Reaction Rates
Reaction Rates
Reaction Rates
H I G H L I G H T S
Potassium carbonate process was simulated using Aspen Plus by equilibrium and non-equilibrium approaches.
The two process models are compared with each other.
The effects of mass transfer coefficients and film discretization were examined.
The thermodynamic model was developed for potassium carbonate solution.
art ic l e i nf o a b s t r a c t
Article history: In this study, the equilibrium and non-equilibrium models for CO2 absorption from natural gas stream by
Received 24 April 2014 DEA-promoted potassium carbonate solution in a tray column were developed and compared with each
Received in revised form other. The Electrolyte NRTL thermodynamic model was utilized to calculate the activity coefficient in the
10 September 2014
liquid phase, and the SRK equation of state was used for the gas phase. The non-equilibrium model was
Accepted 11 September 2014
Available online 22 September 2014
based on the two-film theory, and the effect of film discretization was examined. The equilibrium model
was based on the theoretical number of stages combined with the concept of Murphree efficiency from
Keywords: 0.1 to 0.3 for three stages in the lower section of the column and 0.4 from stage 4 onwards.
Potassium carbonate solution A thermodynamic study was performed to describe the equilibrium behavior of the solvent. All the
CO2 capture
necessary reactions in the liquid phase were considered in all simulations. The models were validated by
Tray column
comparing the obtained results with the published experimental data. Results of absorber column
Equilibrium model
Non-equilibrium model simulation show that the non-equilibrium model gives a better prediction of the temperature and
Murphree efficiency concentration profiles as compared to the equilibrium model.
& 2014 Published by Elsevier Ltd.
http://dx.doi.org/10.1016/j.ces.2014.09.017
0009-2509/& 2014 Published by Elsevier Ltd.
292 T.N.G. Borhani et al. / Chemical Engineering Science 122 (2015) 291–298
been demonstrated to be suitable for partially selective removal of Some equilibrium and non-equilibrium process models have
hydrogen sulfide in the presence of carbon dioxide (Astarita et al., been developed and used to study the CO2 absorption in promoted
1983). This process has been applied in more than 700 plants and un-promoted potassium carbonate solutions. It should be
worldwide for carbon dioxide and hydrogen sulfide removal from noted that in some of these studies, simple thermodynamic
streams like ammonia synthesis gas, crude hydrogen, natural gas, models have been employed (Rahimpour and Kashkooli, 2004;
and town gas (Kohl and Nielson, 1997). Potassium carbonate Sanyal et al., 1988). In some other investigations, rigorous thermo-
solution is low cost, low toxic, easily regenerable, less corrosive, dynamic models such as Electrolyte NRTL model (Al-Ramdhan,
low degradable, and has high chemical solubility of CO2. However, 2001; Mumford et al., 2011; Oexmann et al., 2008; Smith et al.,
the reaction between CO2 and potassium carbonate solution is not 2012) and modified Pitzer model (Thiele et al., 2007) have been
fast that is demonstrating the slow mass transfer in the liquid utilized. Recently, Borhani et al. (in press) studied about the effects
phase (Savage et al., 1984). In addition, fouling in the form of of various promoters on the potassium carbonate solution using
precipitation of the potassium carbonate and accumulation of the rate-based non-equilibrium model.
crystals in unit operations can pose serious problems (Fosbøl et This study focuses on the absorber modeling where its perfor-
al., 2013). mance is much more dependent on accurate modeling of the
In order to improve the potassium carbonate process in terms transfer phenomena and rates. All the necessary experimental data
of reaction with CO2, the promoters (activators) have been used. were taken from the literature. First, a thermodynamic model
The promoters, which have been used for potassium carbonate using the stoichiometric and heterogeneous approaches has been
process, can be divided into two main categories, as organic established. Trustable thermodynamic solubility data of CO2 in
promoters (such as various alkanolamines) and inorganic promo- potassium carbonate solutions have been used to validate the
ters (such as arsenic trioxide, alkali metal salts of selenious or thermodynamic model. Next, the equilibrium and non-equilibrium
tellurous acid, and alkali metal salts of weak inorganic acids such models for capturing the CO2 in DEA-promoted potassium carbo-
as potassium and sodium salts of boric acid, vanadic acid, and nate solution have been implemented in Aspen Plus software
arsenious acid). Utilization of promoters for the potassium carbo- using the Electrolyte NRTL thermodynamic model and appropriate
nate solution leads to substantially lower capital and operating property models. The inlet and outlet experimental data of a real
costs and higher treated gas purity (Kohl and Nielson, 1997). industrial DEA-promoted potassium carbonate process for captur-
Numerous studies have focused on the kinetic reactions of the ing the CO2 from natural gas stream have been used for construc-
potassium carbonate solution in the presence of various promoters tion and validation of the model (Karaj Petrochemical Complex,
(Astarita et al., 1981; Cullinane and Rochelle, 2004; Knuutila et al., 2010). Furthermore, the kinetic and equilibrium reactions, hydro-
2010). dynamics (mass transfer coefficient, interfacial area, liquid holdup,
Equilibrium stage and non-equilibrium stage models are the and pressure drop), film discretization, and flow models have been
two main approaches to model the reactive absorption processes. specified and examined.
Traditionally, modeling and simulation of reactive absorption units
have been based on the well-known equilibrium stage model
(Taylor and Krishna, 1993). More complicated modeling and 2. Models development
simulation of absorption units have been established on the
non-equilibrium (rate-based) model. It should be noted that 2.1. Thermodynamic model
distillation and absorption are non-equilibrium processes. In a
real process, mass and energy are transferred across the fluid In order to reasonably explain the complex phenomena taking
interface at rates, which depend upon the extent to which the place in the CO2 capturing by the DEA-promoted potassium
phases are not in equilibrium with one another. Historically, this carbonate solution, the model must properly apply the thermo-
departure from equilibrium conditions has led to the use of dynamics of DEA–K2CO3–KHCO3–H2O–CO2 aqueous solution
efficiencies (for tray columns) and the Height Equivalent to a (liquid phase speciation and vapor–liquid equilibrium), reaction
Theoretical Plate (HETP) (for packed columns). In the equilibrium kinetics of CO2 with the aqueous solution, and the various
model, vapor and liquid are assumed to enter a tray or cross chemical and physical properties affecting the mass and heat
section of packing in a column, exchange matter and energy, and transfer (Zhang et al., 2009).
leave in equilibrium with each other. Thermodynamic equilibrium The term speciation is used to describe what happens when an
is assumed to exist between the vapor and liquid streams leaving electrolyte solution is dissolved into water. The composition of the
each stage (Seader et al., 2010). In rate-based model, it is assumed liquid solution can be estimated using the equations of speciation
that mechanical, chemical, and thermodynamic equilibrium equilibria. A speciation equilibrium calculation can be implemen-
exist only at the fluid interface (Taylor and Krishna, 1993). In this ted alone or simultaneously with the vapor–liquid equilibrium
approach, in addition to the equations related to equilibrium calculations. After calculating the mole fraction of each species in
modeling, the mass and heat transfer rate equations are solved. the liquid phase using the speciation calculation, the vapor phase
This model totally avoids the approximation of efficiency composition for molecular solute CO2 and solvents H2O and DEA
(Krishnamurthy and Taylor, 1986). There are various rate-based can be obtained from the equilibrium between vapor and liquid. In
models from simple type to complicated (rigorous) one. In the order to calculate the vapor–liquid equilibrium there are two main
simplest non-equilibrium rate-based model, the reaction kinetics approaches: homogeneous approach (Fürst and Renon, 1993) and
in the bulk solution and enhancement factors are considered. In heterogeneous approach (Al-Rashed and Ali, 2012; Barreau et al.,
the most rigorous non-equilibrium rate-based model, the reaction 2006; Cullinane and Rochelle, 2005; Faramarzi et al., 2009). In the
kinetics, film discretization with several segments, and electrolyte homogenous approach, a single equation is used to determine the
thermodynamics are considered (Kenig et al., 2001). In the rate- properties of both liquid and vapor phases. In the heterogeneous
based approach, in addition to the main equations, the mass and approach, which is also well known as gamma–phi approach, an
heat transfer rates, transfer coefficients, hydrodynamics equations, activity coefficient model and an equation of state are utilized to
phase equilibria, and physical properties models must be used. By represent the liquid phase and the vapor phase, respectively. In
using these models, in addition to having reliable results of the this study, the stoichiometric and heterogeneous approaches have
column design, the process mechanism needs to be fully under- been used to perform the speciation and vapor–liquid equilibrium.
stood (Kale et al., 2013). The Electrolyte NRTL thermodynamic model and SRK equation of
T.N.G. Borhani et al. / Chemical Engineering Science 122 (2015) 291–298 293
state have been considered in both thermodynamic and process The data sets reported for CO2 solubility in terms of CO2 partial
models for the liquid and gas phases, respectively. pressure as a function of fractional conversion (loading) of
In the system under study the liquid phase composes of CO2, K2CO3 to KHCO3 and temperature (Tosh et al., 1959) over the
DEA, H2O, K2CO3, and KHCO3. Therefore, nine species must be KHCO3–H2O–CO2 solution.
considered, which are K þ , HCO3 , CO3 2 , H þ , OH , CO2, DEA,
DEAH þ , DEACOO , and H2O. The following chemical reactions
The vapor–liquid equilibrium and liquid phase speciation of the
occur in the DEA–K2CO3–KHCO3–H2O–CO2 aqueous solution and
DEA–K2CO3–KHCO3–H2O–CO2 aqueous solution are calculated
show the effects of potassium carbonate and DEA in absorption of
using a flash model in Aspen Plus software. In the thermodynamic,
CO2. These reactions must be considered for the thermodynamic
equilibrium, and non-equilibrium models presented in this study,
model:
the thermodynamic properties such as fugacity coefficient,
2H2 O⇌OH þ H3 O þ ð1Þ enthalpy, entropy, free Gibbs energy, and volume were calculated
using appropriate thermodynamic methods. On the other hand,
CO2 þ 2H2 O⇌HCO3 þ H3 O þ ð2Þ the transport properties such as viscosity, thermal conductivity,
diffusion coefficient, and surface tension were calculated using the
HCO3 þH2 O⇌CO3 2 þH3 O þ ð3Þ physical property models (Aspen Technology, 2001a).
T CO
The data sets reported for CO2 solubility (Maddox et al., 1987; H O
The data sets reported for mean ionic activity coefficient DEA
1999) and heat capacity of solution (Hilliard, 2005) over the Fig. 1. The concept of two-film theory with film discretization and counter-current
KHCO3–H2O solution. flow model.
294 T.N.G. Borhani et al. / Chemical Engineering Science 122 (2015) 291–298
For the process modeling, two sets of reactions are considered: considered in this section. The non-ideal behavior of stages is
one set is the equilibrium reactions (1)–(5) described above, and accounted using the Murphree efficiency. Different values of
the other one is the kinetic reactions between DEA and CO2 and Murphree efficiency from 0.1 to 0.3 have been selected for three
the reactions of CO2 with OH . Reactions (6) and (7) are the stages in the lower section of the column and 0.4 has been
forward and backward reactions for bicarbonate formation, and considered from stage 4 onwards (Afkhamipour and Mofarahi,
reactions (8) and (9) are the forward and backward reactions of 2013).
DEA carbamate formation.
CO2 þ OH -HCO3 ð6Þ
3. Results and discussion
HCO3 -CO2 þ OH ð7Þ
3.1. Thermodynamic model validation and results
DEA þ CO2 þ H2 O-DEACOO þ H3 O þ ð8Þ
As mentioned before, the thermodynamic model has been
DEACOO þ H3 O þ -DEA þCO2 þ H2 O ð9Þ implemented using a flash calculation in Aspen Plus. For the
thermodynamic model developed in this research, the deviation
The following power law form is used as the kinetic reactions rate:
n N between the experimental data and simulated values was calcu-
T Ej 1 1 α lated by using average absolute relative deviation (%AARD):
r j ¼ kj exp ∏ xi γ i i ð10Þ
T0 R T T0
|fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl} i ¼ 1 Sim Exp
K j ¼ reaction rate constants 100 N Y i Y i
%AARD ¼ ∑ ð11Þ
N i Y Exp
i
where r j is the reaction rate of reaction j, kj is the pre-exponential
factor for reaction j, T is the absolute temperature of the system, T0 where N is the number of process variables and Y Sim
i and Y Exp
i are
is the reference temperature, Ej is the activation energy, n is the the simulated values and experimental data for component i,
temperature exponent, and R is the gas law constant. In this respectively.
equation, the concentration basis is Molarity. E and k which are According to our literature review, there is not any trustable
derived from Pinsent et al. (1956) and Rinker et al. (1996) are solubility data for DEA–K2CO3–KHCO3–H2O–CO2 solution. How-
illustrated in Table 1. ever, there are some appropriate solubility data for other pro-
A number of correlations are available to calculate the mass moted and un-promoted potassium carbonate solutions as
transfer coefficients and effective interfacial area in tray columns. follows:
These correlations vary in their accuracies, limitations, and some-
times system specific applicability. The performances of gas and PZ–K2CO3–KHCO3–H2O–CO2 solution (Cullinane and Rochelle,
liquid mass transfer coefficients presented by Grester et al. (1958) 2005; Hilliard, 2005);
and Scheffe and Weiland (1987) compared to each other. The PZ–K2CO3–H2O–CO2 and 2MPZ–K2CO3–H2O–CO2 solutions
correlation of Scheffe and Weiland (1987) has been used for (Kim et al., 2012);
interfacial area calculations. The Bennett et al.'s (1983) technique MEA–PZ–K2CO3–KHCO3–H2O–CO2 solution (Hilliard, 2008);
was employed as the holdup method. The Chilton–Colburn corre- BA (boric acid)–K2CO3–KHCO3–H2O–CO2 solution and 30 wt%
lation was used to calculate the heat transfer in the absorber of K2CO3–H2O–CO2 solution at 50 and 70 1C (Endo et al., 2011);
(Aspen Technology, 2001b). K2CO3–H2O–CO2 solutions in 5 and 10 wt% of potassium carbo-
There are four different flow models in the RateFrac, which nate at 25 and 50 1C (Park et al., 1997);
determine the bulk properties required to evaluate the mass and K2CO39H2O–CO2 solutions (Pérez-Salado Kamps et al., 2007);
energy fluxes and reaction rates. The four flow models are Mixed, K2CO3–KHCO3–CO2–H2O solutions in 20, 30, and 40 equivalent
Counter-Current, VPlug, and VPlug-Pavg (Aspen Technology, concentration of potassium carbonate at temperatures 70, 90,
2001b). Zhang et al. (2009) illustrated that flow models only have 110, 130 1C (Tosh et al., 1959).
minor impacts on the predicted absorber temperature profiles,
and the mixed flow model has the most reliable results. Thus, the In this study, it is obvious that the mentioned promoted
mixed flow model is chosen. The pressure drop in the packed potassium carbonate solubility data cannot be used because any
columns can be calculated by using various models; but, for tray of the promoters have their effects on the solution. Therefore, only
columns, the user only can fix the pressure at the top or bottom of solubility data of un-promoted potassium carbonate solution have
the column. The film discretization option is set to geometric, and been used to validate the presented thermodynamic model.
the film discretization ration is set to 2.5. The absorber is a tray The predicted CO2 partial pressures and experimental values
column with 4-m diameter and 13 trays. The Weir height is for K2CO3–KHCO3–CO2–H2O solutions are compared in Figs. 2 and
60 mm, and the column pressure is set to 6000 kPa. The tray type 3, respectively. In Fig. 2, the CO2 solubility data in 20 wt%
is Glitsch Ballast. The stage number for liquid stream and gas equivalent concentration of potassium carbonate solution at four
stream iterance numbers are 13 and 1, respectively. different temperatures were used (Tosh et al., 1959). In Fig. 3, the
The equilibrium model is achieved by switching the modeling CO2 solubility data in 30 wt% potassium carbonate solution was
approach option from rate-based (non-equilibrium) to equilibrium utilized (Endo et al., 2011). The average absolute relative deviation
in the RateFrac model. Similar to rate-based model, 13 stages are between the experimental data and the calculated amounts CO2
solubility in Figs. 2 and 3 were 10.7 and 7.4, respectively. The
Table 1 results for Figs. 2 and 3 were satisfactory since the data have been
Parameters k, n, and E in the kinetic reactions rate.
presented by Tosh et al. (1959) and Endo et al. (2011) was
Reaction k E (cal/mol) n Reference trustable, not scatter, and shows appropriate consistency. In
general, there is a good agreement between the model predictions
(6) 4.315 10 þ 13 13,249 0 Pinsent et al. (1956) and the experimental values.
(7) 2.38 10 þ 17 29,451 0 Pinsent et al. (1956) The speciation calculation for the DEA–K2CO3–KHCO3–H2O–
(8) 6.48 10 þ 16 5072 0 Rinker et al. (1996)
(9) 1.43 10 þ 17 11,497 0 Rinker et al. (1996)
CO2 has been done at four different temperatures by using three
various DEA concentrations. The calculated values are summarized
T.N.G. Borhani et al. / Chemical Engineering Science 122 (2015) 291–298 295
1000 6
323 K
343 K
323 K ENRTL
5 343 K ENRTL
100
CO2 Partial Pressure (kPa)
3
343 K
363 K
383 K
403 K
1 343 K ENRTL
2
363 K ENRTL
383 K ENRTL
403 K ENRTL
1
0.1
0 0.2 0.4 0.6 0.8 1
Loading (mol CO2/mol K2CO3)
Table 3
Summary of non-equilibrium and equilibrium model predictions and the experimental conditions (Karaj Petrochemical Complex, 2010).
of the absorber column. The AAD% for the equilibrium model is 0.09
E.M. with M.E.=0.1
more than 27.6 showing a significant difference between the 0.08 E.M. with M.E.=0.2
CO2 mole fraction in gas stream
is assumed that the liquid and gas phases are at equilibrium. 0.05 Experimental
were not available). Profiles in these figures reveal the changes of 0.01
CO2 gas concentration and temperature of the liquid phase along
0
the tray column. It should be noted that in these figures E.M. is 1 2 3 4 5 6 7 8 9 10 11 12 13
equilibrium model, ME is Murphree efficiency, and R.B.M. is rate- Stage Number
based model. Fig. 4. CO2 concentration profile in the natural gas stream along the column.
In Figs. 4 and 5, the bigger bulges can be seen in profiles for
non-equilibrium rate-based model in comparison with the equili-
brium model in the middle of column. These bulges reveal good 415
predictions of model (Zhang et al., 2009). 410
The profiles achieved by the Grester et al.'s (1958) mass
405
transfer coefficient model show the biggest bulge even bigger
Temperature K
than the predictions obtained by Scheffe and Weiland (1987) mass 400
transfer coefficient model. In equilibrium model the best results
395
were obtained by using the Murphree efficiency value of 0.3 for E.M. with M.E.=0.1
five stages in the bottom of the column and fixed value of 0.4 for 390
E.M. with M.E.=0.2
13.85
1 2 3 4 5 6 7 8 9 10 11 12 13
Stage Number Nomenclature
0.07
Acknowledgments
0.06
Water Mole Fraction
0.03
E.M. with M.E.=0.1 References
0.02 E.M. with M.E.=0.2
E.M. with M.E.=0.3
R.B.M. with Scheffe & Weiland Afkhamipour, M., Mofarahi, M., 2013. Comparison of rate-based and equilibrium-
0.01
R.B.M. with Grester et al. stage models of a packed column for post-combustion CO2 capture using
2-amino-2-methyl-1-propanol (AMP) solution. Int. J. Greenh. Gas Control 15,
0
186–199.
1 2 3 4 5 6 7 8 9 10 11 12 13
Al-Ramdhan, H.A., 2001. A Rate-Based Model for the Design and Simulation of a
Stage Number Carbon Dioxide Absorber Using the Hot Potassium Carbonate Process. Colorado
School of Mines, Department of Chemical Engineering Petroleum, Refining,
Fig. 8. Water mole fraction profile along the tray column.
Colorado School of Mines, Golden, CO.
Al-Rashed, O.A., Ali, S.H., 2012. Modeling the solubility of CO2 and H2S in DEA–
due to the mass and energy transfer relations considered in these MDEA alkanolamine solutions using the electrolyte–UNIQUAC model. Sep.
Purif. Technol. 94, 71–83.
models. Aseyev, G.G., 1999. Electrolytes, Equilibria in Solutions and Phase Equilibria.
Calculation of Multicomponent Systems and Experimental Data on the Activ-
ities of Water, Vapor Pressures, and Osmotic Coefficients. Begell House, New
York.
4. Conclusion and remarks Aspen Technology, 2001. Aspen Plus Reference Manual. Aspen Physical Property
System. Physical Property Methods and Models 11.1. Cambridge, MA, USA.
In this study, a thermodynamic model has been proposed to Aspen Technology, 2001. Aspen Plus Reference Manual. Aspen Plus 11.1 Unit
Operation Models. Cambridge, MA, USA.
represent the speciation and vapor–liquid equilibrium for the Aspen Technology, 2001. Aspen Plus Reference Manual. Aspen Plus 11.1 User Guide.
DEA-promoted potassium solution. In addition, non-equilibrium Cambridge, MA, USA.
and equilibrium models have been developed to simulate the CO2 Asprion, N., 2006. Nonequilibrium rate-based simulation of reactive systems:
simulation model, heat transfer, and influence of film discretization. Ind. Eng.
absorption by DEA-promoted potassium carbonate solution in a Chem. Res. 45, 2054–2069.
tray column. In the non-equilibrium model, two different correla- Astarita, G., Savage, D.W., Bisio, A., 1983. Gas Treating with Chemical Solvents. John
tions have been used to calculate the mass transfer coefficients in Wiley & Sons, NY.
Astarita, G., Savage, D.W., Longo, J.M., 1981. Promotion of CO2 mass transfer in
the gas and liquid phases and effective interfacial area in the tray
carbonate solutions. Chem. Eng. Sci. 36, 8.
column. For the equilibrium model various Murphree efficiencies Austgen, D.M., 1989. A Model of Vapor–Liquid Equilibria for Acid Gas–Alkanola-
have been considered. mine–Water Systems. University of Texas, Austin.
For the thermodynamic model, the prediction accuracy was Austgen, D.M., Rochelle, G.T., Chen, C.C., 1991. Model of vapor–liquid equilibria for
aqueous acid gas-alkanolamine systems. 2. Representation of hydrogen sulfide
acceptable for K2CO3–KHCO3–H2O–CO2 solutions. The values and carbon dioxide solubility in aqueous MDEA and carbon dioxide solubility in
of AARD% were 10.7 and 7.4. In addition, the speciation of the aqueous mixtures of MDEA with MEA or DEA. Ind. Eng. Chem. Res. 30, 543–555.
298 T.N.G. Borhani et al. / Chemical Engineering Science 122 (2015) 291–298
Barreau, A., Blanchon, l.B.E., Habchi, T.K.N., Mougin, P., Lecomte, F., 2006. Absorption combustion capture of CO2: results from the solvent absorption capture plant at
of H2S and CO2 in alkanolamine aqueous solution: experimental data and hazelwood power station using potassium carbonate solvent. Energy Fuels 26,
modelling with the electrolyte-NRTL model. Oil Gas Sci. Technol. 61, 17. 138–146.
Bennett, D.L., Agrawal, R., Cook, P.J., 1983. New pressure drop correlation for sieve Oexmann, J., Hensel, C., Kather, A., 2008. Post-combustion CO2-capture from coal-
tray distillation columns. AIChE J. 29, 434–442. fired power plants: preliminary evaluation of an integrated chemical absorp-
Borhani, T.N.G., Akbari, V., Hamid, M.K.A., Manan, Z.A., Rate-based simulation and tion process with piperazine-promoted potassium carbonate. Int. J. Greenh. Gas
comparison of various promoters for CO2 capture in industrial DEA-promoted Control 2, 539–552.
potassium carbonate absorption unit. J. Ind. Eng. Chem., http://dx.doi.org/10. Park, S.B., Shim, C.S., Lee, H., Lee, K.H., 1997. Solubilities of carbon dioxide in the
1016/j.jiec.2014.07.024, in press. aqueous potassium carbonate and potassium carbonate—poly(ethylene glycol)
Cullinane, J.T., Rochelle, G.T., 2004. Carbon dioxide absorption with aqueous solutions. Fluid Phase Equilib. 134, 141–149.
potassium carbonate promoted by piperazine. Chem. Eng. Sci. 59, 3619–3630. Pérez-Salado Kamps, Á., Meyer, E., Rumpf, B., Maurer, G., 2007. Solubility of CO2 in
Cullinane, J.T., Rochelle, G.T., 2005. Thermodynamics of aqueous potassium carbo- aqueous solutions of KCl and in aqueous solutions of K2CO3. J. Chem. Eng. Data
nate, piperazine, and carbon dioxide. Fluid Phase Equilib. 227, 197–213. 52, 817–832.
Endo, K., Nguyen, Q.S., Kentish, S.E., Stevens, G.W., 2011. The effect of boric acid on Pinsent, B.R.W., Pearson, L., Roughton, F.J.W., 1956. The kinetics of combination of
the vapour liquid equilibrium of aqueous potassium carbonate. Fluid Phase carbon dioxide with hydroxide ions. Trans. Faraday Soc. 52, 1512–1520.
Equilib. 309, 109–113. Puchkov, L.V., Kurochkina, V.V., 1970. Saturated vapor pressure over aqueous
Faramarzi, L., Kontogeorgis, G.M., Thomsen, K., Stenby, E.H., 2009. Extended solutions of potassium carbonate. Zhur. Priklad. Khim. 43, 181–183.
UNIQUAC model for thermodynamic modeling of CO2 absorption in aqueous Qi, G., Wang, S., Yu, H., Wardhaugh, L., Feron, P., Chen, C., 2013. Development of a
alkanolamine solutions. Fluid Phase Equilib. 282, 121–132. rate-based model for CO2 absorption using aqueous NH3 in a packed column.
Fosbøl, P.L., Maribo-Mogensen, B., Thomsen, K., 2013. Solids modelling and capture Int. J. Greenh. Gas Control 17, 450–461.
simulation of piperazine in potassium solvents. Energy Procedia 37, 844–859. Rahimpour, M.R., Kashkooli, A.Z., 2004. Enhanced carbon dioxide removal by
Fürst, W., Renon, H., 1993. Representation of excess properties of electrolyte promoted hot potassium carbonate in a split-flow absorber. Chem. Eng.
solutions using a new equation of state. AIChE J. 39, 335–343. Process.: Process Intensif. 43, 857.
Grester, J.A., Hill, A.B., Hochgraf, N.N., Robinson, D.G., 1958. Tray Efficiencies in Rinker, E.B., Ashour, S.S., Sandall, O.C., 1996. Kinetics and modeling of carbon
Distillation Columns. In: Report, A. (Ed.), AIChE Report. dioxide absorption into aqueous solutions of diethanolamine. Ind. Eng. Chem.
Hilliard, M., 2005. Thermodynamics of Aqueous Piperazine/Potassium Carbonate/ Res. 35, 1107–1114.
Carbon Dioxide Characterized by the Electrolyte NRTL Model within Aspen Sanyal, D., Vasishtha, N., Saraf, D.N., 1988. Modeling of carbon dioxide absorber
Plus, Technical Report. University of Texas at Austin, Texas p. 251. using hot carbonate process. Ind. Eng. Chem. Res. 27, 2149–2156.
Hilliard, M., 2008. A Predictive Thermodynamic Model for an Aqueous Blend of Savage, D.W., Sartori, G., Astarita, G., 1984. Amines as rate promoters for carbon
Potassium Carbonate, Piperazine, and Monoethanolamine for Carbon Dioxide dioxide hydrolysis. Faraday Discuss. Chem. Soc. 77, 17–31.
Capture from Flue Gas. The University of Texas, Austin p. 1061. Scheffe, R.D., Weiland, R.H., 1987. Mass-transfer characteristics of valve trays. Ind.
Kale, C., Górak, A., Schoenmakers, H., 2013. Modelling of the reactive absorption of Eng. Chem. Res. 26, 228–236.
CO2 using mono-ethanolamine. Int. J. Greenh. Gas Control 17, 294–308. Seader, J.D., Henley, E.J. et al., 2010. Separation Process Principles. New York, John
Karaj Petrochemical Complex, 2010. Natural Gas Plant. Operating Data of Potassium Wiley & Sons.
Carbonate Process. Smith, K., Anderson, C.J., Tao, W., Endo, K., Mumford, K.A., Kentish, S.E., Qader, A.,
Kenig, E.Y., Schneider, R., Górak, A., 2001. Reactive absorption: optimal process Hooper, B., Stevens, G.W., 2012. Pre-combustion capture of CO2—results from
design via optimal modelling. Chem. Eng. Sci. 56, 343–350. solvent absorption pilot plant trials using 30 wt% potassium carbonate and
Kim, Y.E., Choi, J.H., Nam, S.C., Yoon, Y.I., 2012. CO2 absorption capacity using boric acid promoted potassium carbonate solvent. Int. J. Greenh. Gas Control 10,
aqueous potassium carbonate with 2-methylpiperazine and piperazine. J. Ind. 64–73.
Eng. Chem. 18, 105–110. Taylor, R., Krishna, R., 1993. Multicomponent mass transfer. New York, John Wiley
Knuutila, H., Juliussen, O., Svendsen, H.F., 2010. Kinetics of the reaction of carbon and Sons.
dioxide with aqueous sodium and potassium carbonate solutions. Chem. Eng. Thee, Suryaputradinata, Y.A., Mumford, K.A., Smith, K.H., Silva, G.d., Kentish, S.E.,
Sci. 65, 6077–6088. Stevens, G.W., 2012. A kinetic and process modeling study of CO2 capture with
Kohl, A., Nielson, R., 1997. Gas Purification. Gulf Publishing Company, Houston, MEA-promoted potassium carbonate solutions. Chem. Eng. J. 210, 271–279.
Texas. Thiele, R., Faber, R., Repke, J.U., Thielert, H., Wozny, G., 2007. Design of industrial
Krishnamurthy, R., Taylor, R., 1986. Absorber simulation and design using a reactive absorption processes in sour gas treatment using rigorous modelling
nonequilibrium stage model. Can. J. Chem. Eng. 64, 96–105. and accurate experimentation. Chem. Eng. Res. Des. 85, 74–87.
Maddox, R.N., Bhairi, A.H., Diers, J.R., Thomas, P.A., 1987. Equilibrium Solubility of Tosh, J.S., Field, J.H., Benson, H.E., Haynes, W.P., 1959. Equilibrium study of the
Carbon Dioxide or Hydrogen Sulfide in Aqueous Solutions of Monoethanola- system potassium carbonate, potassium bicarbonate, carbon dioxide, and
mine, Diglycolamine, Diethanolamine and Methyldiethanolamine. GPA water. p. 27.
Research Report. Wang, M., Lawal, A., Stephenson, P., Sidders, J., Ramshaw, C., 2011. Post-combustion
Maddox, R.N., Elizondo, E.M., 1989. Equilibrium Solubility of Carbon Dioxide or CO2 capture with chemical absorption: a state-of-the-art review. Chem. Eng.
Hydrogen Sulfide in Aqueous Solutions of Diethanolamine at Low Partial Res. Des. 89, 1609–1624.
Pressures. GPA Research Report, No. 124. Zhang, Y., Chen, H., Chen, C.C., Plaza, J.M., Dugas, R., Rochelle, G.T., 2009. Rate-based
Mumford, K.A., Smith, K.H., Anderson, C.J., Shen, S., Tao, W., Suryaputradinata, Y.A., process modeling study of CO2 capture with aqueous monoethanolamine
Qader, A., Hooper, B., Innocenzi, R.A., Kentish, S.E., Stevens, G.W., 2011. Post- solution. Ind. Eng. Chem. Res. 48, 9233–9246.