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XXXX, xxx, 000 A Thermodynamic Modeling for CO2 Absorption in Aqueous MDEA Solution with Electrolyte NRTL Model Ying Zhang AspenTech, Limited, Pudong, Shanghai 201203, People s Republic of China Chau-Chyun Chen* Aspen Technology, Inc., Burlington, Massachusetts 01803 Accurate modeling of thermodynamic properties for CO2 absorption in aqueous alkanolamine solutions is essential for the simulation and design of such CO2 capture processes. In this study, we use the Electrolyte Nonrandom Two-Liquid activity coefficient model to develop a rigorous and thermodynamically consistent representation for the
MDEA-H2O-CO2 system. The vapor-liquid equilibrium (VLE), heat capacity, and excess enthalpy data for the binary aqueous amine system are used to determine the NRTL interaction parameters for the MDEA-H2O binary. The VLE, heat of absorption, heat capacity, and NMR spectroscopic data for the MDEA-H2O-CO2 ternary system are used to identify the NRTL interaction parameters for the molecule-electrolyte binaries and the
previously unavailable standard-state properties of the amine ion, MDEA protonate. The calculated VLE, heat of absorption, heat capacity, and the species concentrations for the MDEA-H2O-CO2 system are compared favorably to experimental data. 1. Introduction CO2 capture by absorption with aqueous alkanolamines is considered an important technology to reduce CO2 emissions from fossil-fuel-fired power plants and to help alleviate global
climate change.1 Methyldiethanolamine (MDEA), which is an alternative to monoethanolamine (MEA) for bulk CO2 removal, has the advantage of relatively low heat of reaction of CO2 with MDEA.2 To properly simulate and design the absorption/ stripping processes with MDEA-based aqueous solvents, it is essential to develop a sound process understanding of the transfer phenomena3 and accurate thermodynamic models4 to calculate
the driving forces for heat and mass transfer. In other words, scalable simulation, design, and optimization of the CO2 capture processes start with modeling of the thermodynamic properties, specifically vapor-liquid equilibrium (VLE) and chemical reaction equilibrium, as well as calorimetric properties. Accurate modeling of thermodynamic properties requires availability of reliable experimental data. Earlier literature reviews5,6 suggested that, while
there are extensive sets of experimental data available for the MDEA system, some of the published CO2 solubility data for the aqueous MDEA system may be questionable. The use of a thermodynamically consistent framework makes it possible to correlate available experimental data, to screen out questionable data, and to morph these diverse and disparate data into a useful and thermodynamically
consistent form for process modeling and simulation. Excess Gibbs energy-based activity coefficient models provide a practical and rigorous thermodynamic framework to model thermodynamic properties of aqueous electrolyte systems, including aqueous alkanolamine systems for CO2 capture.4,7 For example, Austgen et al.8 and Posey9 applied the electrolyte NRTL model10-12 to correlate CO2 solubility in aqueous MDEA solution and other aqueous
alkanolamines. Kuranov et al.,5 Kamps et al.,6 and Ermatchkov et al.13 used Pitzer s equation14 to correlate the VLE data of the MDEA-H2O-CO2 system. * To whom correspondence should be addressed. Tel.: 781-221-6420. Fax: 781-221-6410. E-mail: chauchyun.chen@aspentech.com. Arcis et al.15 also fitted the VLE data with Pitzer s equation and used the thermodynamic model to estimate the enthalpy of solution
of CO2 in aqueous MDEA. Faramarzi et al.16 used the extended UNIQUAC model17 to represent VLE for CO2 absorption in aqueous MDEA, MEA, and mixtures of the two alkanolamines. Furthermore, they predicted the concentrations of the species in both MDEA and MEA solutions containing CO2 and in the case of MEA, compared to NMR spectroscopic measurements.18,19 In the
present work, we expand the scope of the work of Austgen et al.8 and Posey9 to cover all thermodynamic properties. We use the 2009 version10 of the electrolyte NRTL model10-12 as the thermodynamic framework to correlate recently available experimental data for CO2 absorption in aqueous MDEA solution. Much new data for thermodynamic properties and calorimetric properties have become available in
recent years, and they cover wider ranges of temperature, pressure, MDEA concentration, and CO2 loading. The binary NRTL parameters for MDEA-water binary are regressed from the binary VLE, excess enthalpy, and heat capacity data. The binary NRTL parameters for water-electrolyte pairs and MDEA-electrolyte pairs and the standard-state properties of protonated MDEA ion are obtained by fitting to the ternary VLE,
heat of absorption, heat capacity, and NMR spectroscopic data. This expanded model should provide a comprehensive thermodynamic representation for the MDEA-H2O-CO2 system over a broader range of conditions and give more reliable predictions over previous works. In conjunction with the use of the electrolyte NRTL model for the liquid-phase activity coefficients, we use the PC-SAFT20,21 equation of state
(EOS) for the vapor-phase fugacity coefficients. While both PC-SAFT EOS and typical cubic EOS would give reliable fugacity calculations at low to medium pressures, we choose PC-SAFT for its ability to model vapor-phase fugacity coefficients at high pressures, which is an important consideration for modeling CO2 compression. The PC-SAFT parameters used in this model are given in Table 1. The
parameters for water and CO2 are taken from the literature21 and the Aspen 10.1021/ie1006855 . XXXX American Chemical Society
B Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX Table 1. Parameters for PC-SAFT Equation of State MDEA H2O CO2 source this work Gross and Aspen Sadowski 21 Databank22 segment number 3.3044 1.0656 2.5692 parameter, m segment energy 237.44 K 366.51 K 152.10 K parameter, e segment size 3.5975 3.0007 2.5637 parameter, s association energy 3709.9 K 2500.7 K 0
K parameter, eAB kAB 0.066454 3 0.034868 3 03 Databank.22 The parameters for MDEA are obtained from the regression of experimental data on vapor pressure, liquid density, and liquid heat capacity. 2. Thermodynamic Framework 2.1. Chemical and Phase Equilibrium. CO2 solubility in aqueous amine solutions is determined by both its physical solubility and the chemical equilibrium for the aqueous phase reactions among CO2,
water, and amines. 2.1.1. Physical Solubility. Physical solubility is the equilibrium between gaseous CO2 molecules and CO2 molecules in the aqueous amine solutions: CO2(V) T CO2(l) (1) It can be expressed by Henry s law: PyCO2 fCO2 )HCO2 xCO2 .*CO2 (2) where P is the system pressure, yCO2 the mole fraction of CO2 in the vapor phase, fCO2 the
CO2 fugacity coefficient in the vapor phase, HCO2 the Henry s law constant of CO2 in the mixed solvent of water and amine, xCO2 the equilibrium CO2 mole fraction in the liquid phase, and .*CO2 the unsymmetric activity coefficient of CO2 in the mixed solvent of water and amine. The Henry s constant in the mixed solvent can be calculated
from those in the pure solvents:23 Hi HiA ln)SxA ln(3) .i 8 A .i8 A () () where Hi is the Henry s constant of supercritical component i in the mixed solvent, HiA the Henry s constant of supercritical component i in pure solvent A, .i 8 the infinite dilution activity coefficient of supercritical component i in the
mixed solvent, .i8 A the infinite dilution activity coefficient of supercritical component i in pure solvent A, and xA the mole fraction of solvent A. We use wA in lieu of xA in eq 3 to weigh the contributions from different solvents.22 The parameter wA is calculated using eq 4: 8 )2/3 xA(ViA wA
) (4) 8 )2/3SxB(ViB B 8 Here, ViA represents the partial molar volume of supercritical 8 component i at infinite dilution in pure solvent A. ViA is calculated from the Brelvi-O Connell model24 with the characteristic volume for the solute (VCO2 BO), which BO ) and solvent (Vs are listed in
Table 2. Table 2. Parameters of the Characteristic Volume for the Brelvi-O Connell Modela Characteristic Volume (m3/kmol) parameter MDEA H2O CO2 source this work Brelvi and O Connell 24 Yan and Chen25 V1,i 0.369b 0.0464 0.175 V2,i 00 -3.38 10-4 a The Brelvi-O Connell model has been described in ref 24. The correlation of the characteristic volume for the Brelvi-O Connell model
BO) BO (Vi is given as follows: Vi )V1,i +V2,iT, where T is the temperature (given in Kelvin). b Here, the critical volume was used as the characteristic volume for MDEA. Table 3. Parameters for Henry s Constant (Expressed in Units of Pa)a solute i CO2 CO2 solvent j H2O MDEA source Yan and Chen25 this work aij 91.344 19.8933 bij -5876.0 -1072.7
cij -8.598 0.0 dij -0.012 0.0 a The correlation for Henry s constant is given as follows: ln Hij )aij +bij/T +cij ln T +dijT, where T is the temperature (given in Kelvin). Henry s law constants for CO2 with water and for CO2 with MDEA are required. The former has been extensively studied,25 although knowledge about the latter is relatively limited. Because it
is not feasible to directly measure CO2 physical solubility in pure amines, because of the reactions between them, the common practice is to derive the CO2 physical solubility in amines from that of N2O for their analogy in molecular structure and, thus, in physical solubility as believed:26 HCO2,MDEA HCO2,water ) (5) HN2O,MDEA HN2O,water In
1992, Wang et al.27 reported the solubility of N2O in pure MDEA solvent as follows: -1312.7 HN2O,MDEA (kPa m3 kmol -1) )(1.524 105) exp() T (6) Based on the work of Versteef and van Swaaij,28 we obtained the following two equations for the solubilities of N2O and CO2 in water: -2284
HN2O,water (kPa m3 kmol -1) )(8.5470 106) exp() T (7) -2044 HCO2,water (kPa m3 kmol -1) )(2.8249 106) exp() T (8) We use eqs 5-8 to determine HCO2,MDEA and the parameters are summarized in Table 3. The Henry s constant of CO2 in pure solvent A is corrected with the Poynting term
for pressure:25 1 P 8 HCO2,A(T, P) )HCO2,A(T, poA ,l) exp(RT . p.A,lVCO2,A dp) (9) where HCO2,A(T,P) is the Henry s constant of CO2 in pure solvent A at system temperature and pressure, HCO2,A(T,p A,l) the Henry s constant of CO2 in pure solvent A at system temperature and 8 the solvent vapor pressure, and VCO2,A
Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX C Table 4. Parameters for the Reference States Properties ig ig 8,aq 8,aq property (J/kmol) (J/kmol) (J/kmol) (J/kmol) source .fG298.15 .fH298.15 .fG298.15 .fH298.15 MDEA -1.6900 108 -3.8000 108 Aspen Databank22 H2O -2.2877 108 -2.4200 108 Aspen Databank22 CO2 -3.9437 108 -3.9351 108 Aspen Databank22 H3O+
-2.3713 108 -2.8583 108 Aspen Databank22 OH1.5724 108 -2.2999 108 Wagman et al.29 HCO3 --5.8677 108 -6.9199 108 Wagman et al.29 CO3 25.2781 108 -6.7714 108 Wagman et al.29 MDEAH+ -2.5989 108 a -5.1422 108 a this work a The values of MDEAH+ are calculated from the chemical equilibrium
constant in Kamps and Maurer,30 which are used as the initial guess to fit experimental data. of CO2 at infinite dilution in pure solvent A calculated from the Brelvi-O Connell model. At low pressures, the Poynting correction is almost unity and can be ignored. 2.1.2. Aqueous-Phase Chemical Equilibrium. The aqueousphase chemical reactions involved in the MDEA-water-CO2
system can be expressed as 2H2O T H3O+ + OH ( 10) CO2 + 2H2O T H3O+ + HCO3 -(11) HCO3 -+ H2O T H3O+ + CO3 2( 12) MDEAH+ + H2O T H3O+ + MDEA (13) We calculate the equilibrium constants of the reaction from the reference-state Gibbs free energies of the participating components: -RT ln
Kj ) .Gj o(T) (14) where Kj is the equilibrium constant of reaction j, .Gj(T) the reference-state Gibbs free energy change for reaction j at temperature T, R the universal gas constant, and T the system temperature. For the aqueous phase reactions, the reference states chosen are pure liquid for the solvents (water and MDEA), and aqueous phase infinite dilution for
the solutes (ionic and molecular). The Gibbs free energy of solvents is calculated from that of ideal gas and the departure function: ig(T) + .Gigfl(T) Gs(T) ) Gs s (15) where Gs(T) is the Gibbs free energy of solvent s at temperature T, Gs s ig(T) the ideal gas Gibbs free energy of solvent at temperature
T, and .Gs igfl(T) the Gibbs free energy departure from ideal gas to liquid at temperature T. The Gibbs free energy of an ideal gas is calculated from the Gibbs free energy of formation of an ideal gas at 298.15 K, the enthalpy of formation of an ideal gas at 298.15 K, and the ideal gas heat
capacity. ig(T) ) .fHig ig G+ .TCdT -T ss,298.15 p,s 298.15 igig ig .fH-.fGC s,298.15 s,298.15 Tp,s dT(16) (+ .) 298.15 298.15 T where Gs ig(T) is the ideal gas Gibbs free energy of solvent s at ig temperature T, .fGs,298.15the ideal gas Gibbs free energy of formation of
solvent s at 298.15 K, .fHsig,298.15the ideal gas ig enthalpy of formation of solvent s at 298.15 K, and Cp,s the ideal gas heat capacity of solvent s. Table 5. Parameters for Ideal Gas Heat Capacity Heat Capacity (J/(kmol K)) parameter MDEA H2O CO2 source this work Aspen Databank22 Aspen Databank22 C1i 2.7303 104 3.3738 104 1.9795 104 C2i 5.4087
102 -7.0176 7.3437 10 C3i 0 2.7296 10-2 -5.6019 10-2 C4i 0 -1.6647 10-5 1.7153 10-5 C5i 0 4.2976 10-9 0 C6i 0 -4.1696 10-13 0 C7i 278 200 300 C8i 397 3000 1088.6 a The correlation for the ideal gas heat capacity is given as follows: ig ) C1i Cp + C2iT + C3iT2 + C4iT3
+ C5iT4 + C6iT5, C7i < T < C8i, where T is the temperature (given in Kelvin). ig ig The reference-state properties, .fGs,298.15and .fHs,298.15, are shown in Table 4. The ideal gas heat capacities are shown in Table 5. For water, the Gibbs free energy departure function is obtained from the ASME steam tables. For MDEA, the departure function is
calculated from the PC-SAFT equation of state. For molecular solute CO2, the Gibbs free energy in aqueous phase infinite dilution is calculated from Henry s law: 8,aq(T) ) .fGi Hi,w Gi ig(T) + RT ln() (17) Pref where Gi 8,aq(T) is the mole fraction scale aqueous-phase infinite ig(T) dilution Gibbs
free energy of solute i at temperature T, .fGithe ideal gas Gibbs free energy of formation of solute i at temperature T, Hi,w the Henry s constant of solute i in water, and Pref the reference pressure. For ionic species, the Gibbs free energy in aqueous-phase infinite dilution is calculated from the Gibbs free energy of formation in aqueous-phase infinite dilution at
298.15 K, the enthalpy of formation in aqueous-phase infinite dilution at 298.15 K, and the heat capacity in aqueous-phase infinite dilution: T Gi 8,aq(T) ) .fHi,298.15 + .Cp,i 8,aq 8,aq dT -T 298.15 8,aq 8,aq 8,aq.fHi,298.15 -.fGi,298.15 T Cp,i 1000 dT+ RT ln (+ .) () 298.15 298.15 TMw (18) Here, Gi 8,aq(T) is the
mole fraction scale aqueous-phase infinite 8,aq dilution Gibbs free energy of solute i at temperature T, .fGi,298.15 the molality scale aqueous-phase infinite dilution Gibbs free 8,aq energy of formation of solute i at 298.15 K, .fHi,298.15 the aqueous phase infinite dilution enthalpy of formation of solute i at 298.15 K, and Cp8,i,aq the aqueous-phase infinite dilution heat capacity of
D Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX Table 6. Parameters for Aqueous-Phase Infinite Dilution Heat Capacitya Heat Capacity (J/(kmol K)) -2 parameter H3O+ OH-HCO3 CO3 MDEAH+ source Aspen Databank22 Aspen Databank22 Criss and Cobble31 Criss and Cobble31 this work C1 7.5291 104 -1.4845 105 -2.9260 104 b -3.9710 105 b 2.9900 105
b 8,aq 8,aq a The aqueous-phase infinite dilution heat capacity is assumed to be constant (Cp,i ) C1). b The Cp,i value of MDEAH+ is calculated from the chemical equilibrium constant in Kamps and Maurer,30 which is used as the initial guess to fit experimental data. The Cp,i -and CO32 8,aq values of HCO3 are the average values of heat
capacity between 298 K and 473 K (taken from Criss and Cobble31). 8,aq .fGi,298.15, as reported in the literature, is based on molality concentration scale while Gi 8,aq is based on mole fraction scale. 8,aq 8,aq 8,aq The standard-state properties .fGi,298.15, .fHi,298.15, and Cp,i are available in the literature for most ionic species, except those
of MDEAH+. (See Tables 4 and 6.) We calculate the referencestate properties of the MDEAH+ ion from the experimental equilibrium constant of eq 13, as reported in 1996 by Kamps 8,aq 8,aq and Maurer.30 The calculated .fGi,298.15 and .fHi,298.15 values are given in Table 4, and the calculated Cp,i 8,aq values are given in Table
6. As will be shown later, we use these calculated reference-state properties for MDEAH+ as part of the adjustable parameters in the fitting experimental data of thermodynamic properties, including VLE, heat of solution, heat capacity, and species concentration from NMR spectra. Also given in Table 6 are estimated values of Cp,i -and CO3 8,aq for HCO3 2-. They
have been taken from the 1964 work of Criss and Cobble.31 2.2. Heat of Absorption and Heat Capacity. The CO2 heat of absorption in aqueous MDEA solutions can be derived from an enthalpy balance of the absorption process: l lg nFinalHFinal -nInitialHInitial -nCO2 HCO2 (19) .Habs ) nCO2 where .Habs is the heat of absorption per mole of CO2, HFinal l
the molar enthalpy of the final solution, Hl Initial the molar enthalpy of the initial solution, HCOg 2 the molar enthalpy of gaseous CO2 absorbed, nFinal the number of moles of the final solution, nInitial the number of moles of the initial solution, and nCO2 the number of moles of CO2 absorbed. There are two types of heat
of absorption: integral heat of absorption and differential heat of absorption. The integral heat of absorption for a certain amine-H2O-CO2 system refers to the heat effect per mole of CO2 during the CO2 loading of the amine solution increasing from zero to the final CO2 loading value of that amine-H2O-CO2 system. The differential heat of absorption for an amine-H2O-CO2 system refers to the heat effect per
mole of CO2 if a very small amount of CO2 is added into this amine-H2O-CO2 system. For calculation of both types of heat of absorption, enthalpy calculations for the initial and final amine-H2O-CO2 systems and for gaseous CO2 are required. The heat capacity of the MDEA-H2O-CO2 system can be calculated from the temperature derivative of enthalpy.
We use the following equation for liquid enthalpy: ll 8,aq + Hex Hl ) xH+ xH+ SxiHi (20) ww ss i Here, Hl is the molar enthalpy of the liquid mixture, Hw l the molar enthalpy of liquid water, Hsl the molar enthalpy of liquid 8,aq nonaqueous solvent s, Hi the molar enthalpy of solute i (molecular or ionic)
in aqueous-phase infinite dilution, and Hex the molar excess enthalpy. The terms xw, xs, and xi represent the mole fractions of water, nonaqueous solvent s, and solute i, Table 7. Parameters for Heat of Vaporization (Expressed in Units of J/kmol)a component i MDEA source this work C1i 9.7381 107 C2i 4.6391 10-1 C3i 0 C4i 0 C5i 0 Tci 741.9b a The DIPPR equation for the heat of vaporization is given as
follows: .vapHi ) C1i(1 -Tri)Z, where Z ) C2i + C3iTri + C4iTri 2 + C5iTri 3 and Tri ) T/Tci (here, Tci is the critical temperature of component i). The temperatures are given in Kelvin. b The Tci value for MDEA is obtained from Von Niederhausern et al.32 The liquid enthalpy of pure water is calculated from the ideal gas model and the ASME Steam
Tables EOS for enthalpy departure: ig igigfl(T, p) Hw l (T) ) .fHw,298.15 + .T Cp,w dT + .Hw (21) 298.15 where Hw l (T) is the liquid enthalpy of water at temperature T, ig .fHw,298.15the ideal gas enthalpy of formation of water at 298.15 ig igfl(T,p) K, Cp,w the ideal-gas
heat capacity of water, and .Hw the enthalpy departure calculated from the ASME Steam Tables EOS. Liquid enthalpy of the nonaqueous solvent s is calculated from the ideal-gas enthalpy of formation at 298.15 K, the idealgas heat capacity, the vapor enthalpy departure, and the heat of vaporization: T ig igdT + .H Hl (T) ) .fH+
.CV(T, p) -.H(T) ss,298.15 p,ss vaps 298.15 (22) Here, Hsl(T) is the liquid enthalpy of solvent s at temperature T, ig .fHs,298.15the ideal-gas enthalpy of formation of solvent s at 298.15 K, Cp,s V(T,p) ig the ideal-gas heat capacity of solvent s, .Hs the vapor enthalpy departure of solvent s, and .vapHs(T) the heat
of vaporization of solvent s. The PC-SAFT EOS is used for the vapor enthalpy departure and the DIPPR heat of vaporization correlation is used for the heat of vaporization. Table 7 shows the DIPPR equation and the correlation parameters for the heat of vaporization. The enthalpies of ionic solutes in aqueous phase infinite dilution are calculated
from the enthalpy of formation at 298.15 K in aqueous-phase infinite dilution and the heat capacity in aqueous-phase infinite dilution: T Hi 8,aq(T) ) .fHi,298.15 + .Cp,i (23) 8,aq 8,aq dT 298.15 where Hi 8,aq(T) is the enthalpy of solute i in aqueous-phase 8,aq infinite dilution at temperature T, .fHi,298.15 the enthalpy of formation
of solute i in aqueous-phase infinite dilution at 298.15 8,aq K, and Cp,i the heat capacity of solute i in aqueous-phase respectively. infinite dilution.
Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX E Table 8. Parameters for Dielectric Constanta component i MDEA source Aspen Databank22 Ai 21.9957 Bi 8992.68 Ci 298.15 a The correlation for the dielectric constant is given as follows: ei(T) ) Ai + Bi[(1/T) -(1/Ci)], where T is the temperature (given in Kelvin). 8,aq Both .fHi,298.15 and Cp,i 8,aq are also used
in the calculation of Gibbs free energy of the solutes, thus impacting chemical 8,aq 8,aq for equilibrium calculations. In this study, .fHi,298.15 and Cp,i MDEAH+ are determined by fitting to the experimental phase equilibrium data, the heat of solution data, and the speciation data, together with molality scale Gibbs free energy of formation 8,aq
at 298.15 K, .fGi,298.15, and NRTL interaction parameters. The enthalpies of molecular solutes in aqueous phase infinite dilution are calculated from Henry s law: . ln Hi,w 8,aq(T) ) .fHi ig(T) -RT 2 Hi () (24) .T where .fHi ig(T) is the ideal gas enthalpy of formation of solute i at temperature T,
and Hi,w Henry s constant of solute i in water. Excess enthalpy (Hex) is calculated from the activity coef ficient model (i.e., the electrolyte NRTL model). 2.3. Activity Coefficients. Activity coefficients are required in phase equilibrium calculations, aqueous-phase chemical equilibrium calculations, heat of absorption, liquid heat capacity, and liquid enthalpy calculations. The activity coefficient of a component in a liquid mixture is
a function of temperature, pressure, mixture composition, and choice of reference state. In VLE calculations, we use the asymmetric mixed-solvent reference state for the molecular solute CO2, and in aqueousTable 9. Parameters Estimated in Modeling phase chemical equilibrium calculations, we choose the aqueousphase infinite dilution reference state for molecular solute CO2 and all ionic species. In applying the electrolyte NRTL
model for liquid-phase activity coefficient calculations, the binary NRTL interaction parameters for molecule-molecule binary, molecule-electrolyte binary, and electrolyte-electrolyte binary systems are required. Here, electrolytes are defined as cation and anion pairs. In addition, solvent dielectric constants are needed to facilitate calculations of long-range ion-ion interaction contribution to activity coefficients. Table 8 shows the dielectric constant correlation used in this work
for MDEA. Unless specified otherwise, all molecule-molecule binary parameters and electrolyte-electrolyte binary parameters are defaulted to zero. All molecule-electrolyte binary parameters are defaulted to (8,-4), average values of the parameters as reported for the electrolyte NRTL model.12 The nonrandomness factor (R) is fixed at 0.2. The calculated thermodynamic properties of the electrolyte solution are dominated by the binary
NRTL parameters associated with the major species in the system. In other words, the binary parameters for the water-MDEA binary, the 2-) water-(MDEAH+, HCO3 -) binary, the water-(MDEAH+,CO3 binary, and the MDEA-(MDEAH+ , HCO3 ) binary systems determine the calculated thermodynamic properties. These binary parameters, in turn, are identified from fitting to available experimental
data. 3. Modelling Results Table 9 summarizes the model parameters and sources of the parameters used in the thermodynamic model. Most of the parameters can be obtained from the literature. The remaining parameters are determined by fitting to the experimental data. parameter component source data used for regression Antoine equation MDEA regression vapor pressure of MDEA
.vapH MDEA regression heat of vaporization of MDEA, calculated from the vapor pressure using the Clausius-Clapeyron equation dielectric constant MDEA Aspen Databank22 Henry s constant CO2 in H2O Yan and Chen25 CO2 in MDEA this work NRTL binary parameters CO2 -H2O binary Yan and Chen25 MDEA-H2O binary regression VLE, excess enthalpy, and heat capacity for the
MDEA-H2O binary molecule-electrolyte binaries regression VLE, excess enthalpy, heat capacity, and species concentration from NMR spectra for the MDEA-H2O-CO2 system ig .fG298.15 H2O, MDEA, CO2 Aspen Databank22 ig H2O, MDEA, CO2 Aspen Databank22 .igfH298.15 Cp H2O, CO2 Aspen Databank22 MDEA regression liquid heat capacity of MDEA 8,aq 2 H3O+,OH-,
HCO3 Aspen Databank22 -,CO3 .fG298.15 MDEAH+ regression VLE, excess enthalpy, heat capacity, and species concentration from NMR spectra for the MDEA-H2O-CO2 system 8,aq 2 H3O+,OH-, HCO3 Aspen Databank22 -,CO3 .fH298.15 MDEAH+ regression VLE, excess enthalpy, heat capacity, and species concentration from NMR spectra for the MDEA-H2O-CO2 system
8,aq Cp H3O+,OH-Aspen Databank22 HCO3 2-Criss and Cobble31 -,CO3 MDEAH+ regression VLE, excess enthalpy, heat capacity, and species concentration from NMR spectra for the MDEA-H2O-CO2 system Table 10. Experimental Data Used in the Regression for Pure MDEA data type temperature, T (K) pressure, P (kPa) data points average relative deviation, .Y/Y (%) reference vapor pressure 293-401 0.0006-1.48 26 1.5 Daubert et al.33 vapor pressure
420-513 3.69-90.4 14 4.0 Noll et al.34 vapor pressure 420-738 3.69-3985 23 2.9 VonNiederhausern et al.32 liquid heat capacity 299-397 5 0.5 Maham et al.35 liquid heat capacity 303-353 11 0.4 Chen et al.36 liquid heat capacity 278-368 19 0.3 Zhang et al.37
F Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX Table 11. Antoine Equation Parameters for Pure MDEAa parameter component i value C1i MDEA 1.2276 102 C2i MDEA -1.3253 104 C3i MDEA -1.3839 10 C4i MDEA 3.20 10-6 *,l a The correlation for the Antoine equation is given as follows: ln Pi)C1i +C2i/T +C3i ln T +C4iT2, where T is the temperature (given in Kelvin).
3.1. MDEA. Extensive experimental vapor pressure data and liquid heat capacity data are available for MDEA. The data used in the regression for MDEA and the correlation results are summarized in Table 10. Table 11 shows the Antoine equation parameters regressed from the recently available vapor pressure data.32-34 The heat of vaporization (from 293 K to 473 K) generated with the regressed
Antoine equation parameters through the Clausius-Clapeyron equation are used to determine the DIPPR heat of vaporization equation parameters (shown in Table 7). The ideal-gas heat capacity correlation parameters are obtained by fitting to the liquid heat capacity data35-37 (shown in Table 5). Table 10 shows the excellent correlation of the experimental data for vapor pressure, with an average relative deviation
of <4%, and liquid heat capacity, with an average relative deviation of <0.5%. The PC-SAFT parameters of MDEA (shown in Table 1) are regressed from the vapor pressure data32-34 (with an average relative deviation of 13.1%), the liquid heat capacity data35-37 (with an average relative deviation of 22.6%), and the liquid density data38,39 (with an average relative deviation
of 2.7%). 3.2. MDEA-H2O System. Extensive literature data on VLE,40-42 excess enthalpy,9,35,43 and heat capacity36,37,44 of the MDEA-H2O binary system are available (see Table 12). These data cover the complete MDEA-H2O binary concentration range from room temperature to 458 K. Together, all of these data are used to identify the NRTL binary parameters, including their temperature dependencies for the MDEA-H2O binary
system. The regressed NRTL parameters are summarized in Table 13. The experimental data for the binary MDEA-H2O system are well-represented. The average relative deviations between the calculated values and the experimental data are summarized in Table 12. Figure 1 shows the parity plot, while Figure 2 shows the comparison for the experimental total pressure data and the calculated
results from the model. Figure 3 shows the comparison results for the MDEA vapor composition. The excess enthalpy fit is given in Figure 4. Both the experimental excess enthalpy data from Posey9 and those of Maham et al.35,43 are represented very well. Figure 5 shows the model also provides satisfactory representation of the heat capacity data. Figure 6 shows the
model predictions for water and MDEA activity coefficients at 313, 353, and 393 K. While the water Table 13. Regressed NRTL Parameters for the MDEA-H2O Binary System with r)0.2a parameter component i component j value standard deviation aij H2O MDEA 8.5092 0.1641 aij MDEA H2O -1.7141 0.0566 bij H2O MDEA -1573.9 45.70 bij MDEA H2O -261.85 22.97 a Correlation for the NRTL parameters: tij )aij +bij/T, where T is the temperature (given
in Kelvin). Figure 1. ParityplotfortheMDEA-H2Osystemtotalpressure,experimentversusmodel:(4)X uetal.,40(O)Voutsasetal.,41and(0)Kimetal.42 Figure 2. ComparisonoftheexperimentaldatafromKimetal.42(representedbysymbols:(O) T )373K,(4)T )353K,(0)T )333K, and()T )313K)fortotalpressureoftheMDEA-H2Obinarysolutionandthemodelresults(repres entedbylines). activity coefficient remains relatively constant, the model suggests that the MDEA activity coefficient varies strongly with MDEA concentration and temperature, especially in dilute aqueous MDEA solutions. Table 12. Experimental Data Used in the Regression for the MDEA-H2O System data average relative data type temperature, T (K) pressure, P (kPa) MDEA mole fraction points deviation, .Y/Y (%)
reference VLE (isoconcentration), TP 326381 13101 0.0160.26 34 3.4a Xu et al.40 VLE (isobaric), Tx 349458 40.066.7 00.93 30 3.3a Voutsas et al.41 VLE (isothermal), TPxy 313373 6100 00.36 61 3.0a Kim et al.42 excess enthalpy (isothermal) 298, 342 0.020.74 19 6.3 Posey9 excess enthalpy (isothermal) 298, 303 0.030.93 26 5.4 Maham et al.35 excess enthalpy (isothermal) 338 0.100.90 9 11.2 Maham et
al.43 heat capacity (isobaric) 303353 100 0.130.80 44 2.2 Chiu and Li44 heat capacity (isobaric) 303353 100 0.200.80 44 2.2 Chen et al.36 heat capacity (isobaric) 278368 100 01.0 228 2.8 Zhang et al.37 a The average relative deviation is that of total pressure.
Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX G Figure 3. ComparisonoftheexperimentaldatafromKimetal.42(representedbysymbols:(O) T )373K,(4)T )353K,(0)T )333K, and()T )313K)forthevaporcompositionoftheMDEA-H2Obinarysolutionandthemodelresults( representedbylines). Figure 6. ModelpredictionsofwaterandMDEAactivitycoefficientsat313,353,and393Kove rtheentiremolefractionrange;solidlinesrepresentwateractivitycoefficientsanddashe dlinesrepresentMDEAactivitycoefficients. Figure 4. ComparisonoftheexperimentaldatafromPosey9(representedbyfullsymbols:(b) T )298K,([)T )342K)andMahametal.35,43(representedbyemptysymbols:(O)T )298K,(4)T )313K,(0)T ) 338K)forexcessenthalpyoftheMDEA-H2Obinarysolutionandthemodelresults(representedb ylines). Figure 5. ComparisonoftheexperimentaldatafromChenetal.36(representedbysymbols:(O )MDEAmolefraction)0.8,(4)MDEAmolefraction)0.6,(0)MDEAmolefraction)0.4,and()MDEAmo lefraction)0.2)forheatcapacityoftheMDEA-H2Obinarysolutionandthemodelresults(repr esentedbylines). 3.3. MDEA-H2O-CO2 System. Extensive VLE,5,6,8,13,45-64 heat of absorption,65,66 heat capacity,67 and NMR spectroscopic68 data of the ternary MDEA-H2O-CO2 system are available. 8,aq 8,aq The terms .fG298.15
, and Cp 8,aq of MDEAH+ and , .fH298.15 the binary NRTL parameters for major molecule-electrolyte pairs are regressed from selected experimental data of the MDEA-H2O-CO2 system. Table 14 summarizes the VLE,5,6,13 heat of absorption,65,66 heat capacity,67 and species concentration68 data used to obtain these parameters. Species concentration data from NMR spectra are very
useful to validate the model predictions for the species distribution in the ternary system. Calculated heat of absorption of CO2 by the MDEA solution also strongly depends on the species distribution. For VLE data, we choose the total pressure data of Kuranov et al.,5 Kamps et al.,6 and the CO2 partial pressure data of Ermatchkov et al.13 in
the regression. Together, these data cover temperatures from 313 K to 413 K, pressures from 0.1 kPa to 6000 kPa, MDEA mole fractions from 0.03 to 0.13, and CO2 loadings from 0.003 to 1.32. The CO2 partial pressure data of Jou et al.45 also cover wide ranges for temperature, pressure, MDEA concentration, and CO2 loading. However, considering the reported inconsistency5,6,13
between these data45 and those of Kuranov et al.,5 Kamps et al.,6 and Ermatchkov et al.,13 we choose to exclude the data of Jou et al.45 from the regression. The Jou et al. data45 and all other available literature VLE data8,46-64 are used only for model validation. The average relative deviations between the correlation results and the various
experimental data are shown in Table 14. The regressed parameters for the MDEA-H2O-CO2 system are summarized in Table 15. As expected, the regressed values of 8,aq 8,aq , and Cp 8,aq for MDEAH+ in Table 15 are .fG298.15, .fH298.15 comparably close to the estimated values reported in Tables 4 and 6.
Figures 7 and 8 show that most of the total pressure data of Kuranov et al.5 and Kamps et al.6 are fitted within (20%. Figures 9-11 show the excellent correlation results for the total pressure data for MDEA concentration from2mto8m,CO2 loading from 0.11 to 1.32, temperature from 313 K to 413 K, and pressure up to 6000 kPa.
Figures 12 and 13 show that most of the CO2 partial pressure data of Ermatchkov et al.13 are fitted within (30%. Figure 12 suggests that there is a slight systematic deviation that changes from negative to positive as the CO2 loading increases. Figures 14-16 show the satisfactory correlation results for the CO2 partial pressure data for MDEA concentration from2mto8m,CO2 loading
from 0.003 to 0.78, temperature from 313 K to 393 K, and pressure from 0.1 kPa
H Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX Table 14. Experimental Data Used in the Regression for the MDEA-H2O-CO2 System temperature, pressure, MDEA data average relative data type T (K) P (kPa) mole fraction CO2 loading points deviation, .Y/Y (%) reference VLE, TPx, total pressure 313413 705000 0.0350.067 01.32 82 6.8 Kuranov et al.5 VLE, TPx, total pressure 313393 2006000 0.126 0.131.15 23 10.5 Kamps et al.6 VLE, TPx, CO2
pressure 313393 0.170 0.0330.132 0.0030.78 101 17.7 Ermatchkov et al.13 heat of solution 313393 0.06 0.11.4 112 6.8 Mathonat65 heat of solution 298 0.0170.061 0.020.25 40 2.1 Carson et al.66 heat capacity (isobaric) 298 0.0610.185 00.64 39 3.0 Weiland et al.67 species concentration 293313 0.04 0.10.7 8 47.5 Jakobsen et al.68 Table 15. Regressed Parameters for the MDEAH2OCO2 System with r)0.2 parameter component i component j value standard deviation
8,aq (J/kmol) MDEAH+-2.5951 108 2.1986 105 .fG298.15 8,aq (J/kmol) MDEAH+-5.1093 108 5.8718 105 .fH298.15 Cp 8,aq (J/(kmol K)) MDEAH+ 3.3206 105 1.2799 104 tij H2O (MDEAH+, HCO3 ) 8.7170 0.2246 tij (MDEAH+, HCO3 ) H2O -4.2995 0.0836 tij H2O (MDEAH+,CO32-) 10.4032 0.3676 tij (MDEAH+,CO32-) H2O -4.9252 0.1248
tij MDEA (MDEAH+, HCO3 ) 5.2964 0.2746 tij (MDEAH+, HCO3 ) MDEA -0.8253 0.0685 to 70 kPa. The correlation results match the experimental data Table 16 shows a comparison of model predictions and well, except that the calculated CO2 pressure at 313 K is slighter experimental VLE data from numerous other sources not
higher than the measured values for the 8 m MDEA solution at included in the regression. The results highlight the fact that high CO2 loading (see Figure 16). Upon further examination, we cannot match all the VLE data because the experimental we find that, under the same conditions, the predicted total pressure matches the experimental data of Sidi-Boumedine
et al.62 well. Figure 7. Ratioofexperimentaltotalpressuretocalculatedtotalpressure, asafunctionofCO2loading((4)datafromKuranovetal.5and(O)datafromKampsetal.6). Figure 9. ComparisonoftheexperimentaldatafromKuranovetal.5(representedbysymbols: (O)T )413K,(4)T )393K,()T )373K, (0)T )353K,and(])T )313K)fortotalpressureoftheMDEA-H2O-CO2systemandthemodelresul ts(representedbylines); theMDEAconcentrationis~2m. Figure 8. ParityplotfortheMDEA-H2O-CO2systemtotalpressure: experimentversusmodel((4)Kuranovetal.5and(O)Kampsetal.6). Figure 10. Comparison of the experimental data from Kuranov et al.5 (represented by symbols: (O) T )413 K, (4) T )393 K, () T )373 K, (0) T ) 353 K, and (]) T ) 313 K) for total pressure of the MDEA-H2O-CO2 system and the
Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX Figure 11. ComparisonoftheexperimentaldatafromKampsetal.6(representedbysymbols:( O)T )393K,(0)T )353K,and(])T )313K)fortotalpressureoftheMDEA-H2O-CO2systemandthe modelresults(representedbylines);theMDEAconcentrationis~8m. Figure 14. ComparisonoftheexperimentaldataforCO2partialpressureoftheMDEA-H2O-CO2 systemandthemodelresults;theMDEAconcentrationis~2m.EmptysymbolsaredatafromErmatc hkovetal.13((O)T )393K,(0)T )353K,(])T )313K),solidlinesrepresentthe2009eNRTLmod elresults,anddashedlinesrepresentthe1986eNRTLmodelresults. Figure 12. RatoofexperimentalCO2partialpressure((O)Ermatchkovetal.13)tocalculate dCO2partialpressure(line),asafunctionofCO2loading. Figure 13. ParityplotforCO2partialpressureoftheMDEA-H2O-CO2system:experiment((O) Ermatchkovetal.13)versusmodel(line). data from different sources can be inconsistent. With the exception of the data from Jou et al.,45 Silkenbaeumer et al.,56 and Ali and Aroua,61 the model predictions are very
satisfactory, with the average relative deviation on pressure (either total Figure 15. ComparisonoftheexperimentaldataforCO2partialpressureoftheMDEA-H2O-CO2 systemandthemodelresults;theMDEAconcentrationis~4m.EmptysymbolsaredatafromErmatc hkovetal.13((O)T )393K,(0)T )353K,(])T )313K),solidlinesrepresentthe2009eNRTLmod elresults,anddashedlinesrepresentthe1986eNRTLmodelresults. Figure 16. ComparisonoftheexperimentaldataforCO2partialpressureoftheMDEA-H2O-CO2 systemandthemodelresults;theMDEAconcentrationis~8m.EmptysymbolsaredatafromErmatc hkovetal.13((O)T )393K,(0)T )353K,(])T )313K),solidlinesrepresentthe2009eNRTLmod elresults,anddashedlinesrepresentthe1986eNRTLmodelresults. pressure or CO2 partial pressure) in the range of 7%-80%. It is particularly significant that the model predictions give an excellent match with the recent data of Kamps et al.,60 Sidi-Figure 17 shows the species distribution
as a function of CO2 Boumedine et al.,62 and Ma mum et al.63 loading for a 23 wt % MDEA solution at 293 K. The calculated
J Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX Table 16. Comparison between Experimental Data and Model Predictions for Total P ressure or CO2 Partial Pressure of the MDEA-H2O-CO2 System source data points temperature, T (K) pressure, P (kPa) MDEA concentration CO2 loading .P/P a (%) Jou et al.45 118 298393 0.0016000 0.0440.128 0.00041.68 204 Chakma and Meisen46 76 373473 1005000 0.030.12 0.010.95 31.5 Maddox et al.47 99 310388 206000 0.020.04 0.171.51 21.1 Austgen et al.8 14 313
0.005100 0.0450.13 0.0030.67 32.2 MacGregor and Mather48 5 313 14000 0.04 0.121.2 22.1 Jou et al.49 37 313373 0.004260 0.07 0.0020.80 37.5 Dawodu and Meisen50 12 373393 1604000 0.12 0.090.8 13.3 Liu et al.51 16 303363 20350 0.09 0.090.85 28.5 Mathonat et al.52 9 313393 200010000 0.06 0.51.3 57.4 Rho et al.53 103 323373 0.1268 0.0080.31 0.0060.68 78.7 Baek and
Yoon54 12 313 12000 0.06 0.121.13 53.6 Rogers et al.55 34 313323 0.000071 0.040.13 0.00020.12 27.1 Silkenbaeumer et al.56 11 313 124000 0.07 0.21.3 135 Xu et al.57 65 328363 4800 0.070.13 0.040.9 20.2 Lemoine et al.58 13 298 0.021.64 0.04 0.020.26 11.9 Bishnoi and Rochelle59 3 313 0.10.7 0.13 0.010.03 17.9 Kamps et al.60 5 313 805000 0.03 1.061.41
8.9 Ali and Aroua61 15 313353 0.08100 0.04 0.050.8 495 Sidi-Boumedine et al.62 103 298348 2.74500 0.050.11 0.0081.30 7.7 Ma mun et al.63 34 328358 66813 0.12 0.170.81 6.5 Dicko et al.64 5 323 6434 0.12 0.10.9 48.5 a Experimental pressure expressed either as total pressure or CO2 partial pressure. Figure 17. ComparisonoftheexperimentaldataforspeciesconcentrationinMDEA-H2O-CO2a ndthemodelresultsatT )293K.MDEAconcentrationis23wt%.Symbolsrepresentexperimental datafrom -2Jakobsenetal.68((O)MDEA,(4)HCO3,(0)MDEAH+,()CO3,(]) CO2);linesrepresentmodelresults((s)MDEA,(---)HCO3,(--)
MDEAH+,(--)CO32-,and()CO2. Figure 18. IntegralCO2heatofabsorptionin30wt%MDEAaqueoussolutionat313K.Symbols(0 )representexperimentaldatafromMathonat;65linesrepresentmodelresults((s)integralheatofabsorption, (--)differentialheatofabsorption,()contributionofreactions, (--)contributionofCO2dissolution,(---)contributionofexcessenthalpies). concentrations of the species are consistent with the experimental NMR measurements from Jakobsen et al.68 Figures 18-20 show comparisons of the model correlations and the experimental data of Mathonat65 for the integral heat of CO2 absorption in aqueous MDEA solution at 313, 353, and 393 K, respectively. The
calculated values are in reasonable agreement with the experimental data. Also shown in Figures 18-20 are the predicted differential heats of CO2 absorption. The integral heat and the differential heat overlap at low CO2 loadings, and then diverge much at high CO2 loadings (i.e., >0.8), where the differential heat decreases by >50%. We further show the computed integral heat of
absorption as the sum of the various contributions from reactions 10-13, CO2 dissolution, and excess enthalpy. k .Habs )S.ni.H i +.Hdissolution +.Hex (25) i)1 where .Habs is the integral heat of absorption per mole of CO2, .H i the standard heat of reaction for reaction i per mole of key component reacted, and .ni the reaction extent
of the reaction key component for reaction i when 1 mol CO2 is absorbed. The heat of CO2 dissolution (.Hdissolution) is calculated as the enthalpy difference between 1 mol of CO2 in the vapor phase and 1 mol of CO2 in aqueous-phase infinite dilution. The contribution of excess enthalpies (.Hex) is computed as the excess enthalpy difference between the
final and initial compositions of the solution per mole of CO2 absorbed. The results in Figures 18-20 show that the heat of absorption is dominated by MDEAH+ dissociation and excess enthalpy. In addition, CO2 dissolution is important near room temperature, whereas CO2 dissociation becomes more important at higher temperatures. Figure 21 shows a comparison of the
model correlations and the experimental data of Weiland et al.67 for heat capacity of the MDEA-H2O-CO2 system. The model results are consistent with the data. To show the impact of the different versions of the electrolyte NRTL model to the model results, we perform
Figure 19. IntegralCO2heatofabsorptionin30wt%MDEAaqueoussolutionat353K.Symbols(4 )representexperimentaldatafromMathonat;65linesrepresentmodelresults((s)integralheatofabsorption, (--)differentialoverallabsorptionheat,()contributionofreactions,(--)contributionofCO2 issolution,(---)contributionofexcessenthalpies). Figure 20. IntegralCO2heatofabsorptionin30wt%MDEAaqueoussolutionat393K.Symbols(O )representexperimentaldatafromMathonat;65linesrepresentmodelresults((s)integralheatofabsorption, (--)differentialheatofabsorption,()contributionofreactions, (--)contributionofCO2dissolution,(---)contributionofexcessenthalpies). Figure 21. ComparisonoftheexperimentaldataforheatcapacityoftheMDEA-H2O-CO2system andthemodelresultsatT )298K.SymbolsrepresentexperimentaldatafromWeilandetal.67(( O)60wt%MDEA, (4)50wt%MDEA,(0)40wt%MDEA,and(])30wt%MDEA);linesrepresentmodelresults. VLE predictions with the same model parameter values given in Table 15 with the 1986 version of the electrolyte NRTL Ind. Eng. Chem. Res., Vol. xxx, No. xx, XXXX K model.11 Figures 14-16 show that the two
versions of the model yield practically identical results at low MDEA concentrations. The difference increases slightly with increasing MDEA concentration. 4. Conclusion To support process modeling and simulation of the CO2 capture process with MDEA, the electrolyte NRTL model has been successfully applied to correlate the available experimental data on thermodynamic properties of the MDEA-H2O-CO2 system. The model has
been validated for predictions of vaporliquid equilibrium (VLE), heat capacity, and CO2 heat of absorption of the MDEA-H2O-CO2 system with temperatures from 313 K to 393 K, MDEA concentrations up to8m(~50 wt %), and CO2 loadings up to 1.32. This model should provide a comprehensive thermodynamic property representation for the MDEA-H2O-CO2 system over a broader range of conditions and
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