Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

Application #2

Content

a. Total Energy Consumption

b. Combustion/Burning Processes. Clean Coal Technology general description
c. Determination of Emissions (SO2, NOx, particulate matter, CO2, fly ash, etc.)

A. Total Energy Consumption

Humans are consuming fossil energy faster than nature can produce it.
Fossil fuel is an exhaustible resource, and the energy consumption by humans grows exponentially in
acvordance with relation (1).

Q = Q0 exp ( T) (1)

where, Q0 - a mean standard energy consumption in the world (based on population number); e = 2.718, T
time (year, AD), and constant (y-1).
This type of growth is inevitably unreasonable. It will double in 18 years even if energy consumption
only increases by 4% per year. For an exhaustible resource, the cumulative production and rate production
will be variable and dependent of social-political context.
Nothing in the natural world can grow through too many doubling periods before it runs into some
constraints. Moreover, all exponential growth curves have to level off, and the growth of energy
consumption is no exception. In the long run, energy inputs and outputs for human society must be in a
steady state. Because population grows exponentially, our consumption is exponential in nature.

Example #1: Our present total energy consumption is expressed as

QT = 1.85 . 10-21 e0.0282 T [Quad/yr] (3)

Considering the actual times (when = 0.0282), calculates the total energy consumption in 2000 and 2016
years and compares its.

Q1T = 1.85 . 10-21 e0.0282 x 2000 = 1.85 . 10-21 e0.0282 x 2000 = ........ [Quad/yr]
Q2T = 1.85 . 10-21 e0.0282 x 2016 = 1.85 . 10-21 e0.0282 x 2016 = ....... [Quad/yr]
The value Q1T was ......(>, or < ) related to Q2T, caused of ..... (an explanation must be given).

Some properties associated with the exponential relation of energy consumption are (i) doubling
time, T2; (ii) yearly fractional increase, R, and (iii) crossover .

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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

(i) Doubling time, T2

ln 2 0.693
T2 = =

(2)

Example #1 : For actual times, = 0.0282 and T2 will be

0.693
T2 = = 25 [yr]
0.0282

(ii) Yearly fractional increase, R

R = e - 1 [% per yr] (4)

Example #1: For actuial times, is0.0282 and R (% increase) is calculated as

R (% Increase) = R (100) = (e - 1)(100) = 2.86 [%]

(iii) Crossover

QT = 1.85 x 10-21 e0.0282 T (5)

Example #1: Gas consumption has become increasingly rapid in recent years. It has the potential to exceed
the total energy consumption, and at its current rate it has increased from 6Q in 1960 to 23Q in 1980.

Thus,
6 = Q0 e1960
23 = Q0 e1980

Solving,
= 0.067 yr-1 and Q0 = 1.1 x 10-56

Hence,
QG = 1.1 x 10-56 e0.067 T

Solving QG = QT, it results that T = 2090, the crossover will take place.

B. Combustion/Burning Processes in a Thermal Power Plant. Solid Fuels (pulverized coal)

Sources of CO2
Power and industry sectors combined dominate current global CO2 emissions, accounting for
about 60% of total CO2 emissions. Future projections indicate that the share of these emissions will decline
to around 50% of global CO2 emissions by 2050.
The CO2 emissions in these sectors are generated by boilers and furnaces burning fossil fuels and
are typically emitted from large exhaust stacks. These stacks can be described as large stationary sources,
to distinguish them from mobile sources such as those in the transport sector and from smaller stationary
sources such as small heating boilers used in the residential sector. The large stationary sources represent
potential opportunities for the addition of CO2 capture plants.
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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

Other sectors of the economy, such as the residential and transport sectors, contribute around 30%
of global CO2 emissions and also produce a large number of point source emissions. However, the emission
volumes from the individual sources in these sectors tend to be small in comparison to those from the
power and industry sectors and are much more widely distributed, or even mobile rather than stationary. It
is currently not considered to be technically possible to capture emissions from these other small
stationary sources, because there are still substantial technical and economic issues that need to be
resolved.
Emissions of CO2 due to fossil fuel burning are virtually certain to be the dominant influence on the
trends in atmospheric CO2 concentration during the 21st century global effects: greenhouse effects and
global warming. Global average temperatures and sea level are projected to rise under all scenarios.
Technological options for reducing net CO2 emissions to the atmosphere include:
- reducing energy consumption, for example by increasing the efficiency of energy conversion and/or
utilization (including enhancing less energy-intensive economic activities) (clean coal technology);
- switching to less carbon intensive fuels, for example natural gas instead of coal;
- increasing the use of renewable energy sources or nuclear energy, each of which emits little or no net
CO2;
- sequestering CO2 by enhancing biological absorption capapacity in forests and soils;
- capturing and storing CO2 chemically or physically.

Types of sources
These sources are present in three main areas:
- fuel combustion activities,
- industrial processes and
- natural gas processing.
The largest CO2 emissions by far result from the oxidation of carbon when fossil fuels are burned.
These emissions are associated with fossil fuel combustion in power plants, oil refineries and large
industrial facilities. Such processes include:
- the use of fuels as feedstocks in petrochemical processes;
- the use of carbon as a reducing agent in the commercial production of metals from ores;
- the thermal decomposition (calcination) of limestone and dolomite in cement or lime production;
- the fermentation of biomass (e.g., to convert sugar to alcohol).
In some instances these industrial-process emissions are produced in combination with fuel
combustion emissions, a typical example being aluminium production.
A third type of source occurs in natural-gas processing installations. CO2 is a common impurity in
natural gas, and it must be removed to improve the heating value of the gas or to meet pipeline
specifications.
CO2 content

Typical CO2 concentrations and their corresponding partial pressures for large stationary
combustion sources are shown in Table 1, which also includes the newer Integrated Gasification Combined
Cycle technology (IGCC).
Typically, the majority of emission sources from the power sector and from industrial processes
have low CO2 partial pressures; hence the focus of the discussion in this section.
Where emission sources with high partial pressure are generated, for example in ammonia or
hydrogen production, these sources require only dehydration and some compression, and therefore they
have lower capture costs.
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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

I. Coal Combustion/Burning in a Power Plant

The combustion/burning chamber in a power plant can be represented as in Fig. 1.

Fig. 1 - Schematic representation of combustion zones

(1-main combustion, 2- post combustion area and 3- finalization area of combustion)

It can be applied at leat two combustion technique in a power plant: (i) simple/common tangential
combustion (only combustion area associated with superior finalization area), and (ii) advanced combustion
with post-combustion area and finalization burning facilities.
(i) The main reactions that take in the area of the combustion chamber (basis of combustion
chamber) (main tangential combustion area, Fig. 1) (considered as oxidation area) are those of combustion
and those that have CO2, CO, SOx, NOx and SOx as a gaseous result and oxidic metal slag as a solid result:

Principal fuel (e.g. coal, petroleum products, methane) + O2 CO2 + CO + H2O + heat + other species
N organic + O2 NOx
N2 (from air) + O2 NOx (6)
S organic + O2 SOx
M (metals) + O2 MOx (inorganic/mineral oxidic mixture of different Mi types of metals - bottom slag)

(ii) If it is applied an advanced combustion technique (with post-combustion area), in the second
area (secondary combustion area), natural gas burners are installed, or in some cases additional pulverized
coal injectors. The amount of fuel in this area needs to generate the rest of the heat needed for the
installation to achieve its target efficiency therefore it must generate 10 - 30 % of the total amount of heat,
depending on the amount of excess air in the first combustion area (primary air, with low air excess). If it is
smaller amount of excess air in the first combustion area, then a smaller amount of fuel is needed in the
post-combustion area (as superior secondary air) for finalization of burning process (reduction area).
The air coefficient in the reduction area is smaller than the unit ( = 0.85-0.95) which leads to the
development of free radicals (NHi, X. as Cl., ClO., CHx.), or molecular species (NH3, HCN), hydrocarbon
fragments (CH, CH2) and a large amount of CO.
In this environment, complex chemical reactions take place involving the NOx, transforming them
into molecular nitrogen, or SOx transformed in sulphur. In this way the polluting agents are reduced:

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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

Recombustion fuel CHx + other species

CHx + NOx CN + NH2 (or NH3) + H2O
NOx + NH2 (or NH3) N2 + H2O (7)
NOx + CO N2 + CO2
SOx + CO S + CO2
SOx + CHx + NOx CSO + HCN + (or H2O)

In the post-combustion area, at the same time with the fuel, a recycled gas flow of unburned gases
can be introduced. In this way the fuel flows depth of peneration is improved, thus increasing the
effectiveness of the air-fuel mixture.
In the thirst area, situated near the top of combustion chamber, the goal is to complete the
combustion, thus the CO emissions and the amount of unburned coal (carbon) to be minimum. In this area
only superior secondary air is introduced, about 20% from the total amount introduced in the combustion
chamber. To achieve a complete combustion, the air in the finalization area needs to be in excess ( = 1,15 -
1.25. (usually, the air amount in the finalization area is high, but the quantity of NOx is relatively small due
to the low temperatures in this part of combustion chamber). The main reactions that take place in the
finalization area are:
Air + CHx + CO CO2 + H2O
CH + NH2 (or NH3) + O2 NOx + CO2 + H2O (8)
Air + CHx + CSO CO2 + SO2 (or SO3) + H2O
The post combustion technique allows for a 40-65% reduction in NOx as compared to the classical
tangential methods therefore it can be said that this technique is very effective when applied to coal
burning furnances, either as a single method or as a part of a combined system.
The efficiency of the methods used depends on some operating parameters, as follows:
- The initial level of emissions,
- The combustion chambers properties,
- The amount of fuel in the reduction area (Fig.1),
- The excess air coefficient in the reduction area (optimum amount is comprised between 0.85-0.95;
in the finalization area is generated 10-30% of the total heat delivered by the boiler.
It is most indicated and simple to work with gaseous fuel in the combustion chamber for better
controling of the combustion process, therefore sometimes it is indicated to produce syngas (i.e. methane)
from coal based and gasification technological process (Fig. 2).

Coal gasification process

Fig. 2 - Coal gasification process

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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

Table 1 - Characteristics of CO2 emissions from different processes

Source CO2 Pressure of gas CO2 partial

concentration stream MPa(a pressure MPa
% vol (dry)
CO2 from fuel combustion
Power station flue gas:
Natural gas fired boilers 7 - 10 0.1 0.007 - 0.010
Gas turbines 3-4 0.1 0.003 - 0.004
Oil fired boilers 11 - 13 0.1 0.011 - 0.013
Coal fired boilers 12 - 14 0.1 0.012 - 0.014
IGCC(b: after combustion 12 - 14 0.1 0.012 - 0.014
Oil refinery and petrochemical plant fired heater 8 0.1 0.008
CO2 from chemical transformations + fuel combustion 20 0.2 - 0.3 0.040 - 0.060
Blast furnace gas(c: Before combustionc After 27 0.1 0.027
combustion 14 - 33 0.1 0.014 - 0.033
Cement kiln off-gas
CO2 from chemical transformations before combustion 8 - 20 2-7 0.16 1.4
IGCC: synthesis gas after gasification
a)
0.1 MPa = 1 bar. b)IGCC: Integrated gasification combined cycle. c)Blast furnace gas also contains significant amounts of carbon
monoxide that could be converted to CO2 using the so-called shift reaction

Clean Coal Technology is imposed the following issues:

- some reduction of impurities in the combustion fuels: pre-treatment of solid fuels, meaning washing
and chemical neutralization as some polluting contents
- post-combustion stages in the combustion chamber,
- additional neutralization agents inserted in the combustion or post combustion stages (i.e. lime or
natural minerals),
- efficient treatment of gaseous emissions before emitted in the air, using dry or wet treatment methods
based on precipitation (with lime or lime-based minerals, for SO x separated as CaSO4 precipitates), S/L
separation (electrofiltration, centrifugation-in cyclone/multi-cyclones, filtration with textile bags, wet
scrubbers), non-catalytic or catalytic oxidation/reduction (for NOx, SOx, etc. (some of its is discussed in
Application #3).

C. Determination of Emissions (CO2, SO2, NOx, particulate matter, fly ash, etc.)

Burning gases can contain species as CO 2, CO, SO2, NOX, fly ash, or other particulated matter that
can influence the combustion process efficiency for high heat and electric energy production. Also knowing
the polluting species amounts in the air emission, the combustion/burning process can be improved by
inserting of a post-combustion stage or an advanced treatment of final burning gases befor final emission in
the air.
Therefore, it is necessary to determine the gaseous emissions from a combustion process.
Emissions of pollutants are expressed, usually in mass concentration (C m), measured in mg/m3 or
mg/Nm3, and volume concentration (Cv), measured in parts per million (ppm). 1 ppm = 1 cm 3/m3, the
relation of transformation volume concentration in mass concentration is:

MG
Cm =C v [mg/Nm3]
22.414

where, MG is the molecular weight of pollutng gas (Kg/kmol) and 22.414 is the molar volume (m3/kmol) in
normal environmental conditions (0C, 1 atm=1013 mbar).

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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

The relations between volume and mass concentrations, for different gaseous pollutants are of the
form:
M SO 64.059 = 2.8580 mg/Nm3
1 ppm SO2 = = 2

22.414 22.414
M NO 46.0055 = 2.0525 mg/Nm3
1 ppm NO2 = = 2

22.414 22.414
M CO 28.02 = 1.25 mg/Nm3
1 ppm CO = =
22.414 22.414

The concentration of different nitrogen oxides (NO x) can be transformed in an equivalent

concentration of NO2 (Ci,NO2) which relates to the normal oxygen content in the flue gas, using the relation
below:
Ci Mi
=
C e , NO2,i M NO 2

Example #1:
Initial concentration of NO (CNO) is equivalent as concentration of NO2 with:
CNO2 = (46/30) CNO
Or, initial concentration of SO3 (CSO3) is equivalent as concentration of SO2 with:
CSO3 = (80/64) CSO3

If the concentration of NO, N2O and NO2 are experimentally determined (CNO, CN2O, CNO2), at a certain
temperature and certain oxygen content, it can calculate the total NO 2 concentration reported in an
outbreak situation which work with coal dust for various temperatures in the range (0-1000)C. For input
data: CNO = 391.4 ppm, CN2O = 3.6 ppm, CNO2 = 45.1 ppm, at temperature of 27C and 4% O 2 content, will
result the data presented in table 2.

Table 2 - Results of the calculation of total equivalent concentration of NO 2

Temperature Concentration of nitrogen oxides equivalent in NO2

(K) ppm, at 4% O2 ppm, at 6% O2 mg/Nm3, at 6% O2
273 590.600 521.117 1069.592
300 649.011 572.656 1175.370
500 1081.685 954.427 1958.961
800 1730.696 1527.084 3134.34
1000 2163.370 1908.856 3917.926
1300 2812.381 2481.613 5093.300

According wit EU methodology, emissions for a given activity can be expressed by a general formula, as follows

Es , a ,t =C a ,t e s , a

where , Es , a ,trelative emission of substance s , released by activity a , for a period of timet .

Ca,t - quantity of products of activity a, for a period of time, t; es,a - emission factor relative to subtance s, released by
activity a.
If measurement results are not sufficient and the processes of fuel flow are not known, the emission
estimation method is involved the use of a relation as

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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

f =n
Es , t = Q f H if e s ,f
f =1

where, Es,f - emission od substance s, in range t; Qf - total fuel consumed f; Hif - lower caloric power value, for fuel f; es,f -
emission factor of substance s, for fuel f.
Some emission factors for some fuels are presented in table 3.

Table 3 - Emission factors for specific combustion

Fuel Code Emission factor [g/GJ]

(NAPFUE) SO2 NOx CO CO2
Brown coal 101-103 623 1601) 200 96.103
2002)
Mixtures of bituminous 104 506 3403) 95.103
4)
coal 280
Lignite 105 * 95-1505) 100.103
Bituminous coal coke 107 578 * * 107.103
Peat 113 500 * * 110.103
Household waste 114 385 * * 109.103
Heavy fuel 203 1430/885/478/240 170-190 15 79.103 / 77.103
Light fuel oil 204 95 100 15 75.103
Gasoline car 208 6.8 / 54 * * 73.103
LPG 303 2.2 / 8.7 * 19 *
Petroleum coke 304 530 42 19 47.103
Note: * - specific values; 1) - classic grill furnace; 2) - pulverized coil furnace; 3) - front burner furnace; 4) - tangential
furnace; 5) - fluidized combustion furnace.

The amount of pollutant discharged into atmosphere, in a certain period of time, is determined with a relation
obtained by customizing the relation:

E=Q c H i e s [kg]

where, Qc - the amount of fuel consumed, during that period [kg]; Hi - initial fuel caloric poer [kJ/kg]; e - the emission
factor, for a certain pollutant [kg/kJ].
Thus, the mass concentration of pollutants Em can be determined with relation:

e
Em = [mg/Nm3]
Fv
Where, e - emission factor for certain pollutant [mg/GJ], and Fv - volume factor, defined as the ratio of total
volume of combustion gases and heat related to the fuel burned in the boiler [Nm 3/GJ]. The Fv-s are
indicated the following values:
Fv = 480 Nm3/GJ - for lignite,
Fv = 380 Nm3/GJ - for bituminous coal,
Fv = 290 Nm3/GJ - for heavy fuel,
Fv = 320 Nm3/GJ - for natural gas.

C1. Determination of emissions - CO2 polluting species

The relation determines emission factor for carbon dioxide (CO 2), according with EU standard used
to forcast calculations is a accurate relation:

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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

M CO 2 C

M C 100 [kg/KJ] (C1.1)
e CO2=
Hi

where, MCO2 - molecular mass of CO2, in kg/kmol; MCS - molecular mass of carbon, in kg/kmol; C - content of
carbon in fuel, in %; Hi - lower caloric power, in kJ/kg.
It is recommended:
- In current calculations, recommended values of lower caloric power for Romanian coals are: H i =
109000 g/GJ - for lignite; H i = 100000 g/GJ - for bituminous coal; H i = 81000 g/GJ - for heavy fuel
and Hi = 59000 g/GJ natural gases.
C2. Determination of emissions - SO2 polluting species

The relation determines emission factor for sulphur dioxide (SO 2):

M SO 2 S

M S 100 [kg/KJ] (C2.1)
e SO 2= (1r )
Hi

where, MSO2 - molecular mass of SO2, in kg/kmol; MS - molecular mass of sulphur, in kg/kmol; S - content of
sulphur in fuel, in %; Hi - lower caloric power, in kJ/kg; r - degree of sulphur retention by ash slag.
It is recommended:
- In current calculations, values recommended are: r = 0.2 - for lignite; r = 0.05 - for bituminous coal; r
= 0 - for heavy fuel and natural gases.
- In forcasting calculations, values recommended are: r = 1.15 - for lignite; r = 2.15 - for bituminous
coal and silt; r = 1.0 - for internal production heavy fuel and r = 3.0 - for import heavy fuel.

C3. Determination of emissions - NO2 polluting species

The relation determines emission factor for nitrogen dioxide (NO 2). To calculate the NOx emissions
there are used the emission factors for eNO, eNO2, eN2O to which it was applied the correction
corresponding to the oxygen content in flue gas (eNO2 100, EU norms for power plant smaller than 300 MW).

NO 2 NO 2 L50
e x =e 100 [a+ ( 1a ) ] [kg/KJ]
50

where, eNO2x - emission factor of charge x; eNO2100 - emission factor at nominal charge; L - partial load of boiler
(between 50% and 100%); a - coefficient dependent on the fuel type and may have the value: 0.85 - for
pulverized coal; 0.75 - for heavy fuel; 0.50 - for natural gas.
Correction with the standard value of O 2 concentration (6% for coal, 3% for natural gas) and
measured value of O2, it corrects also the value of NOx emission values as

E correct
NOx =E measured
NOx .
[ 21Ostandard
2

21Omeasured
2
] (C3.3a)

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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

In more rigurous calculations, that considered also the temperature and humidity of flue gas, the
relation becomes

][ ]
standard
20.9O2
E
correct
NOx =E
measured
NOx .
[ 1+
18 103

][
22.414 W 273+t
273 20.9O2measured
(C3.3b)

where, W - humidity of combustion gases, measured in g H 2O / m3 of dry gases; t - average temperature of

combustion gases, in C.

C4. Determination of emissions - fly ash polluting species

The relation determines emission factor for fly ash is:

f
1

(1e ) [kg/KJ] (C4.1)
A
e ash=
where, A - coal ash content, in %; f - degree of retention of ash in the furnace, in mass %; e - Dust
retention installation efficiency (electrostatic precipitator), in %; Hi - lower caloric power, in kJ/kg.
It is recommended:
- In post calculations, values recommended for A are the average values.
- In forcasting calculations, values recommended for A are: A = 40% - for lignite; A = 30% - for
bituminous coal and silt; A = 40% - for imported bituminous coal; value for f = 15% and values
recommended for e are: e = 97% - if electrostatic precipitator rehabilitation does not exceeded
50% of program, or e = 99% - to finish the electrostatic precipitators rehabilitation program.

Usually, when heavy fuel is burned, the emission of particles is neglected. For rigurous calculations,
it can be an ash content of heavy fuel A = 0.1%, ash which is fully discharged to the stack.

Application #1:

It must evaluate the emissions of polluting species in the atmosphere from a steam boiler, with the
following characteristics presented in table below.

General characteristics of boiler used in fuel burning:

- thermal power higher than 300 MW
- works with pulverized lignite, or heavy fuel
- average charge = 80%
Case I (a),(b) Case II (a),(b)
1. Lignite: 2. Heavy coal:
(a) lower caloric power, Hilignite = 6700 kJ/kg (a) lower caloric power, Hiheavy coal=38560 kJ/kg
(b) lower caloric power, Hilignite = ........ kJ/kg, value from (b) lower caloric power, Hiheavy coal=45650 kJ/kg
calculation of application #1 (maximal value
calculated )
(a) sulphur content, S = 1.15 % (a) sulphur content, S = 3.0 %
(b) sulphur content, S = ...... %, value considered in (b) sulphur content, S = 3.5 %
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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

application #1

(a) carbon content = 18 % -

(b) carbon content = 42 %
(a) / (b) partial load of boiler, L = 80% (a) / (b) partial load of boiler, L = 80%

(a) / (b) Emission factor for CO2 (for lignite) is 98.103 kg/kJ (a) / (b) Emission factor for CO2 (for heavy coal) is
72.103 kg/kJ
(a) / (b) Total amount of lignite is Qlignite = 100 t (a) + (b) Total amount of heavy coal is Qheavy coal = 10 t

What are the emissions if the amount of heavy coal used in the burning process is the same as the lignite
quantity used (100 t)
Some results comparisons must be performed : (i) the highest are for ...; (ii) the lowest are for... when is used
the same fuel amount (100 t).
Others results
Calculated values for emissions are:
ECO2, lignite = ? ECO2, heavy coal = ? ECO2, application #1 coal = ?
ESO2, lignite = ? ESO2, heavy coal = ? ESO2, application #1 coal = ?
ENOx, lignite = ? ENOx, heavy coal = ? ENOx, application #1 coal = ?
Eash, lignite = ? Eash, heavy coal = ? Eash, application #1 coal = ?

Fig. 3 - Energy Sources and Conversions Processes

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Master Discipline: SUSTAINABLE ENERGY PRODUCTION, 5EMSE

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