surface, the arrangement being such that the float and paddles act in combination to
force movement of the armature of the generator relative to its stator, the float by
means of its buoyancy, and the paddle, or paddles, by means of their resistance to
the motion of the seawater. Furthermore, the planar surfaces of the paddle against
which the rising and falling water presses, may be so contoured as to provide as
much resistance as possible to the motion of the water, and therefore to receive the
greatest counter thrust (Wipo 2005; Kelly 2001).
4.5 Gas Hydrates as a Potential Future Energy Resource 133
4.5 Gas Hydrates as a Potential Future Energy Resource
A potential source of natural gas (NG) lies in enormous worldwide gas-hydrate

reserves. It was estimated that the size of this resource range up to 20,000 trillion
m3 (Kvenvolden 1993). These deposits can cause problems and safety concerns
relating to drilling, production of oil and gas, and building and operation of pipe-
lines. Naturally occurring gas hydrates are normally found at the seafloor or in
shallow sediments where the pressures and temperatures are conducive to hydrate
formation (Demirbas 2010b).
Clathrates of natural gas or methane hydrates are crystalline solid hydrocarbon
compounds that form when methane and water coexist at sufficiently low tem-
peratures and high pressures (Sloan 2003). Gas hydrates, potentially one of the most
important energy resources for the future. The largest sources of these hydrocarbons
worldwide are distributed in the permafrost and submarine sediments, and methane
hydrate amounts are estimated to be 2.1 × 1016 m3, which is larger than all car-
boneous fuel reserves (Demirbas 2010c; Boswell and Collett 2011).
Natural gas hydrates are solid, non-stoichiometric compounds of small gas
molecules and water. They form when the constituents come into contact at low
temperature (5–15 °C) and high pressure (2–3 MPa). Methane gas hydrates are
increasingly considered a potential energy resource. Considerable knowledge has
been developed about their occurrence in nature and properties. However, the issues
of technology and economics of natural gas production from gas hydrates are less
well understood.
Gas hydrates are increasingly recognized as a potential future energy resource,
based on the vast amounts of methane trapped within them (Kvenvolden 1993a).
Natural gas hydrate is a vast energy resource with global distribution in permafrost
regions and in the oceans that it can be evaluated as a potential energy source (Feng
et al. 2015; Zhao et al. 2015; Song et al. 2015). Natural gas hydrates represent a
potentially substantial unconventional natural gas resource and the recovery of
permafrost hydrates has seen significant attention over the past decade (Fitzgerald
and Castaldi 2013).
Gas hydrates are of considerable interest for their potential as an energy resource
and for their potential role in global climate change. From an energy resource point
of view, the enormous amounts of gas hydrate under the ocean and beneath arctic
permafrost represent an estimated 53 % of all fossil fuel (coal, oil, natural gas)
reserves on earth, about 10,000 gigatons (Lee and Holder 2001). The worldwide
amounts of organic carbon bound in gas hydrates is conservatively estimated to
total twice the amount of carbon to be found in all known fossil fuels on Earth
(Satoh et al. 1996; Kvenvolden 1998; Collett 2002). Figure 4.4 shows a comparison
of global gas hydrate and fossil fuel resources.
Gas hydrates are crystalline solids that form from mixtures of water and light
natural gases such as methane, carbon dioxide, ethane, propane and butane.
Methane was the dominant component among other hydrocarbon gases in the
Fig. 4.4 Comparation of

global gas hydrate and fossil
fuel resources
sediments (Mazzini et al. 2004; Popescu et al. 2006). Gas hydrates are ice-like
crystalline solids formed from a mixtures of water and natural gas, usually methane.
Methane is formed from the microbiological decay of organic matter in the
absence of oxygen and can also be of thermogenic origin (Gupta 2004). The
methane in gas hydrates is dominantly generated by bacterial anaerobic degradation
of organic matter in low oxygen environments.
Gas hydrates occur in two discrete geological situations: (1) Marine shelf sed-
iments (Kvenvolden 1993b; Kvenvolden and Lorenson 2000); (2) On-shore polar
regions beneath permafrost. Hydrates occur in these two types of settings because
these are the settings where the pressure-temperature conditions are within the
hydrate stability field (Lerche and Bagirov 1998). Gas hydrates can be detected
seismically as well as using well logs (Goldberg and Saito 1998; Hornbach et al.
2003).
The most important characteristic of the sea water is the water temperature that
its effects are very high on the physical and chemical changes in the sea water
(Fitzgerald et al. 2014).
In general, sea water temperature decreases with increasing depth. In the Black
Sea sea water temperatures for the first 50 m are vary depending on the season.
Temperatures are less change in 50–200 m depth and the almost constant (7–9 °C)
in water deeper than 200 m (Stanev 1990; Stanev and Staneva 2001). The natural
gas hydrates (NGHs) are formed from gas and water molecules at low temperature
(5–15 °C) and high pressure (2–3 MPa). The Black Sea is a suitable environment
for formation the NGH. Especially in places where the methane gas hydrate such as
the Black Sea, the temperature of seawater rises above 15 °C the world will be
faced with a huge disaster. Because it is sitting on a ticking time-bomb: methane
gas.
The Black Sea is the world largest water body containing hydrogen sulfide; the
hydrogen sulfide layer begins about 200 m below the surface. The concentrations of
hydrogen sulfide range from 1.5 to 2.3 mL/L in the Black Sea at depths of 200–
1500 m (Eremeev et al. 1998). The Black Sea has suitable conditions (pressure and
temperature) for the formation of natural gas hydrates. On the other hand, the
anaerobic but hydrogen sulfide conditions of the Black Sea, starting at a depth of
200 m from sea level, make it more suitable for hydrate formation.
Methane seepage is extremely intense on the shelf and on the slope of the Black
Sea. Methane hydrates can form in the Black Sea at water depths exceeding 580–
700 m. One of the first reported observations of gas hydrates in marine sediments
was from the Black Sea (Yefremova and Zhizhchenko 1974). The area of the Black
Sea that is suitable for gas hydrate formation is evaluated at 288,100 km2, repre-
senting about 68 % of the total Black Sea or almost 91 % of the deep-water basin.
Methane has discharged into the Black Sea and the global ocean via fluid flow
through submarine mud volcanoes. The areas of active fluid venting and mud
volcanism were investigated in the Black Sea below the oxic zone at depths varying
between 800 and 2200 m. Figure 4.5 shows the average methane levels in the sea
water depth in the Black Sea (Demirbas 2010a).
Methane hydrates are solid, crystalline features that are composed of a combi-
nation of methane, water ice, and other gases. The methane and gases are trapped in
the lattice structure of the water ice, which, like coal beds, can hold much more
natural gas than normal rock features. These hydrate formations are usually found
on the ocean floor where there is high pressure and near freezing temperatures.
There are two gas hydrate reservoirs; Arctic hydrates and marine hydrates. The
Arctic hydrates have the potential to become economically viable sources of natural
gas. Subsurface occurrences of natural gas hydrate can be classified into six types.
Methane hydrate occurs in marine sediments in water depths greater than about
450 m on continental margins of open oceans. The hydrate economic zone is the
combined hydrate, gas, and subjacent sediment zone for which it is important to
characterize methane and the geotechnical properties that have a bearing on the gas
recovery.
16
Methane concentration, micromol/L
14
12
10
0
0 500 1000 1500 2000
Water depth, m
Fig. 4.5 Average methane levels in the sea water depth in the Black Sea
Gas from hydrate may be a new clean energy source. It is now recognized that
there are huge amounts of natural gas, mainly methane, tied up in gas hydrates
globally. Methane gas hydrates are a potential energy resource.
Changes in pressure and temperature will led to decomposition of solid gas
hydrates to gas and water. Continental slope instability caused by hydrate
decomposition is suggested as a trigger mechanism for underwater landslides and
tsunami generation. The formation and subsequent decomposition of gas hydrates
within the sediments affect the physical properties of the sediment as well. If the
methane gas hydrates should break down, this would cause a massive release of
methane into the atmosphere.
Methane can be obtained from natural gas hydrates. Gas hydrates, potentially
one of the most important energy resources for the future. Enormous reserves of
hydrates can be found under continental shelves and on land under permafrost. The
amount of organic carbon in gas hydrates is estimated to be twice that in all other
fossil fuels combined. However, due to solid form of the gas hydrates, conventional
gas and oil recovery techniques are not suitable. The recovery of methane generally
involve dissociating or melting in situ gas hydrates by heating the reservoir above
the temperature of hydrate formation, or decreasing the reservoir pressure below
hydrate equilibrium (Lee and Holder 2001).
If economically extracted from the ocean sediments, the over 160 m3 of methane
trapped each 1 m3 of hydrate constitute a large deposit of an alternate energy
source. The US Geological Survey estimates the resource potential in the United
States to be about 200,000 trillion cubic feet. For comparison, the current annual
consumption of NG is about 22 trillion cubic feet. Based on these estimates, at
about 1 % recovery, the deposit has the potential to fill the NG needs of the nation,
at the present rate of consumption, for the next 100 years. Additionally, direct fuel
combustion of methane not only provides high energy density per weight, but also
contributes as a byproduct minimum CO2 emission; nearly 30 times less than
gasoline and 60 times less than coal (Demirbas 2010d).
Gas hydrates, although the amount of methane to separate them, even though it
probably dramatic changes in the economy or supply model, to be a candidate in the
next few decades, natural gas is the least likely of unconventional sources.
Methane can be recovered from the gas hydrates by the depressurization, thermal
stimulation and chemical inhibitor injection methods. The methods that have been
proposed for natural gas extraction from hydrates include depressurization, thermal
stimulation, chemical inhibitor injections, and CO2 replacement (Makogon 2010).
Demirbas (2010d) proved that The method for reducing pressure (the depressur-
ization method) for gas obtaining from hydrate is more effective and economical
than the thermal stimulation method (Zhao et al. 2013).
The depressurization method involves lowering the pressure inside the well and
encouraging the methane hydrate to dissociate. Its objective is to lower the pressure
in the free-gas zone immediately beneath the hydrate stability zone, causing the
hydrate at the base of the hydrate stability zone to decompose. Natural gas pro-
duction from the dissociation of methane hydrate in a confined reservoir by a
depressurizing down-hole well was studied. The case that the well pressure was
kept constant was treated, and two different linearization schemes in an axisym-
metric configuration were used in the analysis. It was shown that the gas production
rate was a sensitive function of well pressure and reservoir temperature (Ahmadi
et al. 2007).
The thermal stimulation method is applied to the hydrate stability zone to raise
its temperature, causing the hydrate to decompose. In this method, a source of heat
is provided directly in the form of injected steam or hot water or another heated
liquid, or indirectly via electric or sonic means. This causes methane hydrate to
decompose and generates methane gas. The methane gas mixes with the hot water
and returns to the surface, where the gas and hot water are separated (Goel et al.
2001).
The chemical inhibition method seeks to displace the natural gas hydrate equi-
librium condition beyond the hydrate stability zone’s thermodynamic conditions
through injection of a liquid inhibitor chemical adjacent to the hydrate. In this
method, an inhibitor such as methanol is injected from the surface down to
methane-hydrate-bearing layers.
The thermal stimulation method is quite expensive. The chemical inhibitor
injection method is also expensive. The depressurization method may prove useful
for efficient production of methane. Less carbon dioxide is produced by combustion
of methane than by combustion of all other petroleum-derivate fuels, which makes
methane attractive for use as an engine fuel in terms of the greenhouse effect.
A very positive contribution of natural gas to minimization of environmental pol-
lution must also be considered (Davies 2001; Demirbas 2006a).
The thermal stimulation and chemical inhibitor injection methods are quite
expensive. The depressurization method is considered to be the most economically
promising method for the production of methane gas from gas hydrates. Of these
three production methods, the depressurization combined with the thermal stimu-
lation process appears to be the most practical for zones where free gas is trapped
beneath the methane hydrates.
Development, application, distribution strategy and research facilities related
technologies, safety and environmental challenges should be determined in con-
junction with gas hydrates as an unconventional resource.
In recent years, attentions have been attracted on gas production from gas
hydrate sediments; but this production, economic, safe, and still far away from
being commercially viable for many years; so more research are needed.
Gas hydrates are compounds similar to ice crystal formed as a result of being
trapped in the space between the water molecules of gas molecules. The oil and gas
industry fights to prevent formation of hydrates in pipeline by spending significant
amount of dollars. The hydrate formation is good at high pressure and low tem-
perature, determined by means of experiments (Ibrahim et al. 2016).
The world’s largest hydrocarbon resources in the form of methane hydrate are
dispersed in the sea, and undersea sediments, but this hydrocarbon from com-
mercial methane production is not economic and safety point of view is still far
more research is needed in this area.
Table 4.3 Main technical — Natural gas hydrate may play a role in climate change. Methane
and environmental challenges is a strong greenhouse gas, so its escape to the atmosphere from
of natural gas hydrates natural gas hydrate could result in global warming
— The environmental consequences of gas releasing at the seafloor
contributes to the greenhouse effect
— There are important production problems. Gas hydrate is a
hazard in conventional hydrocarbon exploration, from shallow gas
release and from seafloor instability, especially in the Arctic and in
deep water where hydrate is stable
— Their impact on the seafloor stability, as a potential cause for
submarine geo-hazards, and the fuel resource potential of the gas
hydrates, as they contain a great volume of methane
— Methane hydrates hold the danger of natural hazards associated
with seafloor stability and release of methane to the ocean and
atmosphere, and gas hydrates disturbed during drilling are a safety
problem
— Lack of service facilities, lack of information, and lack of
advanced technology, skills, and poor market acceptance facilities
Another very important challenge addressed is the indefinite availability of

unsustainable gas hydrate resources for production of methane and certain rec-
ommendations are given. It was found that the disadvantages of gas hydrate
application prevail significantly over the advantages; however, the major economic
and environmental benefits appear to compensate the technological and other
barriers caused by the unfavorable sources and safety of gas hydrate.
Main technical and environmental challenges of natural gas hydrates are given in
Table 4.3.
4.6 Biofuels from High Quality Microalgae
Algae are aquatic plants. Algae range from small, single-celled organisms to
multi-cellular organisms. Algae are usually found in damp places or bodies of water
and thus are common in terrestrial as well as aquatic environments. Like plants,
algae require primarily three components to grow: sunlight, water and carbon
dioxide. Photosynthesis is an important biochemical process in which plants, algae,
and some bacteria convert the energy of sunlight to chemical energy. Algae are
simple organisms that are mainly aquatic and microscopic. Photosynthetic
micro-organisms living in saline or freshwater environments convert sunlight water
and carbon dioxide to algal biomass (Chisti 2007; Yen et al. 2013; Talebi et al.
2014; Quinn et al. 2014).
Algae are categorized into four main classes: diatoms, green algae blue-green
algae and golden algae. There are two main populations of algae: filamentous and
phytoplankton algae.
Many species exhibit rapid growth and high productivity, and many microalgal
species can be induced to accumulate substantial quantities of lipids, often greater
4.6 Biofuels from High Quality Microalgae 139
than 60 % of their dry biomass (Sheehan et al. 1998a, b). Microalgae are very
efficient solar energy converters and they can produce a great variety of metabolites
(Chisti 2007).
Microalgae are found in both marine and freshwater environments. Microalgae are
unique photosynthetic organisms given that they accumulate storage lipids in sub-
stantial quantities and thrive in high salinity water. Biologists have categorized
microalgae in a variety of classes, mainly distinguished by their pigmentation, life cycle
and basic cellular structure. The three most important classes of microalgae in terms of
abundance are the diatoms (Bacillariophyceae), the green algae (Chlorophyceae), and
the golden algae (Chrysophyceae). The cyanobacteria (blue-green algae)
(Cyanophyceae) are also referred to as microalgae. This applies for example to Spirulina
(Arthrospira platensis and A. maxima). Diatoms are the dominant life form in phyto-
plankton and probably represent the largest group of biomass producers on earth. It is
estimated that more than 100,000 species exist (Talebi et al. 2014; Quinn et al. 2014).
Microalgae are primitive organisms with a simple cellular structure and a large
surface to volume body ratio, which gives them the ability to uptake large amount
of nutrients (Sheehan et al. 1998a, b). The photosynthetic mechanism of microalgae
is similar to land-based plants, but due to a simple cellular structure, and submerged
in an aqueous environment where they have efficient access to water, CO2 and other
nutrients, they are generally more efficient in converting solar energy into biomass
(Carlsson et al. 2007; Chisti 2007). The growth medium must contribute the
inorganic elements that help make up the algal cell, such as nitrogen, phosphorus,
iron, and sometimes silicon (Grobbelaar 2004). Microalgae can be used for
bioenergy generation (biodiesel, biomethane, biohydrogen), or combined applica-
tions for biofuels production and CO2 mitigation (Demirbas 2007; Aburas and
Demirbas 2015; Zhang et al. 2013).
Carbon dioxide can occur in four reaction steps:
C þ O2 ! CO2 ð4:1Þ
2C þ O2 ! 2CO ð4:2Þ
3C þ O2 ! C3 O2 ð4:3Þ
5C þ O2 ! C5 O2 ð4:4Þ
Stages of carbon suboxide (Eq. 4.3) and penta carbon dioxide (Eq. 4.4) are very
faster than those of other stages. Rapid microalgae photosynthesis mechanism may
be due to these steps.
Microalgae cultivation using sunlight energy can be carried out in open or
covered ponds or closed photobioreactors, based on tubular, flat plate or other
designs. Closed systems are much more expensive than ponds, and present sig-
nificant operating challenges (overheating, fouling), and due to gas exchange
limitations, among others, cannot be scaled-up much beyond about a hundred
square meters for an individual growth unit.
The concept of using microalgae as a source of fuel is older than most people
realize. The idea of producing methane gas from algae was proposed in the early
1950s. Industrial reactors for algal culture are at present. There are:
(1) Photobioreactors and (2) Open ponds.
Algal cultures consist of a single or several specific strains optimized for pro-
ducing the desired product. Water, necessary nutrients and CO2 are provided in a
controlled way, while oxygen has to be removed (Carlsson et al. 2007). Algae
receive sunlight either directly through the transparent container walls or via light
fibers or tubes that channel it from sunlight collectors.
Conventional processes used to harvest micro-algae include concentration
through centrifugation, foam fractionation, flocculation, membrane filtration and
ultrasonic separation. Harvesting costs may contribute 20–30 % to the total cost of
algal biomass. The micro-algae are typically small with a diameter of 3–30 μm, and
the culture broths may be quite dilute at less than 0.5 g l-1. Thus, large volumes
must be handled. The harvesting method depends on the species, on the cell den-
sity, and often also on the culture conditions (Carlsson et al. 2007).
Microalgae can be harvested by centrifugation, flocculation or froth flotation.
Alum and ferric chloride are chemical flocculants used to harvest algae. Water that
is brackish or salty requires additional chemical flocculants to induce flocculation.
Harvesting by chemical is a method that is often too expensive for large operations.
However, interrupting the carbon dioxide supply to an algal system can cause algae
to flocculate on its own, which is called “auto-flocculation”.
Photobioreactors have the ability to produce algae while performing beneficial
tasks, such as scrubbing power plant flue gases or removing nutrients from
wastewater. Photobioreactors are different types of tanks or closed systems in which
algae are cultivated.
Most of algal species are obligate phototrophs and thus require light for their
growth. The phototropic microalgae are most commonly grown in open ponds and
photobioreactors. The open pond cultures are economically more favorable, but
raise the issues of land use cost, water availability, and appropriate climatic con-
ditions. Photobioreactors offer a closed culture environment, which is protected
from direct fallout, relatively safe from invading microorganisms. This technology
is relatively expensive compared to the open ponds because of the infrastructure
costs.
Open ponds are the oldest and simplest systems for mass cultivation of
microalgae. The pond is designed in a raceway configuration, in which a paddle-
wheel circulates and mixes the algal cells and nutrients. The raceways are typically
made from poured concrete, or they are simply dug into the earth and lined with a
plastic liner to prevent the ground from soaking up the liquid. Baffles in the channel
guide the flow around the bends in order to minimize space.
Open pond systems are shallow ponds in which algae are cultivated. Nutrients
can be provided through runoff water from nearby land areas or by channeling the
water from sewage/water treatment plants (Carlsson et al. 2007). The water is
typically kept in motion by paddle wheels or rotating structures, and some mixing
can be accomplished by appropriately designed guides. Algal cultures can be
defined (one or more selected strains), or are made up of an undefined mixture of

strains.
The an open pond system or algae farm was given in Fig. 2.7. The ponds are
“raceway” designs, in which the algae, water and nutrients circulate around a
racetrack. Paddlewheels provide the flow. The algae are thus kept suspended in
water. Algae are circulated back up to the surface on a regular frequency. The ponds
are kept shallow because of the need to keep the algae exposed to sunlight and the
limited depth to which sunlight can penetrate the pond water. The ponds are
operated continuously; that is, water and nutrients are constantly fed to the pond,
while algae-containing water is removed at the other end.
The “algae farms” are large ponds. The size of these ponds is measured in terms
of surface area, since surface area is so critical to capturing sunlight. Their pro-
ductivity is measured in terms of biomass produced per day per unit of available
surface area. Even at levels of productivity that would stretch the limits of an
aggressive research and development program, such systems will require acres of
land. At such large sizes, it is more appropriate to think of these operations on the
scale of a farm. Such algae farms would be based on the use of open, shallow ponds
in which some source of waste CO2 could be efficiently bubbled into the ponds and
captured by the algae. Careful control of pH and other physical conditions for
introducing CO2 into the ponds allowed greater than 90 % utilization of injected
CO2. Raceway ponds, usually lined with plastic or cement, are about 15–35 cm
deep to ensure adequate exposure to sunlight. They are typically mixed with
paddlewheels, are usually lined with plastic or cement, and are between 0.2 and
0.5 ha in size. Paddlewheels provide motive force and keep the algae suspended in
the water. The ponds are supplied with water and nutrients, and mature algae are
continuously removed at one end.
Open pond systems are shallow ponds in which algae are cultivated. Nutrients
can be provided through runoff water from nearby land areas or by channeling the
water from sewage/water treatment plants. The water is typically kept in motion by
paddle wheels or rotating structures, and some mixing can be accomplished by
appropriately designed guides.
Photosynthesis is the most important biochemical process in which plants, algae,
and some bacteria harness the energy of sunlight to produce food. Organisms that
produce energy through photosynthesis are called photoautotrophs. Photosynthesis
is a process in which green plants utilize the energy of sunlight to manufacture
carbohydrates from carbon dioxide and water in the presence of chlorophyll.
Power-plant flue gas can serve as a source of carbon dioxide (CO2) for
microalgae cultivation. There are potentially significant benefits to recycling CO2
toward microalgae production. The algal mass produced from power plant CO2 is a
useful product with application in food, fuels, etc. The production of lipids from
microalgae is a possibility because plant storage lipids could be among the best
biomass feedstocks for producing renewable, high-energy liquid fuels such as diesel
fuel (biodiesel) (Pimentel et al. 2015; Balat 2009).
Fertilizer production results in relatively high Chemical oxygen demand
(COD) values and phosphate emissions. Nitrogen and phosphorus are the principal
nutrients of concern in waste-water discharges. The floating plants shield the water
from sunlight and reduce the growth of algae. Systems of this kind have been
effective in reducing BOD, nitrogen, metals and trace organics and in removing
algae from lagoons and stabilization pond effluents.
Many species of algae thrive in seawater, water from saline aquifers, or even
wastewater from treatment plants. Environmental impacts of irrigation are the
changes in quantity and quality of soil and water as a result of the irrigation and the
ensuing effects on natural and social conditions at the tail-end and downstream of
the irrigation scheme. Irrigated agriculture depends on supplies from surface or
ground water. Irrigation agriculture will be an essential component of any strategy
to increase the global food supply. The environmental impact of irrigation systems
depends on the nature of the water source, the quality of the water, and how water is
delivered to the irrigated land (Chisti 2007; Phalan 2009; Demirbas 2009a, 2011a).
Photosynthesis, algae use solar energy to fix CO2 into algal biomass, so the
water used to cultivate algae must be enriched with CO2. This requirement offers an
opportunity to make productive use of the CO2 from power plants into algal bio-
mass, so the water used to cultivate algae must be enriched with CO2 (Demirbas
2011b). CO2 cost plays a central role in process economics. Water resources and
land use are the most important needs affecting the cost. Algae cultivation is flexible
on water quality (Demirbas and Demirbas 2011). Table 4.4 shows typical
wastewater quality for algae cultivation.
Producing microalgal biomass is generally more expensive than growing crops.
Photosynthetic growth requires light, carbon dioxide, water and inorganic salts.
Temperature must remain generally within 20–30 °C. To minimize expense, bio-
diesel production must rely on freely available sunlight, despite daily and seasonal
variations in light levels (Pulz 2007; Gharat and Rathod 2013; Makareviciene et al.
2014; Tuccar et al. 2015).
Algae cultivation has four basic, and equally important, requirements: carbon,
water, light, and space. In order to maximize algal growth, CO2 needs to be pro-
vided at very high levels, much higher than can be attained under natural condi-
tions. Rather than becoming an expense, this need for CO2 fertilization creates a
unique opportunity to offset costs by consuming air pollution. The flue gases from
Table 4.4 Typical Constituent Constituent concentration

wastewater quality for algae
BOD (Biochemical oxygen demand) >20 mg/L
cultivation
TSS (Total suspended solids) >20 mg/L
TOC (Total organic carbon) >30 mg/L
Total phosphorus >10 mg/L
Ammonia >40 mg/L
Total nitrogen >45 mg/L
Turbidity >15 NTU
TDS (Total dissolved solids) >1500 mg/L
Water pH 7.6–8.8
industrial processes, and in particular from power plants, are rich in CO2 that would
normally be released directly into the atmosphere and thereby contribute to global
warming (Molina Grima et al. 1999). Although most of the CO2 will ultimately be
deposited in the atmosphere, we can realize a greater energy return for each
molecule of carbon.
Prior economic-engineering feasibility analyses have conclude that even the
simplest open pond systems, including harvesting and algal biomass processing
equipment, would cost at least $100,000 per hectare, and possibly significantly
more. To this would need to be added operating costs. And algae production
requires a site with favorable climate, available water, a ready and essentially free
source of CO2, nearly flat land, and with a clay soil or liner, as plastic liners would
be too expensive.
Nutrients such as phosphorus must be supplied in significant excess because the
phosphates added complex with metal ions, therefore, not all the added P is
bio-available. Sea water supplemented with commercial nitrate and phosphate
fertilizers and a few other micronutrients is commonly used for growing marine
microalgae (Roessler et al. 1994). Genetic and metabolic engineering are likely to
have the greatest impact on improving the economics of production of microalgal
diesel (Dunahay et al. 1967; Beckher 1994).
While the percentages vary with the type of algae, there are algae types that are
comprised up to 40 % of their overall mass by fatty acids (Demirbas 2010c). The
most significant distinguishing characteristic of algal oil is its yield and hence its
biodiesel yield. According to some estimates, the yield (per acre) of oil from algae
is over 200 times the yield from the best-performing plant/vegetable oils (Sheehan
et al. 1998a, b). The production of algae to harvest oil for biodiesel has not been
undertaken on a commercial scale, but working feasibility studies have been con-
ducted to arrive at the above number (Demirbas 2009b, 2010e, 2011b).
Specially bred mustard varieties can produce reasonably high oil yields and have
the added benefit that the meal left over after the oil has been pressed out can act as
an effective and biodegradable pesticide (Chaumont 2005).
Microalgae are very efficient solar energy converters and they can produce a
great variety of metabolites (Yan and Lin 2009). The culture of algae can yield 30–
50 % oil. Oil supply is based on the theoretical claims that 47,000–
308,000 L/hectare/year of oil could be produced using algae. The calculated cost
per barrel would be only $20. Currently, a barrel of oil in the US market is selling
for over $100 per barrel. Despite all the claims and research dating from the early
1970’s to date, none of the projected algae and oil yields has been achieved
(Goldman and Ryther 1977; Chaumont 2005). Algae, like all plants, require large
quantities of nitrogen fertilizer and water, plus significant fossil energy inputs for
the functioning system (Pimentel et al. 2015).
Harvesting the algae from tanks and separating the oil from the algae are difficult
and energy intensive processes. One difficulty in culturing algae is that the algae
shade one another and thus there are different levels of light saturation in the
cultures, even under Florida conditions. This influences the rate of growth of the
algae. In addition, wild strains of algae invade and dominate the algae culture
strains and oil production by the algae is reduced (Pimentel 2008). Because algae
are mostly water, harvesting the algae from the cultural tanks and separating the oil
from the algae, is a difficult and energy intensive process. This problem was
observed at the University of Florida when algae were being cultured in managed
ponds for the production of nutrients for hogs. After two years with a lack of
success, the algal-nutrient culture was abandoned (Huang et al. 2010).
Producing biodiesel from algae has been touted as the most efficient way to
make biodiesel fuel. Algal-oil processes into biodiesel as easily as oil derived from
land-based crops. The difficulties in efficient biodiesel production from algae lie not
in the extraction of the oil, but in finding an algal strain with a high lipid content
and fast growth rate that isn’t too difficult to harvest, and a cost-effective cultivation
system (i.e. type of photobioreactor) that is best suited to that strain.
Algae are very important as a biomass source. Different species of algae may be
better suited for different types of fuel. Algae can be grown almost anywhere, even
on sewage or salt water, and does not require fertile land or food crops, and
processing requires less energy than the algae provides. Algae can be a replacement
for oil based fuels, one that is more effective. Algae consume carbon dioxide as they
grow, so they could be used to capture CO2 from power stations and other industrial
plant that would otherwise go into the atmosphere. The oil contents of some
microalgae are given in Table 4.5 (Chisti 2007).
Open ponds can be categorized into natural waters (lakes, lagoons, ponds) and
artificial ponds or containers. The most commonly used systems include shallow
big ponds, tanks, circular ponds and raceway ponds. Major capital and operating
costs for an open pond system are tabulated in Table 4.6 (Benemann et al. 1982;
Sheehan et al. 1998a, b). The polymers can be used in very small amounts, without
contributing a major cost to the overall process. The base case (30 g/m2/d) capital
costs were estimated at almost $72,000/ha, without working capital, or almost twice
Table 4.5 Oil contents of Microalga Oil content (wt% of dry basis)
some microalgae
Botryococcus braunii 25–75
Chlorella sp. 28–32
Crypthecodinium cohnii 20
Cylindrotheca sp. 16–37
Dunaliella primolecta 23
Isochrysis sp. 25–33
Monallanthus salina >20
Nannochloris sp. 20–35
Nannochloropsis sp. 31–68
Neochloris oleoabundans 35–54
Nitzschia sp. 45–47
Palmaria palmata 34–49
Phaeodactylum 20–30
tricornutum
Schizochytrium sp. 50–77
Tetraselmis sueica 15–23
Table 4.6 Capital and operating costs for an open pond system
Costs ($/ha) 112 metric ton/hectar/year 224 metric ton/hectar/year
Total capital costs ($/ha) 72,952 89,965
Total operating costs ($/ha) 30,658 41,601
Basi costs ($/ha) 8375 11,286
as high as the prior effort (Benemann 2008). This was due to higher costs for many
components, such as earthworks, which were several-fold higher. Among other
things, higher costs were assumed for rough and fine (laser) grading, which depends
on the type of site assumed to be available. Also the 1987 study estimated about
$5000/ha to provide a 3–5 cm crushed rock layer, specified to reduce the suspen-
sion of silt from the pond bottom. There is, however, little evidence for a need for
such erosion prevention, except perhaps for some areas around the paddle wheel
and perhaps the turns (Benemann et al. 1982).
The operating costs were discussed in terms of mixing, carbon utilization,
nutrient, flocculants, salt disposal, maintenance, labor and the accumulation of
photosynthetically produced oxygen (Sheehan et al. 1998a; Yen et al. 2013).
Table 4.7 shows comparative economics of open ponds and closed photobioreac-
tors (PBRs).
Microalgal cultivation consumes less water than land crops. The tolerance of
microalgae to high CO2 content in gas streams allows high-efficiency CO2 miti-
gation. Microalgal farming could be potentially more cost effective than conven-
tional farming. Nitrous oxide release could be minimized when microalgae are used
for biofuel production.
Microalgae are an economical choice for biodiesel production, because of its
availability and low cost. Many researchers reported that microalgae might better
for higher biodiesl production. Biodiesel is biodegradable, less CO2 and NOx
emissions. Renewable, carbon neutral, transport fuels are necessary for environ-
mental and economic sustainability.
Main advantages and disadvantages of biodiesel from algae are given in
Table 4.8.
Table 4.7 Comparative Parameter Relative advantage

economics of open ponds and
closed photobioreactors Capital/operating costs Open ponds ≪ PBRs
(PBRs) Biomass concentration Open ponds < PBRs
Oxygen inhibition Open ponds > PBRs
Contamination risk Open ponds < PBRs
Water losses Open ponds * PBRs
Carbon dioxide losses Open ponds * PBRs
Process control Open ponds * PBRs
Space required Open ponds * PBRs
Table 4.8 Advantages and disadvantages of biodiesel from algae oil

Rapid growth rates and grows practically Produces unstable biodiesel with many
anywhere polyunsaturates
A high per-acre yield Biodiesel performs poorly
No need to use crops such as palms to High production costs
produce oil Relatively new technology
A certain species of algae can be harvested Limited practical experience in oil and biodiesel
daily production
Algae biodiesel contains no sulfur and Insufficient knowledge on the ecosystem in
toxic growing areas
Algae biodiesel is highly bio-degradable Unclear utilization of waste products
Algae biodiesel is suitable for cold Poor market acceptance
weather climates
It can reduce carbon emissions
4.7 Thermochemical Conversion Processes of Biomass

to Hydrogen-Rich Gas Mixtures
Energy conversion systems are concerned with the transformation of energy from
sources such as fossil and nuclear fuels and the sun into conveniently used forms
such as electrical energy, rotational and propulsive energy, and heating and cooling.
Energy may be transformed so that it may be used by other natural processes or
machines, or else to provide some service to society. For example, an internal
combustion engine converts the potential chemical energy in gasoline and oxygen
into the propulsive energy that moves a vehicle. A solar cell converts solar radiation
into electrical energy that can then be used to light a bulb or power a computer.
For instance a coal-fired power plant involves these power transfers:
1. Potential energy in the coal converted to thermal energy or heat
2. Thermal energy converted to kinetic energy in steam
3. Steam energy converted to mechanical energy in the turbine
4. Mechanical energy of the turbine converted to electrical energy, which is the
ultimate output.
Solar and geothermal energy can be used directly for heating. Other energy
sources are not directly usable; hence some kind of conversion process must be
employed to change the energy to a different form, that is, to one of direct utility.
These highly important energy conversion processes produce thermal energy and
generate power (Sorensen 1983). There are various energy conversion systems.
In the industrial applications, reciprocating machines are generally used for
energy conversion processes. The reciprocating machines are improved energy
converters or transformers. Reciprocating machines may be classified as (1) vapor
(steam) and gas expanders, (2) compressors (gases) and pumps (liquids), (3) inter-
nal combustion engines, and (4) external combustion engines. All of these machines
4.7 Thermochemical Conversion Processes of Biomass … 147
Fig. 4.6 Four main types of Steam turbine

energy conversion systems:
Steam Motion
Vapor (steam) expander,
compressor, internal Waste heat
combustion engine and
external combustion engine
Compressor
Gases Motion
Waste heat
Internal combustion engine
Chemical fuel
Motion
Waste heat
External combustion engine

Heat Motion
Waste heat
affect some kind of energy conversion. Figure 4.6 shows four main types of energy
conversion systems.
Biomass represents a large potential feedstock resource for environmentally
clean hydrogen production. In the thermal conversion processes hydrogen can be
produced in two ways: direct gasification and pyrolysis to produce liquid bio-oil,
followed by steam reforming. Hydrogen typically makes up about 6 % by weight of
dry biomass. To obtain hydrogen from biomass, pyrolysis or gasification can be
applied, which typically produces a gas containing 20 % hydrogen by volume,
which can be further steam-reformed to make higher-purity streams for various fuel
cells (Guo et al. 2007). Figure 4.7 shows the main hydrogen production routes from
biomass. Comparison with other biomass thermochemical processes such as
Biomass conversion to hydrogen
Thermochemical Biological
Pyrolysis Gasification
Biophotolysis Dark fermentation Photofermentation
Fig. 4.7 Main hydrogen production routes from biomass

pyrolysis, gasification, air gasification or steam gasification, the supercritical water

gasification can directly deal with the wet biomass without drying, and have high
gasification efficiency in lower temperature (Demirbas 2004a).
In recent years, pyrolysis of various biomass species was studied by many
researchers (Czernik et al. 2000; Demirbas 2002a) for obtaining hydrogen-rich gases.
Pyrolytic decomposition of biomass is generally observed to follow the reaction:
Pyrolysis of biomass ! H2 þ CO þ CO2 þ Hydrocarbon gases þ Tar þ Char

ð4:5Þ
The application of thermal analysis techniques does not provide accurate iden-
tification and definition of the individual reaction. Since the pyrolysis step consists
of many concurrent and consecutive reactions, it is virtually impossible to identify
all the elementary chemical reactions, which occur when the biomass thermally
decomposed. It is believed that as the reaction progresses, the carbonaceous
material becomes less reactive and forms stable chemical structures, and, conse-
quently, the activation energy increases as the conversion level of biomass
increases. The pyrolysis behavior of the biomass is also strongly relevant to its
chemical composition.
Partial oxidation refers to the conversion of heavy hydrocarbon feedstocks (e.g.,
residual oil from the treatment of crude oil) into a mixture of H2, CO, and CO2
using superheated steam and oxygen. Partial oxidation of hydrocarbons is the
exothermic reaction with oxygen and steam. The amounts of oxygen and water
vapor are controlled so that the reaction proceeds without the need for external
energy. An example reaction for this process is:
2C8 H18 þ 2H2 O þ 9O2 ! 12CO þ 4CO2 þ 20H2 ð4:6Þ
The carbon dioxide from the gas mixture is removed by washing with water and
the carbon monoxide is removed by absorption or membrane separation.
During the pyrolysis processes, cellulose decomposes between 450 and 650 K
(Maschio et al. 1992). Lignin decomposition begins at about 550 K with a maxi-
mum rate occurring between 625 and 725 K and the completion of the reaction
occurs at 725 and 775 K (Sandermann and Augustin 1963). Increases of the yields
of hydrogen may be also resulted from the lignin decomposition of the biomass
samples at higher temperatures. However, it is difficult to make such a discussion
basing only on the structural components. The ash forming mineral matter com-
ponents and their contents in the biomass samples also catalytically affects the yield
of pyrolysis products (Yaman 2004).
The conventional pyrolysis of biomass is associated with the product of interest
that is the high charcoal continent, but the fast pyrolysis is associated with the
products of interest are tar, at low temperature (675–775 K) (Bridgwater 2003),
and/or gas, at high temperature (Encinar et al. 1998). Fast pyrolysis at high tem-
perature is the process in which the gas is the principle product of interest, including
tar. Few publications on the gas product from sugarcane pyrolysis at high
temperature were publicized (Zanzi et al. 1995). The pyrolysis gas can be used as
source energy in many applications like fuel cell plant.
In the previously study, different agricultural biomass samples (cotton cocoon
shells, tea factory waste and olive husk) were subjected to pyrolysis in order to obtain
hydrogen rich gaseous products at 775, 925, 975 and 1025 K final temperatures.
Hydrogen gas can be produced from the waste material by direct- and catalytic
pyrolysis, while final temperature was generally increased from 775 to 1025 K. The
powdered K2CO3 and Na2CO3 catalyst (1–3 wt% of moisture-free biomass) used in
the catalytic pyrolysis experiments were mixed the biomass in the reactor. In
general, the catalytic effect of Na2CO3 was greater than that of K2CO3 for the cotton
cocoon shell, especially for low temperature pyrolysis runs (Demirbas 2001).
Biomass gasification in supercritical water is a promising technology for
hydrogen production by utilizing wet biomass (Lu et al. 2007). The catalyst shows
destructive effect on the organic compounds and H2 and CO2 form end of catalytic
steam reforming process. The main advantage of gasification in supercritical water
is the high solid conversion, i.e. low levels of char and tars. For wet biomass
containing large amounts of water up to 90 %, supercritical water gasification
(SCWG) appears as a useful technology. Hydrogen production from biomass
gasification in supercritical water is a new technology, which was developed in last
two decades. Biomass energy of low quality can be converted to hydrogen energy
of high quality by the SCWG (Guo et al. 2007).
Products from biomass by supercritical water (SCW) depend on the nature and
structure of the biomass. The effects of SCW on the biomass constituents should be
separately studied. For example SCW can affects on unsaturated compounds, and
unsaturated fatty and resin acids than those of saturated ones under different
reaction conditions (Watanabe et al. 2006). Diffusion or mass transfer rate of SCW
into the individual component of biomass could be studied separately (Antal et al.
2000; Feng et al. 2004).
C6 H10 O5 þ 7H2 O ! 6CO2 þ 12H2 ð4:7Þ
In this idealized, stoichiometric equation, cellulose (represented as C6H10O5)

reacts with water to produce H2 and CO2, the commercial production of H2 from
methane by catalytic steam reforming process (Xu and Froment 1989; Wagner and
Froment 1992; Matsumura et al. 2005).
Steam reforming of methane (or natural gas), is one of the most developed and
commercially used technologies. Steam reforming of natural gas involves two steps.
The first step is for the feedstock consisting of light hydrocarbons, usually methane,
to react with steam at elevated temperatures (975–1250 K) to produce synthesis gas
or shortly syngas—a mixture of hydrogen and carbon monoxide (H2 + CO).
C þ H2 O þ 175:3 kJ=mole ! CO þ H2 ð4:8Þ
The process is endothermic, and heat of reaction is supplied by the combustion

of fossil fuels. This process requires a catalyst inside the reformer for the reactions
to occur. The second step reacts CO with steam to produce additional H2 and CO2
at around 625 K.
CO þ H2 O þ 2:9 kJ=mole ! CO2 þ H2 ð4:9Þ
This reaction is known as a water–gas shift reaction or a shift reaction and is

used to increase the H2 content. This also is an endothermic reaction. Total
endothermicity of the gasification reaction and the shift reaction is 178.2 kJ/mole.
Finally, a mixture of CO2 and H2 is sent to a gas purifier, where the hydrogen is
separated from CO2 via one of many methods (wet scrubbing, pressure swing
absorption, or membrane separation).
Recently, the supercritical fluid treatment has been considered to be an attractive
alternative in science and technology as chemical reaction field. The molecules in
the supercritical fluid have high kinetic energy like the gas and high density like the
liquid. Therefore, it is expected that the chemical reactivity can be high in it. In
addition, ionic product and dielectric constant of supercritical water are important
parameters for chemical reaction. Therefore, the supercritical water can be realized
from the ionic reaction field to the radical reaction field. For example, ionic product
of the supercritical water can be increased by increasing pressure then the
hydrolysis reaction field is realized. Therefore, the supercritical water is expected as
a solvent for converting biomass into the valuable substances (Hao et al. 2003).
Especially, the temperature in which the gasification reaction can take place
depends on the category and the structure of the biomass greatly. Many reactions in
supercritical water gasification have begun when the temperature and the pressure
exceeds the critical point of water. In supercritical water gasification, the reaction
generally takes place at the temperature over 875 K and a pressure higher than the
critical point of water. With temperature higher than 875 K, water becomes a strong
oxidant, and oxygen in water can be transferred to the carbon atoms of the biomass.
CO is the primary product in SCWG and it reacts with steam to produce additional
H2 and CO2 by water-gas shift reaction. The hydrogen atoms of water and of the
biomass are set free and form H2. The gas product consists of hydrogen, CO2, CH4
and CO (Antal 1978).
A problem of general nature in SCGW is the required heat exchange between the
reactor outlet and inlet streams. To achieve an acceptable thermal efficiency, it is
crucial for the process that the heat of the inlet stream is utilized as far as possible to
pre-heat the feedstock stream (mainly water) to reaction conditions. At the same time,
heating of the biomass slurry in the inlet tube of a reactor is likely to cause
fouling/plugging problems because the thermal decomposition (>523 K) starts already
far below the desired reaction temperature (>873 K) (Kruse et al. 2000). Schematic
diagram of experimental apparatus of supercritical water gasification is depicted in
Fig. 4.4. Supercritical water is a promising reforming media for the direct production
of hydrogen at 875–1075 K temperature with a short reaction time (2–6 s). In addition
to being a high mass transfer effect, supercritical water also participates in reforming
reaction. The molecules in the supercritical fluid have high kinetic energy like the gas
and high density like the liquid. Therefore, it is expected that the chemical reactivity
can be high in it. In addition, ionic product and dielectric constant of supercritical
water, which are important parameters for chemical reactions, can be continuously
controlled by regulating pressure and temperature. Pressure has a negligible effect on
hydrogen yield above the critical pressure of water (Gadhe and Gupta 2007). As the
temperature is increased from 875 to 1075 K the H2 yield increases from 53 to 73 %
by volume, respectively. Only a small amount of hydrogen is formed at low tem-
peratures, indicating that direct reformation reaction of ethanol as a model compound
in SCW is favored at high temperatures (>975 K). With an increase in the temperature,
the hydrogen and carbon dioxide yields increase, while the methane yield decreases.
The water excess leads to a preference for the formation of hydrogen and carbon
dioxide instead of carbon monoxide. The formed intermediate carbon monoxide reacts
with water to hydrogen and carbon dioxide. The low carbon monoxide yield indicates
that the water-gas shift reaction approaches completion (Byrd et al. 2007).
Thermochemical gasification of biomass has been identified as a possible system
to produce renewable hydrogen with less dependence on exhaustible fossil energy
resources. Compared with other biomass thermochemical gasifications, such as air
gasification or steam gasification, the SCWG has high gasification efficiency at lower
temperature and can deal directly with wet biomass without drying (Yan et al. 2006).
The capillaries (1 mm ID and 150 mm length tubular reactors) are heated rapidly
(within 5 s) in a fluidized sand bed to the desired reaction temperature.
Experimentation with the batch capillary method has revealed that, especially at
low temperatures and high feed concentrations, char formation occurs. A fluidized
bed reactor might be a good alternative to solve the problems related to this char
and ash formation (Kruse et al. 2000).
To study the effect of the Ru/Al2O3 catalyst on hydrogen yield for reforming of
glucose in supercritical water, the experiments were compared to with and without
catalytic runs under identical conditions.. There was a significant reduction in
carbon monoxide and methane yields in the presence of the catalyst. The main
products of the reaction were hydrogen, methane, carbon dioxide, and carbon
monoxide. The low carbon monoxide yield (0.1 % by vol) indicates that the
water-gas shift reaction approaches completion.
Cellulose and sawdust were gasified in supercritical water to produce
hydrogen-rich gas, and Ru/C, Pd/C, CeO2 particles, nano-CeO2 and nano-(CeZr)
xO2 were selected as catalysts. The experimental results showed that the catalytic
activities were Ru/C > Pd/C > nano-(CeZr)xO2 > nano-CeO2 > CeO2 particle in
turn. The 10 wt% cellulose or sawdust with CMC can be gasified near completely
with Ru/C catalyst to produce 2–4 g hydrogen yield and 11–15 g potential
hydrogen yield per 100 g feedstock at the condition of 773 K, 27 MPa, 20 min
residence time in supercritical water (Hao et al. 2005).
Catalysts for low-temperature gasification include combinations of stable metals,
such as ruthenium or nickel bimetallics and stable supports, such as certain titania,
zirconia, or carbon. Without catalyst the gasification is limited (Kruse et al. 2000).
Sodium carbonate is effective in increasing the gasification efficiency of cellulose
(Minowa et al. 1997). Likewise, homogeneous, alkali catalysts have been employed
for high-temperature supercritical water gasification.
The reforming in supercritical water (SCW) offers several advantages over the
conventional technologies because of the unusual properties of supercritical water.
The density of supercritical water is higher than that of steam which results in a high
space-time yield. The higher thermal conductivity and specific heat of supercritical
water is beneficial for carrying out the endothermic reforming reactions (Gadhe and
Gupta 2007). In the supercritical region, the dielectric constant of water is much
lower. Further, the number of hydrogen bonds is much smaller and their strength is
considerably weaker. As a result, SCW behaves as an organic solvent and exhibits
extraordinary solubility toward organic compounds containing large nonpolar
groups and most permanent gases (Demirbas 1998; Byrd et al. 2007). Another
advantage of SCW reforming is that the H2 is produced at a high pressure’ which can
be stored directly, thus avoiding the large energy expenditures associated with its
compression. Figure 4.8 shows schematic diagram of experimental apparatus of
supercritical water gasification (Demirbas 2005). The SCWG process becomes
economical as the compression work is reduced owing to the low compressibility of
liquid feed when compared to that of gaseous H2 (Byrd et al. 2007).
Figure 4.9 shows the plots for yields of gas products from SWE of olive husk
versus pressure. From Fig. 4.9, the yield of total gas products increases from 23.7 to
29.3 % while the pressure increases from 23.2 to 38.7 MPa, respectively. The yield
of hydrogen containing gas increases form 6.6 to 10.8 %, while the pressure
increases from 23.2 to 38.7 MPa, respectively (Demirbas 2005).
The plots for yields of gas products from SWE of cotton cocoon shell versus
pressure are given in Fig. 4.10. From Fig. 4.10, the yield of total gas products
increases from 19.9 to 24.5 % while the pressure increases from 23.2 to 38.7 MPa,
respectively. The yield of hydrogen containing gas increases from 5.9 to 9.4 %,
while the pressure increases from 23.2 to 38.7 MPa, respectively (Demirbas 2005).
Back Pressure
TUBULAR Heat Exchanger Regulator
Biomass
REACTOR
Water Water Preheater

Gas-Liquids
Gas Flow meter Separator
Gas Products Liquid Products
Gas Analyzer Liquid Analyzer
Fig. 4.8 Schematic diagram of experimental apparatus of supercritical water gasification

Fig. 4.9 Plots for yields of gas products from supercritical water extraction of olive husk versus
pressure (wt% of dry and ash-free sample)
Fig. 4.10 Plots for yields of gas products from supercritical water extraction of cotton coon shell
versus pressure (wt% of dry and ash-free sample)
4.8 Biofuels from Sewage Sludge
4.8.1 Biodiesel from Sewage Sludge
Petroleum-based fuels are limited reserves concentrated in certain regions of the

world. These sources are on the verge of reaching their peak production. The
scarcity of known petroleum reserves will make renewable energy sources more
attractive (Sheehan et al. 1998a). The fossil fuel resources are shortening day by
day. Biofuels from biomass is becoming increasingly important globally as a clean
alternative source of energy to fossil fuels (Duku et al. 2011). Biodiesel is attracting
increasing attention worldwide as blending components and holds significant pro-
mise as a potential displacement fuel for petroleum-based diesel fuel. Biodiesel is a
mixture of methyl esters with long-chain fatty acids made from waste and vegetable
triglycerides (Leung et al. 2010). The inventor of diesel engines, Rudolf Diesel
(1858–1913) demonstrated the use of vegetable oils as a substitute for diesel fuel in
the 19th century (Orchard et al. 2007; Talebian-Kiakalaieh et al. 2013).
Biodiesel is produced from vegetable oils and animal fats by the process of
transesterification with simple alcohols such as methanol and ethanol. Biodiesel
fuel typically comprises lower alkyl fatty acid (chain length C14–C20), esters of
short-chain alcohols, primarily, methanol or ethanol. Biodiesel is a renewable,
sustainable, biodegradable, less toxic, and safer for storage and handling has
excellent lubricity and could provide similar energy density to diesel fuel
(Bharathiraja et al. 2014a, b). Biodiesel, an ideal alternative to fossil fuels, is very
imperative for the sustainable development of mankind (Yan et al. 2014).
The major economic factor to consider with respect to the input costs of bio-
diesel production is the feedstock, which is about 80 % of the total operating cost.
The high price of the edible oils used in the production of biodiesel raised its
production cost (Fadhil et al. 2015). Thus, finding cheaper resources for biodiesel
production is an important aim (Fadhil and Ali 2013). Other important costs are
labor, methanol, and catalyst. The cost of biodiesel fuels varies depending on the
base stock, geographic area, variability in crop production from season to season,
the price of crude petroleum, and other factors. Lower-cost feedstocks are needed
since biodiesel from food-grade oils is not economically competitive with
petroleum-based diesel fuel. Biodiesel can be made from cheap feedstocks,
including beef tallow, pork lard, yellow grease, and algae oil. Algae could be a
potential feed stock for biodiesel and other co-products such as animal feed and
chemicals (Martin and Grossmann 2014; Gnansounou and Raman 2016). Inedible
plant oils have been found to be promising crude oils for the production of
biodiesel.
Biodiesel is a technologically feasible alternative to fossil diesel, but nowadays
biodiesel costs 1.5–3 times more than fossil diesel. Oil from sewage sludge is
available with relatively cheap price for biodiesel production in comparison with
fresh vegetable oil costs. There are a number of factors affecting high variable costs
in the production of biodiesel, limiting the fuel’s widespread use (Gunawan et al.
4.8 Biofuels from Sewage Sludge 155
2014). The usage of food grade vegetable oil could result in increased oil prices and
have negative social consequences (Hill et al. 2006; Groom et al. 2008). Biodiesel
expansion is currently limited due to high raw material costs for its production. For
this reason, the search for new possible raw materials for biodiesel fuel production
has been encouraged. Currently the interest in the application of MSS for biodiesel
production is growing.
Alternative approaches for obtaining biodiesel from municipal sludge have been
extensively investigated (Pastore et al. 2013; Tran-Nguyen et al. 2015). The
potential of using municipal wastewater sludge as a lipid feedstock for biodiesel
production was investigated (Mondala et al. 2009).
MSS comes from waste water treatment plant. Sewage sludge is a waste formed
during treatment of wastewater. The sludge samples are collected from waste water
treatment plant. The MSS contains a significant amount of lipid fraction as char-
acterized as oils, greases, fats and long chain fatty acid originating from domestic
and industrial sludge.
Waste water sludge contains a variety of organic and inorganic compounds
(Bharathiraja et al. 2014a). The generation of municipal sewage sludge (MSS) has
increased in parallel to rapid industrialization. Physical and chemical characteristics
of MSS depend on the source, geographical location, and country show different
variations. The (MSS) can be a solid, semi-solid, or liquid muddy residue. Sewage
sludge is generally mixture of domestic and industrial wastes (Bharathiraja et al.
2014b).
The sewage sludge contains mainly lipids, proteins, sugars, detergents, and
phenols. Sewage sludge also includes toxic and hazardous organic and inorganic
pollutants source. The sludge consists a wide range of harmful substances such as
dioxins and furans, polychlorinated biphenyls, organochlorine pesticides, absorbed
and extracted chlorine derivatives, polycyclic aromatic hydrocarbons, phenols and
their derivatives, phthalate and others (Berset and Holzer 1999; Aznar et al. 2009;
Xu et al. 2012a, b, 2013). The carbohydrate-rich WSS can be used in biogas
production as a more efficient material (Imu and Samuel 2014).
Sewage sludge is the waste formed during treatment of waste water. The sewage
sludge consist a variety of organic matter and microorganisms. Activated sludge or
secondary contains a microbial population responsible for the biological treatment
of wastewater. This population mostly consists of heterothrophic bacteria which
utilize the organic content of the wastewater for growth, either as part of their
cellular structures or as energy and carbon storage compounds which are mostly
lipidic in nature (Revellame et al. 2012). The primary sludge is a combination of
floating grease and solids. The secondary or activated sludge is composed mainly of
microbial cells and suspended solids. The activated municipal sewage sludge is a
potential source of lipids (Bharathi et al. 2014). Lipids could yield an unexploited
source of cheap and readily available feedstock for biodiesel production (Olkiewicz
et al. 2012).
Two different approaches have been investigated for the production of biodiesel
from glycerides and free fatty acids (FFAs) extracted from sewage sludge. The first
one is a two-step process consisting of organic solvent extraction followed by
acid-catalyzed transesterification of the isolated oil fraction. The second one is a

one-step direct transformation consisting of the simultaneous extraction and con-
version of the lipid fraction contained in the sewage sludge (Kwon et al. 2013;
Melero et al. 2015; Urritia et al. 2016).
The MSS subjected to pretreatment processes before lipid extraction. Primary
sludge consists to a high portion of organic matters, as feces, vegetables, fruits,
textiles, paper etc. Activated sludge or secondary sludge is obtained after the
removal of dissolved organic matter and nutrients from the wastewater takes place
in the biological treatment step. The resulting sludge from this process is called
activated sludge. The yield of fatty acid methyl esters from primary sludge is greater
than activated sludge. The lipid extraction from the raw sludge requires huge
amount of organic solvent and large vessels with stirring and heating systems
(Pastore et al. 2013).
The optimum production of biodiesel is faced with huge challenges. First, the
lipids containing free fatty acids are usually extracted and then transesterified.
Impurities in the lipids from the sludge would have interfered with the catalytic
process in the conventional production of biodiesel.
Lipids are extracted from primary, secondary, blended and stabilized sludge in a
Soxhlet extractor, using generally hexane as a solvent (Dufreche et al. 2007).
Finally, the lipids are converted by catalytic transesterification into their corre-
sponding fatty acid methyl esters (biodiesel). Results indicated that among four
sludge tested, primary sludge achieved the greatest lipids and biodiesel yields. The
amount of extracted lipids for primary sludge was 25.3 % compared to 21.9, 10.1
and 9.1 % (dry wt basis) for blended, stabilized and secondary sludge, respectively
(Olkiewicz et al. 2012). The extraction and transformation of the lipids could yield
an unexploited source of cheap and readily available feedstock for biodiesel
production.
Alkali-catalyzed transesterification is much faster than acid-catalyzed transes-
terification and is most often used commercially. However, for lipid feedstocks with
greater than 1 % free fatty acids (FFAs) such as in the sewage sludge, acid catalysis
followed by base catalysis is recommended because of soap formation with
alkali-catalyzed transesterification and high FFA (Kargbo 2010).
The reaction may be carried out using either basic or acidic catalysts, but these
processes require relatively time consuming and complicated separation of the
product and the catalyst, which results in high production costs and energy con-
sumption (Han et al. 2005). In order to overcome these problems, Saka and
Kusdiana (2001) and Demirbas (2002b) have proposed that biodiesel fuels may be
prepared from vegetable oil via non-catalytic transesterification with supercritical
methanol. Supercritical methanol is believed to solve the problems associated with
the two-phase nature of normal methanol and oil mixtures by forming a single
phase as a result of the lower value of the dielectric constant of methanol in the
supercritical state (Deslandes et al. 1998).
4.8.2 Biogas from Sewage Sludge
Ji (2015) stated that as a sustainable clean energy carrier, the use of biogas is an
important source of energy in heat and electricity generation. It is a promising hope
for the future to develop large scale biogas production, depending on economic
factors such as the use of waste control and its profitability, the use of agricultural
waste in biogas production, and the evaluation of sewage sludge. The enactment
efforts and supportive subsidies is in this direction in many countries. Biogas is one
of the most promising renewable energy sources in the world (Arthur and
Brew-Hammond 2010; Shane et al. 2015).
The first practical application of biogas from sewage sludge by anaerobic
digestion for energy production took place in England in 1896. Meynell (1976) and
Sadecka et al. (2013) stated that the first methane digester plant was built at a leper
colony in Bombay, India, in 1859. Biogas technology has been known for a long
time, however in the recent years the interest in it has significantly increased
(Acaroglu et al. 2005). Biogas can be produced from all kinds of organic wastes.
Biogas is derived from the anaerobic digestion of organic matter such as manure,
municipal solid waste, sewage sludge, biodegradable waste and agricultural slurry
under anaerobic conditions (Appels et al. 2008; Nasir et al. 2014). Anaerobic
digestion process is used to convert biomass into biogas with the help of
microorganism (Bharathiraja et al. 2014a, b). On the other hand, sewage sludge
consists of by-products of wastewater treatment (Usman et al. 2012). Biogas can be
obtained from digesting the organic material of municipal solid wastes (MSW). It is
a relatively simple and economical method to produce fuel from waste. The
composition of MSW varies by the source of waste; however in all cases, the major
constituents of MSW are organic in nature and the organics accounts for more than
50 % of MSW contents. The management of food and agricultural waste, solid and
liquid waste sourced by food processing and sewage sludge is the center of the
social issues for many societies. Most of the biogas plants utilize animal dung or
sewage sludge as an organic material for both soil regulation and fertilizer material
(Balat 2008).
Approximately 16 % of all discarded MSW is incinerated; the remainder is
disposed of in landfills. Osorio et al. (2014) claimed that disposal of MSW in
sanitary landfills was usually associated with soil, surface water and groundwater
contamination, if the landfill was not properly constructed. The processing of MSW
secures has many advantages and limitations. The greenhouse gas emissions cannot
be reduced by the uncontrolled releasing of methane from improperly disposed
organic waste in a large landfill.
Decomposition in landfills occurs in a series of stages, each of which is char-
acterized by the increase or decrease of specific bacterial populations and the for-
mation and utilization of certain metabolic products. The first stage of
decomposition usually lasts less than a week, which is characterized by the removal
of oxygen from the waste by aerobic bacteria. In the second stage is called the
anaerobic acid stage, which includes the diverse population of hydrolytic and
fermentative bacteria hydrolyzes polymers, such as cellulose, hemicellulose, pro-

teins, and lipids, into soluble sugars, amino acids, long-chain carboxylic acids, and
glycerol. The main components of landfill gas are by-products of the decomposed
organic materials which is usually in the form of domestic waste, and by the action
of naturally occurring bacteria under anaerobic conditions.
Biogas, a clean and renewable form of energy can replace for conventional
sources of energy which are causing ecological–environmental problems. Biogas is
composed by methane (55–75 %), carbon dioxide (25–45 %), nitrogen (0–5 %),
hydrogen (0–1 %), hydrogen sulfide (0–1 %), and oxygen (0–2 %). Among its
components, methane is the most important one, particularly for the combustion
process in vehicle engines. Methane (CH4) and carbon dioxide (CO2) constitute
about 90 % of the gas volume produced. Achieving “sustainable development”
requires methods and tools to help quantifying and comparing the environmental
impacts for providing goods and services the society. Life cycle assessment
(LCA) is a methodological framework for estimating and assessing the environ-
mental impacts attributable to the life cycle of a product, such as climate change,
stratospheric ozone depletion.
Waste water sludge contains a variety of organic and inorganic compounds
(Bharathiraja et al. 2014a, b). The generation of MSS has increased in parallel to
rapid industrialization. Anaerobic digestion is an economically viable and envi-
ronmentally friendly process for the reduction of excess MSS (Zhidong 2011; Ding
et al. 2013). Anaerobic digestion (AD) of the organic food fraction of MSW
co-digested with primary sewage sludge produces high quality biogas, suitable for
renewable energy (Kiely et al. 1997). Integration of anaerobic digestion in life cycle
assessment (LCA) highlights the potential benefits of renewable energy to offset
any conventional energy inputs and assessment of greenhouse gas emission
reduction. The importance of study can be expressed as the findings in this pri-
marily LCA study reveal that renewable energy resources are more important in
terms of sustainable energy development and environmental pollution prevention in
Saudi Arabia.
Physical and chemical characteristics of municipal sewage sludge depending on
the source, geographical location, and country shows different variations. Municipal
sewage sludge (MSS) can be a solid, semi-solid, or liquid muddy residue. Sewage
sludge is generally mix of domestic and industrial wastes (Bharathiraja et al. 2014a,
b). The physical characteristics of sludge plays an important role in the operation of
anaerobic digestion (Dursun et al. 2004; Pollice et al. 2007).
The physical and chemical characteristics of municipal sewage sludge samples
are given in Table 4.9 (Henze 2008a, b; Bharathiraja et al. 2014a, b; Werle and
Dudziak 2014).
The sewage sludge contains mainly proteins, sugars, detergents, phenols, and
lipids. Sewage sludge also includes toxic and hazardous organic and inorganic
pollutants source. The sludge consists a wide range of harmful substances such as
dioxins and furans, polychlorinated biphenyls, organochlorine pesticides, absorbed
and extracted chlorine derivatives, polycyclic aromatic hydrocarbons, phenols and
their derivatives, phthalate and others (Berset and Holzer 1999; Aznar et al. 2009;
Table 4.9 Physical and Characteristic

chemical characteristics of
municipal sewage sludge pH 7.1–8.2
(MSS) Bulk density (kg/L) 1.26–1.38
Particle density (kg/L) 2.40–2.56
Organic matter (g/kg) 418–592
Ash (g/kg) 345–440
Higher heating value (MJ/kg) 11.3–14.2
Organic carbon (g/kg) 205–403
Oxygen (g/kg) 185–219
Nitrogen (g/kg) 45–49
Hydrogen (g/kg) 40–46
Iron (g/kg) 24–38
Phosphorus (g/kg) 22–30
Calcium (g/kg) 21–29
Aluminum (g/kg) 16–22
Sulfur (g/kg) 11–17
Magnesium (g/kg) 3.2–4.8
Barium (g/kg) 2.8–4.2
Zinc (g/kg) 2.4–3.6
Silicon (g/kg) 2.2–2.7
Potassium (g/kg) 1.2–1.6
Copper (g/kg) 0.7–1.2
Chromium (g/kg) 0.5–0.9
Nickel (g/kg) 0.3–0.5
Manganese (g/kg) 0.2–0.4
Lead (g/kg) 0.1–0.3
Sodium (g/kg) 0.1–0.2
Tin (g/kg) 0.1–0.2
Titanium (g/kg) 0.09–0.13
Chlorine (g/kg) 0.03–0.22
Arsenic (g/kg) 0.03–0.18
Fluorine (g/kg) 0.003–0.13
Selenium (g/kg) 0.002–0.011
Cadmium (g/kg) 0.009–0.012
Mercury (g/kg) 0.005–0.009
Boron (g/kg) 0.0013–0016
Xu et al. 2012a, b, 2013). The carbohydrate-rich WSS can be used in biogas

production as a more efficient material (Imu and Samuel 2014).
As it is seen in Table 4.1, the inorganic part of the sewage sludge are mainly the
compounds of iron, phosphorus, calcium, aluminum and sulfur, including traces of
heavy metals such as zinc, chromium, mercury, lead, nickel, cadmium and copper
(Karveles et al. 2003; Marrero et al. 2004; Abad et al. 2005; Cai et al. 2007; Fuentes
et al. 2008; Szymański et al. 2011; Li et al. 2012). Zinc, copper and lead are present
in high quantities, but other heavy metal is found in traces levels. Both phosphorus
and potassium in the sewage sludge have a high fertilizer value. On the other hand,
the sewage sludge contains the cementitious elements such as Ca, Si, Al and Fe.
Sewage ash mainly can be used for cement production.
The biomass materials including animal wastes, sewage sludge, and industrial
effluents can be broken down by anaerobic digestion (AD) approach into methane
and carbon dioxide mixtures called “biogas” (Kapdi et al. 2005).
Anaerobic biogas production process can be carried out in relatively inexpensive
and simple reactor designs and operating procedures. Main steps in a biogas pro-
duction process are given in Fig. 4.11.
Fig. 4.11 Main steps in a Municipal Sewage Sludge (MSS)

biogas production process
Feedstock Handling and Processing
Suspended colloidal organic matter
Enzymatic Hydrolysis
Simple Sugars, Fatty Acids, Amino Acids, Alcohols
Acidogenesis
Volatile Fatty Acids
Acitogenesis
Acetic Acid, Carbon Dioxide, Hydrogen
Methanogenesis (Aneorobic Digestion)
Partial Removing of Carbon Dioxide
Biogas (Methane rich gas)

Anaerobic decomposition is a complex process which is carried out in oxygen

absent medium (Marty et al. 2011). In the process of anaerobic
decomposition/digestion, organic matters are converted into methane, carbon
dioxide, and a nutrient-rich sludge by anaerobic bacteria. On the other hand, sus-
pended colloidal organic matter is converted into simple sugars, fatty acids, amino
acids, alcohols by enzymatic hydrolysis process. As a result, activity of various
microorganisms occurs in three basic stages. In the first stage, a variety of primary
producers (acidogens) breaks down the raw wastes into simpler fatty acids. In the
second stage, a different group of organisms (methanogens) consumes the organic
acids produced by the acidogens, generates biogas as a metabolic byproduct. On
average, acidogens grow much more quickly than methanogens. Finally, the
organic acids are converted to biogas. Methane-generating (methanogenic) anaer-
obic bacteria utilize these acids and complete the decomposition process. After
dewatering and possibly purification, the produced gas can be used in boilers as
gaseous fuels, for cogeneration or for production of vehicle gas.
A variety of factors affect the rate of digestion and biogas production (Demirbas
2004a, b). The most important parameters for the biogas generation were temper-
ature, the digestion time, and the species of feeding substrate, pH, and the acetic
acid concentration in the slurry. Other factors affect the rate and amount of biogas
output. These include the water/solids ratio, carbon/nitrogen ratio, mixing of the
digesting material, and the particle size of the materials being digested.
The methane content of the biogas is in the range of 73–79 % for the runs, the
remainder is principally carbon dioxide. During a 30-day digestion period, 80–
85 % of the biogas is produced in the first 15–18 days. This implies that the
digester retention time can be designed to be 15–18 days instead of 30 days
(Demirbas 2004a, b). Higher yields were observed within the temperature range of
30–60 °C and pH of 5.5–8.5.
The MSS contains low nitrogen and have carbon-to-nitrogen ratios (C/N) of
around 40–70. The optimal C/N ratio for anaerobic digestion should be between 25
and 35 (Hills and Roberts 1981). The process ends with methanogens where biogas
has relationship between carbon and nitrogen (C/N ratio) in the material that is
digested. C/N-ratio of sludge in small scale sewage plants is often low, so nitrogen
can be added in inorganic form such as ammonia or in organic form such as
livestock manure, urea, or food wastes (Davidsson et al. 2007; El-Mashad and
Zhang 2010; Neczaj et al. 2013).
Potential production capacity of a biogas plant with a digestion chamber size of
500 m3 was estimated as 20–36 × 103 Nm3 biogas production per year, or 14–16
Nm3 biogas production per hour (Amigun et al. 2012; Maghanaki et al. 2013; Khan
et al. 2014).
4.9 Biodiesel and Bioethanol from Unconventional

Resources
4.9.1 Biodiesel from Unconventional Resources
There are two global biomass-based liquid transportation fuels that might replace
gasoline and diesel fuel. These are biodiesel for Diesel engine and bioethanol for
Otto engine. Biodiesel is attracting increasing attention worldwide as blending
components or direct replacements and holds significant promise as a potential
displacement fuel for petroleum-based diesel fuel in vehicle engines. Biodiesel fuels
have become more attractive recently because of their environmental benefits and
the fact that it is made from renewable resources.
As most of the feedstocks used for biodiesel are edible and the cost of raw material
is very high to the tune of 60–80 % of the total cost, it becomes essential nowadays to
identify new and underutilized feedstock for biodiesel production. Therefore,
researchers have turned focusing more attention on oils of non-edible nature.
Currently, biodiesel is mainly produced from conventionally grown edible oils
such as soybean, rapeseed, sunflower, and palm. To obtain biodiesel from edible
oils is currently not economically feasible to substitute petroleum diesel. Biodiesel
is a technologically feasible alternative to fossil diesel, but nowadays biodiesel
costs 1.5–3 times more than fossil diesel. The main obstacle to the commercial-
ization of biodiesel is the cost of product. Meanwhile, widespread use of edible oils
for biodiesel production can lead to possible food crisis. These problems can be
solved by using low cost raw materials such as non-edible oils, waste cooking oils,
algae oils and other non-conventional oils for the production of biodiesel.
The high price of the edible oils used in the production of biodiesel raised its
production cost and thus, finding cheaper resources for biodiesel production is an
important aim. Other important costs are labor, methanol, and catalyst. The cost of
biodiesel also varies depending on the base stock, geographic area, variability in
crop production from season to season, the price of crude petroleum, and other
factors.
Municipal sewage sludge (MSS) is a waste formed during treatment of
wastewater. The waste water sewage sludge contains mainly lipids, proteins, sugars,
detergents, phenols, and a variety of organic and inorganic compounds and it also
includes toxic and hazardous organic and inorganic pollutants. The MSS contains a
significant amount of lipid fraction as characterized as oils, greases, fats and free
fatty acids originating from domestic and industrial sludge.
The activated MSS is a potential source of biodiesel. Oil from sewage sludge is
available with relatively cheap price for biodiesel production in comparison with
fresh vegetable oil costs. Biodiesel production from municipal sludge has been
extensively investigated (Pastore et al. 2013; Mondala et al. 2009; Tran-Nguyen
et al. 2015). Lipids could yield an unexploited source of cheap and readily available
feedstock for biodiesel production from the MSS (Olkiewicz et al. 2012; Bharathi
et al. 2014; Olkiewicz et al. 2012).
4.9 Biodiesel and Bioethanol from Unconventional Resources 163
There are two different methods for the production of biodiesel from the MSS
including of triglycerides and free fatty acids (FFAs). The first one is a two-step
process consisting of organic solvent extraction followed by acid-catalyzed trans-
esterification of the isolated oil fraction. The second one is a one-step direct
transformation consisting of the simultaneous extraction and transesterification of
the lipid fraction contained in the MSS.
The MSS subjected to pretreatment processes before lipid extraction. Secondary
sludge is obtained after the removal of dissolved organic matter and nutrients. The
resulting sludge from this process is called activated sludge. The yield of fatty acid
methyl esters from primary sludge is greater than activated sludge (Pastore et al.
2013). Lipids are extracted from each sludge sample in a Soxhlet extractor by using
generally hexane as a solvent (Dufreche et al. 2007). The amount of extracted lipids
for primary sludge was 25.3 % compared to 21.9, 10.1 and 9.1 % (dry wt basis) for
blended, stabilized and secondary sludge, respectively (Olkiewicz et al. 2012).
A simplified flow diagram of biodiesel from municipal sewage sludge (MSS) is
given in Fig. 4.12.
Alkali-catalyzed and supercritical methanol transesterifications are carried out
for production biodiesel from the MSS. For lipid feedstocks with greater than 1 %
Sewage Sludge
Filtration
Drying
Solid Sludge
Solid-Liquid Solvent Extraction of Lipids
Methanol Triglycerides and Fatty Acids Catalyst
Purification
Transesterification
Solvent Evoparation Purification of Methyl Esters Aqueous Phase
Solvent Glycerin
Biodiesel
Fig. 4.12 Simplified flow diagram of catalytic biodiesel processing from municipal sewage
sludge (MSS)
free fatty acids (FFAs) acid catalysis followed by base catalysis is recommended
because of soap formation with alkali-catalyzed transesterification and high FFA
(Kargbo 2010). Supercritical methanol is believed to solve the problems associated
with the two-phase nature of normal methanol and oil mixtures by forming a single
phase as a result of the lower value of the dielectric constant of methanol in the
supercritical conditions (Poddar 2015).
To obtain cheap biodiesel from waste cooking oil (WCO) or waste vegetable oil
(WVO) or waste frying oil (WFO) has been considered a promising option. Water
and free acid contents are important factors in the catalytic transesterification of the
WCO. Transesterification of crude waste oil gave much lower yields, due to the
high levels of free fatty acids in the oil. WCO with high acidity was pretreated
before transesterification and biodiesel with low water content and light color can
be prepared from the WCOs by using of different catalysts (Lam et al. 2010;
Sharma and Singh 2011; Brito et al. 2012; Melero et al. 2012; Patel et al. 2013;
Lopes et al. 2015; Rosa et al. 2015).
WCO is available with relatively cheap price for biodiesel production in com-
parison with fresh vegetable oil costs. Average international prices for selected
vegetable oils and animal fats used as feedstock for biodiesel production (US$/ton)
are given in Table 4.10 (Demirbas 2009c). These prices (from Table 4.10) may
vary depending on from country to country, geographic and agricultural conditions,
the collection and distribution facility and the feedstock quality. Production of
biodiesel from waste/recycled oils can be reduced the cost of biodiesel and decrease
environmental pollution coming from the WCO [80]. The price of waste cooking
oil is 2.5–3.5 times cheaper than virgin vegetable oils (Demirbas 2009c).
Algae are the fastest-growing plants in the world. Industrial reactors for algal
growing culture are open ponds, photobioreactors, closed and hybrid systems.
Microalgal cultivation consumes less water than land crops. Microalgal farming
could be potentially more cost effective than conventional farming.
Microalgae are theoretically very promising source of biodiesel and it could be
only source of renewable biodiesel in the near future. Microalgae are an economical
choice for biodiesel production, because of its availability and low cost. Capital and
operating costs of open ponds are very lover than those of other systems. Many
Table 4.10 Average Crude palm oil 543

international prices for
Rapeseed oil 824
selected vegetable oils and
animal fats used as feedstock Soybean oil 771
for biodiesel production (US Refined cottonseed oil 782
$/ton) Crude corn oil 802
Crude peanut oil 891
Crude tea seed oil 514
Waste cooking oil 224
Yellow grease 374
Poultry fat 256
Fig. 4.13 Production of Macro- and Microalgae

biodiesel from algae
Grinding
Oil extraction
Transesterification
Separation of biodiesel and glycerol
Water washing soap and glycerol
Biodiesel
researchers have reported that biodiesel obtained from microalgae would be more
efficient than other biodiesel production methods.
Figure 4.13 shows a simple block diagram of the production of biodiesel from
algae. Algal oils are obtained by extracting the algae with hexane in a Soxhlet
extractor for 18 h. Algae contain anywhere between 2 and 40 % of lipids/oils by
weight (Demirbas 2009b). The biodiesel from algal oil in itself is not significantly
different from biodiesel produced from vegetable oils. It has estimated that the yield
of oil from microalgae is over 200 times the yield from the best-performing
plant/vegetable oils per acre (Sheehan et al. 1998a), because microalgae are the
fastest-growing photosynthesizing organisms.
Biodiesel obtained from edible vegetable oils presently do not compete eco-
nomically with diesel fuel because they are more expensive for diesel engines.
Extensive use of edible oils may cause other significant problems such as starvation
in developing countries. About 13 % of edible vegetable oil supplies were globally
used for biodiesel production in 2012 (Demirbas et al. 2016). Biodiesel production
accounted for the global demand of vegetable oils is given in Table 4.11.
Non-edible vegetable oils, as a diesel fuel, have advantages such as low cost,
easily availability, portability, renewability, low sulfur and aromatic content and
Table 4.11 Biodiesel Vegetable oil Used for biodiesel production (wt%)
production accounted for the
global demand of vegetable Rapeseed 25.6
oils Soybeen 16.1
Palm 5.9
Others 52.4
Total 100.0
high biodegradability. However, as a major disadvantage, most of the non-edible

vegetable oils contain a high content of free fatty acids (FFAs), which increases the
biodiesel production cost.
There are many species for non-edible oilseed crops such as jatropha tree
(Jatropha curcas), karanja (Pongamia pinnata), mahua (Madhuca indica), castor
bean seed (Ricinus communis), neem (Azadirachta indica), rubber seed tree (Hevea
brasiliensis), tobacco seed (Nicotiana tabacum), rice bran, etc. The production of
biodiesel from different non-edible oilseed plants has been extensively investigated
in recent years (Kumari et al. 2007; Hawash et al. 2009; Padhi and Singh 2010; Ong
et al. 2011; Gimbun et al. 2013; Thangaraj et al. 2014).
The non-edible plant oils are easily available in developing countries and are
very economical comparable to edible plant oils. However, the non-edible oils are
unsuitable for human food because of the presence of some toxic components
(Demirbas 2009b; No 2011).
The vegetable oil contains more than 1 % FFA is pretreated via an
acid-catalyzed esterification (Chai et al. 2014). Sulfuric acid, hydrochloric acid, and
sulfonic acid are usually- preferred as acid catalysts.
It can be obtained the oily extract of 11 % from supercritical solvent extraction
of freshly cut wood and at most 2.6 % of fatty acids from the extract (Demirbas
2009d).
Tall oil obtained from Kraft process of wood pulp has three major components:
resin acids, fatty acids and unsaponifiables or neutral compounds. A typical com-
position of tall oil from coniferous wood is 49 % resin acids, 32 % fatty acids and
19 % unsaponifiables. The composition of crude tall oil varies a lot, depending on
the type of wood used (DeMartini et al. 2004).
The tall oil fatty acids mainly compose of oleic, linoleic and linolenic acids.
Biodiesel can be produced from crude tall oil (CTO). Tall oil fatty acids can be
converted to their methyl esters (biodiesel) in a single step with yields in excess of
94 %.
Main animal fats sources are beef tallow, lard, poultry fat, and fish oils. Yellow
greases are the mixtures of vegetable and animal sources. Biodiesel can be pro-
duced from three types of waste animal fats. Typical properties of three types of
waste animal fats (tallow, lard and poultry fat) are given Table 4.12. Saturated fatty
acid rates and viscosities of animal fats are relatively high compared with those of
vegetable oils. The cetan number (CN) of biodiesel from animal fats is higher than
those of vegetable oils.
Biodiesel mainly obtained from rapeseed, soybean, sunflower, or palm oil. These
raw materials are expected to increase further in the future be used and prices in the
food market, however, the commercialization of biodiesel from these raw materials
will be less competitive compared to what would be the main obstacle fossil fuels.
To produce biodiesel from different types of waste animal fats with a standard
according to EN 14214 is possible. Additional experiments are then performed to
confirm the optimum results. Biodiesel produced from some animal fats represent
an environmental friendly and lower cost alternative.
Table 4.12 Typical properties of waste animal fats

Property Tallow Lard Poultry fat
Kinematic viscosity of fat at 40 °C (mm2/s) 46 40 41
Kinematic viscosity of methyl ester at 40 °C (mm2/s) 3.1 3.2 3.3
Acid value of fat (mg (KOH)/g fuel) 1.06 0.64 0.56
Iodine value of fat (g/100 g) 45 78 77
Myristic acid content (wt% of total acids) 8.5 1.4 –
Palmitic acid content (wt% of total acids) 31.0 24.7 30.0
Stearic acid content (wt% of total acids) 16.4 15.5 6.0
Oleic acid content (wt% of total acids) 40.5 44.0 47.0
Linoleic acid content (wt% of total acids) 3.4 13.4 15.6
Linolenic acid content (wt% of total acids) 0.2 1.0 1.4
The agricultural wastes such as tea seed oil, tobacco seed oil, tomato seed oil,
linseed oil, bay laurel leaves and fruits, cherry seed oil, some non-traditional seed
oils, corn germ oil, rice bran oil, and cherry laurel seed might be a valuable
renewable raw material for the biodiesel production.
Figure 4.14 shows a simplified flow diagram of continuous process for biodiesel
production from sweet cherry seed.
The production of biodiesel from crude seed oils having high free fatty acids
(FFAs) is processed in two steps: the acid-catalyzed esterification following by the
base-catalyzed transesrification. The first step reduces the FFAs level to less than 2 %
Fig. 4.14 A simplified flow Extraction of sweet cherry seed

diagram of continuous
process for biodiesel
production from sweet cherry Kernel oil of sweet cherry seed
seed
Methanol + 3% KOH
Transesterification in potassium methoxide
Phase separation with water Recovered

methanol
Fatty acid methyl esters Aqueous methanol + glycerol + KOH
Glycerol purification
Glycerol Wastewater
Purification Biodiesel Marketing

and the second step converted the product of the first step into biodiesel and glycerol.
Fatty acid compositions of some agricultural wastes are given in Table 4.13.
There are outstanding tobacco seed oil, tea seed oil and corn germ oil potential
for low cost biodiesel production in the world.
Lower-cost feedstocks are needed since biodiesel from food-grade oils is not
economically competitive with petro-diesel fuel. Biodiesel production costs can
vary widely by feedstock, conversion process, scale of production and geographic
region. The cost of feedstock is a major economic factor in the viability of biodiesel
production. Feedstock costs typically account for 70–80 % of the total costs of
biodiesel production.
The crude tea seed oil is one of the cheapest vegetable oil feedstocks for bio-
diesel production. Among common vegetable oils, tea seed kernel oil seems to be
an alternative promising feedstock for biodiesel production. Table 4.14 shows a
Table 4.13 Average fatty acid compositions of some agricultural wastes (wt% of total acids)
Fatty Tea Tobacco Linseed Tomato Corn Bay Cherry Rice
acid seed germ laurel seed bran
Palmitic 10.5 10.7 5.1 18.1 10.0 23.8 8.6 21.3
Stearic 2.8 3.2 2.3 4.0 35 3.8 2.8 2.8
Oleic 62.5 14.1 18.9 26.6 27.2 31.4 43.7 38.6
Linoleic 19.7 68.2 18.1 47.8 55.4 21.5 41.8 34.5
Linolenic 2.7 3.0 55.1 0.6 0.7 0.4 2.3 2.3
Others 1.8 0.8 0.5 2.9 3.2 19.1 0.8 0.5
Table 4.14 Cost analysis of Plant rating, kW 150

tea seed power generation by
Probable application On-site
combustion in coal-fired
boiler assuming a 10 year Installed costs, $/kW
time frame at a 10 % rate of Equipment $2.548
return Civil/Mechanical/Electrical $1.813
Buildings $0.836
Contingency (10 %) $0.474
Utilities $0.135
Land/Transportation access $0.127
Engineering/Permitting $0.636
Total Installed Costs $6.569
Operation and maintenance costs, $/kW $371
Capacity factor 80 %
Capital costs, $/kWh $0.6109
Leveling capital costs, $/kWh $0.0884
Operation and maintenance costs, $/kWh $0.0391
Cleanout costs, $/kWh $0.0134
Cost of production, $/kWh $0.1342
Average electricity retail price, $/kWh $0.0894
cost analysis of tea seed power generation by combustion in coal-fired boiler

assuming a 10 year time frame at a 10 % rate of return. The primary costs included
in the analysis are capital costs, operation and maintenance, and cleanout.
In previously conducted economic studies on biodiesel production, continuous
processes were mainly evaluated (Zhang et al. 2003; Haas et al. 2006; West et al.
2008). To assess the risks involved for any development, sensitivity analysis was
carried to determine the impact of key variables on production costs. The key
variables examined are: raw material costs, plant utilization, by-product cost, capital
cost, and market demand. The cost of biodiesel fuels also varies depending on the
base stock, geographic area, variability in crop production from season to season,
the price of crude petroleum, and other factors.
As a non-conventional source, the MSS is promising lipid feedstock for bio-
diesel production. However, the energy necessary to remove its high water content
is a major inconvenience for scaling up because of the high associated cost. In
addition, the expensive conventional sludge drying methods are not effective
enough for lipid recovery, thus reducing the potential biodiesel production. Primary
and secondary sludge of municipal wastewater treatment facilities are potential
sources of lipids. It contains various lipids and hence it is a promising raw material
for biodiesel production. Lipids can be initially extracted from the sludge.
Biodiesel production from sewage sludge poses huge challenges to overcome if
commercial opportunities are to be realized. Obtaining lipids from the sludge causes
challenges due to the large volume of liquid, the adsorption of lipids onto sludge
solids, and the fact that optimal temperature and other lipid extraction parameters
are different for the primary and secondary sludge fractions. Main the challenge
factors are collecting the sludge, separating lipids, microbial processing, optimum
production of biodiesel and product separation, soap formation in basic catalytic
transesterification, maintaining product quality, bioreactor design, economics of
biodiesel production, and regulatory concerns. Table 4.15 shows the main chal-
lenge factors and their reasons in biodiesel production from sewage sludge.
Table 4.16 shows the production cost estimate for sludge biodiesel. The biodiesel
production from municipal sewage sludge can lower the cost significantly. The
estimated biodiesel production cost from municipal primary and secondary sludge is
USD 3.11 to USD 3.23 per gallon of biodiesel compared to USD 4.00 to USD 4.50
per gallon refined soy biodiesel and USD 3.00 per gallon for diesel. Pokoo-Aikins
et al. (2010) claimed that the overall biodiesel production cost from free sewage
sludge is varied according to the solvent used in initial extraction step and is USD
3.39 per gallon for ethanol, USD 3.37 per gallon for methanol, USD 2.89 for hexane,
and USD 2.79 per gallon for toluene used as the extraction solvent. An economic
analysis estimated the cost of $3.23/gallon for a neat biodiesel obtained from this
process at an assumed yield of 10 % FAMEs/dry weight of sludge.
According to some estimates, the yield (per acre) of oil from algae is over 200
times the yield from the best-performing plant/vegetable oils. Microalgae are the
fastest growing photosynthesizing organisms. They can complete an entire growing
cycle every few days. Approximately 46 tons of oil/hectare/year can be produced
from diatom algae. Different algae species produce different amounts of oil. Some
Table 4.15 The main challenge factors and their reasons in biodiesel production from sewage
sludge
Challenge factors Challenge reasons
Collecting the sludge Collection and precipitation of primary and secondary
sludge can affect the cost of production
Separating lipids Filtration, centrifuge, drying
Microbial processing Separation of pharmaceutical chemicals in sludge
Optimum production of biodiesel The simultaneous extraction and transesterification of
and product separation triglycerides and fatty acids increase the efficiency of
biodiesel
Soap formation Soaps can also cause challenges with glycerol separation
and washing
Maintaining product quality The yield of primary sludge is higher than that of
secondary sludge, but there is a need to improve lipid
solubility in the reaction mixture
Bioreactor design The challenge in boosting biodiesel production depends
on reactor type and design
Economics of biodiesel To be competitive, production cost may need to be
production reduced to levels at or below petroleum diesel costs
Regulatory concerns Sludge cost depends on pretreatment and treatment at the
wastewater facility
Table 4.16 Production cost estimate for sludge biodiesel

Terms of costs Cost per gallon (US $)
Drying (operation and maintenance) 1.29
Biodiesel processing (operation and maintenance) 0.60
Centrifuge (operation and maintenance) 0.43
Extraction (operation and maintenance) 0.34
Capital protection and indemnity service 0.18
Depreciation 0.12
Labor 0.10
Insurance 0.03
Tax 0.02
Total cost 3.11
Assuming 7.0 % overall transesterification yield
algae produce up to 50 % oil by weight. Microalgae have much faster growth rates
than terrestrial crops. The per unit area yield of oil from algae is estimated to be
between 5000 and 20,000 gallons per acre per year, which is 7 to 31 times greater
than the next best crop, palm oil (Sheehan et al. 1998b).
The cost of biodiesel is higher than diesel fuel. Currently, there are seven pro-
ducers of biodiesel in the United States. Pure biodiesel (100 %) sells for about US
$1.50 to US$2.00 per gallon before taxes. Fuel taxes add approximately US$0.50
per gallon (Balat 2011).
4.9.2 Bioethanol from Unconventional Resources
Ethanol (ethyl alcohol, C2H5OH) can be used as transportation fuel. Ethanol that
can be obtained from biological feedstocks is called as bioethanol. Bioethanol is
good alternate fuel that is produced almost entirely from food crops. Biodiesel has
become more attractive recently because of its environmental benefits. Transport is
one of the main energy consuming sectors. It is assumed that biodiesel is used as a
fossil diesel replacement and that bioethanol is used as a fossil gasoline replacement
(Demirbas 2011a).
Ethanol (ethyl alcohol) has been used by humans since prehistory as the
intoxicating ingredient of alcoholic beverages. The ancient Egyptians produced
alcohol by naturally fermenting vegetative materials. Also in ancient times, the
Chinese discovered the art of distillation, which increases the concentration of
alcohol in fermented solutions. Its isolation as a relatively pure compound was first
achieved by Persian alchemist, Zakariya Razi. Ethanol was first prepared synthet-
ically in 1826 through the independent efforts of Henry Hennel in Great Britain.
Ethanol was used as lamp fuel in the United States as early as 1840. In the 1970s,
however, the ethanol industry began to reemerge when ethanol was used as a fuel
extender during gasoline shortages caused by the OPEC oil embargoes. Later, when
gasoline was more plentiful, ethanol began to see widespread use as a cleaner
burning octane enhancer, perfect for replacing other, less desirable, gasoline
components such as lead. As a result of clean air regulations, agricultural interests,
and energy security needs, U.S. ethanol demand has grown from less than 200
million gallons annually in the early 1980s to nearly 2 billion gallons in the year
2000 (Sun 2002).
Global production of bioethanol reached 13.5 billion gallons in 2006. Bioethanol
currently accounts for more than 94 % of global biofuel production, with the
majority coming from sugarcane. About 60 % of global bioethanol production
comes from sugarcane and 40 % from other crops. Brazil and the United States are
the world leaders, which together accounted for about 70 % of the world bioethanol
production exploiting sugarcane and corn respectively. Ethanol has been used in
Germany and France as early as 1894 by the then incipient industry of internal
combustion engines. Brazil has utilized ethanol as a fuel since 1925. By that time,
the production of ethanol was 70 times bigger than the production and consumption
of petrol. Currently, ethanol is produced from sugar beets and from molasses.
A typical yield is 72.5 L of ethanol per ton of sugar cane. Modern crops yield 60
tons of sugar cane per hector of land. Production of ethanol from biomass is one
way to reduce both the consumption of crude oil and environmental pollution. The
use of gasohol (an ethanol and gasoline mixture) as an alternative motor fuel has
been steadily increasing in the world for a number of reasons. Domestic production
and use of ethanol for fuel can decrease dependence on foreign oil, reduce trade
deficits, create jobs in rural areas, reduce air pollution, and reduce global climate
change carbon dioxide buildup (Bala 2005).
The world productions of ethanol and biodiesel between 1980 and 2009 are
shown in Fig. 4.15 (Demirbas 2008). Between 1991 and 2001, world ethanol
production rose from around 16 billion liters a year to 18.5 billion liters. From 2001
to 2007, production is expected to have tripled, to almost 60 billion liters a year.
Brazil was the world’s leading ethanol producer until 2005 when U.S. production
roughly equaled Brazil’s. The United States become the world’s leading ethanol
producer in 2006. China holds a distant but important third place in world rankings,
followed by India, France, Germany and Spain. Table 4.17 shows the top five
bioethanol producers in 2006.
Between 1991 and 2001, world biodiesel production grew steadily to approxi-
mately 1 billion liters. Most of this production was in OECD Europe and was based
on virgin vegetable oils. Small plants using waste cooking oils started to be built in
other OECD countries by the end of the 1990s, but the industry outside Europe
remained insignificant until around 2004. Since then, governments around the
Fig. 4.15 World production 60

of ethanol and biodiesel,
Total world production, billion liters
1980–2010
50
40 Ethanol
Biodiesel
30
20
10
0
1979 1984 1989 1994 1999 2004
Years
Table 4.17 The top ten Producer (Country) Billion gallon

bioethanol producers (billion
gallons) in 2007 USA 6.49
Brazil 5.02
European Union 0.57
China 0.49
Canada 0.21
Thailand 0.08
Colombia 0.08
India 0.05
Australia 0.03
Other 0.26
world have instituted various policies to encourage development of the industry,

and new capacity in North America, south-east Asia and Brazil has begun to come
on stream at a brisk rate. As a result, between 2001 and 2007, biodiesel production
will have grown almost ten-fold, to 9 billion liters (Demirbas 2008). Figure 4.15
shows world production of ethanol and biodiesel, 1980–2010.
Biofuels production costs can vary widely by feedstock, conversion process,
scale of production and region. Only ethanol produced in Brazil comes close to
competing with gasoline. Ethanol produced from corn in the US is considerably
more expensive than from sugar cane in Brazil, and ethanol from grain and sugar
beet in Europe is even more expensive. These differences reflect many factors, such
as scale, process efficiency, feedstock costs, capital and labor costs, co-product
accounting, and the nature of the estimates (Sun 2002). Figure 4.16 shows ethanol
production in different continents.
Average international prices for common biocrude, fat, crops and oils used as
feedstock for biofuel production in 2007 are given in Table 4.18. Agriculture
ethanol is at present more expensive of synthesis-ethanol from ethylene. The
simultaneous production of biomethanol in parallel to the production of bioethanol,
appears economically attractive in locations where hydro-electricity is available at
very low cost (*0.01 $ Kwh) (Demirbas 2009e).
Fig. 4.16 Ethanol production 80

in different continents
70
60
Percent of total
50
40
30
20
10
0
America Asia Europe Africa Oceania
Table 4.18 Average Biocrude 167

international prices for
Crude palm oil 703
common biocrude, fat, crops
and oils used as feedstock for Maize 179
biofuel production in 2007 Rapeseed oil 824
(US$/ton) Soybeen oil 771
Sugar 223
Wheat 215
Yellow grease 412
Cooking oil 146
Production of bioethanol from biomass is one way to reduce both the con-
sumption of crude oil and environmental pollution. In the process evaluated, pre-
hydrolysis with dilute sulfuric acid is employed to hydrolyze hemicellulose and
make the cellulose more accessible to hydrolysis by enzymes. Residual biomass
from hydrolysis and extraction of carbohydrates can be burned in a power plant to
generate electricity and process steam.
Carbohydrates (hemicelluloses and cellulose) in plant materials can be converted
to sugars by hydrolysis process. Fermentation is an anaerobic biological process in
which sugars are converted to alcohol by the action of micro-organisms, usually
yeast. The resulting alcohol is bioethanol. The value of any particular type of
biomass as feedstock for fermentation depends on the ease with which it can be
converted to sugars. Bioethanol is a petrol additive/substitute. Bioethanol and the
biorefinery concept are closely linked. It is possible that wood, straw and even
household wastes may be economically converted to bioethanol. In 2004, 3.4 bil-
lion gallons of fuel ethanol were produced from over 10 % of the corn crop. Ethanol
demand is expected to more than double in the next ten years. For the supply to be
available to meet this demand, new technologies must be moved from the labora-
tories to commercial reality. The world ethanol production is about 60 % from
feedstock from sugar crops (Demirbas 2008).
The corn-starch-to-fuel ethanol industry has been grown up during the past
30 years by bioethanol researchers. The most of bioethanol researchers are focusing
on the challenge of producing bioethanol from lignocellulosic biomass instead of
corn starch. Toward this end, the researchers already have developed effective
technology to thermochemically pretreat biomass; to hydrolyze hemicellulose to
break it down into its component sugars and open up the cellulose to treatment; to
enzymatically hydrolyze cellulose to break it down to sugars; and to ferment both
five-carbon sugars from hemicellulose and six-carbon sugars from cellulose.
Cellulosic biomass is a complex mixture of carbohydrate polymers from plant
cell walls known as cellulose and hemicelluloses. Cellulosic materials are paper,
cardboard, wood, and other fibrous plant material. The cellulose content of wood
varies between species in the range of 40–50 % (Demirbas 2009e). Hydrolysis
breaks down the hydrogen bonds in the hemicelluloses and cellulose fractions into
their sugar components: pentoses and hexoses. These sugars can then be fermented
into ethanol. Bacteria have drawn special attention from researchers because of their
speed of fermentation.
Cellulose is a remarkable pure organic polymer, consisting solely of units of an
hydro glucose held together in a giant straight chain molecule. Cellulose must be
hydrolyzed to glucose before fermentation to ethanol. Conversion efficiencies of
cellulose to glucose may be dependent on the extent of chemical and mechanical
pretreatments to structurally and chemically alter the pulp and paper mill wastes.
The method of pulping, the type of wood, and the use of recycled pulp and paper
products also could influence the accessibility of cellulose to cellulase enzymes.
Figure 4.17 shows the flow chart for the production of bioethanol from cereal grain.
Cellulose fraction of the structural components is insoluble in most solvents and
has a low accessibility to acid and enzymatic hydrolysis. Hemicelluloses
Fig. 4.17 Flow chart for the

Cereal Grain
production bioethanol from
cereal grain
Course powder flour
Acid hydrolysis
Fermentation and distillation
Crude alcohol Stillage
Dehydration Drying
Bioethanol Animal feed
(arabinoglycuronoxylan and galactoglucomammans) are related to plant gums in

composition, and occur in much shorter molecule chains than cellulose. The
hemicelluloses, which are present in deciduous woods chiefly as pentosans and in
coniferous woods almost entirely as hexosanes, undergo thermal decomposition
very readily. Hemicelluloses are derived mainly from chains of pentose sugars, and
act as the cement material holding together the cellulose micells and fiber.
Hemicelluloses are largely soluble in alkali and, as such, are more easily hydrolysed
(Demirbas 2009e).
Bioethanol can be produced from a large variety of carbohydrates with a general
formula of (CH2O)n. Chemical reaction is composed of enzymatic hydrolysis of
sucrose followed by fermentation of simple sugars. Fermentation of sucrose is
performed using commercial yeast such as Saccharomyces ceveresiae. First,
invertase enzyme in the yeast catalyzes the hydrolysis of sucrose to convert it into
glucose and fructose.
C12 H22 O11 ! C6 H12 O6 þ C6 H12 O6

ð4:10Þ
Sucrose Glucose Fructose
Second, zymase, another enzyme also present in the yeast, converts the glucose
and the fructose into ethanol.
C6 H12 O6 ! 2C2 H5 OH þ 2CO2 ð4:11Þ
Gluco-amylase enzyme converts the starch into D-glucose. The enzymatic

hydrolysis is then followed by fermentation, distillation and dehydration to yield
anhydrous bioethanol. Corn (60–70 % starch) is the dominant feedstock in
starch-to-bioethanol industry worldwide.
Carbohydrates (hemicelluloses and cellulose) in lignocellulosic materials can be
converted to bioethanol. The lignocellulose is subjected to delignification, steam
explosion and dilute acid pre-hydrolysis, which is followed by enzymatic hydrol-
ysis and fermentation into bioethanol. A major processing step in an ethanol plant is
enzymatic saccharification of cellulose to sugars through treatment by enzymes; this
step requires lengthy processing and normally follows a short term pretreatment
step.
Hydrolysis breaks down the hydrogen bonds in the hemicellulose and cellulose
fractions into their sugar components: pentoses and hexoses. These sugars can then
be fermented into bioethanol. The most commonly applied methods can be clas-
sified in two groups: chemical hydrolysis (dilute and concentrated acid hydrolysis)
and enzymatic hydrolysis. In the chemical hydrolysis, the pretreatment and the
hydrolysis may be carried out in a single step. There are two basic types of acid
hydrolysis processes commonly used: dilute acid and concentrated acid.
The biggest advantage of dilute acid processes is their fast rate of reaction, which
facilitates continuous processing. Since 5-carbon sugars degrade more rapidly than
6-carbon sugars, one way to decrease sugar degradation is to have a two-stage
process. The first stage is conducted under mild process conditions to recover the
5-carbon sugars while the second stage is conducted under harsher conditions to
recover the 6-carbon sugars.
Concentrated sulfuric or hydrochloric acids are used for hydrolysis of ligno-
cellulosic materials. The concentrated acid process uses relatively mild tempera-
tures, and the only pressures involved are those created by pumping materials from
vessel to vessel. Reaction times are typically much longer than for dilute acid. This
process provides a complete and rapid conversion of cellulose to glucose and
hemicelluloses to 5-carbon sugars with little degradation. The critical factors nee-
ded to make this process economically viable are to optimize sugar recovery and
cost effectively recovers the acid for recycling. The solid residue from the first stage
is dewatered and soaked in a 30–40 % concentration of sulfuric acid for 1 to 4 h as
pre-cellulose hydrolysis step. The solution is again dewatered and dried, increasing
the acid concentration to about 70 %. After reacting in another vessel for 1 to 4 h at
low temperatures, the contents are separated to recover the sugar and acid. The
sugar/acid solution from the second stage is recycled to the first stage to provide the
acid for the first stage hydrolysis. The primary advantage of the concentrated acid
process is the potential for high sugar recovery efficiency. The acid and sugar are
separated via ion exchange and then acid is re-concentrated via multiple effect
evaporators (Demirbas 2009e).
Ethanol from sugar cane, produced mainly in developing countries with warm
climates, is generally much cheaper to produce than ethanol from grain or sugar
beet in IEA countries. Estimates show that bioethanol in the EU becomes com-
petitive when the oil price reaches US$70 a barrel while in the United States it
becomes competitive at US$50–60 a barrel. For Brazil the threshold is much lower
—between US$25 and US$30 a barrel. Other efficient sugar producing countries
such as Pakistan, Swaziland and Zimbabwe have production costs similar to
Brazil’s (Balat 2007).
The largest ethanol cost component is the plant feedstock. Operating costs, such
as feedstock cost, co-product credit, chemicals, labor, maintenance, insurance and
taxes, represent about one third of total cost per liter, of which the energy needed to
run the conversion facility is an important (and in some cases quite variable)
component. Capital cost recovery represents about one-sixth of total cost per liter. It
has been showed that plant size has a major effect on cost (Whims 2007). The plant
size can reduce operating costs by 15–20 %, saving another $0.02 to $0.03 per liter.
Thus, a large plant with production costs of $0.29 per liter may be saving $0.05 to
$0.06 per liter over a smaller plant (Cardona and Sanchez 2007).
For designing fuel bioethanol production processes, the assessment of the uti-
lization of different feedstocks (i.e. sucrose containing, starchy materials, ligno-
cellulosic biomass) is required considering the big share of raw materials in
bioethanol costs (Grassi 1999). Approximately 60 % of the bioethanol produced is
from raw materials (Rogers et al. 2005). The cost of raw material, which varies
considerably between different studies (US$22–US$61 per metric ton dry matter),
and the capital costs, which makes the total cost dependent on plant capacity,
contribute most to the total production cost (WEA 2004). With these relatively high
raw material costs (which includes enzyme pretreatment when starch-based crops
are used), such fermentation products are currently more expensive to produce than
fuels or chemicals produced from lower cost hydrocarbons (Rogers et al. 2005).
Pretreatment has been viewed as one of the most expensive processing steps in
cellulosic biomass-to-fermentable sugars conversion with costs as high as US
$0.3/gallon bioethanol produced (Reijnders 2006). Enzyme pricing is assumed such
that the total contribution of enzymes to production costs is about US$0.15/gallon
of bioethanol with some variation depending upon actual bioethanol yields resulting
from the particular pretreatment approach (Balat 2007).
The costs of producing bioethanol were estimated for a 50 million gallons per
year dry mill bioethanol plant using current data for corn, distillers dried grains
(DDG), natural gas, enzymes, yeast and chemicals, electricity, and wage rates.
A bioethanol plant of this size will produce 51.5 million gallons of denatured
bioethanol annually from 18.1 million bushels of corn. In additional to bioethanol,
the plant will produce 154,500 tons of DDG. The cost of producing bioethanol in a
dry mill plant currently totals US$1.65/gallon. Corn accounts for 66 % of operating
costs while energy (electricity and natural gas) to fuel boilers and dry DDG rep-
resents nearly 20 % of operating costs (Urbanchuk 2007.
Until 2006, Brazil had been the largest producer of bioethanol in the world.
Brazil used sugarcane to produce bioethanol and sugarcane is a more efficient
feedstock for bioethanol production than corn grain. The costs of producing
bioethanol in Brazil are the world’s lowest. Production cost for bioethanol in Brazil
is in the US$0.68 to US$0.95 per gallon range (Shapoury et al. 2006). Factors
contributing to Brazil’s competitiveness include favorable climate conditions, low
labor costs, and mature infrastructure built.
There are a number of different production methods and feedstocks for ethanol
production. It has been focussed on the following feedstocks and production
processes:
1. Corn/Maize: Starch conversion to sugars, fermentation and distillation
2. Sugar beet: Fermentation and distillation
3. Wood: Acid Hydrolysis, fermentation and distillation
Each of the different feedstocks and processes has had their manufacturing costs
should be investigated independently.
The analysis above focuses on the costs of supply. As discussed under biodiesel
above, this is not necessarily the same as the market price of ethanol, which will be
influenced also by world prices of ethanol.
If ethanol competes simply under market prices, its maximum price will be set
by the price of alternatives. If there is competition with other ethanol producers, this
might set the price, but it can rise no higher than the price of petrol.
Biodiesel, for policy purposes, the concern is with the costs of ethanol pro-
duction rather than price. The producer surplus (difference between costs and price)
is not a cost to the nation, unless this surplus is expatriated profit by foreign owned
firms.
Current European Union (EU) policies on alternative motor fuels focus on the
promotion of biofuels. The definition of the marginal producer depends on the
policy stance on biofuels. Biofuel pricing policy should not be employed as an anti
inflationary instrument. It should be applied in such a way, that it does not create
cross subsidies between classes of consumers. In a proposed biofuels directive the
introduction of a mandatory share scheme for biofuels, including as from 2009
minimum blending shares (Demirbas 2009e). Table 4.19 shows the shares of
alternative fuels compared to the total automotive fuel consumption in the EU under
the optimistic development scenario of the European Commission. The EU has set
the goal of obtaining 5.75 % of transportation fuel needs from biofuels by 2010 in
all member states in February 2006. In the Commission’s view mandating the use
of biofuels will (a) improve energy supply security and (b) reduce greenhouse gas
Table 4.19 Shares of alternative fuels in total automotive fuel consumption in the EU under the
optimistic development scenario of the European Commission
Year Biofuel Natural gas Hydrogen Total
2010 6 2 – 8
2015 7 5 2 14
2020 8 10 5 23
(GHG) emissions and (c) boost rural incomes and employment (Jansen 2003). The
European Union accounted for nearly 89 % of all biodiesel production worldwide
in 2005. By 2010, the United States is expected to become the world’s largest single
biodiesel market, accounting for roughly 18 % of world biodiesel consumption, and
followed by Germany.
The general EU policy objectives considered most relevant to the design of
energy policy are (Jansen 2003):
1. Competitiveness of the EU economy
2. Security of energy supply
3. Environmental protection
The main biofuel opportunities where suitable land is available are in developing
countries. The issue of energy security has been accorded top-most priority. Every
effort needs to be made to enhance the indigenous content of energy in a
time-bound and planned manner. The additional benefit of biofuel development is
creation of new employment opportunities in manufacturing, construction, plant
operation and servicing, and fuel supply. Rural jobs are created in fuel harvesting,
transport and maintenance of processing areas.
According to the United States Department of Agriculture’s 2006 figures (USDA
2006), the United States produced 4 billion gallons (15.2 billion liters) of ethanol in
2005, up from 3.4 billion gallons in 2004. In 2005, Brazil, produced 4.2 billion
gallons of ethanol, up from 4.0 billion gallons in 2004. The United States is
predominantly a producer of bioethanol derived from corn, and production is
concentrated in Midwestern states with abundant corn supplies. In 2005 the United
States produced 4 billion gallons of bioethanol, which equates to about 3 % of the
country’s total gasoline consumption (140 billion gallons per year) (Asher 2006).
Prompted by the increase in oil prices, Brazil began to produce bioethanol from
sugarcane in the 1970s and is considered the most successful example of a com-
mercial application of biomass for energy production and use. Extensive experience
in bioethanol production, suitable natural conditions for sugarcane production and
low labour costs have made Brazil the most efficient bioethanol-producing country
(Dufey 2006). Bioethanol represents approximately 1/3 of total vehicle fuels cur-
rently used in Brazil (Eikeland 2006).
EU accounts for about 10 % of global bioethanol production. EU bioethanol is
generally produced using a combination of sugar beets and wheat (Schnepf 2006).
France is currently the front-runner in the EU’s attempt to boost bioethanol use,
accounting for 2 % of global production, mainly from sugar beet and wheat.
However, France is rapidly being overtaken by Germany and Spain as the EU’s
largest bioethanol producer. China accounts for about 9 % of global bioethanol
production, 80 % of which is grain-based–mainly derived from corn, cassava and
rice. India accounts for 4 % of global bioethanol production. This is made from
sugarcane (Dufey 2006). With all of the new government programs in America,
Asia, and Europe in place, total worldwide fuel bioethanol demand could grow to
exceed 125 billion liters by 2020 (Bohlmann 2006).

energy policy are: (1) competitiveness of the EU economy, (2) security of energy
supply, and (3) environmental protection. All renewable energy policies should be
measured by the contributions they make to these goals. Current EU policies on
alternative motor fuels focus on the promotion of biofuels. In a proposed biofuels
directive the introduction of a mandatory share scheme for biofuels, including as
from 2009 minimum blending shares. In the Commission’s view mandating the use
of biofuels will (a) improve energy supply security and (b) reduce greenhouse gas
(GHG) emissions and (c) boost rural incomes and employment. Current regulations
would preclude a notable negative impact on the rural environment. Elements of the
European biofuels policy are (EC 2003):
(a) A Communication presenting the action plan for the promotion of biofuels and
other alternative fuels in road transport.
(b) The Directive on the promotion of biofuels for transport which requires an
increasing proportion of all diesel and gasoline sold in the Member States to
be biofuel.
(c) The biofuels taxation, which is part of the large draft Directive on the taxation
of energy products and electricity, proposing to allow Member States to apply
differentiated tax rates in favor of biofuels.
The EU have also adopted a proposal for a directive on the promotion of the use
of biofuels with measures ensuring that biofuels account for at least 2 % of the
market for gasoline and diesel sold as transport fuel by the end of 2005, increasing
in stages to a minimum of 5.75 % by the end of 2010 (Asher 2006). The French
Agency for Environment and Energy Management (ADEME) estimates that the
2010 objective would require industrial rapeseed plantings to increase from cur-
rently 3 million ha in the EU to 8 million ha.
Gasoline and ethanol mixtures are called as gasohol. Diesohol is a mixture of
diesel fuel and hydrated ethanol blended using a chemical emulsifier. Diesohol is
used in compression ignition engines as an alternative diesel fuel.
The increased utilization of biofuels for heat and power production has provided
to increase political support in European countries. This has resulted in a large
number of biofuels being processed for energy conversion necessities and suit-
ability for choosing the most appropriate method of valorizing the conversion
products with depending on the variability of using raw materials as well as their
composition. In addition, new standard analytical methods are necessary to develop
in order to apply new technologies for biofuel production from biomass materials.
Diesel-alcohol blends are known by a number of names—including E-diesel,
M-diesel, Oxy-diesel and diesohol. Diesohol is used in compression ignition
engines as an alternative diesel fuel. Ethanol performs well as a fuel in cars, either
in a neat form or in a mixture with gasoline. In addition to ethanol/gasoline blend
markets, ethanol has other motor fuel applications including: (1) use as E85, 85 %
ethanol and 15 % gasoline, (2) use as E100, 100 % ethanol with or without a fuel
additive, and (3) use in oxy-diesel, typically a blend of 80 % diesel fuel, 10 %

ethanol and 10 % additives and blending agents.
Gasoline and ethanol mixtures are called as gasohol. E10, sometimes called
gasohol, is a fuel mixture of 10 % ethanol and 90 % gasoline that can be used in the
ICEs of most modern automobiles. Gasohol a gasoline extender made from a
mixture of gasoline (90 %) and ethanol (10 %; often obtained by fermenting
agricultural crops or crop wastes) or gasoline (97 %) and methanol (3 %)
(Demirbas 2009e).
Anhydrous ethanol will readily blend with petrol. Hydrated ethanol containing
more than 2 % by volume of water is not completely miscible with petrol. Hydrated
ethanol is not miscible with diesel but can form an emulsion using a suitable
emulsifier. Diesohol is a mixture of diesel fuel and hydrated ethanol blended using a
chemical emulsifier. Diesohol is a fuel containing alcohol that comprises a blend of
diesel fuel (84.5 %), hydrated ethanol (15 %) and an emulsifier (0.5 %). The
emulsifier that allows the ethanol and the diesel to blend consists of a
styrene-butadiene copolymer which is dissolved in the diesel fuel and a
polyethyleneoxide-polystyrene copolymer which is dissolved in the hydrated
alcohol (Demirbas 2009e).
Hydrated (or azeotropic) ethanol is ethyl alcohol that contains approximately
5 % water. Hydrated ethanol derived from sugar, or ethanol derived from wheat
starch, may be used for production of diesohol. Hydrated ethanol production is a
one-stage refining. Ethanol is produced by the fermentation of sugar solutions from
sugar cane or grain crops. The action of yeast on the sugar produces a solution
containing about 12 % ethanol. The alcohol can be concentrated by distillation to
produce up to 96 % ethanol. Removal of the remaining 4 % water requires special
treatment.
Table 4.20 shows the emission impacts of gasoline and diesel fuel blends with
15 vol.% ethanol. The use of blends of ethanol with gasoline and No 2 diesel fuel
are preferred in internal combustion engines, in order to decrease carbon monoxide
and carbon dioxide emissions. The total net emissions of carbon dioxide from
gasohol and diesohol blends are considerably less than those of gasoline and No 2
diesel fuel. Ethanol reduces CO2 emissions. The reductions of carbon monoxide
and carbon dioxide were 32.0 and 29.0 % for CO emissions and 43.0 and 45.0 %
for CO2 emissions of E15 gasohol and diesohol, respectively (Demirbas 2008).
Table 4.20 Emission Emission type Gasohol Diesohol

impacts of gasoline and diesel
fuel blends with 15 vol.% Total unburned hydrocarbons –27 –24
ethanol (percent change in Carbon monoxide –32 –29
emissions) Carbon dioxide –43 –45
Particulate matter –21 –18
Sulfates –15 –15
Fig. 4.18 Plots for 100
Reduction of unburned hydrocarbon, %

reductions of unburned Gasohol
hydrocarbon (%) versus Diesohol
ethanol (% by volume) in the 80
blend of gasoline (gasohol)
and diesel fuel (diesohol)
60
40
20
0
0 20 40 60 80 100
Ethanol, % by volume
Figure 4.18 shows the plots for reductions of unburned hydrocarbon (%) versus
ethanol (% by volume) in the blend of gasoline (gasohol) and diesel fuel (diesohol).
Gasohol has higher octane, or antiknock, properties than gasoline and burns
more slowly, coolly, and completely, resulting in reduced emissions of some pol-
lutants, but it also vaporizes more readily, potentially aggravating ozone pollution
in warm weather. The major effect of diesohol on engine performance is a signif-
icant reduction in visible smoke and particulate emissions. Engine thermal effi-
ciency increases by up to 8 % when operating on diesohol. There is also a
significant overall reduction in emission of carbon dioxide (Demirbas 2009e).
The cetane number (CN) of neat alcohols is very low (8 for ethanol and 3 for
methanol) and as such they are extremely poor compression ignition engine fuels.
The cetane number of diesohol is dependent on the ignition quality of the base
diesel, the percentage of the alcohol in the blend, and the addition of cetane
improver additives. Cetane will be important to manage for diesohol, especially
given the potential for alcohols to reduce cetane. CN appears to be the appropriate
measure for diesohol as it reflects the addition of cetane improvers (Demirbas
2009e).
Gasohol and diesohol are fuel mixtures which can be used in internal com-
bustion engines. Gasohol has higher octane, or antiknock, properties than gasoline.
The major effect of diesohol on engine performance is a significant reduction in
visible smoke and particulate emissions. Engine thermal efficiency increases by up
to 8 % when operating on diesohol.
Biomethanol have such low emissions because the carbon content of the alcohol
is primarily derived from carbon that was sequestered in the growing of the
bio-feedstock and is only being re-released into the atmosphere.
4.10 Gasoline-like Products from Plastic and Tire Wastes 183
4.10 Gasoline-like Products from Plastic and Tire Wastes
4.10.1 Gasoline-like Products from Plastic Wastes
The disposal of waste plastic is generally achieved by conventional ways such as

landfill or incineration. These methods will cause the air pollution, soil contami-
nation, and the economical problems. The recycling of plastic wastes as a cheap
source of raw materials has become the environmental and economical solution.
Petroleum is the largest single source of liquid transportation fuels, diesel fuel
and gasoline. Because of price surges, shortages and concerns supply and green-
house gas emissions, alternative oil for liquid transportation must be developed in
the long term (Van Gerpen et al. 2004). Interestingly, the renewable energy
resources are more evenly distributed than fossil or nuclear resources. Recovery of
fuels from biomass and other organic wastes such as plastic and tire is recom-
mended methods. Pyrolysis is one among several promising recycling methods.
Conversion techniques specifically designed to treat the pyrolysis of scrap plastic
and refers to the depolymerization technology. Plastic-to-fuel (PTF) technologies
offer the potential to manage petroleum-based plastic wastes as a resource to create
a valuable alternative vehicle fuel source. Plastic materials are generally made from
nonrenewable petroleum resources.
There is a major dilemma now faced by producer is how to invest in regarding
plastics utilization. Integrated Solid Waste Management (ISWM) system based on
3R principle: reduce, reuse and recycle. There are two major recycle methods for
conversion of plastic wastes to synthetic fuels: (1) pyrolysis and (2) thermal and/or
catalytic cracking. Previous researches have been carried out to convert plastic
wastes into oil by means of pyrolysis process. Pyrolysis is a complex series of
chemical and thermal reactions to decompose or depolymerize organic material
under oxygen-free conditions. The products of pyrolysis include oils, gases and
char. The oil obtained from plastic pyrolysis could improve performance by
modifying engine. The cracking process yields a highly unstable low-grade fuel oil
which can be acid-corrosive, tarry, and discolored along with a characteristically
foul odor (Marongiu et al. 2003; Hernandez et al. 2007).
The most affecting variables of plastic pyrolysis are catalyst type and shape,
temperature and residence time. The presence of catalysts can help reducing the
degradation temperatures, increasing cracking rate and shortening residence time,
increasing pyrolysis yield, improving the quality of products, etc. (Aguado and
Serrano 1999; Fukushima et al. 2009). Variety of suitable catalysts can be selected
according to the desired product quality (Walendziewski and Steininger 2001). The
catalytic pyrolysis of waste high-density polyethylene over modified zeolites was
found to be a promising plastic waste recycle method to produce petroleum
fuel-like products (Zeaiter 2014).
Certain types of waste plastics such as polystyrene (PS), polyethylene (PE) and
polypropylene (PP) were generally used in pyrolysis. The plastic wastes can be
pyrolyzed into liquid, gas and solid residue products. The liquid products are
usually composed of higher boiling point hydrocarbons. In order to obtain useful

gasoline-range hydrocarbons from the pyrolytic oily products, fractional distillation
is preferred for product separation. More valuable chemical raw materials including
benzene, toluene and other condensed aromatic hydrocarbons may be obtained by
refining the pyrolytic oil (Demirbas 2004b).
Pyrolysis refers to the thermal decomposition of the matter under an inert gas
like nitrogen. The plastic pyrolysis process is the thermal depolymerization process
in the absence of oxygen which is able to convert plastic into gasoline-range
hydrocarbons. The polystyrene (PS), Polyethylene (PE) and Polypropylene
(PP) which are the main component of the plastic in municipal solid waste are used
in the process in order to prevent the contamination of chlorine in the oil (Demirbas
2004b).
Catalytic pyrolysis and catalytic cracking processing has a potential to become
an important process for conversion of plastic wastes into hydrocarbon fuels. Both
pyrolysis and cracking are thermal decomposition processes. Pyrolysis is the
decomposition of waste material on heating in the absence of air. Cracking is the
massive breakdown of large organic compounds by use of a catalyst at low tem-
perature to generate fewer different compounds. Final pyrolysis temperature is
usually higher than at cracking process (Hu 2015).
For the production process of liquid fuel, the plastics that are suitable for the
conversion are introduced into a reactor where they will decompose at 450–550 °C.
Then require removal acids because they can be corrosive to the PTF systems as
well as the engines that will consume the fuel. In terms of fuel output, the products
derived from pyrolysis can be quite different. Liquid fuel is defined as
plastic-derived liquid hydrocarbons at a normal temperature and pressure. Some of
the systems produce a gasoline-diesel fuel blend that needs further refining. The
mixture of final products subjected to refining and final blending process to make
the gasoline-range hydrocarbons consumer ready. Char contains the additives and
contaminants that enter the system as part of the feedstock. The char can be a
powdery residue or substance that is more like sludge with a heavy oil component.
Because the starting raw material from direct pyrolysis has straight chain
hydrocarbons which were break down into short chain hydrocarbons as well as long
chain hydrocarbons by using pyrolytic and fractional distillation processes (Sarker
et al. 2012).
Literature reports several papers on pyrolysis of plastics (Fink and Fink 1997;
Kiran et al. 2000; Vasile et al. 2001; Bagri and Williams 2002). The decomposition
of a polymer mixture over HZSM-5 (Zeolite Socony Mobil with High Si/Al ratio-5)
and orthophosphoric acid modified (PZSM-5) zeolite catalysts has been compara-
tively studied (Vasile et al. 2001). Catalytic decomposition increased the amount of
gaseous products, lowered the condensate, and changed their composition with
respect to the non-catalytic at the same pyrolysis temperature.
The influence of zeolite catalytic upgrading of the pyrolysis gases derived from
the pyrolysis of polyethylene at 500 °C has been investigated (Bagri and Williams
2002). Polyethylene was pyrolyzed in a fixed bed reactor and the pyrolysis gases
passed to a secondary reactor containing Y-zeolite or zeolite ZSM-5 (Zeolite
Socony Mobil Si/Al ratio-5) catalyst. The oils consisted of mainly aliphatic com-
pounds represented by alkadiene, alkene and alkane hydrocarbons and their bran-
ched chain derivatives. The Y-zeolite produced significantly greater concentration
of aromatic hydrocarbons in the derived oils compared to when zeolite ZSM-5
catalyst was used (Bagri and Williams 2002). Plastics wastes are converted into
synthesis gas. The crude synthesis gas is injected into exhausted oil reservoirs (Fink
and Fink 1997).
Table 4.21 shows the yield of pyrolysis product (wt%) at 425 °C in the absence
and presence of catalysts. Catalyst presence enhanced the yield of both oil and gas
products, whereas it reduced the yield char product. The yields of liquid products
obtained from no catalytic pyrolysis of municipal plastic waste at different tem-
perature are given in Table 4.22 (Demirbas 2004b). These pyrolytic products can be
divided into a gas fraction and a liquid fraction consisting of paraffins, olefins,
naphthenes and aromatics, and solid residues (Table 4.22).
Pyrolysis of plastic wates has been studied extensively in the past (Schoeters and
Buekens 1979; Kaminsky et al. 1979). Recycling of plastic wastes into gasoline-range
hydrocarbons via pyrolysis in the absence of a catalyst has been investigated by
Kaminsky (1992). Four types of mechanisms of plastics pyrolysis have been pro-
posed (Cullis and Hirschler 1981): (1) End-chain scissions or depolymerization,
(2) Random-chain scission, (3) Chain-stripping and (4) Cross-linking.
Thermal decomposition of PE and PS is accompanied with a free radical chain
reaction. When free radicals react with hydrocarbons, hydrocarbons and new free
radicals are generated. These free radicals could be decomposed into olefins and
new radicals. The high-density polyethylene is pyrolyzed through the random-chain
scission into smaller molecules with various chain lengths (Scheirs and Kaminsky
2006). The addition of catalyst in the pyrolysis can be a more efficient method to
produce high valuable products with mainly gasoline-range hydrocarbons.
Pyrolysis of polystyrene with cyclic structure is occurred by both end-chain and
random-chain scissions and its breakage randomly into smaller molecules of one or
more benzene-ring structures.
Table 4.21 Yield of Product No catalyst Natural zeolite catalytic

pyrolysis product (wt%) of
municipal plastic waste at Liquid 72.5–78.1 80.4–83.4
425 °C in absence and Gas 7.6–8.7 9.1–10.6
presence of catatyst Solid residual 15.8–17.9 8.6–9.6
Table 4.22 Yields of the Temperature (°C) 400 450 525 600
liquid products obtained by
no catalytic pyrolysis of Paraffinics 32.5 31.4 31.1 33.2
municipal plastic waste at Olefinics 37.3 33.6 32.3 31.6
different temperatures Naphthenics 20.7 21.5 23.0 22.7
Aromatics 7.9 13.6 12.5 11.6
Others 1.6 1.9 1.1 0.9
Only several types of thermoplastics undergo thermal decomposition to yield

liquid hydrocarbons used as liquid fuel. PE, PP, and PS, are preferred for the
feedstock for the production of liquid hydrocarbons.
Recovery of petroleum basic plastic waste to gasoline-range hydrocarbons are
given in Fig. 4.19. There may be variations in the feeding methods used depending
on the characteristics of the waste plastic. Pretreatment of plastic waste material
includes size reduction and moisture removal. The waste plastic used in pyrolysis
process is needed to be sorted and cleaned. Contaminants like metal and glass are
removed from the plastic stream. Pyrolysis is used to convert the plastic to liquid,
gas and char products. Pyrolytic gas is cooled and condensed into oil, fuels, and
petroleum products. The production method for the conversion of plastic wastes to
liquid fuel is based on the pyrolysis of the plastics and the condensation of the
resulting hydrocarbons.
Direct pyrolysis or thermal decomposition and catalytic decomposition of heavy
hydrocarbons have been comparatively described by Scheirs and Kaminsky (2006).
The catalytic degradation was produced much more light hydrocarbons (C5–C12)
than that of thermal degradation, and moreover ZSM-5 and zeolite Y were more
effective than mordenite. Especially, ZSM-5 with a smaller pore size, rather than that
of zeolite Y was more cracked into light hydrocarbons such as C6–C12 hydrocarbons
and gas products. ZSM-5 is superior to zeolite Y in terms of aromatic formation.
Also, the hydrogenatoms in ZSM-5 catalytic degradation contribute to the formation
of naphthenes with largely C6–C8 hydrocarbons. Optimization of gasoline-range fuel
from pyrolysis in absence and presence of catalyst is given in Table 4.23.
Fig. 4.19 Recovery of

Petroleum Basic Plastic Waste
petroleum basic plastic waste
to gasoline-range
hydrocarbons
Cleaning
Size Reduction
Moisture Removal
Pyrolysis
Acid Removal
Refining
Gasoline -Range Hydrocarbons

Table 4.23 Optimization of gasoline-range fuel from pyrolysis of plastic waste in absence and
presence of catatyst
Characteristic Pyrolysis (no catalyst) Catalytic pyrolysis Impact on fuel
property
Classification Classification is simple Classification of the technology Poor market acceptance
is unclear
Conversion Relatively slow reactions Short in the reaction time Effect on fuel cost
Molecular Olefins less branched Olefins more branched by Effect on gasoline
branching isomerization formation
Temperature Some diolefins made at high Lower decomposition Effect on product
temperature temperature selectivity
Gas High production of CH4 and High production of C3 and C4 Effect on gas formation
formation C2H6 hydrocarbons
Distribution Wide distribution in the More C5–C10 hydrocarbons in Effect on gasoline
of molecular liquid product (poor the liquid product (high gasoline selectivity
weight gasoline selectivity) selectivity)
Aromaticy Low aromaticy High aromaticy Aromatic cyclization
Solid residue High solid residue Low solid residue Effect on yield of oil
Paraffin Low paraffin formation Paraffins produced by hydrogen Effect on gasoline
formation transfer selectivity
Reactivity Low reactivity More reactive for larger Effect of radical
molecules formation
The investment and expenses of plastic waste pyrolysis plant is analyzed to

estimate the production cost of gasoline-range fuel as shown in Table 4.24. The
feed input is assumed to be 7 day/tons and the plastic waste is collected from
landfill sites. Plastic pyrolysis plant a ranking system carry high capital costs and
raw material costs, but in return, the higher the amount of fuel production. It has
been found that the pyrolysis fuel is suitable to use as gasoline replacement
energy-poor countries.
Table 4.24 Cost estimation Total capital cost 300,000 USD

of gasoline-range fuel from
Capital cost 822 USD/Day
catalytic pyrolysis of plastic
waste Expenses for:
Feedstock (7 Ton/Day) 960 USD/Day
Operation 150 USD/Day
Labor 90 USD/Day
Maintenance 50 USD/Day
Utilities 40 USD/Day
Taxes, Insurance 20 USD/Day
Total 1282 USD/Day
Profit 30 % 384 USD/Day
Total production 2516 USD/Day
Fuel production capacity 5000 L/Day
Production cost 0.5032 USD/Liter
4.10.2 Gasoline-like Products from Tire Wastes
Waste tires can be converted to liquid and gas fuels with catalytic pyrolysis. Char is
also obtained as a byproduct during the process and can be used in the removal of
heavy metals and toxic gases and wastewater purification in activated carbon form.
The base material of tire is latex, which is obtained from natural rubber trees
(Hevea brasiliensis). The rubber tree is a fast-growing tropical crop, mainly cul-
tivated for latex production, which provide a baseline material for various rubber
products such as waste tires (Rodrige et al. 2004). Latex is collected by cutting a
thin strip of bark from the tree and allowing the latex to exude into a collecting
vessel over a period of hours.
Rubber trees are tapped about once every two days to yield a cupful of latex.
Approximately 2.5 ton of raw rubber can be produced per hectare per year. The
state of Sao Paulo has the highest rubber tree yielding in the world averaging 1.2
ton/ha of dry latex. In Thailand, Indonesia and Malaysia on average 1.1, 1, and 0.9
ton/ha of latex is produced respectively (Pushparaja 1983).
During the tapping process, part of the bark is scrapped at the location of latex
cut (Pushparaja 1983; Rodrige et al. 2004). The production of natural rubber is a
labor-intensive sector involving many farmers. Tapping and latex collection are
normally carried out by paid laborers or household workers. Most of synthetic
rubber is produced from two materials, styrene and butadiene, which are petroleum
derivatives (IRSG 2015). Currently, the natural rubber in the world market is
competed by synthetic rubber, which is derived from petroleum products (Rodrige
et al. 2004). More than 2.7 million tons of recyclable wastes in the form of scrap
tires are generated every year in the EU states.
Rubbers are elastomeric materials, whose dimensions can be greatly changed by
applying and removing the stress (Vijayaram 2009). Moreover, rubber is a polymer
of isoprene, which is formed with double bonds between each of the individual
monomers. The other primary ingredient in tire rubber is carbon black. Sulfur and
other chemicals are also used in tires manufacturing. Tires contain around 20
different metals, which can’t be destroyed by burning as they are elements. Zinc is
present in particularly high amounts, as zinc oxide is used in the vulcanization
process.
Many studies have carried out on the pyrolysis of waste tires and reported in the
literature for its energy and value-added products (Roy et al. 1999; Kyari et al.
2005; Charpenteau et al. 2007).
The basic physical, chemical and adsorption properties of pyrolytic char from
tires are presented by Helleur et al. (2001). An important char property is its
morphological similarity with natural carbon black and thus can be used in removal
of heavy metal and toxic gases and wastewater purification in activated carbon
form. However, the high ash content reduces its recycling potential and utilization
in tires manufacturing. Nevertheless, it can be used in the rubber manufacturing as
catalytic material (Merchant and Petrich 1993; Chen et al. 2001; Helleur et al. 2001;
Quek and Balasubramanian 2011).
During the tires pyrolysis, gases are produced particularly the syngas, which is
capable to produce energy due to its high heating value.. It mainly contains
methane, ethane, propane, butane, nitrogen, hydrogen, carbon dioxide and carbon
monoxide (Quek and Balasubramanian 2011) and thus can be used as fuel for
generating heat and electricity.
Gas yield increases with increase in temperature due to higher thermal cracking,
while the liquid yield is stable at 775 K and decreases by raising temperature (Islam
et al. 2008). Higher temperature raise lighter yield of products such as benzene and
kerosene content, while the char yield reduces with increase in temperature.
This study was carried conversion of the waste tire into liquid fuel by pyrolysis
and in the presence of Na2CO3.
Firstly, the air dried waste tire samples were treated and washed to remove
impurities, steel wires, bead and dust etc. before the experiments. Afterwards, the
air dried waste tire samples were chopped to fine particles and their moisture
contents were removed by drying in oven (Fig. 4.20). In the catalytic runs, an
aqueous solution of the catalyst was used as sample adsorbent and dried.
The pyrolysis experiments were carried out in a laboratory scale apparatus. The
main element of this device was a vertical reactor of stainless-steel. The pyrolysis
tube reactor has a cylindrical shape with dimensions of 6 cm in diameter and 10 cm
in height and with cylindrical shape neck with dimensions of 2 cm in diameter and
20 cm in height (Demirbas et al. 2015a). The reactor was inserted vertically into an
electrically heated furnace and provided with an electrical power sourced heating
system. The nominal heating time was 45 min. The electrical heaters have special
resistance heaters, which can heat the feedstock at up to 600 °C. The heating rate
was regulated by a control unit with voltage adjustment to keep desired levels of
temperatures. Temperature measurement was carried out by means of thermocouple.
Fig. 4.20 Crude oil from

Treatment of waste tire to remove
waste tire by pyrolysis steel wires, bead etc.
process
Washing to remove impurities and dust
Chopped tires
Removal of moisture from tire chips
Pyrolysis of tire chips in a reactor
Crude oil Char Gases

The catalyst known as sodium carbonate (Na2CO3) was added to the clean tire in
the reactor and blended with mass basis of 2, 5 and 10 % separately.
Liquid products were produced from pyrolysis of waste tires. Thermal and
physical characteristics of the liquid products samples such as flash point, density,
viscosity and sulfur contents, and distillation tests, were examined by using stan-
dards ASTM approved measurement devices.
The volatile fractions of the pyrolysis products were partly analyzed by using
Fisons Ins. gas chromatograph (model GC 8000) equipped with a flame ionization
detector and 30 m long and 0.25 I.D. ZB-624 capillary column.
The rates of catalytic conversion were increased with temperature and Na2CO3
catalyst. The conversion of 45.4 % was achieved at 458 °C temperature without
Na2CO3 additive with 39.6 % liquid. In the presence of Na2CO3 runs, the highest
yield of 54.8 % was obtained at 452 °C temperature by using 10 % sodium car-
bonate with 49.2 % liquid product.
The physical properties of the produced liquids were measured for the values of
density, viscosity, flash point, sulfur content, water content and higher heating
value, which range in the standard values of the diesel oil or reasonably close to the
standard values. However, the sulfur content is considerably higher than its typical
value and thus it should be decreased below the value of 50 ppm. Density is another
important property of diesel fuel. It is the weight of a unit volume of fluid. The
density of diesel fuel ranges between 820 and 845 kg/m3. Density of produced
fuel-oil was 824 kg/m3, which is close to the lowest limit. Viscosity is also one of
the important properties of diesel fuels, since it affects the operation of the fuel
injection equipments particularly at low temperatures when the increase in viscosity
affects the fluidity of the fuel. High viscosity leads to poorer atomization of the fuel
spray and less accurate operation of the fuel injectors. Higher heating value
(HHV) of the waste tire was observed 46.2 MJ/kg using adiabatic bomb
calorimeter, which is close to HHV of typical diesel fuel, which is 42.7 MJ/kg.
Therefore, a diesel fuel having this heating value gives good engine performance
during combustion in a diesel engine.
Sooty combustion of liquid fuels indicates its high aromatic content.
Table 4.25 shows the results of gasoline evaporation, diesel fuel and liquid
products from waste tire at different temperatures by using Na2CO3 catalyst at
different weight basis rates such as 0, 2, 5 and 10 %.
The distillation temperature of the liquid products with 5 % Na2CO3 additive run
resembles to the distillation temperature of the gasoline up to 190 °C (approximately
50 % of the fuel-oil) and diesel fuel. Approximately, 45 % of liquid products is
gasoline-like fuel. The distillation temperature of the liquid products is smooth and
increases gradually. The higher distillation temperature will give the higher com-
bustion efficiency, which will increase engine performance. Approximately 40 % of
liquid products is diesel-like fuel. Therefore, 85 % obtained liquid products from
waste tire pyrolysis can be used as a fuel in Internal Combustion Engines. Gasoline
and diesel fuel contents of the resulting liquid products are 45 and 40 %, respectively.
As seen from Table 4.25, it is clear that 2 % of Na2CO3, which is blended with
the waste tire, decreases the distillation temperature, and increases the volatility of
Table 4.25 The results from evaporation of gasoline, diesel fuel and liquid fuels from waste tire
at different temperatures
Evaporation Temp. (°C) Temp. (°C) Temp. (°C) Temp. (°C) Temp. (°C) Temp. (°C) for
(%) for Gasoline for diesel for liquid for liquid for liquid liquid with
fuel from 0 % from 2 % from 5 % 10 % Na2CO3
Na2CO3 run Na2CO3 run Na2CO3 run run
0 28 142 85 74 51 59
5 33 169 94 83 62 70
10 38 182 101 94 70 81
15 44 194 121 99 78 90
20 49 201 138 108 87 101
25 55 210 159 117 99 111
30 61 219 177 134 112 125
35 69 227 193 156 123 142
40 75 238 224 181 137 156
45 82 247 248 196 153 173
50 88 259 271 218 168 192
55 96 271 286 241 184 214
60 103 283 297 263 201 236
65 110 295 314 291 225 258
70 117 306 335 314 250 271
75 124 318 349 334 276 293
80 134 330 360 347 305 320
85 145 346 373 362 335 349
90 157 359 385 376 358 369
95 175 364 396 387 370 388
100 193 370 413 400 388 401
the sample. Under the same conditions, when 5 and 10 % of Na2CO3 are mixed
with the liquid, the distillation temperatures increase and volatility decreases due to
additives. Therefore, it is recommended to add more additives to the liquid fuel in
order to decrease the amount of sulfur. Moreover, it is necessary that distillation
curve of any liquid fuel should be parallel with the distillation curve of diesel fuel
after 150 °C, and also it is necessary that its thermos-physical properties are suit-
able to the same values of the diesel fuel. Gasoline content of liquid products should
be separated for use in diesel engines.
When the waste tire is blended with 2 % of Na2CO3, distillation results of the
samples indicate parallel behavior with the temperatures of the present diesel fuel in
a volume of 40 %. This is a very important criterion due to the gradual increment of
distillation temperature at a finite value. When the sample is used as a fuel in a
diesel engine, there will be no damage to engine components. Approximately 40 %
amount of the samples is lighter than the diesel fuel. This information is useful for
the initial starting operation of the engine, but it is detrimental for the engine when
the temperature of the engine increases. When 10 % amount of the additive is
blended with the waste tire, distillation temperatures increase, but they continue to
show a behavior parallel to the diesel fuel sample.
The additives decrease the sulfur amounts present in the pyrolytic liquid prod-
ucts of waste tire. It is known that there are several catalysis mechanisms to absorb
sulfur present in the liquid fuel (Guchhait et al. 2005). The effects of catalyst
Na2CO3 amounts on sulfur content of the purified liquid (fuel-oil) samples were
carried out. Sulfur content in the waste tire decreases when the amount of the
additive increases. The highest decrease (78 %) of sulfur in the fuel-oil of waste tire
was achieved, when the ratio of 10 % Na2CO3 is blended with the liquid. Na2CO3
is a good catalytic additive for removal of sulfur in waste tire fuel-oil due to its
strong basic character.
The results of GC analysis showed the volatile fraction of pyrolysis products
from waste tire (wt% dry basis) at 5 % Na2CO3 catalytic run (Table 4.26). The
volatile fraction of the pyrolysis products consists of three phases: gaseous phase
Table 4.26 Gas Compound % by weight

chromatographic analysis
results of the volatile fraction Methane 3.7
of pyrolysis products from Ethane 1.3
waste tire (wt% dry basis) Propane 1.2
(5 % Na2CO3 catalytic run) Propene 0.4
Butane 0.7
Butene 0.2
Butadiene 10.7
2-butanone 0.7
2-methyl-cyclopenten-1-one 0.5
Pentane 1.4
Pentene 0.3
Isopentane 0.6
2,3-pentanedione 0.6
2-methyl-cyclopentanone 0.9
Hexane 1.2
Cyclohexane 3.2
Heptane 0.5
Octane 0.4
Isooctane 1.2
Nonane 0.6
Decane 0.4
Undecane 0.2
Dodecane 0.5
Hexadecane 0.3
2-methyl-2,6-dimettoxy phenol 2.4
Toluene 4.1
Benzene 3.0
Styrene 26.1
Not identified 31.7
containing C1–C4 hydrocarbons, carbon dioxide, carbon monoxide, nitrogen,

oxygen, hydrogen sulfur, hydrogen etc.; liquid phase and tarry materials phase.
Styrene (28.1 %) and butadiene (10.7 %) are dominant compounds. The gaseous
phase includes C1–C4 hydrocarbons (4.8 %), while the liquid phase includes C5–C8
hydrocarbons, (6.5 %) of total products. High yields of valuable light olefins such
as ethylene and propylene and light aromatics such as benzene, toluene, xylene and
naphthalene derivatives have been observed in the produced fuel-oil, as reported by
Lazaro et al. (2001, 2002).
4.11 Conversion of Oil Shale to Liquid Fuels
Oil shale is a sedimentary rock that contains the solid hydrocarbon wax kerogen in
tightly packed limy mud and clay. The kerogen may be decomposed at elevated
temperatures (723 K), resulting in an oil suitable for refinery processing (Dorf
1977). The origin of kerogen, a fossil substance, is attributed to plankton that for
millions of years existed in prehistoric lakes. The remains of the plankton sank to
the bottom of the lake in layers, embedded with the silt washed into the water from
the surrounding ranges. Streaked oil shale was thus formed that appears today as
deposits in the dry basins of early lakes. Actually, the rock formation is more
appropriately described as a marlstone rather than shale (Sorensen 1983). Oil found
in shale is actually a solid, high-molecular-weight organic compound called kero-
gen that has the following ultimate analysis in percent by mass: carbon 80.3,
hydrogen 10.4, nitrogen 2.3, sulfur 1.1, and oxygen 5.9 (Prien 1964). Briefly, in
order to extract the oil, the shale is mined and subsequently heated in a retort to
about 823 K. Approximately 10 % by mass of the shale is recovered as oil or gas,
while the remaining matter is waste material (Sorensen 1983).
Oil shale represents a large and mostly untapped hydrocarbon resource. Like tar
sand and coal, oil shale is considered unconventional because oil cannot be pro-
duced directly from the resource by sinking a well and pumping. Oil has to be
produced thermally from the shale (Baughman 1978; Lee 1996; Scouten 1990;
Speight 2007, 2013). Shale oil is refined in the crude distillation section of the
refinery into the primary components of gasoline including light hydrocarbons,
naphtha, jet fuel, kerosene, diesel oil, and residual fuel oils.
Oil shale can contribute significantly to energy requirements by producing
unconventional oils through thermal treatment. Oil shale is a sedimentary rock that
contains the solid hydrocarbon wax kerogen in tightly packed limy mud and clay.
Oil shale is a porous rock containing kerogen, an organic bituminous material. Oil
found in shale is actually a solid, high-molecular-weight organic compound called
kerogen. The origin of kerogen is attributed to plankton that for millions of years
existed in prehistoric lakes.
Oil shale sources are distributed widely in the world—more than 600 known. Oil
shale is located in the world with the greatest concentration in the entire USA. The
Green River Basin formation which covers portions of Colorado, Utah and
Wyoming is the largest such formation in the world. The majority of oil shale bed is
located on federal land. The USA includes all over 60 % of the world’s oil shale.
Oil shale well located in China, Estonia, Australia, Brazil, Canada, France, New
Zealand, South Africa, Spain, United Kingdom, Sweden, Switzerland and Turkey.
Shale oil from oil shale consists of the hydrocarbons; paraffins, olefins,
isoparaffins and naphthenes, isoolefins and cycloolefins, monocyclic aromatics, and
policyclic aromatics. The thermal decomposition of the organic matter generates
liquid and gaseous products.
Shale oil can be obtained from oil shale. The shale oil was a dark viscous organic
liquid obtained by pyrolyzing the samples of oil shale. It consists of the valuable
hydrocarbons such as paraffins, olefins, isoparaffins and naphthenes, isoolefins and
cycloolefins, monocyclic aromatics, and policyclic aromatics. The hydrocarbons
can be converted to petroleum-like liquid fuels such as gasoline and diesel fuel after
refining process.
The kerogen can be pyrolyzed and distilled into petroleum like oil. Oil shale and
bituminous materials suitable for obtaining petroleum like products. The process
designed study has the ability to control unwanted volatile materials. The mineral
matter is removed from oil shale before pyrolysis. The pyrolysis of the oil shale is
performed in a retort. The decomposition begins at 300 °C, but proceeds more
rapidly and completely at higher temperatures. Decomposition takes place most
quickly at a temperature between 475 and 525 °C.
Oil sands or tar sands generally consist of extra heavy crude oil or crude bitumen
trapped in unconsolidated sandstone. They cannot be produced by conventional
methods, transported without heating or dilution with lighter hydrocarbons, or
refined by older oil refineries without major modifications. Tight oil, including light
tight oil is crude oil contained in petroleum-bearing formations of low permeability,
often shale or tight sandstone.
Today, shale gas is the fastest growing unconventional resource here in the
United States and worldwide.
The extractives were recovered from the crude oil shale by using an ethyl
alcohol + benzene (1/1, v/v) solvent mixture. The procedures for obtaining the
demineralized extractive-free oil shale from crude oil shale are given in Fig. 4.21.
Elemental analysis of demineralized samples of typical oil shale (wt%) are given in
Table 4.27.
Any carbonization procedure requires an oxygen-free atmosphere as a basis for
carbonaceous matter or semicoke production. This practice is required to prevent
any combustion that may occur due to production of volatile matter and com-
bustible gases.
For carbonization the sample is preheated at 380 K for 1 h to get rid of extra
moisture that might affect further grinding. The sample is then transferred to a
Wiley mill, where it is ground to small grains, and was then screened to pass a
screen of 0.2-mm aperture. The ground meal is uniformly mixed before gasification
procedures.
The carbonization system is depleted from air by means of the vacuum pump,
after which the valves are both closed. The gasification chamber is then placed
4.11 Conversion of Oil Shale to Liquid Fuels 195
Fig. 4.21 Bitumious matter CRUDE OIL SHALE

and demineralized
extractive-free oil shale from
crude oil shale
Extraction with ethanol + benzene (1/1, v/v)
Bitumious matter Remainder
Demineralization
Extractive-free oil shale
Table 4.27 Elemental Carbon 59.7

analysis of demineralized
Hydrogen 7.5
samples of typical oil shale
(wt%) Oxygen 16.4
Sulfur 3.5
Nitrogen 1.3
Ash 11.6
inside the muffle furnace and the valve between heat exchanger units is opened for
enough time to allow the existing gases to escape to the main heat exchanger; then
the valve is closed and the valve between the main heat exchanger and the vacuum
pump is opened, so that gases were sucked through the vacuum pump. This opening
and closing cycle of valves is repeated every 3 min for the whole period of car-
bonization. The outlet gases could be collected easily and separated for their
constituents (Demirbas 2000).
The studies on hydropyrolysis of Göynük oil shale from Turkey in a Heinze
retort gave a relatively high tar yield (56 % daf shale), including paraffins (23.3 %),
aromatics (17.0 %), asphaltens (8.9 %), and polars (7.8 %), with a low yield of
hydrocarbon gases (4 %) (Citiroglu et al. 1990). The ratio of n-alkanes increased
with increasing steam velocity in hydropyrolysis. High-molecular-weight n-alkane
(C20–C30) distribution obtained from steam pyrolysis of Göynük oil shale indicated
that the shale included the general characteristic type 1 kerogen (Okutan et al.
1993).
The shale oil is a dark viscous organic liquid obtained by carbonizing the
samples of oil shale. Minimum temperature to achieve complete carbonaceous
matter production from the samples is 775 K, with a minimum heating time of
1.5 h. This temperature and time led to a reasonably fast procedure for producing
carbonaceous matter. Heating at 775 K for 1 h resulted in partial carbonization.
Carbonized materials were tested for their respective higher heating values and
compared with higher heating values of noncarbonized materials. It was concluded
that the higher heating values for carbonized materials (14,840 kJ/g) are lower than
for the noncarbonized (20,076 kJ/g), which indicates that the carbonization process
was successful, since part of the volatile matter including some combustible gases
was extracted by heating (Demirbas 2000).
4.12 Conversion of Used Oils to Gasoline-like Products
It is known that the waste engine oil (WEO) is highly viscous and contains plenty of
sulfur, carbon soots, small metal particles and some gum-like materials. The con-
taminants exist originally in the lubricating oils. In order to understand the pro-
duction processes of the waste oil, procedures of the processes should be explained
briefly. The production processes can be described in three sections, which are
purification, thermal treatment and distillation processes.
A recycling process was developed which eventually led to comparable results
with some of the conventional methods (Hamawand et al. 2013). This gives the
recycled oil the potential to be reused in cars’ engines after adding the required
additives. The advantage of using the acetic acid is that it does not react or only
reacts slightly with base oils. The recycling process takes place at room temperature.
It has been shown that base oils and oils’ additives are slightly affected by the acetic
acid. Upon adding 0.8 % by volume of acetic acid to the waste engine oil, two layers
were separated, transparent dark red colored oil and a black dark sludge at the bottom
of the container. The base oils resulting from other recycling methods were com-
pared to the results of obtained from acetic acid treatment method. The comparison
showed that the recycled oil produced by acetic acid treatment is comparable to those
recycled by the other conventional methods (Hamawand et al. 2013).
Optimum conditions for recycling used engine oil using this method are room
temperature and atmospheric pressure. The process for recycling is simple, as it
only requires mixing at room temperature, settling, centrifugation and finally
mixing with kaolinate. The base oil produced by the glacial acetic acid method is of
comparable quality to that produced by the acid-clay method. Also, it has a
potential to be reused in cars’ engines after adding the required additives
(Hamawand et al. 2013).
Waste engine oil is a high pollutant material that requires responsible manage-
ment. Waste engine oil may cause damage to the environment when dumped into
the ground or into water streams including sewers. This may result in groundwater
and soil contamination (Hamawand et al. 2013; Hopmans 1974). The oxidized and
polymerized products dissolved and suspended in the oil may cause an increase of
the oil viscosity, while decreases in the viscosity of engine oils indicate fuel con-
tamination. Oxidation of base oils during use in an engine environment produces
corrosive oxidized products, deposits, and varnishes which lead to an increase in the
viscosity (Diaz et al. 1996).
4.12 Conversion of Used Oils to Gasoline-like Products 197
Before experiments the air dried WEO samples are filtered to pass 250 mesh
sieves to separate metal particles and other particular materials. While the WEO is
flowed through the filters, it is purified from the oil from small dust, carbon soot,
small metal particles and some gum type materials.
The pyrolysis experiments are carried out in a laboratory scale apparatus. The
scheme of the pyrolysis is depicted in Fig. 4.22. The main element of this device is
a vertical reactor of stainless-steel. Figure 4.23 shows pyrolysis reactor. The reactor
is inserted vertically into an electrically heated furnace and provided with an
electrical heating system power source. The nominal heating time is 35 min. For
each run, the heater is started at 25 °C and terminated when the desired tempera-
ture. The most important part of the system is the reactor in which thermal treatment
of the WEO is carried out. It has a cylindrical shape with dimensions of 6 cm in
diameter and 10 cm in height and with cylindrical shape neck with dimensions of
2 cm in diameter and 20 cm in height. It has a capacity that will be able to produce
90 mL of fuel (Demirbas 2013).
The reactor is isolated with glass wool having a thickness of 5 cm to minimize
heat loss from the reactor. Electrical heaters with a total heating capacity of 3.5 kW
are used to heat the oil and were placed around the reactor container. The electrical
heaters have special resistance heaters which can heat the waste oil sample up to
600 °C. The heating rate can be controlled by the control unit adjusting voltage to
keep temperature of the oil at desired levels. Temperature measurement is per-
formed by means of thermocouple. It is placed in locations where temperature
measurement was needed, namely in the middle of the reactor. The other important
Fig. 4.22 The scheme of the pyrolysis. Heater, (2) Tube reactor, (3) Thermometer, (4)
Condensers, (5) Supports, (6) Erlenmeyer flask, (7) Balance (in Sila Science Lab.)
Fig. 4.23 The pyrolysis

reactor (in Sila Science Lab.)
component of the system is the condenser which is employed to condense the oil
exposed to pyrolitic distillation process. The fuel in the condenser is cooled and
condensed by cooling water.
The pyrolysis products are condensable liquids, non-condensable gaseous
products and solid residue. The yield of liquid products is defined as
Condensed liquids from pyrolysis

Yield of liquid products ¼ 100 ð4:12Þ
Mass of sample loaded into reactor
The yield of conversion was defined as
Condensed liquids and gases from pyrolysis

Yield of pyrolysis ¼ 100 ð4:13Þ
Mass of sample loaded into reactor
Two additives known as Na2CO3 and calcium oxide (CaO) were added to the
clean oil in the reactor and blended with mass basis of 2, 4, 6, 8 and 10 %,
separately. The new sample was mixed continuously and kept for 30 min at a room
temperature of 25 °C. Then, it was exposed to thermal and pyrolitic treatments. The
thermal and pyrolitic treatments of the samples were performed in the presence of
additives. Each sample mixed continuously was distillated and collected in a
container. Characteristics of the produced fuel such as density, viscosity, flash and
fire points, sulfur content, heat of combustion and distillation were examined, and
results were given in Table 4.28 and the tables in the following section.
This study was carried about purification and conversion of the waste engine oil
(WEO) into diesel-like fuel (DLF) by blending purified oil and additives of Na2CO3
and CaO with mass basis of 2, 4, 6, 8 and 10 %. Fuels were produced from the
WEO by applying pyrolytic distillation method. Thermal and physical character-
istics of the produced fuel samples such as flash point, density, viscosity and sulfur
contents, and distillation tests, were examined by using measurement devices. The
results obtained from the measurements were given in Table 4.28 and in relevant
figures.
Characteristics of any fuel are very important from the point of deciding whether
the fuel can be used for desired application or not. Therefore, some characteristics
of the produced DLF are measured, and these characteristics are shown in
Table 4.28, together with standard values of a diesel fuel and heavy fuel oil.
Table 4.28 shows that some of the parameters of density, boiling point, viscosity,
flash point and lower heating value are in the standard values of the diesel oil or
reasonably close to the standard values. But, sulfur amount is considerably higher
than that value. It should be decreased below the value of 50 ppm. Density is
another important property of diesel fuel. It is the weight of a unit volume of fluid.
The density of diesel fuel ranges between 820 and 845 kg/m3. Density of DLF is
Table 4.28 Physical properties of diesel fuel, heavy fuel oil and DLF obtained in the study
Physical property Diesel fuel TS3082-EN 590 Heavy fuel oil DLF
Density at 15 °C (kg/m3) 820–845 940 820
Viscosity at 40 °C (mm2/s) 2–4.5 – 3.6
Flash point (°C) >55 – 58
Sulfur (ppm) 50 60 3400
Water (mg/kg) <200 110 130
Lower heating value (kJ/kg) 42,700 42,675 42,525
Temperature at 250 °C, max. volume (% v/v) 65 – 20
Temperature at 250 °C, min. volume (% v/v) 85 – 90
Volume at 95 %, max. temperature (°C) 360 – 360
measured as 820 kg/m3, which is close to the lowest limit. Viscosity is one of the
most important properties of diesel fuels, since it affects the operation of the fuel
injection equipments particularly at low temperatures when the increase in viscosity
affects the fluidity of the fuel. High viscosity leads to poorer atomization of the fuel
spray and less accurate operation of the fuel injectors. Lower heating value
(LHV) of the DLF is obtained as 42,525 of kJ/kg by using adiabatic bomb
calorimeter. It is close to LHV of typical diesel fuel, which are 42,700 of kJ/kg.
A diesel fuel having of the heating value gives good engine performance during
combustion in a diesel engine (Demirbas 2013).
The distillation test results of the DLF, together with the diesel fuel, are shown in
Table 4.29.
It is clear that the distillation temperature of the DLF resembles to the distillation
temperature of the diesel fuel. Its distillation temperature is smooth and increases
gradually, like the diesel’s temperature, and its boiling point is closer to that of the
diesel. But its distillation temperature for each droplet is higher than that of the
diesel sample used in the study. The higher distillation temperature will give the
higher combustion efficiency, which will increase engine performance.
The effects of additives (Na2CO3 and CaO) on distillation temperatures are
shown in Tables 4.30 and 4.31, respectively. It is evident in Table 4.30 that dis-
tillation temperatures do not decrease for any values of the additives of Na2CO3, but
they increase for all Na2CO3 amounts.
As seen from Table 4.30, weight of the oil sample increases considerably, and its
volatility decreases depending on the amount of Na2CO3. However, it is clear in
Table 4.31 that 2 % of CaO, which is blended with the WEO, decreases the dis-
tillation temperature, and increases the volatility of the sample. Under the same
conditions, when 6 and 10 % of CaO are mixed with the oil, the distillation tem-
peratures increase and volatility decreases due to additives. It is not useful to add
the additives to the oil because of the increase in volatility. But, it is very useful to
add more additives to the oil in order to decrease the amount of sulfur. It is
Table 4.29 Distillation values of standard diesel fuel and DLF samples
Distillation volume (cm3) Temperature (°C) of Diesel fuel Temperature (°C) of diesel-like fuel
0 143 145
10 183 224
20 188 246
30 198 265
40 225 278
50 253 286
60 278 294
70 304 310
80 334 336
90 360 350
95 – 360
Table 4.30 Effect of Na2CO3 on distillation temperature

Distillation Temperature (°C) Temperature (°C) Temperature (°C) Temperature (°C)
volume (cm3) for 0 % Na2CO3 for 2 % Na2CO3 for 6 % Na2CO3 for 10 % Na2CO3
0 52 48 54 73
10 121 133 138 152
20 171 204 197 227
30 218 262 273 283
40 256 294 302 316
50 285 316 320 340
60 308 341 350 355
70 327 352 359 363
80 351 362 368 369
90 364 375 373 375
95 366 381 382 385
Table 4.31 Effect of CaO on distillation temperature

Distillation Temperature Temperature Temperature Temperature Temperature
volume (°C) for 0 % (°C) for 2 % (°C) for 4 % (°C) for 6 % (°C) for 10 %
(cm3) CaO CaO CaO CaO CaO
0 52 49 54 46 50
10 121 118 125 109 118
20 171 165 176 158 165
30 218 206 229 203 211
40 256 242 268 243 248
50 285 273 298 271 275
60 308 296 312 295 297
70 327 320 336 315 334
80 351 346 355 337 357
90 364 354 372 347 368
95 – 360 383 – –
necessary that distillation curve of any DLF should be parallel with the distillation
curve of diesel fuel, and also it is necessary that its thermophysical properties are
suitable to the same values of the diesel fuel. Under these conditions, utilization of a
fuel in a diesel engine will be suitable. It will be useful to compare the distillation
test results obtained with the distillation results of a diesel fuel.
Tables 4.32 and 4.33 show the distillation test results of the two samples
comprised of oil and additives of Na2CO3 and CaO with ratios of 2 and 10 %,
respectively.
Distillation test result of diesel fuel is also shown in these tables in order to
compare the effects of the additives on distillation temperatures. The tables
demonstrate that there is no positive effect of the additive of Na2CO3 blended with
the WEO except for the reduction in the sulfur amount in the sample. Moreover, the
Table 4.32 Effect of additives (2 %) on distillation temperature

Distillation Temperature (°C) for Temperature (°C) for Temperature (°C) for 2 %
volume (cm3) diesel fuel 2 % CaO Na2CO3
0 151 49 48
10 182 118 133
20 203 165 204
30 225 206 262
40 239 242 294
50 260 273 316
60 277 296 341
70 298 320 352
80 329 346 362
90 360 354 375
95 – 360 –
Table 4.33 Effect of additives (2 %) on distillation temperature

Distillation Temperature (°C) for Temperature (°C) for Temperature (°C) for
volume (cm3) diesel fuel 10 % CaO 10 % Na2CO3
0 151 50 73
10 182 118 152
20 203 165 227
30 225 211 283
40 239 248 316
50 260 275 340
60 277 297 355
70 298 334 363
80 329 357 369
90 360 368 375
95 – – –
distillation temperatures of the sample are far away from the distillation tempera-
tures of the diesel fuel.
When the WEO is blended with 2 % of CaO, distillation results of the samples
indicate parallel behavior with the temperatures of the present diesel fuel in a
volume of 30 %. This is a very important criterion due to the gradual increment of
distillation temperature at a finite value. This gradual increment is important
because the starting ability and warm-up property of the fuel is evaluated with the
evaporation temperatures of 20–70 % vaporization region of the distillation tem-
peratures (Archie 1991; Yumrutas et al. 2008). Vaporization at a very narrow band
of temperature is not desirable since it will result in an immediate burning and high
rate of pressure rise. The burning of all the fuel increases temperature and the
pressure of gas in the combustion chamber. Such a condition can give rise to
dangerous effects on engine components (Yumrutas et al. 2008). It is necessary that
a fuel sample burns gradually in a combustion chamber of an engine. When the

sample is used as a fuel in a diesel engine, there will be no damage to engine
components. 30 % amount of the samples is lighter than the diesel fuel. This is
useful for the initial starting operation of the engine, but it is detrimental for the
engine when the temperature of the engine increases. When 10 % amount of the
additive is blended with the oil sample, distillation temperatures increase, but they
continue to show a behavior parallel to the diesel fuel sample. That is, it is far away
from the diesel fuel sample. According to these data, it gives the best results by
utilizing 2 % of CaO as an additive after 30 % of total volume of the blend. The
best result of the decrease in sulfur amount in the waste oil and the effect of the CaO
on the distillation temperatures.
Light and heavy fuels need to be separated from each other in order to eliminate
the light portion of the fuel or the detrimental effects of the light portion on an
engine. Therefore, purified WEO was blended with 2 % CaO, and the blended oil
sample was distilled. Light amount of the sample comprising approximately first
25 % of the purified sample or 20 % of total oil sample was collected in a flask, and
the remaining 75 % part of the purified sample or 60 % of total oil sample was
collected in another flask. The first and second distilled portions were distilled
again. The distillation test results of the heavy fuel, together with the diesel fuel, are
shown in Table 2. It is clear that the distillation temperature of the heavy fuel
resembles to the distillation temperature of the diesel fuel. Hence, the produced
heavy fuel from the purified waste oil is named as diesel-like fuel (DLF). The
higher distillation temperature will give the higher combustion efficiency, which
will increase engine performance (Demirbas 2013).
The flash point of a flammable fuel is the lowest temperature at which it can
form an ignitable mixture in air. At this temperature the vapor may cease to burn
when the source of ignition is removed. The flash point is often used as one
descriptive characteristic of liquid fuel, but it is also used to describe liquids that are
not used intentionally as fuels. Density is also important property of a fuel since
air–fuel mixture and flame can propagate uniformly in combustion chamber of an
engine. Therefore, effects of the additives on the flash point and density are studied
in this work. The results show that flash points and densities increase with
increasing the additive content. Densities of the samples increase as a dependence
of densities of the additives. It is observed that the effect of the Na2CO3 on the flash
point is higher than the other additives, whereas the effect of the CaO is fairly
lower.
One very important consideration in the selection of a diesel fuel is its sulfur
content. While sulfur is one of the combustible elements in the fuel and generates
energy, the primary product of that combustion is sulfur dioxide (SO2), which is a
major environmental pollutant. The sulfur dioxide reacts with atmospheric water
vapor to produce sulfurous and sulfuric acids, both of which contribute to acid rains
(Archie 1991). That is why sulfur amount present in any fuel should be decreased
below the standard values if it is possible.
The additives decrease the sulfur amounts present in the waste engine oil. It is
known that there are several catalysis mechanisms to absorb sulfur present in the
waste oil. One of them is given by Guchhait et al. (2005).
Na2CO3 and CaO are used to investigate effects of them on density, viscosity,
flash point, sulfur content, heating value and distillation temperature. The effects of
additive amounts used in the present study on sulfur content of the purified oil
samples. It is that all of the additives have an important role in the decreasing of
sulfur content in the WEO. Sulfur content in the WEO decreases when the amount
of the additives increases. The highest decrease (65 %) in sulfur present in the
waste oil takes place when the CaO with the ratio of 10 % is blended with the oil.
CaO is the best additive for removal of sulfur in waste oil, due to its strong basic
character.
Two additives known as Na2CO3 and CaO with ratios of 2, 4, 6, 8 and 10 % are
blended with the purified waste engine oil. After the pyrolitic distillation of the
mixed samples is performed. Fuel characteristics of the DLF, such as density, flash
point, viscosity, sulfur content and heating value are tested and found to be close to
the values of the diesel fuel used.
4.13 Conversion of Heavy Oil to Light Products
Petroleum is separated into components in the refinery. An oil refinery can be

accepted as a factory that converts crude oil into a usable range of products by
distillation. Distillation is carried out in a fractionating column. The configuration
of refineries refinery changes from the refinery to another one. Other refinery
middle distillate production as a configuration more similar to jet fuel and gas oil
can be directed at, but some may have turned to gasoline production refinery
(Demirbas 2012).
Hundreds of different processed crude oil refinery in the world. Each is unique
and crude oil is a complex mixture of thousands of compounds. Most of the
compounds are hydrocarbons in crude oil. Any hydrocarbon species, or physical
and chemical properties of the molecule, and the total number of carbon atoms in
the molecule, also depend on the nature of chemical bonds between them.
Geographical religion, oil rigs, platforms and transport costs of bringing resource
efficiency and economic value, and environmental impact and ecological costs of
geological and geophysical characteristics affect the cost of all crude oil (Yin et al.
2015).
Petroleum consists of crude oil, natural gas, and heavy oil. Manufacturing plants
are used to separate oil into fractions of an oil refinery in a group. Refineries may
change the configuration of the refinery from the refinery. Production of middle
distillates such as jet fuel configuration other than refining and gas oil can be
oriented toward, but some refineries may be oriented toward the production of more
gasoline.
4.13 Conversion of Heavy Oil to Light Products 205
Table 4.34 Petroleum constituents from oil refinery

Fraction Distillation range (°C) Carbon number
Gas Below 20 C1–C4
Petroleum ether 20–60 C5–C6
Ligroin (light naphtha) 60–100 C6–C7
Natural gasoline 40–205 C5–C10, and cycloalkanes
Jet fuel 105–265 C8–C14, and aromatics
Kerosene 175–315 C10–C16, and aromatics
No. 1 diesel fuel 170–325 C9–C18, and aromatics
Gas oil (No 4 and 5 fuel oils) Above 275 C12–C70, and aromatics
Gas oil (No 6 fuel oils) Above 365 C20–C70, and aromatics
Lubricating oil Non-volatile liquids Long chains attached to cyclic structures
Asphalt or petroleum coke Non-volatile solids Polycyclic structures
An oil refinery typically consists of 24 units and it cleans and separates the crude
oil into a variety of fuels and byproducts, including gasoline, diesel fuel, heating oil,
and jet fuel. Petroleum constituents from oil refinery products are listed in
Table 4.34. Because the various components boil at different temperatures,
refineries use a heating process called distillation to separate the components. For
example, gasoline has a lower boiling point than kerosene, allowing the two to be
separated by heating to different temperatures. An important task of the refineries is
to remove pollutants from the oil. For example, sulfur from gasoline or diesel to
reduce air pollution from the automobile exhausts.
Fuel oils (numbers 1–6) are fractions of crude oil. The boiling point and carbon
chain length of the fuel increases with fuel oil number. Viscosity increases with the
number, and need to flow the heated heavy oil. Viscosity is a major important
property for heavy industrial and bunker fuel.
The term fuel oil is used in heavy commercial fuel that can be obtained from
crude oil, for example, heavier than gasoline and naphtha. Fuel oils are divided into
broad classifications: distillates (Nos. 1–3), distillates and residuals (No. 4), and
residuals (Nos. 5 and 6). No. 4 fuel oils are used as burner fuel for domestic and
industrial heating and have to raise steam for power generation and marine
propulsion. The physical properties such as flash point, ash, and density (at 15 °C)
values of grade No. 4 fuel oil are given as 38–55 °C, 0.05–0.10 % mass,
and >876 kg/m3, respectively (ASTM 1998).
Fuel oil No. 4 usually a very light residual, but it sometimes contains heavy
distillate. It is designed to be used in burners equipped with devices higher
atomizing oils of higher viscosity than native burners can handle. Its viscosity range
allows it to be allowed pumped and atomized at relatively low storage temperature.
Heating devices require heating before use. This must be heated by a special
heating system before it is used, so that the viscous and pollutants, combustion, and
sulfur forms, particularly sulfur dioxide, can contain relatively high amounts
because less fuel oil is no longer useful (Demirbas 2015a, b, c). However, it is very
cheap and has undesirable characteristics. In fact, it was the cheapest fuel available.
The thermal conversion of organic materials to valuable liquid, solid (char) and
gaseous products can be carried out using direct and catalytic pyrolysis methods.
In the 1980s, researchers found that the pyrolysis liquid yield could be increased
using fast pyrolysis where a fuel oil feedstock is heated at a rapid rate and the
vapors produced are also condensed rapidly. It is believed that as the pyrolysis
progresses the unreacted material becomes less reactive and forms stable chemical
structures, and consequently the activation energy increases as the conversion level
of the rest increases. Therefore, the reaction rate gradually decreases during the
pyrolysis.
Before experiments the samples were filtered to pass 0.25 mm screen opening
and then uniformly mixed before applying for experiments.
The pyrolysis diagram was depicted in a previous study (See Fig. 4.22). This
device included a tube reactor of stainless steel (Demirbas et al. 2015). The tube
reactor is inserted vertically into an electrically heated oven, and is provided with a
power supply of an electrical heating system. The nominal heating time was
45 min. For each study, the heater was started at 25 °C and was terminated at the
desired temperature. The most important part of the species system is a reactor in
which thermal treatment of the grade No. 4 fuel oil was carried out. It has a
cylindrical shape with dimensions of 6 cm diameter and at the height of 10 cm and
with a cylindrical shape neck with dimensions of 2 cm diameter and at the height of
20 cm. This reactor has a production capacity of 90 mL No. 4 fuel oil.
The heating rate can be controlled by control unit oil temperature adjusting
voltage to maintain a desired level. Temperature measurement was carried out by
means of thermocouples. Temperature measurement (i.e., the middle of the reactor)
is disposed where necessary. Another important component of the system used to
concentrate the No. 4 fuel oil subjected to the pyrolytic distillation condenser. The
obtained full product was cooled and is condensed by cooling water.
The pyrolysis products are condensable liquids, noncondensable gases, and solid
residue. The liquid yield is defined as
Condensed liquids from pyrolysis

Yield of liquid products ¼ 100 ð4:14Þ
Mass of sample loaded into the reactor
The yield of conversion was defined as
Condensed liquids and gases from pyrolysis

Yield of pyrolysis ¼ 100 ð4:15Þ
Mass of sample loaded into the reactor
Sodium carbonate (Na2CO3) was added to the clean No. 4 fuel oil sample in the
reactor and blended with a mass basis of 5 and 10 %, separately. The new sample
was mixed continued and kept for 30 min at a room temperature of 25 °C. Then,
the thermal and pyrolitic treatments of the samples were performed in the presence
of Na2CO3 at different heating rates: 20, 40, 60, and 80 °C/min. Each sample mixed
has continuously been distillates and collected in a dark flask.
This study was carried about conversion of the grade No. 4 fuel oil into gasoline
and No. 2 diesel fuel by pyrolysis with blending purified sample and catalyst
amount of Na2CO3 with a mass basis of 5 and 10 %.
Table 4.35 shows the yields of pyrolytic distillation obtained from No. 4 fuel oil
at different temperatures (between 160 and 340 °C) and different heating rate values
(between 20 and 80 °C/min) without catalytic pyrolysis. Tables 4.36 and 4.37 show
the yields of pyrolytic distillation obtained from No. 4 fuel oil at different tem-
peratures (between 160 and 340 °C) and different heating rate values (between 20
and 80 °C/min) by 5 and 10 % Na2CO3 catalytic pyrolyses.
As seen in Table 4.34, the yields of pyrolytic distillation from noncatalytic runs
of No. 4 fuel oil (sample: 30.78 g) were 0.15, 0.21, 0.29, and 0.40 g by using 20,
40, 60, and 80 °C/min heating values, respectively, at 115–160 °C. The yields of
pyrolytic distillation of No. 4 fuel oil (sample: 30.78 g) were 9.40, 9.62, 9.89, and
10.44 g by using 20, 40, 60, and 80 °C/min heating values, respectively, at 340 °C.
The yields of pyrolytic distillation from noncatalytic runs of No. 4 fuel oil sharply
increase between 230 and 255 °C at all runs. These results indicate the highest yield
is 33.9 %.
As seen in Table 4.35, the yields of pyrolytic distillation from 5 % Na2CO3
catalytic runs of No. 4 fuel oil (sample: 32.64 g) were 0.25, 0.34, 0.47, and 0.62 g
by using 20, 40, 60, and 80 °C/min heating values, respectively, at 160 °C. The
yields of pyrolytic distillation from 5 % Na2CO3 catalytic runs of No. 4 fuel oil
(sample: 32.64 g) were 11.65, 12.30, 13.75, and 14.80 g by using 20, 40, 60, and
80 °C/min heating values, respectively, at 340 °C. According to these results the
highest yield is 45.3 %.
As seen in Table 4.37, the yields of pyrolytic distillation from 10 % Na2CO3
catalytic runs of No. 4 fuel oil (sample: 32.62 g) were 0.21, 0.30, 0.42, and 0.56 g
by using 20, 40, 60, and 80 °C/min heating values, respectively, at 160 °C. The
yields of pyrolytic distillation from 10 % Na2CO3 catalytic runs of No. 4 fuel oil
(sample: 32.62 g) were 11.79, 12.55, 14.35, and 14.96 g by using 20, 40, 60 and
80 °C/min heating values, respectively, at 340 °C. According to these results the
highest yield is 45.9 %.
The conversion of No. 4 fuel oil was high (45.9 %) and the product distribution
was depended on the pyrolysis temperature, heating rate, catalyst, residence time,
and reactor size. The pyrolysis products consisted of liquid (gasoline and
No. 2 diesel fuel), gas (CO, CO2, H2), and water. The yields of conversion increase,
increasing temperature from 195 to 340 °C and sharply increase between 230 and
255 °C at 135 all runs. The yields of distillate from the distillation were 14.7 %
(Table 4.34) and 28.4 % at 230 K and 255 °C, respectively. The yields of distil-
lates reach plateau values between 275 and 310 °C.
The yield of conversion slightly increased with increasing catalyst percentage.
The highest yields were 45.3 and 45.9 % in 5 and 10 % Na2CO3 catalytic runs,
respectively. The yields of conversion increase, increasing heating rate between 20
and 80 °C/min at all runs.
Table 4.35 Non-catalytic pyrolytic distillation results. Sample: 30.78 g

Temperature (°C) 20 (°C/min) 40 (°C/min) 60 (°C/min) 80 (°C/min)
160 0.15 0.21 0.29 0.40
165 0.24 0.30 0.38 0.50
170 0.51 0.57 0.66 0.77
175 0.86 0.94 1.03 1.15
180 1.25 1.33 1.43 1.61
185 1.68 1.75 1.86 1.95
190 2.12 2.21 2.30 2.38
195 2.58 2.64 2.70 2.80
200 2.81 2.89 3.01 3.11
205 3.06 3.15 3.20 3.27
210 3.28 3.37 3.47 3.60
215 3.47 3.55 3.71 3.85
220 3.65 3.74 3.90 4.05
225 3.81 3.89 4.05 4.20
230 3.98 4.08 4.23 4.37
235 4.37 4.47 4.65 4.81
240 4.92 5.02 5.30 5.57
245 5.39 5.50 5.82 6.03
250 5.98 6.15 6.37 6.59
255 6.66 6.81 7.08 7.36
260 6.98 7.18 7.36 7.58
265 7.09 7.29 7.55 7.73
270 7.40 7.57 7.78 7.94
275 7.68 7.86 8.11 8.32
280 7.93 8.09 8.23 8.46
285 8.14 8.32 8.45 8.62
290 8.29 8.44 8.62 8.78
295 8.43 8.60 8.83 9.02
300 8.50 8.67 8.89 9.10
305 8.60 8.76 8.97 9.21
310 8.74 8.94 9.14 9.43
315 8.87 9.05 9.29 9.62
320 9.00 9.21 9.42 9.84
325 9.12 9.33 9.54 10.03
330 9.22 9.37 9.67 10.21
335 9.31 9.48 9.78 10.34
340 9.40 9.62 9.89 10.44
The yields of conversion increase, increasing residence time. The residence time
generally depends on reactor size. The residence time is increase, increasing the
reactor size.
Table 4.36 5% catalytic pyrolytic distillation results. Sample: 32.64 g

160 0.25 0.34 0.47 0.62
165 0.33 0.44 0.58 0.85
170 0.59 0.65 0.77 1.64
175 0.94 1.22 1.35 2.44
180 1.34 1.62 1.75 2.80
185 1.79 2.20 2.44 2.98
190 2.24 2.66 2.90 3.10
195 2.70 3.11 3.36 3.48
200 2.93 3.35 3.62 3.84
205 3.20 3.62 3.90 4.35
210 3.39 3.83 4.12 4.88
215 3.58 3.74 4.23 5.34
220 3.76 3.93 4.33 5.64
225 3.92 4.06 4.47 6.32
230 4.13 4.30 4.72 6.82
235 4.51 4.85 6.14 7.32
240 6.09 6.61 6.90 7.78
245 6.86 7.39 7.68 8.50
250 7.28 7.81 8.11 9.16
255 8.13 8.66 8.97 9.30
260 8.49 9.03 10.34 9.66
265 9.06 9.60 10.92 9.96
270 9.41 9.95 11.27 10.20
275 9.64 10.19 11.52 10.64
280 9.93 10.49 11.84 11.04
285 10.16 10.72 12.07 11.38
290 10.29 10.86 12.23 11.88
295 10.47 11.05 12.43 12.10
300 10.53 11.10 12.50 12.27
305 10.64 11.22 12.61 12.46
310 10.84 11.43 12.82 12.78
315 10.99 11.59 12.99 13.08
320 11.17 11.78 13.19 13.74
325 11.26 11.88 13.30 14.02
330 11.39 12.02 13.45 14.48
335 11.52 12.16 13.60 14.66
340 11.65 12.30 13.75 14.80
The yield of gasoline-like from No. 4 fuel oil was 10.6 % in the noncatalytic
conversion, while of 13.3 % was obtained in the catalytic conversion by the method
of pyrolytic distillation.
Table 4.37 10% catalytic pyrolytic distillation results. Sample: 32.62 g

160 0.21 0.30 0.42 0.56
165 0.28 0.40 0.53 0.80
170 0.52 0.61 0.72 1.57
175 0.90 1.17 1.30 2.38
180 1.30 1.56 1.69 2.72
185 1.73 2.15 2.38 2.90
190 2.18 2.60 2.88 3.02
195 2.60 3.05 3.29 3.10
200 2.83 3.30 3.56 3.18
205 3.14 3.56 3.82 3.89
210 3.31 3.77 4.03 4.71
215 3.50 3.68 4.17 5.22
220 3.70 3.87 4.33 5.58
225 3.84 4.00 4.40 6.21
230 4.05 4.24 4.65 6.69
235 4.43 4.79 6.08 7.24
240 6.00 6.54 6.84 7.70
245 6.80 7.31 7.60 8.44
250 7.20 7.73 8.03 9.11
255 8.05 8.60 8.90 9.25
260 8.41 9.00 10.27 9.62
265 9.00 9.62 10.85 9.90
270 9.36 9.99 11.21 10.15
275 9.63 10.23 11.46 10.59
280 9.96 10.56 11.76 11.00
285 10.22 10.78 12.00 11.35
290 10.37 10.91 12.10 11.85
295 10.56 11.12 12.16 12.10
300 10.62 11.18 12.25 12.30
305 10.73 11.28 12.47 12.51
310 10.93 11.49 12.76 12.85
315 11.13 11.66 12.98 13.16
320 11.30 11.87 13.38 13.83
325 11.41 11.96 13.70 14.13
330 11.52 12.15 13.95 14.61
335 11.64 12.44 14.16 14.80
340 11.79 12.55 14.35 14.96
The yield of No. 2 diesel-like was 23.3 % in the noncatalytic conversion, while
of 32.6 %was obtained in the catalytic conversion. The yield of No. 2 diesel-like
obtained from the catalytic conversion was higher 39.9 % than that of the non-
catalytic conversion.
4.14 Upgrading of Crude Oil and Heavy Oil 211
4.14 Upgrading of Crude Oil and Heavy Oil
4.14.1 Introduction
A crude oil has four main constituents: Saturates; aromatics, resins and asphaltenes
(SARA constituents). Main properties of crude oil SARA fractions are given in
Table 4.38. Saturates are non-polar aliphatic hydrocarbons, without double bonds,
but including straight-chain and branch alkenes as well as cycloalkanes (naphtenes).
Figure 4.24 shows a representative structure of resins fraction in crude oil (Akmaz
et al. 2011). The aromatics consist of aromatic groups with aliphatic side chains.
Crude oil contains a wide variety of aromatic hydrocarbons ranging from mono
aromatics hydrocarbons such as benzene to poly aromatic hydrocarbons (PAHs)
with many fused aromatic rings. Figure 4.25 shows a representative structure of
aromatics fraction in crude oil.
Resin is composed of fused aromatic rings with branched paraffin and polar
compounds often containing heteroatoms such as nitrogen, oxygen or sulfur. The
resin fraction is operationally defined as the fraction soluble in light alkanes such as
Table 4.38 Main properties of crude oil SARA fractions

Satrurates The saturate fraction mostly contains aliphatic compounds. The saturates are
non-polar aliphatic hydrocarbons, without double bonds, but including
straight-chain and branch alkenes as well as cycloalkanes (naphtenes)
Aromatics The aromatic fraction consists of aromatic groups with aliphatic side chains.
Crude oil contains a wide variety of aromatic hydrocarbons ranging from mono
aromatics hydrocarbons. More than 85 % of the aromatic hydrocarbons in
crude oil contain one or more alkyl substituent on their aromatic rings
Resins Resin is composed of fused aromatic rings with branched paraffins and polar
compounds often containing heteroatoms such as nitrogen, oxygen or sulur.
Resin is a heavier fraction than aromatics and saturates. The resin fraction is
operationally defined as the fraction soluble in light alkanes such as pentane
and heptane, but insoluble in liquid propane. Resins are structural similar to
asphaltenes, but smaller in molecular weight
Asphaltenes Asphaltenes fraction is insoluble in n-alkane solvents and the most complex
fraction of crude oils. In these circumstances higher asphaltene content in crude
oil causes processing problems during refining operations
Fig. 4.24 Representative structure for saturate fraction of crude oil

Fig. 4.25 Representative

structure for aromatic fraction
of crude oil
pentane and heptane, but insoluble in liquid propane. Resin is a heavier fraction
than aromatics and saturates.
Figure 4.26 shows a representative structure of resins fraction in crude oil
(Akmaz et al. 2011). Resins and asphaltenes have high aromatic structure.
However, the aromaticity of the asphaltenes is higher than those of the resins
(Andersen and Speight 2001).
The color of dissolved asphaltenes is deep red at very low concentration in
benzene, as 0.0003 % makes the solution distinctly yellowish. The color of crude
oils and residues is due to the combined effect of the neutral resins and asphaltenes.
The black color of some crude oils and residues is related to the presence of
asphaltenes, which are not properly peptized (Demirbas 2002a, b).
The resin fraction can contain constituents of equal polarity to the constituents of
the asphaltene fraction, gas well as form high yields (approximately 35 % by
weight) of thermal coke and contribute to catalyst deactivation. And it is the resin
fraction that apparently is extremely important in terms of the structure and stability
of petroleum (Andersen and Speight 2001). Figure 4.27 shows the separating of
crude oil into the four fractions: saturates, aromatics, resins and asphaltenes. Main
upgrading processes of crude oils are given in Table 4.39.
Heavy oil is a type of crude oil. Heavy oil is considered an unconventional oil
source primarily because it does not readily flow out of the earth like conventional
petroleum crude oil. Specific gravity of heavy oil is considerably higher than the
specific gravity of light oil.
Heavy oil is less expensive than light crude oil, but heavy oil is more expensive
to obtain light oil products. Conventional light crude oil resources are decreasing
heavy oil resources will be needed more in the future. There are huge differences
from field to field for heavy oil deposits. Similarly, the recovery methods also vary

structure of resin fraction in
crude oil
Fig. 4.27 Separating of CRUDE OIL

crude oil into the four
fractions: saturates, aromatics,
resins and asphaltenes N-hexane treatment
Insolubles Solubles
Maltenes (Malthenes or Petrolenes)

Asphaltenes
Adsorbtion on silica
Eluted with Eluted with Adsorbed

n-alkane toluene
Saturates Aromatics Resins
Table 4.39 Main upgrading processes of crude oils

Refining Refining is the manufacture of petroleum products from crude oil. Refining
involves two major branches; separation processes and conversion processes
Extraction The crude oil extraction includes primary, secondary and tertiary recovery
treatments
Distillation A mixture of many types of hydrocarbons is boiled and re-condensed to separate
the crude oil into components based on ranges of boiling points in fractionation
column (See Fig. 1.2)
Hydro-processing The objective of this process is to remove sulfur from the component stream. Low
sulfur content of crude oil is particularly preferred
Reforming This process converts a low value component called ‘naphtha’ into a higher
octane number product known as gasoline using a platinum catalyst
Catalytic This process involves the breaking up of large hydrocarbon molecules into
Cracking smaller molecules using a combination of heat and catalytic action
Secondary These are mainly involved with further polishing of components and products to
Processes remove sulfur and other impurities
Deasphalting Most of harmful components for the subsequent upgrading processes could be
removed by solvent deasphalting processes
Blending The major refinery products produced by the product blending process are
gasoline, jet fuels, heating oils and diesel fuels. Blending is the physical mixture
of a number of different liquid hydrocarbons to produce a finished product with
certain desired characteristics. Gasoline blending is a refinery operation that
blends different component streams into various grades of gasoline. Additives
including octane enhancers, metal deactivators, anti-oxidants, anti-knock agents,
gum and rust inhibitors, detergents, etc. are added during and/or after blending to
provide specific properties not inherent in hydrocarbons
from well to well. The aim of the research done recently is to reduce the cost of
lighter products from heavy oil. However, heavy oil offers many challenges to
traditional refining technologies. Future refining strategies will focus on upgrading
the heavy oils and the importance of differences between the properties of the heavy
oil feedstocks. Currently, more than half of the world’s oil reserves are in the form
of restorable oils such as heavy oil, extra heavy oil, oil sand, tar sands, oil shale and
bitumen. Table 4.40 shows total world oil reserves.
Heavy oil feedstocks contain resins, asphaltenes and waxes dissolved in the oil
fraction. Resins fraction of crude oil is comprised of polar molecules often con-
taining heteroatoms such as nitrogen, oxygen or sulphur. The resin fraction is
soluble in light alkanes such as pentane and heptane, but insoluble in liquid pro-
pane. The H/C ratio of resins is between 1.2 and 1.7 than that of higher of
asphaltenes; the H/C ratio of asphaltenes is between 0.9 and 1.2. Resins are
structural similar to asphaltenes, but smaller in molecular weight. The resin fraction
is very important with regard to crude oil properties. Naphthenic acids are com-
monly regarded as a part of the resin fraction (Ficken et al. 2002).
As said earlier that the world’s supply of light crude oil is depleting and as a
result the transportation fuels demand including gasoline has significantly
increased. Therefore, the sources of heavy oil and petroleum fractions residue are
gaining special attention for keeping the constant future fuel supply (Santos et al.
2014). The oily sludge fuel processing technology provides a new route for the
environmental disposal and utilization of oily sludge as a fuel source (Xu et al.
2009). A new combined process of atmospheric flash evaporation with solvent
deasphalting was initiated as a way forward for oily sludge treatment. According to
Ning et al., the optimum operating conditions of solvent deasphalting process were
recorded at isopentane solvent, temperature (175 °C), pressure (3.7 MPa) and
solvent volume ratio (5.0).
The critical materials from petroleum processing and refining industry are heavy
oils and asphalt. They have different applications in petroleum industry due to
inherent differences in structure and composition. For example, the structure and
composition of paving asphalt dictates its properties (Shui et al. 1997). A large
fraction of oily sludge is produced from the refineries during the crude oil refining.
This sludge contains benzenes, phenols, anthracenes, pyrenes, and other smelly and
toxic substances that are legally classified as hazardous waste. Moreover, the sludge
results in environmental pollution when discharged untreated into the environment
(Hou et al. 2013).
The hydrocarbons, heterocyclic and polyaromatic and organometallic com-
pounds such as porphyrins are the larger molecular weight components with
Table 4.40 Total world oil Reserve Percent of total

reserves
Conventional oil 46.7
Oil sands/Bitumen 32.0
Heavy oil 21.3
Recoverable oils 53.3
complex organic chemical structures present in heavy crude oil (Bhatia and Sharma
2006). Viscosity of heavy oils is a critical characteristic parameter in designing of
any potential optimized oil recovery process (Raut et al. 2013). Recycling and
re-refining are the application processes for converting petroleum based heavy
products into light products such as gasoline and diesel fuel. In this regard,
pyrolysis, cracking and hydrocracking processes are considered appropriate and
promising. According to Meng et al. (2006), the catalytic pyrolysis is an emerging
technology for the conversion of heavy oil into light olefins. Figure 4.28 shows
heavy oil upgrading via thermochemical conversion processes.
The content of carbon (C) and hydrogen (H2) are more than 95 % in most heavy
crude oil (Lin 2000). Therefore, the small amount of nonhydrocarbon elements
have little influence on the physical properties of molecules, thus it is acceptable to
ignore them in the distillation simulation of crude oil (Jiang et al. 2013). According
to Stratiev et al., heavy oils contain different fractions, which cannot be separated at
atmospheric distillation and remain as residue. Oil sand is also one of the uncon-
ventional oil resources that is found very useful in past few years (Li et al. 2011).
According to Wu et al. (2015), exploring extremely shallow oil sand in reservoirs of
heavy oil is also an effective and economical way. The conversion of heavy stock to
lighter products is based on the thermal conversion reaction of heavy oil e.g.
delayed coking and breaking with cleavage. The thermal conversion mechanism
becomes complicated due to the complexity of heavy oil components (Xiao et al.
2002). The factors affecting the heavy oil upgrading are catalyst management,
heavy oil features, process design and financial aspects (Akhavan et al. 2014).
The process of heavy oil recovery using biological wastewater treatment method
is based on the microorganisms with high oil degrading capability, organic loads,
process stability, resistance to shock loading, minimum production of waste sludge
byproducts and using anaerobic and aerobic processes (Kang 2014). Two most
common technologies for heavy oil upgrading are hydrocracking and thermal
Fig. 4.28 Heavy oil upgrading via thermochemical conversion processes

cracking. Both technologies upgrade the heavy vacuum residues by breaking down
the heavy components into lighter compounds with more valuable hydrocarbon
fractions. In hydrocracking, two beneficial roles of water were considered. Water
allows formation of highly crystalline metal oxides (smaller particles) as being a
high potential medium containing low dielectric constant and density at critical
point of 374 °C, 22.1 MPa.
The upgrading of heavy oil depends on the variations in its properties and thus
changes from oil field to oil field. According to Demirbas (2005), a facility can
process whole heavy crude oils containing API as low as 6. Such facility is consist
of atmospheric and vacuum distillation columns and a reaction section, where
unconverted bottoms are recycled into synthetic sour crude product. According to
Nemli (2015), the Feedstock Test Facility (FTF) has the capability to process 10–15
barrels of heavy oil per day on a constant basis.
The technology is comparable to a fluidized catalytic cracking unit in a standard
petroleum refinery for upgrading the highly variable and low value petroleum without
using catalyst. The chemistry of catalytic cracking of heavy oils is fundamental and
crucial in the development of advanced catalytic cracking techniques (Gao and Xu
1999). The catalyst technologies are constantly improving, as previously they were
not suitable for upgrading heavy oil due to the large quantities of coking that inac-
tivates the catalysts. Moreover, the catalysts are expensive in comparison to common
silica sand used in this new process. This upgrading makes a syncrude, which can
easily flow and contain less density and contamination in the form of S and metals in
comparison to the initial phase of heavy oil (Meng et al. 2006).
For heavy oil upgrading, the FTF with a fluidized bed unit is a small facility
considered as the technology center. The technological advantages of the fluid
catalytic cracker (FCC) units are critical for FTF comparable operations (Nemli
2015), as they convert low value and heavy end refining byproducts to high value
petroleum products such as gasoline, diesel and kerosene. Therefore for today
refinery, the FCC units are the significant parts. Moreover, they access refiners to
use most of the crude oil through converting the high boiling point portion of the
substrate into the boiling point range of specialized fuels. This conversion also
changes the refinery production parameters to produce more valuable products
(Santos et al. 2014).
4.14.2 Deposition and Flocculation of Asphaltenes

from Petroleum
Asphaltenes are one of the most complex, highest molecular weight (approximately
1000–2,000,000) and heavy organic compounds present in crude oils. Asphaltenes
can be obtained from five different sources such as crude oil, asphaltite, oil shale, tar
sand and bituminous coal. All types of heavy oils contain asphaltenes and thus are
considered very dense substances. They have structurally condensed polynuclear

structure of asphaltene
fraction in crude oil
aromatic rings mainly with chains of alkyl side. The number of these rings differs
from 6 to 15 in asphaltenes. Figure 4.29 shows a representative structure of
asphaltene in crude oil.
The asphaltenes contain different hydrocarbon components such as condensed
aromatic hydrocarbons, hetero-aromatic compounds, bi or poly-functional mole-
cules (such as ketones, amides, phenols and carboxylic acids) and metals (such as
Ni and V) (Demirbas 2015a, b, c). They are generally characterized based on their
solubility in alkanes such as pentane and heptanes. Moreover, they tend to make
clusters and precipitate that cause fouling in process equipment (Garcia-Hernandez
1989; Mousavi-Dehghani et al. 2004).
The asphaltene fraction of a crude oil is defined according to Nellensteyn (1924)
as the fraction insoluble in low boiling point paraffin hydrocarbons but soluble in
carbon tetrachloride and benzene. According to Pfeiffer (1950), asphaltene is
defined as the fraction insoluble in n-heptane but soluble in toluene.
Many problems could become apparent during production, processing, storage
and transportation of crude oils due to heavy organic separation. Heavy organic
compounds, such as wax, resin, asphaltene, diamondoid, mercaptans and
organometallic compounds, may be present in crude oil in various amounts and
forms. Such compounds may cause a blockage in the oil reservoir in the wells, in
the pipelines and can be precipitated from the crude solution in the oil production
and processing facilities (Mansoori 1997).
Changes in pressure, temperature, composition and shear rate may cause
asphaltene precipitation and deposition. Asphaltenes can precipitate on metal sur-
face. Cleaning the precipitation site as well as possible appears to slow reprecipi-
tation. Deposition of asphaltenes in petroleum crude and heavy oil can cause a
number of severe problems (Lichaa 1977; Leontraritis and Mansoori 1988;
Mansoori 1997; Branco et al. 2001). To prevent deposition inside the reservoir, it is
necessary to estimate the amount of deposition due to various factors. Asphaltene
flocculation is generally followed by the deposition of precipitate containing which

are insoluble in crude oils and containing other heavy organics and mineral
deposits. The precipitation of asphaltene aggregates can cause such severe problems
as reservoir plugging and wettability reversal (Collins and Melrose 1983;
Leontaritis and Mansoori 1988).
The processes can be changed to minimize the asphaltene flocculation, and
chemical applications can be used effectively to control depositions when process
changes are not cost effective. Flocculation of asphaltene in paraffinic crude oils is
known to be irreversible. Asphaltene and its flocculates are known to be surface
active agents. It is known that as gas is injected into a reservoir, the likelihood of
asphaltene flocculation is increased (Borchardt 1989).
A common practice in the petroleum industry is to separate the crude oil into
four chemically distinct fractions. The standard procedures for asphaltene separa-
tion consist mainly of precipitation of asphaltenes by excess n-alkanes (typically 40
volumes of n-alkane to 1 volume of oil). Figure 4.30 shows the separating crude oil
into asphaltenes and maltenes (saturates, aromatics and resins).
Asphaltenes are a solubility range that is soluble in light aromatics such as
benzene and toluene, but is insoluble in lighter paraffins. The particular paraffins,
such as n-pentane and n-heptane, used to precipitate asphaltenes from crude oil.
Asphaltenes and resins are important, heavy organics present in crude oils.
Asphaltenes are operationally defined as the non-colatile and polar fraction of
petroleum that is insoluble in n-alkanes. Conversely, resins are defined as the
CRUDE OIL
n-alkane filtration
Precipitate
Insolubles Solubles
Deasphaltened oil Maltenes
Aromatic washing
Adsorbtion on silica
Solubles Insolubles
Asphaltenes Carbenes
and carboids Eluted with Eluted with Adsorbed
n-alkane toluene
Saturates Aromatics Resins
Fig. 4.30 Separating petroleum into asphaltenes, saturates, aromatics and resins
non-colatile and polar fraction of petroleum that is soluble in n-alkanes and aro-
matic solvents and insoluble in ethyl acetate (Demirbas 2000, 2002a, b, c). Unlike
resins, asphaltenes contain highly polar species that tend to associate.
A sample containing asphaltene is mixed with pentane and centrifuged. The
asphalt solution is decanted, and the precipitate is washed twice with pentane, dried,
and weighed. For toluene-insoluble constituents a separate sample of the asphalt is
mixed with pentane and centrifuged. The precipitate is washed twice with pentane,
once with toluene-alcohol solution, and once with toluene. The insoluble material is
then dried and weighed (Speight 2007).
Deasphalting processes of the residues carried out in a very short time. In this
way, costly studies and refinery or pilot-plant trial runs may be avoided or mini-
mized with the corresponding savings in cost and time. Most of harmful compo-
nents for the subsequent upgrading processes could be removed by solvent
deasphalting processes. However, solvent deasphalting processes would associate
de-oiled asphalt with high softening point and low penetration (Cheng et al. 2014).
The deasphalting process of crude oil in supercritical conditions is a promising
and efficient alternative to the separation of asphalt from oil (Cárdenas Concha
2010; Lodi et al. 2014, 2015a, b; Filho and Maciel 2015). Solvent deasphalting
process is an effective pretreatment upgrading technology for vacuum residuum
(Cheng et al. 2014).
Supercritical fluid treatment is generally carried out in a mechanically stirring or
in a rocking batch reactor at the critical temperature and the pressure of the solvent.
The yield of soluble material increases with increasing pressure. Supercritical fluid
treatment depends on various parameters such as pressure, temperature, extraction
time, solvent type and chemical composition of the extracted material.
A supercritical fluid above its critical temperature and critical pressure is any
substance showing both liquid and gas properties. It can penetrate through solid like
a gas and can dissolve materials like a liquid (Dey and Bhattacharya 2016).
The supercritica1 solvent extraction is a very attractive process since the solvent
can be easily removed from the extraction mixture by without additional separation
process and operating cost (Ely and Baker 1983). The extraction residue obtained
near the critical temperature and over the critical pressure of propane solvent
showed appropriate properties as a precursor pitch for carbon materials, high
asphaltene contents, low toluene insolubles and the adequate softening point of
128–151 °C. The extraction yields of deasphalted oil were increased as the system
pressure was increased corresponding to the increased density of propane solvent
(Kim et al. 1997).
Water above its critical point is potentially quite important as a solvent for
organic compounds. Above 350 °C, water becomes miscible with oils and aro-
matics, since the dielectric constant of supercritical water are reduced about 10
times, which is similar to that of polar organic solvents at room temperature
(Demirbas 2011a, b, c; Timko et al. 2015).
The residual fractions of the bitumens after supercritical water extraction were
mixed with n-hexane to yield asphaltenes as hexane insolubles. The asphaltenes
contain highly polar substituents and are insoluble in an excess of n-heptane (or
n-pentane). The measured asphaltene content of the residual fractions was com-
pared with the asphaltene content of the original bitumen. On the basis of mass
balance for asphaltenes, it is expected that liquid extractions obtained after super-
critical reaction have no asphaltene. As a result, it is possible to remove most
asphaltene in bitumen feed through supercritical extraction (Park and Son 2011).
A petroleum residue sample subjected to supercritical carbon dioxide extraction.
In supercritical conditions, the products in the deasphalted oil (DAO) stream pre-
sent adequate characteristics for the production of lubricant oils and those in the
asphalt residue stream present an elevated concentration of asphalt molecules (Lodi
et al. 2015a, b).
Figure 4.31 shows the supercritical fluid extraction (SFE) for determination of
asphaltene in crude oil. The yield of the asphaltene removal in SFE residue from
crude oil can be defined as Eq. (4.16).
wt of asphaltene in SFE residue

Asphaltene removal ðwt% ) ¼ 100 ð4:16Þ
wt of asphaltene in crude oil
CRUDE OIL
Supercritical fluid extraction (SFE)
Gas product Mixture of fluid and residue

CO2, CO, CH4, H2, SO2 and H2S
Filtering
A mixture of solvent and the deasphalted oil Residue
Separator vessel Drying
Asphaltenes
Solvent Deasphalted oil (DAO)
Asphaltene
analysis
Fig. 4.31 Supercritical fluid extraction for determination of asphaltene in crude oil
Table 4.41 Main impacts of four different solvents (water, carbon dioxide, propane and ethanol)
on deasphalting under the supercritical conditions
Solvent Main impacts
Water Under the supercritical conditions the dielectric constant of water is much lower.
The asphaltenes can be removed from the crude oil residues by using supercritical
water (SCW). The SCW is an excellent solvent for removing of high molecular
weight organic compounds such as asphaltenes from crude oils
Carbon dioxide It can be obtained compounds from petroleum residue are low molar mass from a
sample of petroleum residue with carbon dioxide in the supercritical phase and a
sample of the oil remains low molar mass compounds. The yield of the extraction,
the samples used low API was lower than that from the oil residue
Propane The deasphalting process with propane is an efficient process for light oil extraction
from heavy petroleum residues. The supercritical conditions present the best results
in view of the products’ properties, which are directed to the production of asphalt
and lubricants
Ethanol Crude oil residues example with low molar mass of the components of the solvent
ethanol selectivity for deasphalting is obtained at such a high average molecular
weight which is lower temperature and pressure applied during the extraction, it is
characterized as DAO
Table 4.41 shows main impacts of four different solvents (water, carbon dioxide,
propane and ethanol) on the deasphalting process under the supercritical conditions.
Supercritical water (SCW) is an excellent solvent for removing of high molecular
weight organic compounds such as asphaltenes from crude oils under the super-
critical conditions.
4.14.3 Removing of Resins from Petroleum
The saturate fraction, as a pale-yellow oily liquid, mostly contains aliphatic com-
pounds. The aromatic fraction, as a yellow oily liquid, consists of aromatic groups
with aliphatic side chains. The asphaltenes fraction, as a dark brown–black sus-
pended solid, contains the largest percentage of heteroatoms (O, S, N) and
organometallic constituents (Ni, V, Fe) in the crude oil. Resin is a heavier fraction
than aromatics and saturates (Akmaz et al. 2011). Resins are composed of fused
aromatic rings with branched paraffin and polar compounds.
The resin fraction of the crude oil was eluted as a wine red liqued from the
chromatographic column using toluene—methanol solution.
Crude oils samples have been separated into four chemical group classes, namely
saturates, aromatics, resins, and asphaltenes using high-performance liquid chro-
matography (HPLC) (Hammami et al. 1998; Aske et al. 2001). Resins and
asphaltenes from stable and unstable crude oils have been separated by size exclusion
chromatography in three molecular mass ranges (Carbognani and Espidel 2003).
A preparative chromatographic separation methodology for petroleum resins and
asphaltenes was developed. Resins isolated from stable crudes show components
both in the medium/low molecular mass ranges. Those from unstable materials
appear enriched primarily in the low molecular mass end (Carbognani 2003).
The resins are adsorbed on a solid such as alumina, clay, or silica, and subse-
quently recovered by use of a more polar solvent and the oils (aromatics and
saturates) remain in solution. The resins often co-precipitate with the asphaltenes in
controlled propane deasphalting procedures, and the product has a low melting
point and is generally used for asphalt manufacture. The composition of the resins
fraction can vary considerably and is dependent on the kind of precipitating liquid
and on the temperature of the liquid system (Andersen and Speight 2001).
The overall fractionation of petroleum is given in Fig. 4.32. This fractionation
schema is the most part for petroleum fractionation is a modification of the ASTM
(American Society for Testing and Materials) D-4124 procedure. The overall
product of these fractionation methods, with the ensuing subfractionation, provides
the representation of petroleum as a composite of the four fractions (Andersen and
Speight 2001).
A separation method (applied by the German Petroleum Institute) of the pet-
roleum colloids into asphaltenes and resins is obtained by solvent extraction of the
petroleum colloids (asphaltenes and resins). Figure 4.33 shows the separation of
resins and asphaltenes using ethyl acetate. In this method (Fig. 4.33), the petroleum
colloids are insoluble and are separated from each other by the use of solvents such
as n-pentane or n-heptane.
Crude Oil
Pretreatmen
N-hexane treatment
CS2 or Pyridine Asphaltenes Deasphalting oil (Maltenes)

(Insolubles) (Solubles)
Carbenes Carboids Adsorption on Silica or Alumina

(Solubles) (Insolubles)
Methanol elution Toluene elution Heptane elution
Resins Aromatics Saturates
Fig. 4.32 Overall fractionation of petroleum

Crude Oil
Ethyl Acetate
Aromatics and Saturates Petroleum Colloids

Adsorption on Silica
N-pentane Treatment
Toluene elution Heptane elution Insolubles

Solubles
Toluene
Aromatics Saturates Resins
Asphaltenes
Fig. 4.33 Separation of resins and asphaltenes using ethyl acetate
4.14.4 Dewaxing Processes of Petroleum
Waxes are complex mixtures of high molecular weight or high-carbon number

alkanes that consist of straight, branched, and cyclic chains (Demirbas 2016). The
aromatic rings contain 22 or more carbon atoms. Waxes can be solid or liquid at
room temperature; a unique property used in conventional determination of wax
formation in crude oils. Figure 4.34 shows main paraffin structures. Paraffin wax is
mainly composed of straight chain hydrocarbons (C20–C30) with 80–90 % normal
paraffin contents, while the rest is composed of branched paraffins (iso-paraffins)
and cycloparaffins. Normal paraffin is a saturated hydrocarbon with molecules
containing carbon atoms linked in a straight (unbranched) chain. Wax contents of
crude oils range up to 32.5 % (As’ad et al. 2015).
Wax deposition is one of the chronic problems in petroleum applications (Kok
et al. 2007). Both types of waxes; paraffin and microcrystalline occur generally in
lubricating oil fractions from crude oil and negatively influence the quality and
applications of the oil (Ajayi 2013). Wax contents of various crude oils are given in
Table 4.42. Wax is crystallized in crude oil upon cooling, leading to flow problems
in production and processing units and pipelines. Paraffin wax deposition occurs
during petroleum transportation (Kok and Saracoglu 2000). Improper insulation and
heating systems are the precursors of wax deposition of the clean waxy crudes
Fig. 4.34 Main paraffinic wax structures
Table 4.42 Wax contents of various crude oils

Crude oil Wax content (wt%) Reference
Eastern Egyptian 3.3–4.5 Abu El-Ella and Nassef (2014)
Venezuelan (Boscan) 4.1 Lu and Redelius (2007)
Russian 9.4–12.2 Lu and Redelius (2007)
Sudan 21.2 Chen et al. (2004)
Daqing 26.3 Chen et al. (2004)
Shengli 9.6 Chen et al. (2004)
Qiuling 10.9 Chen et al. (2004)
Malu Isan 5.8 Musser and Kilpatrick (1998)
South China Sea 32.5 Musser and Kilpatrick (1998)
Arab heavy 12.7 Musser and Kilpatrick (1998)
Arab Berri 1.7 Musser and Kilpatrick (1998)
Alaska North Slope 1.5 Musser and Kilpatrick (1998)
Maya 3.9 Musser and Kilpatrick (1998)
San Joaquin Valley 0.7 Musser and Kilpatrick (1998)
Alba 1.5 Musser and Kilpatrick (1998)
Gulf of Mexico 7.8 Musser and Kilpatrick (1998)
(Paso 2014). When the heavy paraffin hydrocarbons precipitate due to temperature
change, a wax-oil gel is formed (Maria et al. 2012). Therefore, temperature change
is the main cause of wax appearance in the pipelines (Spiecker et al. 2003).
Wax deposition and its flowing behavior result in flow strings plugging,
hydrocarbon’s loss and overall high production cost (Adesina et al. 2010; Pu et al.
2014). Up to 32.5 % wax is present in worldwide crude oils that crystallize during
oil production, transportation, and storage. This causes significantly high oil vis-
cosity and pour point values and oil gelation that brings difficulties during oil
transportation and oil refining activities (Chen et al. 2004; Adesina et al. 2010; Pu
et al. 2014). The increased viscosity reduces the flow tendencies of the fluid
mixtures, and it increases the cost of pumping that is necessary for the fluid flow
(Ajayi 2013).
Wax depositions were examined in oil production systems, and the deposition
mechanism seems to be understood with relation of heat and mass transfer, disso-
lution of a mixture of hydrocarbons and the temperature gradient between the wall of
pipeline and the bulk fluid (Aiyejina et al. 2011; Huang et al. 2011; Valinejad and
Nazar 2013). Wax precipitation in oil creates an increase in the non-Newtonian
behavior of petroleum mixture and hence increased viscosity (Elsharkawy et al.
2000). Depending on the temperature and pressure, hydrocarbon components of wax
can exist in any states of matter. The wax forms crystals on freezing. When the
paraffin wax forms crystals, they are called macro-crystalline wax.
The determination of wax percentage within crude oil is very important for
petroleum industry, particularly for crude oil production, its storage and trans-
portation. Various methods have been reported for estimating the amount of wax
present within crude oil. The wax precipitation has been a common problem for a
wide range of petrochemical related industry for many years (Musser and Kilpatrick
1998).
Xiaohu et al. (2008) have developed a simple test method to determine the
percentage of wax in crude oils including bitumen. For many years, natural waxes
present in bitumen and their effect on the performance of asphalt has been a hot
topic for scientific debate. Currently the two European standard methods used for
wax content determination are EN 12606-1 (Method by distillation) and 12606-2
(Method by extraction). However, these methods are generally very time con-
suming and may result in low accuracy of estimated wax percentages.
The recent technological advancement in laboratory equipment has greatly
improved the analysis of wide range of components in pipeline deposits (Zhang et al.
2014). The high temperature gas chromatography (HTGC) and supercritical fluid
chromatography (SFC) helps the detection of waxes of up to 100 carbon atoms as
compared to the conventional detection limit of around 40 carbon atoms (Maria et al.
2012). During the HTGC analysis, the higher boiling point compounds are also kept
mobile because the column is more stable even when heated to higher temperatures
of 500 °C as compared to conventional analysis at 400 °C. The waxes are analyzed
by gas chromatography (GC) using a capillary column of 12 m × 0.2 mm coated
with non-polar silicons such as SE-30, DC-200 and OV-1 (Shen et al. 2014).
Many researchers have correlated the performance of asphalt to the presence of
natural waxes within bitumen (Mckay et al. 1995; Such et al. 2000; Richter 2002). For
example, a recently published study reported that wax adversely affected the low
temperature properties of asphalt; however these negative impacts on moisture sus-
ceptibility and wheel tracking resistance were not considered (Lu and Redelius 2007).
Solvent dewaxing is a common method used to remove the wax from both dis-
tillates and residual base stocks during distillation processes. Methyl Ethyl Ketone
(MEK) was used as a selective solvent to dewax heavy crude oil at optimum con-
ditions. The results indicated that MEK dewaxing performance improved at higher
mixing temperatures and it was found that a lower cooling temperature resulted in a
greater extraction of wax from the mixture (Musser and Kilpatrick 1998).
The amount of wax increases due to several factors such as increase in initial
weight of the crude oil, decrease in temperature, increase of cooling time and
solvent ratios (Pu et al. 2014). Oil refineries have exerted major efforts to develop
methods for economic exploitation of the petroleum wax fractions, speeding huge
money and time.
Extensive use of solvents for dewaxing progress over the last 25 years has
resulted. Difficulties asphaltene emulsions and waxes are bound colloidal collection
during oil recovery (Abu El-Ella and Nassef 2014). Petroleum colloids (waxes, resins,
and asphaltenes) can be separated by elution processes on an activated Silica Gel
column. Figure 4.35 shows the sequential elution chromatography setup for sepa-
rating petroleum colloids into asphaltenes (1), resins (2) and waxes (3), respectively.
The wax precipitation within the crude oil streams may cause operational
problems whilst transported in undersea pipelines (Ajayi 2013).
Generally the wax crystals are formed and separated with adsorbed resin and
asphaltene as the temperatures are lowered and thus the crude oil changes from
liquid into suspension. Further decrease in temperatures result in formation of a
Crude Oil
Ethyl Acetate Treatment
Aromatics and Saturates Petroleum Colloids

Adsorption on Activated Silica Gel
80% Tetrahydrofuran 30% Methylene Cloride + 100% Heptane

+ 20% Acetone 40% Acetone + 30% Toluene
Elution Elution Elution
Asphaltenes Resins Waxes
Fig. 4.35 Sequential elution chromatography setup for separating petroleum colloids into waxes,
resins, and asphaltenes
continuous phase of wax crystal lattice, whereas the remaining liquid hydrocarbons
turn into a dispersed phase (Abu El-Ella and Nassef 2014; Musser and Kilpatrick
1998).
The waxy crude oil has poor flow properties due to high viscosity and also
normally high pour point. The waxy crude oil is heated to enhance its flowability
during transportation in pipelines. However, the long distance pipelines are
sometimes closed for maintenance or operational purpose or due to some emer-
gencies, resulting in a temperature drop in warm waxy crude oil, causing problems
in its smooth flow.
Wax precipitation in crude oil is one of the most critical flow assurance problems
leading to economic losses. Wax has very low solubility and it precipitates out due
to a decrease in temperature. Recently, an investigation was carried out to study the
effect of various parameters, such as crude oil initial weight, cooling time and
temperature, on amount of wax produced (Pu et al. 2014). It was found that the
amount of wax produced increased with decrease in crude oil initial weight and
temperature and increase in cooling time and solvent ratios. Normally, the wax
precipitation occurs at lower temperatures and the wax crystals adsorb resin and
asphaltene, resulting in crude oil transformation from liquid into suspension (Majhi
et al. 2015).
The waxy crudes are a worldwide issue and the major challenges, during their
processing and transportation, are not only precipitation of wax content at lower
temperatures but also the formation of deposits that cannot be completely removed
by heating and pigging (Maria et al. 2012). Understanding wax and wax related
process has been a subject of concentrated research for the development of new
solutions for deeper, colder, longer fields as well as for field developments in arctic
and remote locations (Aiyejina et al. 2011). The viability of many of these new
developments is strongly linked to proven multiphase transport strategy techno-
logically justified at prevailing economic realities. The wax solidifies when the
temperature of the hydrocarbon fluid drops below the wax crystallization temper-
ature, causing flow assurance problems (Kok et al. 2007).
The membrane process is used for selective separation of solvent from the wax
filtrate in solvent dewaxing unit (SDU). The importance of dewaxing application
lead to the development of first commercial scale organic membrane process for
liquid-liquid hydrocarbon separation in petrochemical based industry.
The solvents MEK and toluene used in the dewaxing process can be removed
from the dewaxed oil filtrate stream. The solvents are recovered close to dewaxing
temperatures and recycled back to be used again in the dewaxing process without
further cooling.
4.14.5 Sulfur Removal from Petroleum
The removal of sulfur-containing compounds from crude oil is increasingly

important due to steady increases in the sulfur content of remaining petroleum
resources. The primary sulfur removal method is hydrodesulfurization (HDS), a

process that has long been used at the refinery level (Ates et al. 2014).
With the growing demand for energy and the depletion of conventional crude
oil, heavy oil in huge reserve has attracted extensive attention (Li et al. 2015).
Inorganic materials of crude oil contain a number of inorganic constituents, espe-
cially sulfur, which plays an important role in almost all fueling systems. Some
methods have been applied to crude oil to remove its inorganic materials from the
organic part. Main desulfurization methods are chemical desulfurization, leaching,
extraction, flotation, oxydesulfurization and biodesulfurization (Demirbas and Balat
2004). The alkaline desulfurization is more effective in removing the pyritic sulfur
from the crude oil, which is the less abundant form than the organic sulfur.
Low sulfur content of crude oil is particularly preferred. Sulfur is naturally
present as an impurity in fossil fuels. The removal of organo-sulfur compounds
from crude oil is an important aspect of all countries to reduce air pollution. The
sulfur compounds from gasoline are generally removed by treating it with an
alkaline solution sodium plumbite. An at large scale, the most economical method
for converting hydrogen sulfide into sulfur is the Claus process (Demirbas et al.
2015b). Sulfur in vehicle fuels leads to undesirable vehicle emissions of sulfur
compounds and interferes with vehicle emission control systems.
The sulfur content of crude oil and refinery streams is usually expressed in
weight percent (wt%) or parts per million by weight (ppmw). In the refining
industry, crude oil is called sweet (low sulfur) if its sulfur level is less than a
threshold value (e.g., 0.5 wt% (5000 ppmw)) and sour (high sulfur) if its sulfur
level is above a higher threshold. Most sour crudes have sulfur levels in the range of
1.0–2.0 wt%, but some have sulfur levels >4 wt% (Demirbas et al. 2015c).
The desulfurization processes including variations thereon that are discussed
include hydrodesulfurization, extractive desulfurization, oxidative desulfurization,
biodesulfurization and desulfurization through alkylation, chlorinolysis, and by
using supercritical water (Javadli and De Klerk 2012).
Different methods of desulfurization have been developed based on physical and
chemical principles. These processes can in general be classified into two main
groups: wet processes and dry processes (Yan 1976; Palmer et al. 1995; Yaman and
Kucukbayrak 1997; Stromberg and Karlsson 1998). Specific desulfurization
methods are washing the containing extract with alkaline solutions or organic and
inorganic acids. Total sulfur contents were considerably reduced by aqueous NaOH
treatment (Lolja 1999).
A mathematical model has been developed to predict the conversion of sulfur
during batch type bio-desulfurization of model compounds as well as diesel having
known distribution of organo-sulfur compounds (Guchhait et al. 2005).
At large scales, the most economical technology for converting hydrogen sulfide
into sulfur are the Claus process according to Eq. (4.17). This well-established
process uses partial combustion and catalytic oxidation to convert about 97 % of
the H2S to elemental sulfur (Demirbas et al. 2015c). Hydrodesulfurization (HDS) is
a catalytic process widely used to remove sulfur from refined petroleum products
such as diesel fuel, gasoline, jet fuel and fuel oils. The purpose of removing the
sulfur is to reduce the SO2 emissions.
The HDS process involves catalytic treatment with hydrogen to convert the
various sulfur compounds present to hydrogen sulfide. From this point some of the
hydrogen sulfide is oxidized to sulfur dioxide by air and sulfur is formed by the
overall reaction:
2H2 S þ SO2 ! 3SðsÞ þ 2H2 O ð4:17Þ
The HDS represents a crucial component of current petroleum refining opera-

tions in terms of both environmental and economic considerations. At the same
time that crude oils are becoming heavier with increasing amounts of sulfur, pro-
duct regulations are becoming more stringent. Because of the large size of the
organic molecules in the heavy oil fractions, HDS catalyst supports contain pri-
marily mesopores and macropores. Typical HDS catalysts consist of Co-Mo or
Ni-Mo sulfides on an alumina support material.
The removal of organo-sulfur compounds (ORS) from diesel fuel is an important
aspect of all countries to reduce air pollution. One of the easily and fast method to
remove sulfur from diesel oil is the adsorption desulfurization process.
Desulfurization of crude oil using supercritical water is one of promising non-
conventional methods. Supercritical water desulfurization (SCWDS) has potential
as a technique for removing sulfur from feedstocks such as heavy oil and bitumen.
Conversion and sulfur removal of coal in sub- and supercritical water was
studied in a micro reactor in the temperature range of 340–400 °C and water density
0–0.27 g/mL for 0–90 min under nitrogen atmosphere (Park et al. 2007). Removal
of organic sulfur requires the use of chemical cleaning methods. Recently, super-
critical water (SCW) processing of coal has been receiving increasing attention
because the physicochemical properties of SCW can be easily controlled by the
reaction temperature and pressure (Park et al. 2007).
Under the supercritical conditions the dielectric constant of water is much lower.
Organic sulfur compounds can be removed from the petroleum products by using
supercritical water (Demirbas 2011a, b, c). The SCW is an excellent solvent for
high molecular weight organic compounds in crude oils.
The supercritical process required a high temperature and pressure, making this
desulfurization process uneconomic, and the sulfur removal could be strongly
affected by the change of fluid properties around the critical point of solution. It is
understood that desulfurization methods require considerable investment, operating
and maintenance costs and careful process control, therefore their efficiency is
under question (Demirbas and Balat 2004).
Hydrothermal desulfurization was evaluated for the upgrading of bitumen in
supercritical water with alkali, based on the formation and decomposition of
thiophene derivatives (Kishita et al. 2006).
The decomposition rates of the aliphatic and aromatic sulfides varied depending
on their molecular structure, with conversions after 31 min at 400 °C ranging from
less than 3 % to more than 90 % (Patwardhan et al. 2013). Supercritical water

upgrading (SCWU) of crude oils reduces sulfur content and decreases average
molecular weight, without rejecting carbon as coke products. Catalytic investigation
found that ZnO has potential to improve sulfur removal during SCWU, without
addition of molecular hydrogen (Timko et al. 2015).
Alkhyl sulfide decompositions occur during SCW treatment of crude oil mix-
tures. It was shown that SCW treatment had two effects on sulfur compounds:
cracking of heavy sulfur compounds into smaller compounds, mainly benzothio-
phenes (BT) and dibenziophenes (DBT), and cracking of long alkyl chains on these
BTs and DBTs causing a shift to lower molecular weight BTs and DBTs. SCW was
found to be ineffective in breaking the stable aromatic rings of these thiophenic
compounds (Kida 2014).
Catalytic desulfurization of residual oil has been carried out through partial
oxidation in supercritical water (Yuan et al. 2005). Catalytic desulfurization of a
model sulfur-containing compound benzothiophene through partial oxidation in the
SCW was investigated in a bomb reactor at 350–450 °C and 30–40 MPa over
sulfided CoMo/γ-Al 2O3. Vacuum residuum was used to confirm the desulfurization
rate and efficiency, and the desulfurization mechanism of vacuum residuum was
determined by the pyrolysis temperature of the vacuum residuum. Obvious
reduction of sulfides up to 67 % was obtained (Yuan et al. 2005).
Figure 4.36 shows the supercritical water extraction for determination of sulfur
in crude oil.
The yield of the sulfur removal in gaseous effluent from crude oil can be defined
as Eq. (4.18).
wt of sulfur in gas product

Sulfur gas removal ðwt % ) ¼ 100 ð4:18Þ
wt of sulfur in crude oil
The sulfur contents in residue were defined as sulfur remains of residue. The
total sulfur removal can be obtained from sulfur remain through Eq. (4.19).
wt of sulfur in residue
Total sulfur removal ðwt % ) ¼ 100 100 ð4:19Þ
wt of sulfur in crude oil
4.15 Gasoline and Diesel Range Hydrocarbons

from Waste Vegetable Oils
There are two theories about biogenic and nonbiogenic or abiotic formation of
petroleum. According to not-well-accepted abiogenic theory, petroleum origin is
natural hydrocarbons. The theory proposes that large amounts of carbon exist
naturally in the planet, some in the form of hydrocarbons. Due to its lower density
than aqueous pores fluids, hydrocarbons migrate upward through deep fracture
networks.
4.15 Gasoline and Diesel Range Hydrocarbons from Waste Vegetable Oils 231
Crude oil
Supercritical water extraction
Gas product Mixture of water and residue

CO2, CO, CH4, H2, H2S and SO2
Filtering
Determination of
sulfur in gas phase
Liquid product Residue
Purification Drying
Clean light oil Sulfur analysis
Fig. 4.36 Supercritical water extraction for determination of sulfur in crude oil
According to well-accepted biogenic theory, crude oil is the product of com-

pression and heating of ancient vegetation and animal remains over geological time
scales. According to this theory, an organic matter is formed from the decayed
remains of prehistoric marine animals and terrestrial plants (Ahsan et al. 1997). The
resulting high pressure and heat caused the remains to transform, first into a waxy
material known as kerogen, and then into liquid and gaseous hydrocarbons by
catagenesis process (Hunt et al. 2002). Three important elements of an oil reservoir
are a rich source rock, a migration conduit, and a trap (seal) that forms the reservoir
(Robinson 1966).
Used cooking oil is a very potential feedstock for production of hydrocarbon via
pyrolysis regardless of cost perspective. It has high calorific value, low heavy metal
content and low moisture. Vegetable oils can be converted to new liquid fuels by
pyrolysis, catalytic pyrolysis, and cracking and catalytic cracking processes.
Decarboxylation and deoxygenation mainly occur during pyrolysis and cracking
reactions. Downloaded by With long chain of palmitic acid and oleic acid, it has the
potential to be cracked by thermal cracking or catalytic cracking for possible for-
mation of hydrocarbon chain.
There is a very small amount of hydrocarbons in the content of vegetable oils.
These hydrocarbons were reviewed as an important part of minor constituents of
vegetable oils (Moreda et al. 2001). The hydrocarbon compounds were detected in
soybean oil deodorizer distillate; large amounts of terpenic hydrocarbons accom-

panied by smaller amounts of n-alkanes confirmed that crude vegetable oils contain
elements of the n-alkane series from C10 to C35, with the odd numbered elements
being the most abundant (Chang et al. 2000).
In general, vegetable oils are triglycerides, which consist of 18-carbon fatty
acids. There is no boiling point of vegetable oils, because oils start to decompose
when heated to a certain temperature after removing smoke. These are smoke points
or smoke temperatures. The smoke point is the temperature at which the oil is
decomposed and where possibly toxicological relevant compounds are formed. The
smoke points of some vegetable oils are as follows: olive 191 °C, soybean 257 °C,
corn 246 °C, peanut 227 °C, and sesame 216 °C. Typically, it was not possible to
distill all of the vegetable oil and some brownish residue remained in the distillation
flask. However, the soaps obtained from the vegetable oils can be distilled into
hydrocarbon-rich products with higher yields. These findings are in general
agreement with results given in the literature (Barsic and Humke 1981).
Thermal cracking of triglycerides has been carried out for over 100 years, with a
recent focus on converting fats and oils to liquid fuels (Maher and Bressler 2007).
There are many studies that have investigated the thermal conversion (pyrolysis and
cracking) of triglycerides for obtaining hydrocarbon fuels (Alencar et al. 1983; Ali
and Hanna 1994; Dandik and Aksoy 1998; 1999; Gusmao et al. 1989; Kubicka
et al. 2010; Lima et al. 2004; Maher and Bressler 2007; Schwab Simacek et al.
2009). Results showed that conversions ranged between 54 and 100 % and were
heavily dependent on operating variables. The products essentially consisted of C4
and C5 hydrocarbons, aromatic and C6–C12 aliphatic hydrocarbons, and C2–C4
olefins as well as a diesel-like fuel and hydrogen (Maher and Bressler 2007).
A mechanism for vegetable oil cracking is proposed in Fig. 4.37. The vegetable
oils contain mainly palmitic, stearic, oleic, and linoleic acids. These fatty acids
underwent various reactions, resulting in the formation of different types of
hydrocarbons.
Vegetable oil
Primary decarboxylation and cracking
Oxygenates Heavy hydrocarbons
Secondary decarboxylation and cracking
Light olefins Light olefins, CO2, CO, H2O Light paraffins
Fig. 4.37 Reaction pathway of cracking of used sunflower oil over cracking catalyst
The variety of reaction path and intermediates make it difficult to describe the
reaction mechanism. Besides, the multiplicity of possible reactions of mixed
triglycerides make pyrolysis reaction more complicated (Zhenyi et al. 2004).
Generally, thermal decomposition of these structures proceed through either a
free-radical or carbonium ion mechanism (Srivastava and Prasad 2000).
The vegetable oil is converted by two simultaneous reactions: cracking and
condensation. The heavy hydrocarbons produced from primary and secondary
deoxygenation and cracking to produce light olefins and light paraffins, water,
carbon dioxide, and carbon monoxide.
Catalytic pyrolysis and catalytic cracking processing has a potential to become
an important process for conversion of vegetable oils into hydrocarbon fuels. Both
pyrolysis and cracking are thermal decomposition processes. Pyrolysis is the
decomposition of a compound on heating in absence of air. Cracking is the massive
breakdown of large organic compounds by use of a catalyst at low temperature to
generate fewer different compounds. Final pyrolysis temperature is usually higher
than at cracking process (Demirbas et al. 2015c; Hu 2015).
The liquid hydrocarbon products obtained from catalytic pyrolysis and cracking
processes were analyzed using GC-MS and grouped into three lumps (i.e., C5–C11,
C12–C15 and C16–C22) that have similarity to gasoline, kerosene, and diesel fraction.
The experimental results show that the process with two stages of thermal conver-
sion can improve the selectivity of fraction C5–C11 from 33.3 % up to 74.03 %.
The cracking process has generally been performed by using a solid catalyst with
good shape selectivity and a suitable pore size, such as HZSM-5 (Zeolite Socony
Mobil with High Si/Al ratio-5) and zeolite. This process has an advantage over
biodiesel production via transesterification, including lower processing costs, com-
patibility with engines and fuel standard, and feedstock flexibility without consid-
ering the level of free fatty acid (Biswas and Sharma 2012: Ramya et al. 2012).
Pyrolysis of vegetable oils, which is a direct thermal decomposition method, operates
at very high temperature (400–750 °C) and yields mostly gaseous products con-
taining straight chain hydrocarbon fuels (Ramya et al. 2012). The catalytic cracking
can convert vegetable oils into hydrocarbons in the absence of oxygen at atmospheric
pressure and at relatively low temperature (300–600 °C; Lima et al. 2004).
Liquid hydrocarbons obtained from pyrolysis of used sunflower oil was carried
out in the presence of different amounts of HZSM-5 at 400 and 420 °C in a reactor
equipped with a fractionating packed column. Maximum conversion yield (96.6 %)
of the used oil and the maximum liquid hydrocarbon yield (33 %) were obtained at
the highest temperature (420 °C). The hydrocarbons were gasoline range and the
yield increased with the increase in catalyst content (Dandik and Aksoy 1998).
The catalytic pyrolysis of used cooking oil to liquid fuel by magnesium oxide
supported on activated carbon in a continuous reactor was investigated. Increasing
the temperature from 380 to 430 °C significantly increases the weight of the diesel
fraction from 38.75 to 52.5 % while lowering long residue. The resulting liquid fuel
product is composed of many high-value light hydrocarbons.
Under the best conditions, the liquid yield is 81.42 % and contains a diesel
fraction of 57.07 % by weight (Jungjaroenpanit and Vitidsant 2013). In the earlier
study, the chief products of pyrolysis of babassu, piquim and palm oils were
straight-chain alkanes and 1-alkenes (Alencar et al. 1983).
The cracking of used palm oil was carried out in presence of CaCO3 as a
catalyst. Various runs were carried out at different temperature and catalyst con-
centration and the maximum liquid hydrocarbon were obtained in presence of 5 %
CaCO3 catalyst (Deshpande et al. 2015).
A hydrocarbon liquid was obtained from cracking of castor oil (Deshpande et al.
2013). The catalytic cracking of palm oil involves parallel cracking reactions that
produce organic liquid product, noncondensable gas, and coke. The organic liquid
product consists of gasoline, kerosene, and diesel.
The results show that the highest yield of organic liquid product was 60.7 wt% at
O/C ratio of 32.50 and weight hourly space velocities of 19.38 h−1 (Siswanto et al.
2008). An option with great potential is used cooking oil recycling, which includes
a variety of processes such as catalytic pyrolysis and catalytic cracking, designed to
transform waste cooking oil into hydrocarbon products for use in the preparation for
refined chemicals or fuels (Khalisanni et al. 2008).
Used cottonseed oil was pyrolyzed in the presence of Na2CO3 as catalyst at
450 °C to give hydrocarbons containing mainly C8–C20 alkanes (69.6 %) besides
alkenes and aromatics. The pyrolysis product had lower viscosity, pour point, and
flash point than No. 2 diesel fuel and equivalent heating values. The cetane number
of the product was lower than that of No. 2 diesel fuel (Demirbas 2015a, b, c).
Palm oil has been cracked at atmospheric pressure, at a reaction temperature of
450 °C to produce hydrocarbon-rich product in a fixed-bed microreactor (Sang
et al. 2003). The reaction was carried out over microporous HZSM-5 zeolite,
MCM-41 (Mobil Composition of Matter No. 41) mesoporous, and composite
micromesoporous zeolite as catalysts (Buzetzki et al. 2011). The products were
composed of gas, organic liquid product, water, and coke. The organic liquid
product was composed of hydrocarbons corresponding to gasoline, kerosene, and
diesel boiling point range. The maximum conversion of palm oil, 99 wt%, and
gasoline yield of 48 wt% was obtained with composite micromesoporous zeolite
(Sang et al. 2003). Table 4.43 presents the catalytic cracking of the palm oil over
HZSM-5 with different Si/Al ratios catalyst. The gasoline yield increased with the
increase in the Si/Al ratio due to the decrease in the secondary cracking reactions
and the drop in the yield of gaseous products (Sang et al. 2003).
Using mesoporous MCM-41 as a catalyst showed lower gas production than
H-ZSM5, with the best results being observed for palm oil, with 97.72 % being
converted overall and a yield of linear hydrocarbons C13–C17 in the diesel range of
42.5 wt%. Palm oil differs from soybean oil with a higher fraction of shorter chain
triglycerides, 50 % C12, and 16 % C14 and so these results may not relate directly to
the conversion of soybean oil (Deshpande et al. 2015).
Hydrocarbon yields vegetable oils via hydrogenation that is usually carried out
under defined reaction conditions precisely (Chen 2012). Total hydrogenation of
vegetable oil triglycerides, the hydrocarbons are based on two general reaction
schemes: hydrodeoxygenation (HDO) and hydrodecarboxylation (HDC). Carbon
number will vary based on different chemical process: n-alkanes originating from
Table 4.43 Catalytic cracking of palm oil over HZSM-5 with different Si/Al ratios
Catalyst ID HZSM-5(50) HZSM-5(240) HZSM-5(400)
Conversion, wt% 96.9 96.0 94.0
Gas yield, wt% 17.5 14.0 8.2
Water, wt% 6.8 4.6 6.1
Organic liquid product, wt%
Total organic liquid yield, wt% 70.9 76.0 78.0
Gasoline like fuel, wt% 44.6 45.9 49.3
Kerosene like fuel, wt% 19.6 24.6 26.1
Diesel like fuel, wt% 6.7 5.5 2.6
Coke, wt% 1.7 1.4 1.7
HDO have the same carbon number as the original fatty acid chain (i.e., even
carbon number), typically 16 or 18, while the main reaction by-products of this
route are water and propane; hydrocarbons originating from HDC one carbon atom
less in the molecule than the original fatty acid chain (i.e., odd carbon number)
while the dominant by-products are CO, CO2 and propane.
The researchers showed that the yield of straight-chain alkanes decreases at
temperatures >350 °C since the alkanes undergo cracking and isomerization at
higher temperatures (da Rocha Filho et al. 1993).
The literature was divided and discussed as (a) direct thermal degradation and
(b) combination of thermal and catalytic degradation. The relevant literature on
catalytic thermal degradation of vegetable oils may be grouped into five main major
types of catalysts including (a) sodium carbonate catalyst, (b) activated alumina
catalysts, (c) transition metal catalysts, (d) molecular sieve catalyst, and (e) other
catalysts (ZnCl2, cement, CaO, MgO, CaCO3, K2CO3 (Idem et al. 1996; Katikaneni
et al. 1996; Maher and Bressler 2007).
The vegetable oils and animal fats contain polyunsaturated fatty acid chains that
their double bonds have highly chemical reactivity. The thermal degradation occurs
on the double bonds of unsaturated aliphatic carbons chains in fatty acids. The
content of linoleic acid in the sunflower seed oil was 72.4 %, while the linoleic acid
account for 62.5 % of the total fatty acids in the biodiesel (Demirbas 2015a, b, c).
Table 4.44 shows the average yields of pyrolysis and cracking from vegetable oils.
The proportion of the linoleic acid is lower in the biodiesel obtained by
supercritical methanol transesterfication method. Partial degradation of the linoleic
acid may be occurred in the supercritical methanol transesterification due to high
temperature (<240 °C). In oxidative instability, the methylene group ðCH2 Þ
carbons between the olefinic carbons are the sites of first attack (Williard et al.
1998).
CH2 þ OH ! CH þ H2 O ð4:20Þ
Oxidation of biodiesel is results in the formation of hydroperoxides. The for-

mation of the hydroperoxide follows a well-known peroxidation chain mechanism.
Table 4.44 Average yields Without catalyst

of pyrolysis and cracking
Liquid product, wt% 59–67
from vegetable oils
Gas, wt% 25–29
Bituminous residue, wt% 8–12
With catalyst
Liquid product, wt% 76–84
Gas, wt% 6–10
Bituminous residue, wt% 3–5
Range of hydrocarbons
C1–C4, wt% 0.9–1.5
C5–C11, wt% 26–34
C12–C15, wt% 19–25
C16–C20, wt% 43–51
Yield of hydrocarbons
Alkanes, wt% 37–40
Alkanes, wt% 21–24
Alkadiens, wt% 8–13
Aromatics, wt% 2–3
Petroleum range of hydrocarbons
Gasoline, wt% 43–54
Diesel, wt% 32–42
The unsaturated fatty acids were produced in significant concentrations in olefin

yield low concentrations of olefins and aromatics with high; however, saturated
fatty acids formed from aromatic concentration is too low in the presence of 1 %
Na2CO3 catalyst at 500 °C pyrolytic conditions (Konwer et al. 1989). Cottonseed
oil was pyrolyzed in the presence of 1 % Na2CO3 and obtained liquid phase
contained mostly C5–C11 hydrocarbons (19.5–32.9 %) and the gaseous phase was
mainly composed of C1–C3 hydrocarbons (13.7–26.2 %) (Zaher and Taman 1993).
The cracking occurs at higher temperatures, (400–500 °C) and is obtained short
chain hydrocarbons (Crossley et al. 1962).
In an attempt to better understand the pyrolysis of vegetable oils this research
group studied the thermodynamics of vegetable oil process by computer simulation.
The main findings were that cleavage of the C–O bond takes place at 288 °C and
that scission of C C takes place at 400 °C. Schwab et al. proposed a mechanism to
account for the formation of alkanes, alkenes, alkadienes, aromatics, and carboxylic
acids from the pyrolysis of unsaturated triglycerides. Idem et al. (1996) proposed a
mechanism for the thermal cracking of canola oil in the presence and absence and
of both the unsaturated and saturated components. Decarboxylation and decar-
bonylation can occur before or after the C–C bond cleavage. If the triglyceride is
unsaturated, the cleavage most likely occurs before the decarboxylation and
decarbonylation (Alencar et al. 1983; Konwer et al. 1989). It has also been shown
that C C bond cleavage for unsaturated and saturated molecules results in different
products (Idem et al. 1996). Table 2 shows the average yields of pyrolysis and
cracking from vegetable oils. Triglycerides convert to free fatty acids by thermal
hydrolysis and the reaction produces a byproduct of glycerol.
Triglyceride þ H2 O ! RCOOH þ Glycerol ð4:21Þ
To form a long-chain alkane (RH). There are two competing hydrogenation

reactions: decarboxylation and decarbonylation. The desired reaction is
decarboxylation:
Catalyst; H2
RCOOH ! RH þ CO2 ð4:22Þ
Here is a competing reaction called decarbonylation, which produces carbon

monoxide as a byproduct:
Catalyst
RCOOH þ H2 ! RH þ CO þ H2 O ð4:23Þ
The pyrolysis of triglycerides has been studied, the cracking behavior of fatty
acids has not been studied extensively. In a previously study, oleic acid was pyr-
olyzed, however, only 11.3 % (v/v) of the pyrolysis products were accounted for in
the form of cycloalkanes (Alencar et al. 1983). There have been some studies
conducted on the pyrolysis of fatty acid salts or soaps of various oils (Demirbas
2002c; Fortes and Baugh 1994). The tung oil was saponified with lime and the
calcium soap was pyrolyzed into yield a diesel-like fuel and small amounts of
gasoline and kerosene.
The vegetable oil is converted to lower molecular products by two simultaneous
reactions: cracking and condensation. In a first step of pyrolysis the triglycerides are
converted into carboxylic acids, which are further decomposed by decarboxylation
(forming alkanes and carbon dioxide) or decarbonylations (forming alkenes, water,
and carbon monoxide) (Gusmao et al. 1989).
The variety of reaction path and intermediates make it difficult to explain the
reaction mechanism. This, as well as mixed triglycerides multiplicity of possible
reactions of the pyrolysis reactions are more complex (Zhenyi et al. 2004).
Generally, pyrolysis of triglycerides proceed through either a free-radical or car-
bonium ion mechanism (Srivastava and Prasad 2000). Maximum of gasoline
fraction may be obtained under suitable pyrolysis reaction conditions. The initial
decomposition of vegetable oils occurs with the breaking of C–O bond at lower
temperature and fatty acids are the main product. The pyrolysis temperature should
be higher than 400 °C; the maximum diesel yield with high content of oxygen can
be obtained at <400 °C (Zhenyi et al. 2004). The effect of temperature, the use of
catalysts and the characterization of the products have been investigated by
Srivastava and Prasad (2000). The macromolecular structures which are broken into
smaller molecules and pyrolysis of hydrocarbons as broadly as given, high
molecular substances, is heated to a high temperature. The pyrolytic products can

be divided into a gas fraction; a liquid fraction consisting of paraffins, olefins, and
naphthenes; and solid residue (Gusmao et al. 1989).
Pyrolysis of triglycerides was categorized as (a) destructive distillation and
subsequent cracking of the vapors, (b) direct pyrolysis with or without a catalyst,
and (c) cracking of soaps from vegetable oils. Palmitic, stearic, oleic, and linoleic
acids with long chain were used for the possible formation of catalytic cracking or
pyrolysis hydrocarbon chain having a potential.
In pyrolysis, vegetable oils and animal fats could be converted to liquid product
containing gasoline boiling range hydrocarbons. The results show that the product
compositions are affected by catalyst content and temperature. The high molecular
materials are heated to high temperatures, so their macromolecular structures are
broken down into smaller molecules and a wide range of hydrocarbons are formed.
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Chapter 5
Optimization of Energy Systems
5.1 Optimization of Energy Conversion Processes
General optimization concept is desired factors in maximizing and minimizing

undesired effects, the most cost-effective under given constraints or find an alter-
native with the highest achievable performance.
Energy optimization contains energy production strategies and system design.
The purpose of energy optimization is to provide the most cost-effective energy.
Optimizing productivity while reducing operating costs is the common goal shared
by nearly every manufacturing plant. Energy optimization can be done without any
upfront cost is a form of energy efficiency. It includes energy optimal applications,
work schedule changes, cost reductions and efficiency rises.
An energy management system contains energy production and consumption
plans, energy acquisition plan, alarm controls and measurements, report and
invoices for the monitoring of official information and saving goals, and improving
of novel energy optimization models (Demirbas 2015a).
With the rapid economic growth and the increase in the difficulty in the
development of conventional energy sources, to develop unconventional energy
reserves has become an important energy strategy in the world. The International
Energy Agency (2006) emphasized that the world is facing two energy-related
threats: inadequate and unsecure supplies of energy at affordable prices, and
environmental harm caused by consuming too much of energy.
Optimization determining the resulting advantages and disadvantages, they are
at least likely to be encountered barriers and challenges we are taken into account.
Table 5.1 shows the main advantages and disadvantages of biofuels from algae.
Table 5.2 shows the advantages and disadvantages of bladeless wind turbines.
Figure 5.1 shows value added wood products (Increasing value as one climbs the
wood).

258 5 Optimization of Energy Systems
Table 5.1 Main advantages and disadvantages of biofuels from algae

Renewable, sustainable and environment High production costs for growing, collection
friendly material and storage
High productivity with rapid growth rate Limited practical experience in biofuel
Easily cultured and readily and rapidly production
bioengineered Indefinite availability of sustainable algae
Mostly nonedible, no competition with feeds resources
and foods Damage of natural ecosystems and land use
Social benefits with creation of new jobs and changes
income Unclear utilization of waste products
High energy conversion efficiency by Disturbance of the ecosystem balance in
photosynthesis growing areas
Grow almost anywhere Technological challenges during algae
Highly biodegradable resource with quick production and use
bioremediation Use of extra water during algae processing
Reduction of algae residues and wastes Insufficient knowledge on composition and
emissions
Table 5.2 Advantages and disadvantages of bladeless wind turbines

The shaking and vibrating movements of the Requiring quick shaking and vibrations
constructions is converted into energy by an especially in stormy weather, it requires
alternator at the base. Vibration energy additional motor and accessory cost, lack of
generated from wind farms could be much service facilities, lack of information, lack of
cheaper skills
If you compare a bladeless wind turbine to a Vortex generation turbines constitute about
conventional wind turbine with similar 30 % less electricity than traditional
energy generation, the bladeless wind turbine spinning-blade turbines, lack of service
would cost significantly less, around 45 % facilities, lack of information, lack of skills,
less poor market acceptance
As compared to the modern wind turbines, Lack of service facilities, lack of information,
bladeless wind turbines operate, only 20 % of lack of skills, poor market acceptance
maintenance costs
They operate noiseless as possible as Lack of information, lack of skills, poor
market acceptance
As compared to the modern wind turbines, Lack of information, lack of skills, advanced
establishment costs of bladeless wind technology, lack of service facilities, poor
turbines is very low market acceptance
A very small capacity turbine (3–5 kW) may Lack of information, lack of skills, advanced
be manufactured economically for individual technology, lack of service facilities, poor
homes market acceptance
Environmental effects of the bladeless wind Lack of information, lack of skills, advanced
turbines on human, birds and other flying are technology
almost zero
5.2 Waste Heat Utilization Facilities 259
Fig. 5.1 Value added wood products (increasing value as one climbs the wood)
5.2 Waste Heat Utilization Facilities
Cogeneration is defined as the combined production of two forms of energy

(electric or mechanical power plus useful thermal energy) in one technological
process. The electric power produced by a cogenerator can be used on site or
distributed through the utility grid, or both. Cogeneration systems recapture thermal
energy that would otherwise be wasted, usually from a heat engine that produces
electricity (such as a steam turbine, gas turbine, or diesel engine), and use it for
space conditioning, industrial processes, or as an energy source for another energy
component.
Cogeneration, in and of itself, is an example of pollution prevention.
Cogenerators, by using excess heat, may enhance the efficiency of total energy use
by up to 80 % or more from the typical 33–38 % efficiency of electricity-only
generation.
A typical cogeneration system consists of an engine, steam turbine, or com-
bustion turbine that drives an electrical generator. Figure 5.2 shows a gas turbine
topping cycle cogeneration system. Figure 5.2 is a diagram of a gas turbine of the
type used for cogeneration power plants with sizes from about 500 kW–50 MW.
These turbines are similar to jet engines used in aircraft. In this size range, gas
turbines are more efficient than any other type of fossil fuel fired power plants,
reaching electrical efficiencies of up to 45 % and with the addition of waste heat
Exhaust
STEAM
EXHAUST
GAS
BOILER Condensate
Return PLANT
BIOFUEL
GAS GENERATOR ELECTRICITY

AIR TURBINE
Fig. 5.2 A representative cogeneration: a gas turbine topping cycle
recovery (cogeneration), efficiencies of over 80 %. When used for cogeneration, the

hot exhaust gases from the gas turbine are passed through a heat exchanger where
the heat is transferred to water in pipes producing steam. A waste heat exchanger
recovers waste heat from the engine and/or exhaust gas to produce hot water or
steam. Cogeneration produces a given amount of electric power and process heat
with 15–35 % less fuel than it takes to produce the electricity and process heat
separately.
Smaller power plants can be built in a much shorter period of time than massive
(>1000 MW) generating stations. At a time in history when the future demand for
electricity is very uncertain in many areas, building a large power plant which can
take up to 10 years to complete can be a very risky proposition for an electric
utility.
The thermal efficiency increases from the cogeneration and results an inverse
relationship to carbon dioxide emissions. At a time when there is increased
emphasis on both increased thermal efficiency and the mitigation of carbon dioxide
emissions, electricity generation by cogeneration appears a logical choice. An
additional advantage of cogeneration is that the plant is usually located near the end
user and as such no power transmission losses are suffered.
Traditional coal, oil or natural gas fired thermal generating stations convert only
about one-third of the initial energy contained within the fuel into useful electricity.
The remainder of the energy is discarded as heat without serving any useful pur-
pose. From 10 to 35 % of primary energy use is wasted as conversion losses in
power plants. Cogeneration can increase the efficiency of a fossil fuel from an
average of 40 % to over 80 %. This increase in efficiency can translate into lower
costs and fewer emissions of pollutants than the conventional alternative of gen-
erating electricity and heat separately.
The demand for both electricity and heat in individual houses is so variable over
time (both time of day and season) that micro cogeneration units in these appli-
cations are not as efficient because they may rarely be called on to produce an
optimum ratio of electricity/heat. Table 5.3 shows the typical cogeneration per-
formance parameters (Sorensen 1983).
5.2 Waste Heat Utilization Facilities 261
Table 5.3 Typical cogeneration performance parameters

Efficiencies %
Type of converter Nominal Electrical Thermal Overall
capacity conversion recovery cogeneration
Steam turbines 10–100 MW 17–34 – –
Diesel engines 10–3000 kW 23–38 50 73-88
Smaller reciprocating gas 10–500 kW 20–32 50 74-82
engines
Larger reciprocating gas 500–3000 kW 26–36 50 76-86
engines
Smaller gas turbines 0.8–10 MW 24–31 50 74-81
Smaller gas turbines 10–100 MW 26–31 50 78-81
A steam power plant is actually a two-fluid system, that is, energy is exchanged
between the combustion gases and water. The feasibility of combining gas and
steam expansion in a power cycle has been extensively explored. Because steam
generation involves the flow of large volumes of combustion gases, gas expansion
is most appropriately accomplished gases in a gas turbine.
The future of biomass electricity generation lies in biomass integrated
gasification/gas turbine technology, which offers high-energy conversion efficien-
cies. The electricity is produced by direct combustion of biomass, advanced gasi-
fication and pyrolysis technologies are almost ready for commercial scale use.
Biomass power plants (BPPs) use technology that is very similar to that used in
coal-fired power plants. For example, biomass plants use similar steam-turbine
generators and fuel delivery systems. BPP efficiency is about 25 %. Electricity costs
are in the 6–8 c/kWh range. The average BPP is about 20 MW in size, with a few
dedicated wood-fired plants in the 40–50 MW size range. As the
biomass-to-electricity industry grows, it will be characterized by larger facilities of
50–150 MW capacity, with gas turbine/steam combined cycle.
Biomass is burned to produce steam, the steam turns a turbine and drives a
generator, producing electricity. Because of potential ash build up (which fouls
boilers, reduces efficiency and increases costs), only certain types of biomass
materials are used for direct combustion. Gasifiers are used to convert biomass into
a combustible gas (biogas). The biogas is then used to drive a high-efficiency,
combined-cycle gas turbine. Heat is used to thermochemically convert biomass into
pyrolysis oil. The oil, which is easier to store and transport than solid biomass
material, is then burned like petroleum to generate electricity (Demirbas 2000,
2002).
Practically all biomass-based electricity generation plants employ steam turbine
systems. Such electricity generation is established in developed countries in order to
upgrade lignocellulosic-based waste materials. Most systems are based on
low-pressure boilers (about 20–25 bar) with efficiencies slightly below 20 %.
Modern biomass powered high pressure (60–100 bar) boiler turbine systems pro-
duce electricity with efficiencies approaching 32 % (Bain 1993).
(a) 100 Units Fuel Input
50 Units Heat
50 Units Power
Electricity Generator Boiler

(Efficiency 30%) (Efficiency 80%)
Output 15 units electricity Output 40 units heat
Overall Usable Energy 55 Units
(b) 100 Units Fuel Input
Electricity Generator Heat Transmission

(Efficiency 30%) (Efficiency 80%)
Output 30 units electricity Output 56 units heat
Overall Usable Energy 86 Units
Fig. 5.3 a Separate heat and power system with 100 units fuel inputs; b Combined heat and
power (COGEN) system with 100 units fuel inputs
Figure 5.3 shows (a) Separate heat and power system with 100 units fuel inputs;
(b) Combined heat and power (COGEN) system with 100 units fuel inputs.
Figures 5.3a, b illustrate the comparison between energy inputs to separate and
cogenerative generation systems, respectively (Demirbas 2005).
Traditional coal, oil, natural gas or biomass fired thermal generating stations
convert only about one-third of the initial energy contained within the fuel into
useful electricity. The remainder of the energy is discarded as heat without serving
any useful purpose. From 10 to 35 % of primary energy use is wasted as conversion
losses in power plants. COGEN can increase the efficiency of a fossil fuel from an
average of 40 % to over 80 %. Figure 5.2 (b) illustrates the increase in efficiency.
5.3 Importance of Unconventional Energy Sources 263
5.3 Importance of Unconventional Energy Sources
Unconventional energy sources can be classified as

(1) Unusual energy sources
(2) Inactive energy sources
(3) Waste energy sources
Unconventional energy sources cover unusually unconventional energy, with
little or no unused, inactive cases and the energy resources sometime available
waste form. Waste energy covers unused or used with low efficient energy
resources. Table 5.4 shows unconventional energy sources.
Finding approaches new energy sources, evaluation of unused waste of energy, it
has become inevitable to be commissioned recently inactive and unconventional
energy source. New systems are becoming increasingly important in energy pro-
duction and optimization of these resources.
Reducing the use of fossil fuels would considerably reduce the amount of air
pollutants produced. Hence, current efforts focus on advancing technologies that
emit less carbon or no carbon such as nuclear, hydrogen, hydropower, solar, wind,
geothermal, wave and tidal or on using energy more efficiently and on developing
sequestering carbon dioxide emitted during fossil fuel combustion. Therefore, the
future trend is towards using alternate energy sources such as “Unconventional
Energy Sources”.
Above all we must not forget that human energy is a renewable energy as soon
as possible. The most important and the most suitable and available renewable
energy is the kinetic energy of people. Human energy is one of the most appropriate
energy for use. Human brain provides the power benefits and immediately to decide
very quickly. The heart energy makes it possible to sustain life. The heart energy
makes it possible to sustain life cycle assessment.
Kinetic energy is generated by movement, such as people walking or dancing.
The electricity is used to power the light-emitting diode (LED) lights in the floor
itself. The sustainable dance floor converts kinetic energy into electricity. The
technology used in the sustainable dance floor could potentially be applied to other
situations and locations, such as a bus train station for example, to make the most of
kinetic energy generated by movement.
Sound wave is one of unusual energy sources. Sound waves can be converted in
electricity through something called piezoelectricity. Piezoelectric materials gen-
erate energy when put under some form of mechanical stress, such as a sound wave.
Every day we feel the energy that sound waves can generate: we feel a big truck
Table 5.4 Unconventional energy sources

Unusual energy sources Little or no unused energy resources
Inactive energy sources Never used energy resources
Waste energy sources Unused or used with low efficient energy resources
passing by, or the annoying woofer of our neighbors. Since sound waves can make
almost any material in the earth vibrate, some scientists are trying to transform these
waves into electricity by using wires and electrodes. The amount of electricity
utilizing piezoelectric materials that can be obtained with sound waves is not
exactly enormous, but current research is exploring the possibilities of using it to
charge small electronics such as mobile phones, to produce self-charging devices.
A number of initiatives currently are being pursued look to harness the kinetic
energy created by groups of people performing energetic tasks. Accordingly, it uses
piezoelectric floor pads positioned where pedestrian commuters are more likely to
tread: outside train stations and beneath ticket turnstiles, for instance.
The electricity can be obtained from sea wave motion. It is facility designed to
convert kinetic wave power into electricity. It is equipped with kinetic-energy
harvesters called floats. The motion of the floats is transferred via hydraulics to
rotate power generators. The facility enables continuous energy production and a
smooth output. In the event of a storm the floats can be lifted to a safe position. If
we could capture just 0.1 % of the ocean’s kinetic energy caused by tides. We could
satisfy the current global energy demand over 5 times.
The facility could also be upgraded to utilize wind such as wind power gener-
ation using shaking energy and solar power.
The heat can be obtained through the use of radio waves. The oven temperature
warmed by this method may be increased up to 500 °C.
Methane is a much more reactive greenhouse gas compared to carbon dioxide
and unlike CO2, it burns quite nicely. If only there were some practical ways to
capture the methane emitted by cows, sheep, goats, llamas. A cow weighing 550 kg
can make 750 g per day methane emissions. This amount of methane gas is
equivalent to about 2 kg of coal.
Geothermal energy is heat from inside the Earth. Deep inside the Earth the rock
is very hot and molten. Sometimes we see this as lava when it erupts through the
surface in volcanoes. However, we don’t need access to a volcano to be able to use
geothermal energy. In some places where the ground is hot we can use heat-pumps
to transfer the energy to the surface. Sometimes when water is next to hot ground
can produce steam, which can be used to heat buildings directly or to drive turbines
for electricity generation.
Gasoline is made from oil, which is a non-renewable source and so scientists and
engineers are developing alternative fuel for cars. One possible solution is the
hydrogen fuel cell. This works a bit like a battery. It sounds simple but the tech-
nology is highly complicated.
5.4 Energy Economy
Energy is an essential input driving economic development. Therefore, in devel-

oped economies energy policies constitute an important component of overall
regulatory frameworks shaping the improving overall competitiveness and market
5.4 Energy Economy 265
integration of the private business sector. Overall competitiveness includes liber-

alization of the electricity and gas markets as well as by separation of energy
production, transportation, and distribution activities.
Energy demand, energy production, energy optimization and cost have always
been a concern for researchers as well as policy makers. Energy policy is often
classified as
(1) Production-related energy policy,
(2) Energy production policy,
(3) Energy distribution policy,
(4) Energy marketing policy.
Population and income growth are the key drivers behind the growing demand
for energy. By 2030 world population is projected to reach 8.3 billion, which
means an additional 1.3 billion people will need energy; and world income in 2030
is expected to be roughly double the 2011 levels in real terms. Low and medium
income economies outside the OECD account for over 90 % of population growth
to 2030. Due to their rapid industrialization, urbanization and motorization, they
also contribute 70 % of the global GDP growth and over 90 % of the global energy
demand growth.
Global energy policies aiming at climate change stabilization will strongly affect
fossil fuel markets. The energy market response to climate policy intervention
shows several features that are robust to changes in energy demand and fossil fuel
supply. Despite the continued use of oil in the climate policy scenarios, the loss of
oil rents is the largest among the fossil fuels because oil is scarce and difficult to
substitute, and climate policy prevents the transition to high cost deposits
(Demirbas 2015b).
Energy production will grow in all regions, but Europe. Prices, technology and
policy drive changes in the fuel mix. Fossil fuels are converging on a market share
of 26–28 % each and non-fossil fuels groups on a market share of 6–7 % each. Oil
follows a long run trend of decline in its market share, with oil increasingly con-
centrated in the sectors where it commands the highest value. Gas remains on a
trend of modest but steady gains in share.
There is no oil in the world as a homogeneous region. The cost is $ 3 per barrel
of crude oil extraction from underground; the sales price has risen to $ 130.
Petroleum is one of the world’s most profitable sources of raw materials. Oil market
sales prices vary from country to country.
Global energy intensity in 2030 is 31 % lower than in 2011, declining at 1.9 %
p.a. compared to a decline rate of 1.0 % p.a. for 2000–2010. Energy intensity
declines in all regions. The impact of declining energy intensity can be seen clearly
in the gap between GDP and energy consumption. Without the projected intensity
decline, the world would need to almost double energy supply by 2030 to sustain
economic growth, rather than the 36 % increase required in our
After the oil price shocks of the 1970s, oil’s share in primary energy con-
sumption fell from a peak of 48 % in 1973 to 39 % in 1985. Rising oil prices have
again increased the burden of oil on the economy in recent years and oil has lost
market share again—falling to 33 % in 2011. High relative prices have led to the
substitution of oil by other fuels outside the transport sector where cheaper alter-
natives are available. Oil’s share in power generation, for example, fell from 22 %
in 1973 to 4 % in 2011 and is forecast to decline to just 2 % by 2030.
High prices and technological innovation have unlocked vast unconventional
resources in the US, reversing the trend of falling output and altering global energy
balances. Globally there are estimated technically recoverable resources of 240
billion barrels (Bbbls) for tight oil and 200 trillion cubic meters (Tcm) for shale gas.
Asia has an estimated 57 Tcm of shale gas and 50 Bbbls of tight oil, versus 47 Tcm
and 70 Bbbls respectively for North America. In 2012, 2.1 Mb/d (24 %) of US oil
production was from tight oil and 24 Bcf/d (37 %) of natural gas from shale. These
resources have boosted gas output by nearly 20 % and oil by 30 % in the past five
years. Assessing both global resources and “above ground” factors, North America
will continue to dominate production by 2030, even as other regions gradually
adapt to develop their resources.
Global liquids consumption is projected to reach 104 Mb/d by 2030 but growth
slows to 0.8 % p.a. (from 1.4 % p.a. in 1990–2010 and 1.9 % p.a. in 1970–90).
OECD consumption will fall to 40.5 Mb/d, 1 Mb/d below the 1990 level.
Non-OECD consumption is likely to overtake the OECD by 2014, and reach
63 Mb/d by 2030—2½ times the 1990 level.
The US will likely surpass Russia and Saudi Arabia in 2013 as the largest liquids
producer in the world (crude and biofuels) due to tight oil and biofuels growth, but
also due to expected OPEC production cuts. Russia will likely pass Saudi Arabia
for the second slot in 2013 and hold that until 2023. Saudi Arabia regains the top oil
producer slot by 2027. The US, Saudi Arabia, and Russia will supply over a third of
global liquids in our outlook.
The largest increments of non-OPEC supply will come from the US (4.5 Mb/d),
Canada (2.9 Mb/d), and Brazil (2.7 Mb/d), which offset declines in mature pro-
vinces such as Mexico and the North Sea. The largest increments of new OPEC
supply will come from NGLs (2.5 Mb/d) and crude oil in Iraq (2.8 Mb/d).
Russia will remain the world’s largest energy exporter, with increases in exports
of all fossil fuels. Net energy exports will rise by 25 % in volume terms. By 2030,
Saudi Arabia will be the world’s largest oil exporter, although the trajectory over
time will be impacted by the likelihood of OPEC production cuts discussed earlier.
By 2030, oil exports in volume terms are likely to be 17 % above the 2010 level.
As a region, Africa will become an increasingly important source of fossil fuel
exports as well. Once again adjusting for expected economic growth, Russia—and
the African countries as a group—is likely to remain significantly less dependent on
energy exports than Saudi Arabia.
The price of a barrel (42 gallons or 159 L) of crude oil is highly dependent on
both its grade (e.g., specific gravity, sulfur content, viscosity) and location.
References to the crude oil prices are usually either references to the spot price of
either WTI/Light Crude as traded on New York Mercantile Exchange (NYMEX)
for delivery in Cushing (Oklahoma, USA); or the price of Brent as traded on the
International Commodities Exchange (ICE) for delivery at Sullom Voe (Shetland,

Scotland). The price is highly influenced by the demand, current supply, and per-
ceived future supply. Both demand and supply are highly dependent on global
macroeconomic and political conditions. It is often claimed that OPEC sets a high
oil price, and the true cost of oil production is only $2/barrel in the Middle East.
These cost estimates ignore the cost of finding and developing the oil fields.
The oil price volatility results in different impacts on net oil exporter and
importer countries, combining both the crude oil and products. The oil importer or
energy-dependent countries suffer from limited purchasing power, low industrial
activity and elevated inflation when the prices are high. Moreover, the higher oil
prices didn’t assure the fluffing of the world oil demands, and as a result the oil
export countries suffer a decline in development of trade and exports (Jawad 2013).
The Middle East countries cover more than half OPEC’s total oil exports and
area major player in setting the oil price worldwide. The reserves of
petroleum-based fuels are limited and concentrated in certain regions of the world.
These sources are depleting very fast in recent decades. The Middle East countries
and the Russian federation hold 70 % of the world’s dwindling reserves of oil and
gas (Aburas and Demirbas 2015). The US is a member of the organization for
economic co-operation and development (OECD) that is an international organi-
zation of 30 different countries, which accept the principles of free-market economy
and representative democracy. An international energy agency (IEA) was made by
OECD in 1970s, similar to OPEC to see the energy demand-supply gas in the
western world in order to avoid energy crises.
There are many factors that cause the fluctuations in the oil prices, including the
invariant and variable factors. The invariant factors are the costs associated with oil
exploration, drilling, production, distribution, marketing and packaging and storage
and chemical composition. While, the variable factors include the levels of oil
production and consumption, global economic activity, exchange value of the US
dollar ($), current supply and demand, geopolitical reasons, weather-related
developments, and political events.
The oil cost estimations some time overlook the cost of finding and developing
the oil fields. The production cost is determined by marginal oil, not by the oil price.
For instance, by limiting the oil production, OPEC has caused more expensive
production development areas like the North Sea. While, financing in spare capacity
is also costly and the low oil price environment of 1990s has led to decline in
investment. Consequently, after the oil price rally since 2003, OPEC’s spare
capacity couldn’t stabilize the oil prices. Figure 5.4 shows imported crude oil prices
for US refineries (Demirbas 2007; Gupta and Demirbas 2010).
Table 5.5 shows the crude oil prices based on WTI index by year and month
(Saka and Demirbas 2015; EIA 2015). Traditional fundamental factors explain the
crude oil price volatility over the 1946–2015 periods, as shown in Table 5.5. These
factors include weather, marginal cost of oil production, OPEC spare capacity
levels, world oil supply and demand, crude oil inventory level, and technological
changes that have played an important role in determining the oil prices for decades.
Fig. 5.4 Imported crude oil prices for US refineries
Most of the crude oil reserves in the world are located in regions where political
turmoil and geopolitical events have a history. These events not only affect the oil
supply and demand, but also affect the prices of crude oil. For instance, the major
events included the Arab Oil Embargo (1973–1974), Iranian Revolution (1978),
Iran-Iraq War (1979), technological improvements (1982–1984), early 1980s
recession, growing non-OPEC supply (1985), Gulf War (1991), lack of OPEC
action (1997) and series of OPEC cuts (2000).
More interestingly, the oil price volatility events have happened at the same time
when the supply was disrupted, most notably during the Arab Oil Embargo during
1973–74, the Iranian revolution in the late 1970s and Iran-Iraq war in the early
1980s and Persian Gulf War in 1990. This reflects that the current supply and
demand can play a key role in the future movement of oil prices. For example, the
oil prices were lower in the United States (US) between 1982 and 1984 period than
expected due to the new technology for the high production levels (Cakir 2015).
Evidently, there is a lack of extensive research on modeling oil price volatility
(Salisu and Fasanya 2012). The oil price volatility shows the degree of rise or fall in
oil prices overtime. The known current prices on an active market and supply and
demand factors could affect and reflect the expected future oil prices. When market
prices tend to change significantly over relatively a short period of time, the market
is said to have high volatility. Similarly, when stable prices prevail, the market is
said to have low volatility. It is widely accepted that there is a strong correlation
between crude oil prices and global economic activity, as it one of the most
demanding products in the world (Morard and Bălu 2014).
Table 5.5 Crude oil prices based on WTI index by year and month ($/barrel)
March 1946 15.21 March 1982 71.71 March 1998 22.03
October 1946 17.39 June 1982 86.03 August 1998 19.45
June 1947 20.23 July 1982 83.35 September 1998 21.74
October 1947 19.35 October 1982 86.45 December 1998 16.38
March 1948 26.13 January 1983 75.89 May 1999 25.42
April 1949 25.59 February 1983 70.35 March 2000 41.55
March 1950 25.91 July 1983 75.41 September 2000 46.42
January 1952 23.08 January 1984 69.33 August 2001 36.84
July 1953 25.04 October 1984 65.02 November 2001 26.38
December 1954 25.13 December 1984 57.47 May 2002 35.75
March 1956 25.04 March 1985 63.14 September 2002 39.02
December 1956 24.31 May 1985 61.26 November 2002 34.47
April 1957 26.18 November 985 67.26 March 2003 43.35
September 1959 24.12 March 1986 27.60 April 2003 36.58
February 1962 23.48 July 1986 25.16 September 2003 36.35
March 1965 22.20 August 1986 32.73 June 2004 47.68
November 1966 21.48 January 1987 39.93 October 2004 66.20
January 1969 20.52 July 1987 41.98 August 2005 78.74
May 1969 21.90 March 1988 33.12 October 2005 74.53
September 1970 20.09 October 1988 27.32 July 2006 86.99
January 1971 21.29 February 1989 34.89 September 2007 91.20
April 1972 20.41 April 1989 40.67 July 2008 144.38
July 1973 19.12 August 1989 35.37 January 2009 47.04
October 1973 22.49 February 1990 41.10 September 2009 76.50
March 1974 50.33 June 1990 30.91 May 2010 80.56
August 1974 48.11 October 1990 64.01 June 2010 82.28
November 1974 51.56 February 1991 36.22 August 2010 83.73
December 1975 47.84 October 1991 40.23 December 2010 96.70
April 1976 51.61 January 1992 32.43 April 2011 116.42
August 1976 50.44 July 1992 36.86 September 2011 86.16
November 1976 57.03 December 1992 32.55 February 2012 111.08
July 1977 54.22 April 1993 33.49 October 2012 88.16
September 1977 57.54 October 1993 29.64 January 2013 101.17
December 1978 52.20 March 1994 23.69 May 2013 95.58
July 1979 70.80 July 1994 31.50 August 2013 109.82
October 1979 91.76 December 1994 27.27 December 2013 100.83
January 1980 99.39 May 1995 30.85 June 2014 105.86
February 1980 111.59 February 1996 29.29 September 2014 91.17
May 1980 114.91 April 1996 35.87 November 2014 66.47
(continued)
Table 5.5 (continued)

October 1980 101.02 June 1996 31.04 February 2015 50.54
February 1981 102.87 October 1996 37.42 March 2015 48.10
October 1981 89.18 January 1997 37.65 June 2015 59.30
March 1946 15.21 August 1997 29.50 November 2015 41.68
October 1946 17.39 October 1997 31.29 December 2015 34.68
Forecasting volatility is a key to the risk-management process and oil prices’

evaluation. High oil prices and volatilities impact the global economic growth and
eventually the financial markets (Hamilton 2009). For example, the oil prices affect
the United Kingdom (UK) financial growth and caused inflation during the period
of 1950–1979 (Jawad 2013). Crude oil is a commodity with huge strategic
importance to all countries in the world. It is one of the most important natural
resources of the industrialized countries (Morard and Bălu 2014).
According to Mileva and Siegfried (2012), the high oil cost producer countries
can sell their produced oil, and the low-cost producer countries can fulfil the rest of
the demand at existing prices and even can reduce their oil production if required.
The low-cost suppliers are mainly the Arabian countries. The global oil market and
OPEC play a key role and impact the global oil supply and demand. OPEC is
considered one of the main players in the oil market. Its importance and power
come from the high level of oil reserves and exports.
The mean and standard deviation for the thirteen-year period, starting 2003 to
the end of 2015 is calculated. An upper control limit can be set at US $128.63 per
barrel that would support the respective oil-producing countries in gaining large
amounts of cash surplus in their fiscal budgets. However, it could decrease their oil
market share, if the average oil price per barrel prolongs for an extensive period at
such a high rate. Control limits of the OPEC annual prices per barrel for 2003–2015
are given in Fig. 5.5. Furthermore, a lower control limit can be set at US $ 16.97
(Fig. 5.5), whose impact varies on the main OPEC countries as well as the
non-OPEC oil-producing countries. For example, this lower rate would have a
severe impact on the Kingdom of Saudi Arabia (KSA), but far less negative in
comparison to non-OPEC oil-producing countries such as Russia. According to
data compiled by Rystad Energy published on November 23, 2015, the cost of
production per barrel of crude oil is US $17.20 in Russia compared to US $ 9.90 in
KSA (OPEC 2015). The KSA and Russia (RSX) have 15.7 and 6.1 % of the
world’s total crude oil reserves.
OPEC member countries are struggling to finance their fiscal deficits due to
lower crude oil prices and are maintaining the current production level without any
plans for reducing the daily oil production rate. As a result, the oversupplied market
is being flooded with high crude oil inventory levels. The lower crude oil prices are
a direct loss for crude oil exporters. Oil exports account for a significant portion of
OPEC members’ GDP (gross domestic product). Countries like Libya and Algeria
Fig. 5.5 Control limits of the OPEC annual prices per barrel for 2003–2015
are facing a high fiscal deficit. Thus, higher volumes are the only way to drive the
revenue at lower energy prices that can lead to lower crude oil prices.
Oil price volatility depends on the combined effects of invariant and variable
factors. Invariant factors are feedstock prices, exploration costs, drilling costs,
chemical composition of oil, production costs, distribution costs, marketing costs,
and packaging and storage costs. Variable factors are global economic activity,
level of production, level of consumption, exchange value of the US $, current
supply and demand, geopolitical reasons, weather-related developments, and
political events. Table 5.6 shows the effects of invariant and variable factors on oil
price volatility.
Global oil demand is very much determined by global macroeconomic situations
and have affected the oil prices significantly in the first half of 2015 (Ratti and
Vespignani 2013). Weather is another critical factor in oil supply. Severely cold
weather can stress product markets, as producers attempt to supply enough prod-
ucts, e.g. heating oil in a short period of time. This will result in higher oil prices.
Moreover, the grow-ing foreign exchange value of the US dollar ($) is another
potential reason for oil price volatility (Cakir 2015). Historically, there is evidence
that a stronger dollar has declined the oil prices (Akram 2009; Basher et al. 2012).
Table 5.6 Effects of invariant and variable factors on oil price volatility
Invariant factors Variable factors
Feedstock prices Global economic activity
Exploration costs Level of production
Drilling costs Level of consumption
Chemical composition of oil Exchange value of the US dollar
Production costs Current supply and demand
Distribution costs Geopolitical reasons
Marketing costs Weather-related developments
Packaging and storage costs Political events
5.5 Energy Policy and Barriers
Current energy policies address environmental issues including environmentally

friendly technologies to increase energy supplies and encourage cleaner, more
efficient energy use, air pollution, greenhouse effect, global warming and climate
change.
In general, energy policy includes issues of energy production, distribution and
consumption. It is the manner a given entity has decided to address these issues.
The attributes of energy policy may include international treaties, legislation on
commercial energy activities (trading, transport, storage, etc.), incentives to
investment, guidelines for energy production, conversion and use (efficiency and
emission standards), taxation and other public policy techniques, energy-related
research and development, energy economy, general international trade agreements
and marketing, energy diversity, and risk factors contrary possible energy crisis.
Current energy policies also address environmental issues including environmen-
tally friendly technologies to increase energy supplies and encourage cleaner, more
efficient energy use, air pollution, greenhouse effect, global warming and climate
change.
There is considerable uncertainty in the economic analysis, associated with the
costs of feed stocks and oil prices, and also because of the rapid development of the
technologies. Policy options include incentive payments or tax breaks. Due to rising
prices for fossil fuels (especially oil, but also natural gas and to a lesser extent coal)
the competitiveness of biomass use has improved considerably over time. Biomass
and bioenergy are now a key option in energy policies. Security of supply, an
alternative for mineral oil and reduced carbon emissions are key reasons. Targets
and expectations for bioenergy in many national policies are ambitious, reaching
20–30 % of total energy demand in various countries. Similarly, long-term energy
scenarios also contain challenging targets.
5.5 Energy Policy and Barriers 273

energy policy are (Kim and Seo 2007):
1. Competitiveness of the EU economy
2. Security of energy supply
3. Environmental protection.
Energy is an essential input driving economic development. Therefore, in
developed economies energy policies constitute an important component of overall
regulatory frameworks shaping the improving overall competitiveness and market
integration of the private business sector. Overall competitiveness includes liber-
alization of the electricity and gas markets as well as by separation of energy
production, transportation, and distribution activities.
The result has been an improvement in the efficiency with which energy is used
in industry and power generation as well as in lighting, household appliances,
transportation, and heating and cooling of buildings. This more efficient use of
energy is a major factor contributing to the improvements in energy intensity that
have occurred historically in almost all OECD countries, and more recently in many
transition economies, as well as in some in fast-growing developing countries.
Increasingly, engineering practitioners and managers need to know how to respond
to challenges of integrating environmentally conscious technologies, techniques,
strategies, and objectives into their daily work, and, thereby, find opportunities to
lower costs and increase profits while managing to limit environmental impacts.
Engineering practitioners and managers also increasingly face challenges in com-
plying with changing environmental laws.
The interaction of climate policy and fossil fuel markets is of great interest for
climate and energy economists and for policy makers. Climate change stabilization
imposes limitations on carbon dioxide (CO2) emissions from fossil fuel combus-
tion, thus leading to a re-allocation of the use and prices of fossil fuels.
A comprehensive assessment of the macroeconomic and energy sector conse-
quences of policy action requires a thorough quantification of energy market effects
(Safari and Mekhilef 2011).
Renewable energy can contribute substantially to electricity supply, to biomass
based transport fuels and for space and hot water heating in buildings and industry
in developed countries. By early 2014, at least 144 countries had renewable energy
targets and 138 countries had renewable energy support policies in place, up from
the 138 and 127 countries, respectively, that were reported in GSR 2013.
Developing and emerging economies have led the expansion in recent years and
account for 95 of the countries with support policies, up from 15 in 2005. The rate
of adoption remained slow relative to much of the past decade, due largely to the
fact that so many countries have already enacted policies (REN21 2014).
In 2013, there was an increasing focus on revisions to existing policies and
targets, including retroactive changes, with some adjustments made to improve
policy effectiveness and efficiency, and others aimed to curtail costs associated with
supporting the deployment of renewables. At the same time, some countries
expanded support and adopted ambitious new targets. Policy mechanisms contin-
ued to evolve, with some becoming more differentiated by technology. Feed-in
policies in many countries evolved further towards premium payments in the power
sector, and continued to be adapted for use in the heating sector. Particularly in
Europe, new policies are emerging to advance or manage the integration of high
shares of renewable electricity into existing power systems, including support for
energy storage, demand-side management, and smart grid technologies (Jacobson
and Delucchi 2011; REN21 2014).
Thousands of cities and towns worldwide have policies, plans, and targets to
advance renewable energy, often far outpacing the ambitions of national legislation.
Policy momentum continued in 2013 as city and local governments acted to reduce
emissions, support and create local industry, relieve grid capacity stress, and
achieve security of supply. To accomplish these goals, they increasingly made use
of their authority to regulate, make expenditure and procurement decisions, facil-
itate and ease the financing of renewable energy projects, and influence advocacy
and information sharing. As cities seek to share and scale up best practices,
highlight their commitments to renewable energy, and account for their achieve-
ments, local governments are increasingly prioritising systematic measurement and
reporting of climate and energy data (Jacobson and Delucchi 2011; REN21 2014).
As in past years, most renewable energy policies enacted or revised during 2013
focus on the power sector. A mix of regulatory policies, fiscal incentives, and public
financing mechanisms continued to be adopted. Feed-in policies and renewable
portfolio standards (RPS) remained the most commonly used support mechanisms,
although their pace of adoption continued to slow. Public competitive bidding, or
tendering, gained further prominence, with the number of countries turning to
public auctions rising from 9 in 2009 to 55 as of early 2014 (IEA 2014).
Renewable energy policies and barriers include subsidies for conventional forms
of energy, high initial capital costs coupled with lack of fuel-price risk assessment,
imperfect capital markets, lack of information or skills, poor market acceptance,
Table 5.7 Main renewable energy policies and barriers

Policy Barriers
Power sector Transaction costs, lack of information, high cost
restructuring
Distributed Unfavorable power pricing rules
generation
Ruler electrification Interconnection requirements, transaction costs, lack of skills, lack of
information
Renewable energy High costs, unfavorable power pricing rules, transaction costs,
promotion perceived risks, lack of access to credit, information, and skills
Transport biofuels High costs, lack of fuel production or delivery infrastructure
Emission reduction Environmental externalities
5.5 Energy Policy and Barriers 275
technology prejudice, financing risks and uncertainties, high transaction costs, and a
variety of regulatory and institutional factors. Table 5.7 shows main renewable
energy policies and barriers.
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Green Energy and Technology

Waste Energy for Life

ISSN 1865-3529 ISSN 1865-3537 (electronic)

© Springer International Publishing Switzerland 2016

Printed on acid-free paper

This Springer imprint is published by Springer Nature

fuels, conversion of used oils to gasoline-like products, conversion of heavy oil to

Jeddah, Saudi Arabia Ayhan Demirbas

3.2.1 Waste Heat Recovery by Cogeneration

4.11 Conversion of Oil Shale to Liquid Fuels. . . . . . . . . . . . . . . . . . 193

1.1 Energy and Force Concepts

Energy is deﬁned as the ability to do work of a system or an object. However, the

What is force? Force is a factor acting alone an influence on an object or a

1.1.1 Electric and Magnetic Fields and Forces

According to Arrhenius theory, which is evidently very hypothetical, but which

E ¼ fð@u=@xÞ; ð@u=@yÞ; ð@u=@zÞg ð@A=@tÞ ðelectric fieldÞ ð1:1Þ

Fem ¼ fð@U=@xÞ; ð@U=@yÞ; ð@U=@zÞg ð@Q=@tÞ þ v P

Fem ¼ qfð@u=@xÞ; ð@u=@yÞ; ð@u=@zÞg qð@A=@tÞ þ qv B

Fem ¼ qE þ qv B ðElectromagnetic force or Lorentz forceÞ ð1:3Þ

where v in Eq. (1.3) is the velocity of the particle.

Table 1.1 Phenomenon related to type of effect and driving force

Sunlight wave + K ! K þ þ e ð1:4Þ

Equation (1.4) is less scientiﬁc.

Sunlight energy ðlight wave and/or photon, flow or moving energyÞ þ K

Equation (1.5) is more scientiﬁc because it is agree with observations. However,

Light wave with high energy þ Cu ! Cu þ þ e ðless scientificÞ ð1:6Þ

Light wave with high energy þ Cu ! Heat wave

Friction between stick of ebonite or glass and wool:

Friction energy ðstatic energyÞ ! Heat energy þ Static electric ð1:8Þ

1.1.2 Geometric Energy Concept

Photosynthesis is an electrochemical event, but rather an event that took place in

1.2 Energy Sources

Fig. 1.1 Basic classiﬁcation Energy Sources

Non-renewables Fissile Renewables

Conventional Non-conventional Conventional Non-conventional

1.2.1 Fossil Energy Sources

Table 1.2 1973 and 2012 Region 1973 2012

Furnace for Multi-stage

Fig. 1.2 A generalized fractional distillation column

Industrial distillation is typically performed in large, vertical, steel cylindrical

Table 1.3 Common process units found in an oil reﬁnery

Table 1.3 (continued)

production, aromatics, naphthenes and isoalkanes are highly desirable, whereas

Table 1.4 World’s recoverable coal reserves

Table 1.5 World natural gas Country Percent of world total

sectors of the world, as resource availability, rate, and environmental considerations

1.2.2 Renewable Energy Sources

Table 1.6 World’s top Country Installed MWt Production (GWh/a)

1.2.3 Nuclear Energy Sources

Table 1.7 Energy reserves of the world

The essence of a conventional nuclear reactor is the controlled ﬁssion chain

1.3 World’s Present Energy Situation

Today the energy world is facing ﬁve major challenges:

Table 1.8 World’s energy Years World’s energy consumption

Table 1.9 The world’s Resources of energy consumption %

Table 1.10 Global oil Years Percent of today’s production

regions of the world, as resource availability, cost, and environmental considera-

Demirbas A (2005a) Potential applications of renewable energy sources, biomass combustion

© Springer International Publishing Switzerland 2016 33

2.2 Renewable Energy Scenarios

Renewable energy is a promising alternative solution because it is clean and envi-

Table 2.1 Global renewable energy scenario by 2040

Table 2.2 Growth scenarios Years Stagnat Moderata Strong