Improved Kent-Eisenberg model for

predicting CO, solubilities in aqueous

diethanolamine (DEA) solutions
A. Chakma and A. Meisen*

Department of Chemical and Petroleum Engineering, The University of Calgary, Calgary,

Alberta, Canada, TZN 1 N4
*Department of Chemical Engineering, The University of British Columbia, Vancouver,
BC, Canada, V6T 1W5

Received 12 June 1989; revised 25 September 1989

The Kent and Eisenberg model for the determination of COP solubility in aqueous diethanolamine (DEA)
solutions has been improved by recorrelating the equilibrium constant relating the main DEA-CO,
reaction using 626 experimental data points. The new correlation for the equilibrium constant is
expressed as functions of temperature, DEA concentration and free CO* concentration. The improved
model predicts experimental data much better than the original model specially under high temperature
and low COP partial pressure conditions.

Keywords: CO1 solubilities; diethanolamine; models

Nomenclature
[CO*1 Concentration of physically dissolved Equations (7)-( 11)
CO2 (kmol m-‘) MDEA Methyldiethanolamine
DEA Diethanolamine PCO2 Partial pressure of CO* (kPa)
IDEA1 Concentration of diethanolamine R -C,H,-OH
(kmol mm3) T Temperature (K)
H Henry’s law constant oco, CO1 loading (mol CO* per mol DEA)
KFk, Equilibrium constants defined in

Introduction entire operating range of temperatures and acid gas

loadings.
Aqueous diethanolamine (DEA) solutions are widely
used in the gas processing industry for the removal of acid
gases during natural or refinery gas processing, bitumen Mathematical modelling
or heavy oil upgrading, coal gasification. ammonia
production and for the recovery of CO, to be used in The equilibrium between DEG CO* and H,O is assumed
enhanced oil recovery (EOR) projects. Typical operating to be governed by the following ionic reactions:
temperatures and acid gas loadings range from 40 to
120°C and 0.001 to 1.0 moles of acid gas/mole of DEG R,NH; = R,NH + H+ (1)
respectively. Accurate information on equilibrium solu-
bility of acid gases in DEA solutions covering the entire R,NCOO- + H,O = RzNH + HCO; (2)
range of temperature and acid gas loading is needed for
the design ofabsorbers and strippers used in conventional Hz0 + CO1 = H+ + HCO; (3)
gas plants. Although substantial CO* equilibrium solu-
bility data in aqueous DEA solutions are available’-” in Hz0 = H+ + OH- (4)
the open literature, they are only reliable in the middle
range of pressures and loadings”. Typical experimental HCO; = H+ + CO;- (5)
techniques used in the solubility determination do not
provide accurate data at low partial pressure and acid gas Henry’s law relates acid gas partial pressures to physically
loading conditions. Therefore, mathematical models are dissolved acid gas concentration in the solvent according
needed to predict acid gas solubility accurately for the to:

0950-42 14/90/o 10037-04

0 1990 Butterworth Et Co (Publishers) Ltd. Gas Separation Et Purification 1990 Vol 4 March 37
Improved Kent-Eisenberg model: A. Chakma and A. Meisen

Pco>= Hcoz[C@ 1 (6) K4 = expi39.5554 - 987.9X IO'T-'+ 568.828 X 105T-'

The corresponding equilibrium expressions are: - 146.451 X IO'T-'f 136.146 x 10"T-4} (21)

K, = [R>NH] [H+]/[RzNH;J (7) K, = exp(-294.74+ 364.385

x lO'T_'- 184.158
x IO'T-'

+ 415.793
X 10xT-'- 354.291 x IO”’ Tm4j (22)
K, = (R,NH] (HC0,]/[R2NCOO-] (8)

K, = [H+] [HCO,]/[COJ (9) H co:= exp(22.2819 - 138.306 X IO'T-'

Kz,= [H’j [OH-] (10) + 691.346 x IO4 T-’ - 155.895 x IO'T-'

KS = [H+j/[CO;~]/[HCO,J (11) + 120.037 X IO'T-4}/7.50061 (23)

In addition, the total molar and charge balances may be

The above empirical correlations were derived by Kent
written as:
and Eisenberg” in 1976 using equilibrium soluhility data
available at that time. Since then more data have become
[DEA] = [R,NH] + [R,NH;] + (R,NCOO-J available and in some cases. particularly at low acid gas
(12) loadings and high temperature situations above corre-
lations do not predict experimental data very well.
[DEA]aco, = [CO11 + [HCO,] + [CO;-) Therefore. there is a need to re-evaluate the DEA-CO,
+ [R,NCOO-J (13) equilibrium constant expression including all of the
experimental data. The DEA-CO, equilibrium constants
[R?NH+] + [H+] = [OH-] + [HCO,] + 2(CO;-] given by Equations (I 8)-(22) are functions of temperature
alone since the Kent and Eisenberg” model assumes ideal
+ [R2NCOO-] (14) behaviour of the CO?-DEA-H,O system. In reality.
however, the system is a non-ideal one and system non-
Equations (6)-( 14) can be written to express acid gas idealities as represented by activity coefficients are
partial pressure as a function of acid gas loading in the included in the evaluation of the equilibrium constants.
solution: Since the activity coefficients are composition dependent.
the equilibrium constants thus derived should also he
Pco2= (H,,,lK,K,)I(lDEAla,,~
- Pco~IHc.~)[H+121 composition dependent. Danckwerts and McNeil”
/{I+ [H+]/K, + [DEA] [H+]/KIK,K"l (15) attempted to relate this composition dependency on ionic
strength. However, ionic strength alone is insufficient to
[H+] = {(IDEA] + K,K")/K,i represent the composition dependency of the equilibrium
constants. Jou er ~1.‘~ as well as Chakma and Meisen’<
l(WW~,o~ - PcoJf&oJW+l’) found the equilibrium constant governing the main
amine reaction not only to be a function of temperature
X {1 + K,KSl(K,KF+ K,[H+])[DEA] [H+]lK”j but also to depend on acid gas partial pressure. solution
loading and amine concentration for methyldiethanol-
+ K,W+l I (16)
amine (MDEA) solutions. Since amine-acid gas systems
are non-ideal ones. by deriving an expression for the
K” = 1 + W+lIK, + (Pm2WW~4o~[H+l) (17)
equilibrium constants of main DEA-CO, reactions as
Provided the CO,-DEA-H,O system behaves ideally. functions of these variables one can lump system non-
the Henry’s law and equilibrium constants defined by idealities in it. In the present case. Equations (I) and (2)
Equations (6)-( 11) should only be functions of tempera- represent the main DEA-CO2 reactions. Equation (I)
ture. Kent and Eisenberg” assumed this to be the case for represents a simple proton transfer reaction which is
C02-MEA-H20 and C02-DEA-H20 systems. They first instantaneous. Equation (2) represents the carhamate
fitted published data to obtain empirical expressions for formation reaction. We have decided to keep the Kent-
the Henry’s law constant, Hcoz,and ionization constants Eisenberg” expression for K, and attempted to correlate
K,-KS.Then they fitted H2S-DEA equilibrium data to Kz as functions of temperature, free CO2 concentration
obtain an expression for K,,which represented the simple [COz]. and DEA concentration using 626 experimental
proton transfer reaction, and CO,-DEA equilibrium data data points covering a wide range of temperature. CO,
to obtain a similar expression for K2.Their empirical partial pressure. and DEA concentration. These data
expressions for the equilibrium and Henry’s law constants points were taken from References 2, 3 and 5-10. All the
are given below in SI units: data points from these references were included and given
the same weight, in the evaluation of the new correlation.
K, = exp( -2.5510 - 5652/T] The resulting correlation is:
(18)

Kz = expI4.825 - 1885/T) (19) K2 = exp(1.03439 + 2.92237 X IO-'T+ 26.2071 T-'

K, = exp{-241.818 + 298.253 X IO'T-' - 10.394767 In {T)+ 3.7497 158 [CO,]

- 148.528 x 10h Tm' + 332.648 X 10HT-j + 0.19298 In{ [CO,] 1 + 9.0007 X IO-’ IDEA]

- 282.394 x 10”’ T-4] (20) + 74.28267 X In ( [ DEA] I }

38 Gas Separation & Purification 1990 Vol 4 March

 Improved Kent-Eisenberg model: A Chakma and A Meisen

Results and discussion

-_ ImprovedKent & Eisenberg
For the 626 data points, the root mean square (RMS) - Original Kent 8 Eisenberg
deviation for the original Kent-Eisenberg model was 61.5 0 Experimetal data - Ref. 7

while that of the improved model was 3 1.O, indicating an

overall improvement in model predictions. However, the
improved model predictions were much better for high
temperature and low CO1 partial pressure conditions.
This is understandable as high temperature and low CO1
partial pressure data used in the present work were not
available when the Kent and Eisenberg” model was
developed. In addition, the inclusion of the effect of CO,
partial pressure through free CO2 concentration [CO,]
and DEA concentration in the correlation for K, allowed
better prediction with the improved model.
For 156 high temperature data points of Kennard and 10

1
Meisen’ the RMS deviation for the original model was
40.2 as compared to 8.8 for the modified model. A typical
comparison of model predictions at high temperatures is /
,
shown in Figure I. As can be seen, the new model predicts
solubility data much better than the original model. The / 0
original model predictions are generally lower than the
experimental values and the deviation becomes greater
with increasing temperature.
11111111
0.0
t
0.2 0.4 0.6 0.6 1 0 1.2 14
Figure 2 shows a comparison of model predictions and
experimental data of Lawson and Garst’ for CO, partial CO2 Solubility (mol C02/mol DEA)

pressure range of 2-320 kPa. In this case, the original

Figure 2 Comparison of model predictions and low CO, partial
model overpredicts CO, solubility. The improved model pressure CO, solubilitydata of Lawson and Garst7 in 2.38 kmol mm3
also overpredicts CO, solubility, however, its predictions DEA solution
match experimental data better than the original model.
Figure 3 compares model predictions and experimental 1.00

data of La1 et al? for very low CO, partial pressure range
0.014-0.85 kPa. The original model overpredicts while the
improved model underpredicts the experimental results.
However, the predictions of the improved model are still
better than those of the original model

Improved Kent & Eisenberg

- Original Kent & Eisenberg -
Experimetal data. Ref. 9

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Improved Kent 8 Eisenbq
Original Kent 8 Elsenberg CO2 Solubility (mol C02/mol DEA)
Expenmetal data - Ref. 8
Figure 3 Comparison of model predictions and low CO, partial
pressure CO, solubility data of Lal et ~4.~ in 2.0 kmol me3 DEA
solution
1001 I I I I I I

0.0 0.2 0.4 0.6 0.6 1.0 1.2 1.4

CO2 Solubility (mol C02/mol DEA) Conclusions

Figure 1 Comparison of model predictions and high temperature

An improved Kent-Eisenberg model for the prediction of
CO2 solubility data of Kennard and Meisens in 3 kmol mm3 DEA CO2 equilibrium solubility in aqueous DEA solutions is
solution presented where the equilibrium constant for the major

Gas Separation & Purification 1990 Vol 4 March 39

Improved Kent-Eisenberg model: A, Chakma and A. Meisen

DEA-CO2 reaction has been determined by fitting a total dioxide in aqueous diethanolamine solutions at high pressures
of 626 experimental data points and expressed as J Chem Eng Data (1972) 17 465-468
6 Lee, J.I., Otto, F.D. and Mather, A.E. The solubility of
functions of temperature, DEA concentration and free mixtures of carbon dioxide and hydrogen sulphide in aqueous
CO2 concentration. Overall predictions of the improved diethanolamine solutions at high pressures Can J Chem Eng
model are superior to those of the original model. The new (1974) 52 125-127
model predicts high temperature and low CO2 partial 7 Lawson, J.D. and Garst, A.W. Gas sweetening data: equilib-
rium solubility of hydrogen sulphide and carbon dioxide in
pressure equilibrium solubility data much better than the
aqueous monoethanolamine and aqueous diethanolamine
original model. solutions J Chem Eng Data (1976) 21(l) 20-32
8 Kennard, M.L. and Meisen, A. Solubility ofcarbon dioxide in
aqueous diethanolamine solutions at elevated temperatures
Acknowledgement and pressures J Chem Eng Data (1983) 29(3) 309-312
The financial aid provided by the Natural Sciences and 9 Lal, D., Otto, F.D. and Mather, A.E. The solubility of HZS and
CO? in a diethanolamine solution at low partial pressures Cut1
Engineering Research Council of Canada in support of
J Chem Eng (1985) 63(8) 681-685
this work is gratefully acknowledged. IO Bhairi, A., Mains, G. and Maddox, R.N. Experimental
equilibrium between CO? and ethanolamine solutions froreed-
ingy of the Annual Gas Processing Association Convention ( 198s)
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Bottoms, R.R. Organic bases for gas purification Ind Eng Chem rhemicalsolvents Wiley Interscience. New York. USA (1983) 53
(1931) 23(5) 501-504 12 Kent, R.L. and Eisenberg, B. Better data for amine treating
Mason, J.W. and Dodge, B.F. Equilibrium absorption of Hvdrocarhon Process (1976) 55(2) 87-90
carbon dioxide by solutions ofthe ethanolamines Trans Am Insr 13 Danckwerts, P.V. and McNeil, K.M. The absorption of
Chetn Eng (1936) 32 21-47 carbon dioxide into aqueous amine solutions and the effects ol
Reed, R.M. and Wood, W.R. Recent design development in catalvsis Tram Inst Chem Enn f’UKj f 1967) 45 T32-T49
amine gas purification plants TrunsAm lr?srChem Erlg (1941) 37 14 Jou,‘F., Mather, A.E. and &to, F.D. Solubility of H,S and
363-384 CO, in aqueous methyldiethanolamine solutions Ind Eng Chew
Murzin, V.I. and L&es, I.L. Partial pressure of carbon Proce.u Des Dev (1982) 21 539-544
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diol Zhur Fiz Khim (1971) 45 2642-2644 methyldiethanolamine and N.N-bis(hydroxyethyl)piperazine
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40 Gas Separation B Purification 1990 Vol 4 March