Optimization and validation of the [628920]

Benchmarking of the pre/post-combustion chemical absorption
for the CO 2capture
Cristian Dincaa,*, Nela Slavua, Adrian Badeaa,b
aThe Power Energy Department, POLITEHNICA University of Bucharest, Bucharest 060042, Romania
bThe Romanian Academy of Scientists, Bucharest 050094, Romania
article info
Article history:
Received 10 October 2016Received in revised form
17 January 2017
Accepted 25 January 2017Available online xxx
Keywords:
CO
2capture
Chemical absorption
Pre/post combustion
Monoethanolamineabstract
The aim of the article was to compare the pre- and post-combustion CO 2capture process employing
the chemical absorption technology. The integration of the chemical absorption process before or after the
coal combustion has an impact on the power plant ef ficiency because, in both cases, the thermal energy
consumption for solvent regeneration is provided by the steam extracted from the low pressure steamturbine. The solvent used in this study for the CO
2capture was monoethanolamine (MEA) with a weight
concentration of 30%. In the case of the pre-combustion integration, the coal gasi fication was analysed
for different ratios air/fuel (A/F) in order to determine its in fluences on the syngas composition and
consequently on the low heating value (LHV). The LHV maximum value (28 MJ/kg) was obtained for an A/F
ratio of 0.5 kg air/kgfuel, for which the carbon dioxide concentration in the syngas was the highest (17.26%).
But, considering the carbon dioxide capture, the useful energy (the difference between the thermal energyavailable with the syngas fuel and the thermal energy required for solvent regeneration) was minimal. The
maximum value (61.59 MJ) for the useful energy was obtained for an A/F ratio of 4 kg
air/kgfuel. Also, in both
cases, the chemical absorption pre- and post-combustion process, the power plant ef ficiency decreases with
the growth of the L/G ratio. In the case of the pre-combustion process, considering the CO 2capture ef ficiency
of 90%, the L/G ratio obtained was of 2.55 mol solvent /mol syngas and the heat required for the solvent
regeneration was of 2.18 GJ/tCO 2. In the case of the post-combustion CO 2capture, for the same value of the
CO2capture ef ficiency, the L/G ratio obtained was of 1.13 mol solvent /mol flue gas and the heat required was of
2.80 GJ/tCO 2. However, the integration of the CO 2capture process in the power plant leads to reducing the
global ef ficiency to 30% in the pre-combustion case and to 38% to the post-combustion case.
©2017 Energy Institute. Published by Elsevier Ltd. All rights reserved.
1. Introduction
At the moment, fossil fuels cover globally an important part of the demand for primary energy resources. Coal is used frequently
worldwide in the energy sector for power generation, because coal reserves are more signi ficant than the ones of natural gas and oil [1,2] .
The current trend in the energy sector aims to reduce carbon dioxide emissions [3e5], especially regarding coal fired power plants, so
that the energy technologies which use coal can be compared with the ones which use natural gas. Increasing the global ef ficiency of power
plants is possible only with very large investments which are more or less justi fied for the energy units with a life period higher than 20
years [6]. In this context, one of the solutions which has a high potential for reducing CO 2emissions consists in integrating in the CO 2capture
energy units, transport and storage processes [7,8] .
Today, the CO 2capture process by chemical absorption is validated technically and economically for different power plants [9,10] or in the
cement industry [11], and in the oil industry for natural gas extraction, respectively [12,13] . Thus, in this study, for separating the carbon
dioxide from different gases, we employed the CO 2capture process by chemical absorption by means of primary amines (e.g.
monoethanolamine).
*Corresponding author.
E-mail address: crisflor75@yahoo.com (C. Dinca).
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Please cite this article in press as: C. Dinca, et al., Benchmarking of the pre/post-combustion chemical absorption for the CO 2capture, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.01.008

Although the chemical absorption process was validated to an industrial scale, its integration in a power plant leads to reducing the
power plant global ef ficiency by 8 e14 percentage points [14]. Consequently, the parameters which in fluence the power plant ef ficiency are
the following: the CO 2capture ef ficiency, the size of power plant, the type and weight concentration of the chemical solvent, and the
solution of regeneration used. The most used method for chemical solvent regeneration consists in extracting a steam flow rate from the low
pressure steam turbine, which could be up to 30 e40% from the initial steam flow of the steam turbine [15]. After integrating the CO 2capture
technology in the power plant, the cost of the electricity produced increases from 50 to 90 ( V/MWh) [16].
In this study, we analysed the consequences of the chemical absorption integration in pre- or post-combustion processes in order to
reduce its technical and economic effects resulted from integrating it in a power plant. Therefore, two cases were considered: a) post-
combustion CO 2capture by chemical absorption; b) pre-combustion CO 2capture by chemical absorption. Case “a”was considered as
reference. The first case is analysed in different studies: C. Dinca et al. designed the absorber unit in order to separate the CO 2from the flue
gases resulted from coal combustion whose design model was made for various types of packages using plastic, ceramic or metal rings [17],
A. Lawal et al. studied the dynamic responses of a post-combustion CO 2capture plant by modelling and simulation [18], Se Young Oha et al.
constructed, in the UniSim simulator process, a superstructure including the conventional amine-based CO 2capture con figuration and four
different types of structural modi fications [19], L. Duan et al. studied the effects of the key parameters on the MEA regeneration in order to
reduce the thermal energy consumption [20]. The integration of the pre-combustion chemical absorption is studied only in a few papers: M.
Asif et al. modelled and simulated a large-scale of an IGCC system in three con figurations: IGCC without CO 2capture, IGCC with pre-
combustion capture by chemical absorption, and IGCC with post-combustion capture by chemical absorption finally obtaining the
optimal IGCC system [21], M. Kawabata et al. studied two CO 2capture options: pre-combustion by a mixture of dimethyl ethers of poly-
ethylene glycol (DEPG) and post-combustion by monoethanolamine (MEA), which were assessed to compare the power plant global ef-
ficiency and the necessity for implementing future technologies [22]. In both cases, for the solvent regeneration there is used a part of the
steam flow generated in the steam turbine.
On the other hand, the pre-combustion CO 2capture is studied for analysing different CO 2capture techniques, Sung Ho Park et al.
conducted redesign and modelling of the two-stage pre-combustion CO 2capture process, using three different physical solvents
(Selexol, Rectisol, Purisol). The Selexol process was evaluated as the most ef ficient pre-combustion CO 2capture process from the points
of electric/thermal energy consumption [23]. See Hoon Lee et al. developed a pilot scale water gas shift reactor with multi-layer
membrane module for to maximize CO 2capture and H 2recovery in integrated gasi fication combined cycle (IGCC) [24]. Anna Skorek-
Osikowska et al. studied two methods of CO 2capture pre-combustion, by chemical absorption and membrane CO 2separation, a
comparison of the energy intensity of both processes shows that the membrane separation has a much lower, by approximately 15-fold,
energy requirement than the amine absorption process. However, the purity of the separated CO 2significantly depends on the type and
surface of the membrane and on the process parameters [25e28]. Calin-Cristian Cormos investigated the most important techno-
economic and environmental indicators for IGCC with pre-combustion capture using gas eliquid absorption (Selexol) applied to the
shifted syngas. He is obtained that the carbon capture penalty is 9.5% for gasi fication reactor Shell and 7.1% for gasi fication reactor
Siemens for a 90% carbon capture rate [29].
The novelty of this paper consists in adapting the CO 2capture chemical absorption process to the pre-combustion processes and in
comparing the results with those obtained in the benchmark case (the chemical absorption process in the post-combustion processes). The
purpose is to increase the quality of the syngas produced in the IGCC technologies by separating the CO 2. In this case, the challenge consists
in determining the energy balance with considering the heat required for the solvent regeneration and the gain of energy by syngas
treatment. The advantage of using the IGCC technology which includes the pre-combustion CO 2capture by chemical absorption is to obtain
a clean fuel gas (syngas) (H 2,C H 4,N2, CO and H 2S) with a high LHV (low heating value) [22,30] . The syngas composition obtained depends on
the oxidizing agent type (air or oxygen) or the moderator agent type (water or steam) [31e33]. In this study, we only analysed the air
gasification process characterized by a lower cost than using water or a steam moderator agent [34].
2. Method
The functional unit is mandatory for all the energy processes analysed. In this paper, the functional unit was de fined by the net amount of
electricity generated by the power plant ( Ey). The installed power of the power plant ( P) and the annual power plant operation ( dyp)a r e
required for determining the functional unit.
Ey¼P,dyp (1)
For simplifying the study, the annual power plant operation is considered constant for both cases analysed. For maintaining the same
functional unit, the fuel flow is changed according to the global ef ficiency of the systems analysed. The coal composition used is presented in
Table 1 .
The elemental composition of the lignite was determined in the Renewable Energy Laboratory of the Power Engineering Faculty. For
determining the coal (lignite) elemental composition the proximate analysis was used [35]. The proximate analysis technique is related to a
dry basis, thus the carbon, volatile matters and ash were determined in our analysis. On the other hand, the ultimate analysis method
consisted in determining the carbon, oxygen, hydrogen and so on. After heating the flue gasses, the content of the volatile matters is
highlighted by the volatile organic compounds content in the flue gasses.
Table 1
Coal composition.
Elementary coal analysis
C [%] H [%] N [%] O [%] S [%] W [%] A [%] LHV (kJ/kg)
58 2 1 1.8 0.8 18.1 18.3 21335C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 2
Please cite this article in press as: C. Dinca, et al., Benchmarking of the pre/post-combustion chemical absorption for the CO 2capture, Journal of
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The cases studied in the article are the following:
a) The coal power plant without CO 2capture;
b) The coal power plant with post-combustion CO 2capture by chemical absorption (case “2a”);
c) The coal gasi fication with pre-combustion CO 2capture by chemical absorption and syngas conversion in the coal power plant
(case “2a”).
InFig. 1 there are presented the processes of the coal power plants equipped with pre- and post-combustion CO 2capture. Inside the
continuous line there are presented the components of the power plant including the coal gasi fication with air; the CO 2capture from the
syngas; and the electricity generation using the clean syngas in the coal power plant. Inside the dashed line the following processes are
presented: coal combustion and electricity generation in the coal power plant; CO 2capture from the flue gases.
In the chemical absorption process, the rich loading solvent was maintained constant, that is of 0.21 mol CO2=mol MEA, both for the pre-
and post-combustion process [17].
Chemical absorption ( Fig. 2 ) is the process where the carbon dioxide from the flue gases/syngas reacts with a chemical solvent to form an
intermediate product characterized by a weak bonding of the molecules. The regeneration of the rich solvent in the CO 2is made at high
temperatures, of approximately 120/C14C, to obtain a concentrated stream of CO 2with 95% purity [36]. The gas stream ( flue gases or syngas)
resulted from the combustion or the coal gasi fication enters the absorber at the bottom, and comes out at the top of it. The chemical solvent
(the amines) is introduced at the top of the absorber unit, and it is removed at the bottom of it. In the case of the power plant equipped with
post-/pre-combustion CO 2capture, the amount of thermal energy required for the chemical solvent regeneration is obtained by using a
steam ratio from the low pressure steam turbine. Taking into account the steam ratio used for the solvent regeneration, the thermal ef fi-
ciency of the steam turbine decreases considerably [15].
The reactions between the CO 2and MEA solution have been described in the literature by two mechanisms, namely the zwitterion
mechanism and the thermo molecular mechanism [30].
Further there is presented the zwitterion mechanism. Reactions (2 e14)may occur when the CO 2absorbs into and reacts with the
aqueous MEA. All the species represented are in aqueous solution [37e42].
Ionization of water [37e42]:
2H2! K1OH/C0țH3Oț(2)
Dissociation of the dissolved CO 2in carbonic acid [37e42]:
CO2ț2H2O! k2;k/C02;K2HCO/C0
3țH3Oț(3)
Dissociation of bicarbonate [37e42]:
HCO/C0
3țH2O! K3CO2/C0
3țH3Oț(4)
Zwitterion formation from the MEA and CO 2reaction [37e42]:
CO2țRNH 2! k4;k/C04;K4RNHț
2COO/C0(5)
Carbamate formation by deprotonation of the zwitterion [37e42]:
RNHț
2COO/C0țRNH 2! k5;k/C05;K5RNHț
3țRNHCOO/C0(6)
Fig. 1. Energy systems with pre- and post-combustion CO 2capture by chemical absorption.C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 3
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the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.01.008

RNHț
2COO/C0țH2O! k6;k/C06;K6H3OțțRNHCOO/C0(7)
RNHț
2COO/C0țOH! k7;k/C07;K7H2OțRNHCOO/C0(8)
Carbamate reversion to bicarbonate (hydrolysis reaction) [37e42]:
RNHț
2COO/C0țH2O! k8;k/C08;K8RNH 2țHCO/C0
3 (9)
Dissociation of the protonated MEA [37e42]:
RNHț
3țH2O! k9;k/C09;K9RNH 2țH3Oț(10)
Bicarbonate formation [37e42]:
CO2țHO/C0! k10;k/C010;K10HCO/C0
3 (11)
RNHț
2COO/C0țHCO/C0
3! k11;k/C011;K11H2CO3țRNHCOO/C0(12)
RNHț
2COO/C0țCO2/C0
3! k12;k/C012;K12HCO/C0
3țRNHCOO/C0(13)
Based on this reaction scheme, the general rate of reaction of the CO 2with MEA via the zwitterion mechanism could be described as in
the following equation [37e42]:
rCO2/C0MEA¼½CO2/C138½RNH 2/C138/C0k/C04=k4/C2RNHCOO/C0/C3/C0Pk/C0b/C2BHț/C3/C14Pkb½B/C138/C1
1=k4țðk/C04=k4Pkb½B/C138Ț(14)
where B designates any species in the solution which can act as a base to abstract the proton from the zwitterion. In this case, the expected
species for a loaded MEA solution are the following: [ RNH 2], [H2O], [OH/C0],½HCO/C0
3/C138,½CO/C0
3/C138.Fig. 2. The chemical absorption process [14].C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 4
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the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.01.008

The global thermal energy (heat duty) required for regenerating the solvent represents the sum of the following: the energy required for
breaking the chemical bond between the solvent and the CO 2molecule, the energy required for heating the solvent ( Qsensible ) and the energy
required for water vaporization ( Qdilution ). In order to determine each component of the global energy, the following mathematical relations
are used (15, 16) [36] :
ðQsensibleȚ
mCO2¼rðTin;grichȚ,cpðTin;grichȚ,DT
ðgrich/C0gleanȚ,Camin e,Mw;CO2(15)
where: ( Qsensible ) is the energy needed to heat the chemical solvent solution to the boiling point, in [kJ]; mCO2is the mass of CO 2;cpis the
speci fic heat for the rich chemical solvent solution, in [kJ/(kg K)]; ris the density of the rich chemical solvent solution, in [kg/m3];DTis the
difference between the inlet temperature Tinand the boiling temperature of the CO 2rich feed, in [K]; ( grich/C0glean) is the mole fraction CO 2
sent to compression per mole chemical solvent; Camin eis the concentration of the chemical solvent in the rich solvent solution, in [kmol/
m3];mCO2is the mass of CO 2, in [kg]; and Mw;CO2is the mole weight CO 2, in [kg/kmol] [36].
Qdiluation
mCO2¼psat
H2OðTinȚ,xH2O
pCO2ðTin;grichȚ,Mw;CO2,DHvap
H2OðTinȚ (16)
where: ( Qdilution ) is the heat required to keep the psat
CO2>pCO2, in [kJ]; DHvap
H2Ois the energy required to evaporate the water, in [kJ/kmol]; xH2Ois
the fraction of liquid water, psat
H2Ois the water saturation pressure, in [bar], pCO2is the partial pressure of the CO 2, in [bar].
The required global energy is procured from the heat recovery of the flue gases or the syngas ( Qfg/sg) and from the electrical re-boiler ( Qre-
boiler). Each of these was determined using the equations listed below (17, 18) [36] .
Qfg=sg
Vgas¼hex,r/C0Tgas/C1,cp/C0Tgas/C1,DTst (17)
where: Qfg/sgis the heat which is recovered from the flue gases or syngas, in [kJ]; Vgasis the volume of gas, in [m3];hexis the heat exchanger
efficiency; cpis the speci fic heat for the gases, in [kJ/(kg K)]; ris the density of the rich chemical solvent solution, in [kg/m3];DTstis the
difference between the flue gas temperature in and out the stripper, in [K].
Qre/C0boiler
mMEA¼r/C0TMEA ;grich/C1,cp/C0TMEA ;grich/C1,DTr
ðgrich/C0gleanȚ,Camin e,Mw;CO2(18)
where: Qre-boiler is the heat produced at the re-boiler, in [kJ]; mMEAis the amount of chemical solvent, in [kg]; cpis the speci fic heat for the rich
chemical solvent solution, in [kJ/(kg K)]; ris the density of the rich chemical solvent solution, in [kg/m3];DTris the difference between the
flue gas temperature in and out of the electrical re-boiler, in [K].
The separation process by chemical absorption applied to the cases studied is analysed according to several parameters such as: the CO 2
capture ef ficiency, the CO 2lean/rich loading solvent, the L/G ratio (solvent flow/flue gases or syngas flow) and the concentration of amine in
the solvent.
Fig. 3. Coal power plant with post-combustion chemical absorption [31].C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 5
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Fig. 3 shows the process of case “2a”: power plant with CO 2capture by chemical absorption.
The characteristics of the power plant are presented in Table 2 . The parameters, also presented in Table 2 , are speci fied for the power plant
without CO 2capture. Once the CO 2capture is integrated, the net power installed decreases due to the mechanical work used for solvent
regeneration. The steam used for the solvent regeneration is extracted at a pressure of 2.25 bar (for both pre- and post-combustion cases).
The process of the power plant with pre-combustion CO 2capture is presented in Fig. 4 .
The main data for the chemical absorption process used in the pre- and post-combustion case are presented in the second part of Table 2 .
One observes that the power installed decreases from 250 MW (the power plant without CO 2capture) to 217.3 MW (the power plant with
CO2capture using an L/G ratio of 1.8 mol solvent /mol flue gases ). The size of the absorption and desorption unit is maintained constant in both
cases: pre- and post-combustion.
The CO 2capture ef ficiency was calculated using the following equation [15]:
EfCO2CO2in/C0CO2ex
CO2in,100 (19)Table 2
Main data of the coal power plant with chemical absorption.
Coal power plant operating parameters
Power installed, MW 250Net power plant ef ficiency, % 37.6
Air equivalence ratio 1.55HP steam,
/C14C/bar 560/170
MP steam,/C14C/bar 557/34
LP steam,/C14C/bar 282/4.84
Steam turbine isentropic ef ficiency HP/IP/LP, % 85/92.5/86.5
Condenser pressure, bar 0.05
Chemical absorption with MEA epost-combustion
Absorber/stripper stages number 10/15MEA concentration, wt. % 30Lean solvent temperature,
/C14C4 0
Rich solvent temperature,/C14C ~120
L/G ratio 1 e1.8
Speci fic heat at re-boiler, GJ/tCO 2 1.77e3.62
CO2capture ef ficiency, % 84.6 e99.2
Net power, MW 233.7 e217.3
Chemical absorption with MEA epre-combustion
A/F ratio 0.5; 0.8; 1.15L/G ratio 2.55; 1.7; 1.08Speci fic heat at re-boiler, GJ/tCO
2 2.18; 2.15; 2.13
CO2capture ef ficiency, % ~90
Net power, MW 248, 247, 246
Fig. 4. Coal power plant with pre-combustion chemical absorption [43].C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 6
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where: EfCO2is the CO 2capture ef ficiency, in [%]; CO2inis the amount of CO 2from the flue gases/syngas, in [kg]; CO2exis the amount of CO 2
released in the atmosphere, in [kg].
The power plant ef ficiency (the global ef ficiency) is calculated using Eq. (20), where the global ef ficiency was de fined as the ratio between
the net electricity generation ( Eel) and the primary energy content in the fuel extracted ( Ep). The primary energy content in the fuel was
calculated with the formula presented below, where the amount of fuel extracted ( Mfuel) is introduced in kg and the LHV (low heating value)
is introduced in kJ/kg [15].
hgl¼Eel
Ep,100 ;Ep¼LHV ,Mfuel
3:6,106(20)
In the chemical absorption process, the solvent used for the CO 2capture was the monoethanolamine (MEA) with a MEA weight con-
centration of 30%. The weight concentration was restricted to 30% due to the corrosion of the equipment's metal surfaces [44]. In the sci-
entific literature, for the weight concentration chosen, the CO 2capture ef ficiency was of 90% for a heat amount required of 3.2 GJ/tCO 2[17].
3. Results and discussion
The chemical absorption process was compared from the energy consumption point of view for post- and pre-combustion. In both cases,
the energy consumption is provided by the steam extracted from the steam turbine at the pressure of 2.25 bar. In the pre-combustion case,
the amount of solvent used (L) is lower, for the same electricity amount generation, than in the post-combustion case because the syngas
flow has a higher LHV (due to the lack of the inert components such as CO 2) than the coal fuel.
3.1. Case “2a”echemical absorption process in pre-combustion
The gasi fication process with and without chemical absorption is simulated in CHEMCAD tools (the schema process is presented in Fig. 5 .
Thus, after the gasi fication and the absorption column processes, the mass composition of the syngas was determined for different air/fuel
ratios (0.3 e5k g air/kgfuel). The composition of the syngas was used for determining its low heating value.
For different ratios A/F the syngas composition is shown in Table 3 in volume concentration. One observes that by increasing the A/F ratio
of 0.5 kg air/kgfuel, the quantity of H 2increases; after this value, the content of H 2begins to decrease. Instead, the quantity of CH 4decreases
with increasing the air/fuel ratio and the CO and H 2S increase. The volume concentration of CO 2decreases to an A/F ratio of 3.5 kg air/kgfuel;
after this ratio it begins to increase, because by increasing the amount of air introduced to the gasi fication unit, the gasi fication process is
replaced with the combustion process.
The useful energy was calculated as the difference between the energy content of syngas and the global thermal energy (heat duty)
required for regenerating the solvent.
Consequently, the low heating value variation of the syngas is heavily dependent on the air/fuel ratio. For values of the ratio between 0.3
and 1.7 kg air/kgfuel, the low heating value of the syngas is higher than that of the coal.
The simulation of the CO 2capture processes by pre-/post-combustion chemical absorption was made in Chemcad, version 6.0.1 [45].
When the A/F ratio increases, the useful energy of the syngas has had a maximum for the A/F ratio of 4 kg air/kgfuel(Fig. 6 ). On the contrary,
the L/G ratio presented a minimum value for an A/F ratio of 2.2 kg air/kgfuel.
For a CO 2capture ef ficiency of 90%, there was determined the energy content of the syngas ( Table 4 ) according to the A/F ratio. The syngas
energy content in the case without (w/o) CO 2capture was calculated as the product of the syngas flow and its LHV; in the same way, there
was determined the syngas energy content in the case with CO 2capture. The useful energy after the chemical absorption process integrationTable 3
Syngas composition for various ratios A/F before the CO 2chemical absorption process.
Syngas composition
Air/Fuel (m air/mfuel)H 2(%) CH 4(%) N 2(%) CO (%) CO 2(%) H 2S (%) LHV (kJ/kg)
0.3 15.30 4.99 57.43 0.78 21.35 0.14 21113.02
0.35 19.00 3.33 55.00 1.92 20.61 0.14 24869.780.4 20.87 2.36 53.65 3.40 19.59 0.13 26789.720.5 22.05 1.35 52.54 6.67 17.26 0.13 28043.980.6 21.85 0.89 52.37 9.73 15.03 0.14 27878.920.7 21.23 0.63 52.54 12.38 13.09 0.14 27270.650.8 20.51 0.47 52.84 14.62 11.43 0.14 26542.070.9 19.78 0.37 53.17 16.52 10.02 0.14 25809.14
1.15 18.19 0.22 54.00 20.13 7.31 0.15 24176.01
1.4 16.91 0.14 54.75 22.63 5.42 0.15 22834.241.7 15.69 0.09 55.53 24.71 3.83 0.15 21548.982.3 13.95 0.05 56.80 27.11 1.95 0.15 19663.492.8 12.92 0.03 57.69 28.0 1.12 0.15 18502.773.5 11.82 0.02 58.77 28.69 0.55 0.15 17234.443.7 10.96 0 60.27 27.25 1.37 0.15 16041.41
4 9.38 0 62.85 25.00 2.62 0.15 13901.40
4.3 7.85 0 65.31 22.98 3.72 0.14 11837.324.7 6.00 0 68.31 20.42 5.13 0.13 9347.255 4.82 0 70.31 18.54 6.19 0.12 7729.91C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 7
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is the difference between the syngas energy content, S inges, (in the case of CO 2capture) and the heat duty required, Q, for the solvent
regeneration (Eq. (21)).
Useful energy¼Esyngas/C0Q;½GJ=h/C138; (21)Table 4
The energy content of the syngas before and after the CO 2capture technology integration.
A/F ratio
(kg/kg)Syngas flow w/o
CO2capture (kg/h)LHV syngas w/o
CO2capture (kJ/kg)Syngas flow with
CO2capture (kg/h)LHV syngas with
CO2capture (kJ/kg)Syngas energy w/o
CO2capture (GJ/h)Syngas energy with
CO2capture (GJ/h)Heat
duty (GJ/h)Useful
energy (GJ/h)
0.3 385.51 21113.02 264.46 26135.84 8.14 6.91 0.34 6.57
0.35 454.16 24869.78 311.20 30519.49 11.29 9.50 0.40 9.10
0.4 521.33 26789.72 361.95 32550.41 13.97 11.78 0.45 11.330.5 650.85 28043.98 471.97 33215.46 18.25 15.68 0.50 15.180.6 775.80 27878.92 587.06 32280.23 21.63 18.95 0.53 18.420.7 897.80 27270.65 707.99 30914.92 24.48 21.89 0.53 21.360.8 1017.91 26542.07 829.03 29596.81 27.02 24.54 0.53 24.010.9 1136.73 25809.14 952.31 28365.98 29.34 27.01 0.52 26.50
1.15 1430.08 24176.01 1259.86 25872.90 34.57 32.60 0.48 32.12
1.4 1720.09 22834.24 1568.78 23996.78 39.28 37.65 0.43 37.221.7 2065.25 21548.98 1937.03 22311.67 44.50 43.22 0.37 42.852.3 2749.01 19663.49 2662.75 20007.71 54.06 53.28 0.25 53.032.8 3313.44 18502.77 3253.29 18687.78 61.31 60.80 0.17 60.623.5 4097.12 17234.44 4060.88 17317.04 70.61 70.32 0.10 70.223.7 4283.09 16041.41 4191.32 16241.47 68.71 68.07 0.28 67.804 4545.39 13901.40 4362.53 14239.06 63.19 62.12 0.53 61.59
4.3 4805.46 11837.32 4536.85 12249.91 56.88 55.58 0.77 54.81
4.7 5154.09 9347.25 4770.25 9798.60 48.18 46.74 1.08 45.665 5419.11 7729.91 4941.62 8183.51 41.89 40.44 1.35 39.09
Fig. 6. The A/F ratio in fluence on the energy content of the syngas.Fig. 5. Gasification process with pre-combustion chemical absorption in Chemcad [45].C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 8
Please cite this article in press as: C. Dinca, et al., Benchmarking of the pre/post-combustion chemical absorption for the CO 2capture, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.01.008

We can see ( Fig. 7 ) that the pre-combustion CO 2capture integration by chemical absorption does not signi ficantly in fluence the energy
content of the syngas, the energy penalty (the heat duty) for regenerating the solvent being small as compared with the useful energy of the
syngas in the benchmark case. This is an advantage of the pre-combustion CO 2capture integration compared with the post-combustion one.
In the future, it is preferable to use the syngas produced by removing the CO 2, in different energetic power plants in order to reduce the
amount of the CO 2generated.
For comparing the pre- and post-combustion chemical absorption, the in fluence of the L/G ratio on the power plant and on the CO 2
capture ef ficiency was determined ( Fig. 8 ). For all the three cases (A/F ¼0.5; 0.8 and 1.15 kg air/kgfuel), the L/G ratio was established
considering the CO 2capture ef ficiency of approximately 90%. In the pre-combustion case, the global ef ficiency also takes into account the
coal gasi fication ef ficiency. The pre-combustion global ef ficiency is much lower than in the post-combustion case due to the lower ef ficiency
of the coal gasi fication process (30 e35%) [46]. Also, the power plant ef ficiency decreases as the L/G ratio increases due to the higher thermal
energy required for the solvent regeneration.
The heat duty required for the solvent regeneration according to the A/F ratio, is presented in Fig. 9 . We mention that the syngas flow (G)
is maintained constant. So, the L/G ratio increases only if the solvent flow increases.
A lower amount of thermal energy is required for the solvent regeneration in the pre-combustion case due to the small amount of the
syngas flow compared to the flue gases amount (the post-combustion case). When the A/F ratio increases, the L/G ratio for a CO 2capture
efficiency of 90% decreases because the A/F ratio in fluences the carbon dioxide concentration in the syngas produced, consequently the
thermal energy has a small decreasement.
3.2. Case ”2b”echemical absorption process in post-combustion
The in fluence of the L/G ratio on the power plant performance was determined following the simulations performed in Aspen Hysys
(Fig. 10 ), highlighting the heat required for the solvent regeneration. This heat required for the solvent regeneration comes from the steam
extracted from the low pressure steam turbine in both cases (pre- and post-combustion).
One observed that with increasing the L/G ratio (and obviously the CO 2capture ef ficiency), the power plant ef ficiency decreased. For a
CO2capture ef ficiency of 90% (for an L/G ratio of 1.13 mol solvent /mol flue gas ), the power plant ef ficiency was of approximately 37%.
In this paper, for a CO 2capture process ef ficiency of 90% (for an L/G ratio of 1.13 mol solvent /mol flue gas ) the heat duty required was of
2.5 GJ/tCO 2(Fig. 11 ).
In the pre-combustion process, the CO 2capture ef ficiency was maintained of 90% for each A/F ratio of 0.5; 0.8 and 1.15 kg air/kgfuel, and
for the L/G ratio of 2.55, 1.7, 1.08 mol solvent /mol syngas . For each case represented by the A/F ratio, the heat duty required was of 2.18; 2.15;
2.13 GJ/tCO 2.
Fig. 7. Useful energy of the syngas w/o and w/CO 2capture according to the A/F ratio.
Fig. 8. The L/G ratio in fluence on the power plant ef ficiency and on the CO 2capture process.C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 9
Please cite this article in press as: C. Dinca, et al., Benchmarking of the pre/post-combustion chemical absorption for the CO 2capture, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.01.008

4. Conclusions
In this paper a benchmarking analysis was made between the pre- and post-combustion process for CO 2capture by chemical absorption.
To highlight the differences between the two ways, the chemical absorption was integrated in the pre-combustion (considering the coal
gasification process before the coal power plant) and in the post-combustion in a coal fired power plant. The syngas obtained after the
treatment has a higher LHV compared to the coal used, thus, a smaller amount of syngas is required for producing the same amount of
electricity. However, in the post-combustion case, for a CO 2capture ef ficiency of 90%, the L/G ratio is higher than in the pre-combustion case
only for an A/F ratio bigger than 0.8 kg air/kgfuel. In the pre-combustion case, the heat duty used for the solvent regeneration is smaller than in
the post-combustion case due to the smaller amounts of syngas employed. However, considering the CO 2capture ef ficiency of 90%, the CO 2
flow generated in the environment is higher in the pre-combustion case (7.08 kg/s) than in the post-combustion case (3.48 kg/s) due to the
carbon dioxide oxidation in the syngas combustion process (after the pre-combustion case, a rest of 2% of CO 2is found in the syngas).
The purpose of this paper was to compare the chemical absorption technology integration in the pre- or post-combustion process in
order to increase the quality of the fuel burnt and to reduce the greenhouse gases emissions.
Fig. 10. The effects of L/G ratio on the power plant and CO 2capture process ef ficiency.
Fig. 11. The effects of L/G ratio on the heat duty.
Fig. 9. The effect of A/F ratio on the heat duty and L/G ratio.C. Dinca et al. / Journal of the Energy Institute xxx (2017) 1 e12 10
Please cite this article in press as: C. Dinca, et al., Benchmarking of the pre/post-combustion chemical absorption for the CO 2capture, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.01.008

In the pre-combustion capture process the lignite (coal) reacts with the oxygen/air or steam in order to produce a synthesis gas which is
composed mainly of CO and H 2. In the catalytic reactor the CO reacts with the steam to generate CO 2and H 2. In order to produce a synthetic
gas with a higher LHV (low heating value) it is necessary to separate the carbon dioxide using the chemical or physical absorption process.
Compared to the post-combustion technology, in the pre-combustion system the high pressure of the syngas (in the range of 20 e70 bar)
allows to separate the CO 2whose composition in the syngas varies between 15 e50 % in dry basis [47,48] .
In the pre-combustion CO 2capture process, the lower energy consumption for the separation process is compensated by the higher
energy consumption in the reforming and air separation processes [49]. Also, according to this study concerning the ef ficiency losses due to
the CO 2capture by means of the pre-combustion integration in the gasi fication process, the biggest losses (~3.5% points) were obtained in
the water egas shift reactor, due to the heat amount produced, as in the research study [50]. The heat loss for the CO 2removal in the
chemical absorption process was of 1.7% points of the total ef ficiency loss. The steam used for the water gas shift reaction and, also, for the
chemical solvents regeneration is extracted from low pressure steam turbine which leads to reducing the power production. In this study,
the compression and drying stages are not included but according to [51,52] , the energy used in these stages leads to reducing the global
efficiency with almost 3% points.
As a future development, the pre-combustion capture by the chemical absorption technique has advantages to produce CO 2at higher
pressure reducing the power consumption for its compression required for the transportation to the storage site [53]. Moreover, the CO 2
capture by pre-combustion processes could accelerate the introduction of the H 2as an energy vector for developing the energy systems with
low carbon emissions. Also, for becoming a mature technology, the low temperature fuel cells application requires a higher puri fication of
the H 2stream and the CO 2capture technologies have to be integrated. Another advantage of the pre-combustion possibility to capture CO 2is
the openness to power or hydrogen co-production according to the electricity or hydrogen demand [54]. The flexibility of the fossil fuel
power plant with CO 2capture in generating both electricity and hydrogen becomes very important today due to the amount of the elec-
tricity generation by the intermittency of the wind and solar energy systems.
However, if we take into account the investment cost in the equipment for the synthetic gas generation, the chemical absorption process
in the pre-combustion way is less attractive than in the post-combustion case [55].
In order to improve the performance for an Integrated Gasi fication Combined Cycle equipped with CO 2capture in pre-combustion
process, the optimization of the water gas shift reactor is required since its contribution of total ef ficiency penalty is of almost 3.5% points. In
different research studies, the cost of one tone of CO 2avoided varied in the range of 25 e65Vdue to the methodology used to calculate the
avoided cost [56e59].
For estimating in which way (pre- or post-combustion technology) it is better to use the chemical absorption for the CO 2mitigation in the
power plants, an economical method will be analysed in the future studies.
Acknowledgements
The study has been funded by the UEFISCDI within the National Project number 51/2017 with the title: “Optimization and validation of the
CO2capture demonstrative pilot installation by chemical absorption technology ”eCHEMCAP.
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