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h i g h l i g h t s
" Exergy analysis was used as decision-making tool for evaluation of microalgae oil extraction.
" A robust composition of Chlorella sp. biomass was modeled and used for simulation.
" Three solvent-based microalgae oil extraction methods at large scale were compared.
" Hexane based extraction presented the highest exergetic efciency.
a r t i c l e
i n f o
Article history:
Received 10 December 2011
Received in revised form 19 June 2012
Accepted 29 June 2012
Available online 24 August 2012
Keywords:
Microalgae biomass
Exergy analysis
Oil extraction
Third generation biofuels
a b s t r a c t
Several technologies for microalgae oil extraction are being evaluated in order to nd the most adequate
for large scale microalgae processing. In this work, exergy analysis was used as an instrument for screening three design alternatives for microalgae oil extraction in a large-scale process and as a decisionmaking tool for evaluation and selection of novel technologies from the energy point of view. Routes were
simulated using dedicated industrial process simulation software, taking as feedstock a representative
and robust modeled composition of Chlorella sp. microalgae biomass. Mass, energy and exergy balances
were performed for each alternative, and physical and chemical exergies of streams and all specic microalgae constituents modeled were calculated with the help of the thermodynamic properties of biomass
components and operating conditions of streams.
Exergetic efciencies, total process irreversibilities, energy consumption and exergy destruction were
calculated for all solvent-based microalgae oil extraction pathways evaluated. It was shown that exergy
analysis led to identify the hexane-based oil extraction (HBE) as the most adequate alternative of the
routes assessed for scaling up from the energy point of view, presenting a maximum exergy efciency
of 51% and exergetic losses of 982,000 MJ considering a production of 104,000 t of microalgae oil per year.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Nowadays, the continued use of fossil-derived fuels is recognized as unsustainable due to the exhaustion of supplies and their
contribution to environmental pollution. This kind of fuels has to
be replaced with clean and renewable energy. In response to this
issue, environmental policies worldwide have favored the increase
in research, development and the use of biofuels, mainly those that
can replace fossil fuels used in transportation. Biofuels offer many
benets associated with energy security, economic stability and
reduction of the environmental impact of greenhouse gases [1].
Third-generation biofuels are derived from microorganisms,
such as yeast, fungi and microalgae, some of these microbes can
Corresponding author. Address: Research Center for Sustainable Development
in Industry and Energy, Department of Chemical Engineering, Industrial University
of Santander, K 27 Cll 9 Bucaramanga, Colombia. Tel.: +57 7 6344000x2603.
E-mail address: Kafarov@uis.edu.co (V. Kafarov).
0306-2619/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2012.06.065
biosynthesize and accumulate large amounts of lipids and/or sugars [2], fungi like Trichosporon fermentans have been studied for
microbial oil production and biodiesel preparation [3,4], however,
the most attractive source for third generation biofuels production
are microalgae. They have recently been rediscovered as promising
candidates for biotechnological applications and efcient energy
production systems [5]. Depending on the strain, microalgae can
grow in a wide range of temperatures, pH and nutrients availability. They have a growth rate between 20 and 30 times higher than
other sources for biofuels, some microalgae species have the ability
to produce up to 20 times more oil per unit area than palm [6], oil
content of certain strains in some cases exceeds 80% in dry weight
biomass under appropriate conditions [7]. Microalgae can grow in
warm, tropical, and subtropical climates, for biomass production it
only requires water, some nutrients, a carbon source and a high
and constant sun irradiance. Microalgae can be cultivated in photobioreactors which offer high biomass productivities and an
adaptable illumination, open ponds which can be natural systems
227
(e.g. lagoons and lakes) or articial systems (e.g. stirred tanks and
raceway ponds) which require low energy consumption and are
easy to maintain. This condition makes feasible the use of nonarable lands for photobioreactor assembly or open pond building.
Microalgae can also be cultivated using as culture media waste
water or sea water. Due to its high growth rate, microalgae biomass can be harvested 365 days per year. Taking into account
the issues mentioned above, microalgae presents a theoretical potential to become a viable alternative to replace petroleum-based
liquid fuels in the future without the disadvantages associated
with food vs. fuel discussion and use of land, showing a prospective
of a continuous biofuel production chain as occurs in traditional oil
reneries. However, to make this possible, it is important to improve technical, environmental and economic aspects such as
water requirements, production costs, environmental impacts
and process efciency, among others [1].
However, biodiesel-from-microalgae production chain is still
away from sustainability by several factors, in energy terms, Khoo
et al. [8], presented a comparison of energy and environmental
performance of biodiesel from microalgae case studies previously
developed by several authors referenced in the paper, with two
additional cases proposed by the authors mentioned, using the
methodology of Life Cycle Assessment (LCA) including energy
and CO2 balance, in which, for all systems analyzed, the comparison of life cycle energy demands in MJ per MJ of biodiesel are positive, even if energy requirements of lipid extraction and biodiesel
production are not included as occurs in two of compared cases.
Total energy inputs for the system proposed by authors were calculated in 85% for lipid extraction, 13% for biomass production
and 2% for transesterication, concluding that main bottleneck
lie in high energy requirements for lipid extraction and pointing
out this issue as a main challenge to overcome in order to make
biodiesel from microalgae production chain feasible and practical.
These results show the necessity of future studies related to microalgae lipid extraction in order to improve this process in terms of
efciency, purity of product, energy requirements, costs and environmental impacts.
Studies about microalgae oil extraction for biodiesel production
are taking signicance because the efciency of biodiesel production chain from microalgae depends in a great way on the oil
extraction efciency. There are several oil extraction methods
which have been used on microalgae, these methods can be divided in:
Methods assisted by mechanical disruption which uses cell
homogenizers, ball mills, pressing systems, among others;
these methods are not suitable for a lab-scale oil extraction
because presents high biomass losses and low selectivity to
lipids.
Enzyme-assisted extraction methods, where microalgae cell
wall is degraded by enzymes allowing lipids release, however, enzymatic activity is affected by several variables
including concentration and ratio of system compounds,
fatty acid prole, microalgae composition, temperature,
among others. These issues make this route hard to maintain in this moment for a large scale biomass processing.
Other methods evaluated on microalgae are ultrasound-assisted
extraction, microwave-assisted extraction, supercritical uid
extraction, autoclave and solvent based extractions [9].
A wide variety of organic solvents are often used to extract oil
from microalgae, where hexane and ethanol are the most popular.
However, ethanol is a polar solvent and its selectivity to lipids is
relatively low compared to other solvents, so in extractions with
ethanol, other microalgae components may also appear, such as
sugars, pigments or aminoacids. Using a mixture hexane-ethanol,
_ i in Ri m
_ i out
Ri m
_ 0
_ i hi in Ri m
_ i hi out Q_ W
Ri m
Q_ i _
Sgeni
Ti
_ i si in Ri m
_ i si out Ri
Ri m
_ mass;in Ex
_ mass;out Ex
_ heat Ex
_ work Ex
_ loss
Ex
Mass exergy component expressed as is shown in Eq. (5), is divided into four specic components: the physical exergy (Exphy) related to temperature, enthalpy and entropy given by Eq. (6);
chemical exergy (Exchem) related to the chemical exergy of each
compound per mol (Exoch ); potential exergy, Expot and kinetic exergy, Exkin. The calculation of the chemical exergy of each compound
per mol (Exoch ) is given by Eq. (7), and is a function of the chemical
exergy of each elemental compound (Exoch;elem ), the number of
atoms of each element contained into the stream (nelem) and the
Gibbs free energy of formation for the compound (DGof ) [20]. The
228
_ mass Ex
_ phy Ex
_ chem Ex
_ pot Ex
_ kin
Ex
_ phy H_ H_ o T o S_ S_ o
Ex
_ heat
Ex
1
_ Work W
_
Ex
To
T
Q_
9
10
Exergy analysis can be used as a decision-making tool for selecting and improving technologies from the energy point of view. This
analysis has been recently used to study existing and emerging
technologies proposed for biofuels production chains from several
feedstocks [2123] including microalgae [22,23]. Peralta et al. [22],
studied microalgae oil transesterication using four fatty acids and
four triglycerides for modeling microalgae oil composition nding
an exergy efciency of 79% for this stage. Ofori-Boateng et al. [23],
used exergy analysis to study the feasibility of microalgal and
jatropha biodiesel production plants using three triglycerides as
representative microalgae oil, performing extraction with methanol at temperatures between 333 and 338 K by the use of a liquidliquid extraction tower, and concludes that oil extraction
units showed the highest exergy loses, however, microalgae oil
extraction stage is not deeply studied in this reference. Is clear that
exergy analysis of microalgae oil extraction stage focused the evaluation and comparison of different solvent-based techniques using
a robust model of a microalgae strain which includes carbohydrates, proteins, aminoacids and a detailed fatty acid prole has
not been developed until now.
In this work, three solvent-based microalgae oil extraction
methods were evaluated using exergy analysis as an instrument
for screening design alternatives for scaling up and as a decisionmaking tool for evaluation and selection of novel technologies
from the energy point of view, exergetic efciency of the routes, total irreversibilities, energy utilities required and exergy destruction
were calculated for each oil extraction method. Through this research, four contributions to the microalgal biotechnology research
were made:
Development of a robust model of microalgae Chlorella sp.
biomass composition, for use in process simulation, based
on experimental strain characterization reported, which
includes proteins, aminoacids, carbohydrates, triglycerides
and fatty acids.
The simulation in large scale of three detailed solvent-based
microalgae oil extraction methods: hexane based extraction
(HBE), oil extraction using the mixture ethanol/hexane (EHE)
and extraction with methanolchloroform mixture (SHE).
The calculation of chemical exergies for all specic microalgae constituents used for simulation.
The evaluation based on exergy analysis of simulated microalgae oil extraction methods and selection of the best
method from the energy point of view.
229
operating conditions for simulation. The routes selected were hexane-based extraction (HBE), oil extraction using the mixture ethanol/hexane (EHE) and extraction with methanolchloroform
mixture (SHE). The rst one is a batch microalgae oil extraction
method and was reported by Garca et al. [36].
To perform this method, hexane is added to microalgae biomass
under environmental conditions (298 K, 101.325 kPa) in a 20:1
mass ratio, after that, mixture is separated and ltered, obtaining
a liquid stream rich in hexane and oil, and a stream of biomass rich
in carbohydrates and proteins. Oil/hexane stream is separated
through distillation and hexane is recirculated to the process, liquid components present in biomass stream after ltration are
Fig. 1. Schematic ow sheet of oil extraction methods evaluated using exergy analysis.
230
w1
Exergy loss
Exergy input
11
Table 1
Modeled composition of Chlorella sp. microalgae.
Components
C14:00
C16:00
C16:01
C16:02
C16:03
C18:00
C18:01
C18:02
C18:03
Total free fatty acids
0.14
0.38
0.03
0.15
0.14
0.01
0.08
0.31
0.29
1.53
Triglycerides
TAG-C14:00
TAG-C16:00
TAG-C16:01
TAG-C16:02
TAG-C16:03
TAG-C18:00
TAG-C18:01
TAG-C18:02
TAG-C18:03
Total triglycerides
2.56
7.15
0.57
2.85
2.56
0.26
1.42
5.69
5.41
28.47
Aspartic acid
Glutamic acid
Glycine
Alanine
Valine
Leucine
Proline
Lysine
Total amino acids
4.49
5.47
4.35
5.40
3.86
4.28
5.05
7.15
40.05
Cellulose
Lignin
Hemicellulose
Total carbohydrates
7.10
1.52
16.30
24.92
Amino acids
Carbohydrates
Water
Total microalgae
5.03
100.00
of other biofuels and high value products by the presence of essential aminoacids a lysine and their low lignin percentage.
4.1. Simulation of three solvent-based microalgae oil extraction
methods
According to simulation of microalgae oil extraction methods
four general stages are common in all methods: biomass-solvent
mixing, oil extraction, solvent recovery (oil separation) and solids
drying, simulation of hexane-based extraction route (HBE) is
shown in Fig. 2. The system with four mixing units for fresh solvent
input, solvent biomass mixing post-extraction solids mixing and liquid oil/hexane streams combination have to be incorporated. Solids streams after oil extraction are rich in carbohydrates and
proteins as shown in Table 2, composition of this stream conrms
the potential of coproduct as a feedstock for downstream processing, stream 101 which corresponds to microalgae oil extracted,
presents a free fatty acid mole fraction of 0.14 which shows that
lipids obtained can be used for a transesterication process without the need of previous free fatty acids esterication.
Results of ethanolhexane route (EHE) simulation (Fig. 3), show
that more steps are needed for a continuous extraction process, as
occurs in lab-scale; this means the installation of more equipment
affecting the technical practicability of the route and the economy
of the process. However the use of ethanol gives the possibility of
several operation alternatives in a complete production chain, for
231
Table 2
Main process streams conditions for hexane based microalgae oil extraction (HBE).
Streams
101
106
109
111
112
114
116
117
118
Pressure (kPa)
Temperature (K)
Mass ow (kg/h)
101.325
554.8
12236.44
101.325
298
726857
101.325
298
36669
101.325
298
746488.20
101.325
298
745839
70.927
298
44461.65
101.325
298
43451.43
70.927
298
1010.22
101.325
433
23820.18
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.01
0.99
0.06
0.01
0.17
0.05
0.05
0.1
0.1
0.05
0.05
0.07
0.08
0
0
0
0
0
0
0
0
0
0.01
0.01
0
0.01
0.01
0
0
0.01
0.01
0.14
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.01
0.99
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0.04
0.01
0.1
0.03
0.03
0.06
0.06
0.03
0.03
0.04
0.04
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.52
0.04
0.01
0.1
0.03
0.03
0.06
0.06
0.03
0.03
0.04
0.04
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.53
0.05
0.01
0.14
0.04
0.04
0.08
0.08
0.04
0.04
0.06
0.06
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.37
0.08
0.02
0.21
0.06
0.06
0.13
0.13
0.07
0.06
0.09
0.1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
example, the use of stream 112 which corresponds to ethanol output at 350 K from DESTL-2 can be used in transesterication stage
for ethylesters production. As shown in Table 3, an effective lipid
separation was reached and mass ow distribution in route stages
is different to mass ow in HBE route, caused by the presence of
additional steps.
The simulation of solvent-based oil extraction with homogenization using the mixture methanolchloroform (SHE), involves
the use of two solvents, these are added in the same process unit
(MIX-1), for this reason, only one hydrocyclone is necessary for
oil separation as is shown in Fig. 4. Route needs less equipment
in comparison to EHE route, but two separation units are also need
for chloroform-lipids and methanolwater mixtures. Table 4
shows the main process streams conditions for SHE route, differences in temperatures of streams are caused by the nature of solvents used in this route.
4.2. Exergy analysis of microalgae oil extraction methods
The process of extracting oil from microalgae for all routes can
be divided into four general steps: biomass-solvent mixing, oil
extraction, solids drying and solvent recovery. Taking into account
232
Fig. 3. Simulation of microalgae oil extraction using the mixture ethanolhexane (EHE).
Table 3
Main process streams conditions for microalgae oil extraction using the mixture ethanolhexane (EHE).
Streams
115
118
119
122
124
125
128
129
130
132
Pressure (kPa)
Temperature (K)
Mass ow (kg/h)
101.325
302
653366.7
101.325
604.6
12212.38
101.325
297.7
177640.3
101.325
298
36662
101.325
297.7
210744.3
101.325
297.9
128752.5
101.325
302.2
1286204
101.325
297.7
33104.07
101.325
297.9
28405.48
51.67
297.9
31675.21
0
0
0
0
0
0
0
0
0
0
0
0.01
0.04
0
0.02
0.01
0
0.01
0.03
0.03
0.09
0.22
0.02
0.09
0.08
0.01
0.04
0.16
0.15
0
0.01
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.15
0
0.84
0.06
0.01
0.17
0.05
0.05
0.1
0.1
0.05
0.05
0.07
0.08
0
0
0
0
0
0
0
0
0
0.01
0.01
0
0.01
0.01
0
0
0.01
0.01
0.14
0
0
0
0
0.01
0
0
0.01
0.01
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.14
0
0.81
0.01
0
0.02
0
0
0.01
0.01
0
0
0.01
0.01
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.12
0
0.8
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.62
0.21
0.17
0.04
0.01
0.1
0.03
0.03
0.06
0.06
0.03
0.03
0.04
0.04
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.08
0
0.45
0.03
0.01
0.09
0.02
0.03
0.05
0.05
0.03
0.03
0.04
0.04
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.08
0
0.5
0.04
0.01
0.11
0.03
0.03
0.07
0.07
0.04
0.03
0.05
0.05
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.06
0
0.4
233
Fig. 4. Simulation of microalgae oil extraction using the mixture methanolchloroform (SHE).
Table 4
Main process streams conditions for microalgae oil extraction using the mixture methanolchloroform (SHE).
Pressure (kPa)
Temperature (K)
Mass ow (kg/h)
109
110
111
113
114
118
120
123
124
101.325
299
447383.7
101.325
586.8
12212.6
101.325
296.6
651982.8
101.325
296.6
651298.4
101.325
298
36687
101.325
296.6
691686.7
101.325
299.1
810963.3
51.67
296.6
40388.27
101.325
427.7
23831.88
0
0
0
0
0
0
0
0
0
0
0
0.01
0.04
0
0.02
0.01
0
0.01
0.03
0.03
0.09
0.22
0.02
0.09
0.08
0.01
0.04
0.16
0.15
0
0
0.01
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.01
0.65
0.34
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.01
0.65
0.34
0.06
0.01
0.17
0.05
0.05
0.1
0.1
0.05
0.05
0.07
0.08
0
0
0
0
0
0
0
0
0
0.01
0.01
0
0.01
0.01
0
0
0.01
0.01
0.14
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.01
0.64
0.33
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.43
0.37
0.2
0.03
0.01
0.1
0.03
0.03
0.06
0.06
0.03
0.03
0.04
0.04
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0.36
0.19
0.08
0.02
0.21
0.06
0.06
0.13
0.13
0.07
0.06
0.09
0.1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
234
Table 5
Specic chemical exergies of main components.
Component
Specic chemical
exergy (kJ/kmol)
Cellulose
Lignin
Hemicellulose
Aspartic
Glutamic
Glycine
Alanine
Valine
Leucine
Proline
Lysine
2834125
5352170
2313790
2079030
2475000
1114980
2000300
3307400
3962170
3005530
3900890
Component
Specic chemical
exergy (kJ/kmol)
Component
Specic chemical
exergy (kJ/kmol)
C14H2-01
C16H3-01
C16H3-O2
C16H3-03
C16H3-04
C18H3-01
C18H3-02
C18H3-03
C18H3-04
C6H14-02
H2O (liquid)
H2O (vapor)
8774870
10085570
9929620
9773740
9617860
11394270
11174370
11048870
10925044
4114133.66
770
9495
TGC14-01
TGC16-01
TGC16-02
TGC16-03
TGC16-04
TGC18-01
TGC18-02
TGC18-03
TGC18-04
C2H6OH
CHCL3
CH4OH
28019930
31948550
31480910
31013270
30545630
35877170
52903360
34941890
34474250
1362935
458386
722115
Table 6
Energy consumption of main equipment used in oil extraction routes evaluated.
Energy consumption (kW h)
HBE
EHE
SHE
Hydrocyclone 1
Hydrocyclone 2
Filter
Pump
74.25
14.3
53.4
6.3
0.5
0.5
0.5
21
8.2
13.1
Fig. 5. Destroyed exergy by stage for microalgae oil extraction methods evaluated.
235
236
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