Separation and Purication Technology 94 (2012) 7183

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Separation and Purication Technology

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Modeling the solubility of CO2 and H2S in DEAMDEA alkanolamine solutions

using the electrolyteUNIQUAC model
Osama A. Al-Rashed ,1, Sami H. Ali
Department of Chemical Engineering, University of Kuwait, P.O. Box 5969, Safat, Kuwait

a r t i c l e i n f o a b s t r a c t

Article history: A thermodynamic model was developed to represent the solubility of CO2 and H2S in single and blend of
Received 18 January 2011 aqueous solutions of DEA and MDEA. The model accounts for chemical equilibria in the liquid phase and
Received in revised form 2 April 2012 physical equilibria between the liquid and vapor phases. The SoaveRedlichKwong (SRK) equation was
Accepted 9 April 2012
used to represent the fugacity coefcient in the vapor phase. The liquid phase was treated as an electrolyte
Available online 18 April 2012
solution and activity coefcients were represented by the electrolyteUNIQUAC equation. The electrolyte
UNIQUAC equation is composed of two parts, one to account for long range interactions and the other to
Keywords:
account for short interactions. Contribution from long range ionion interactions were represented by a
Vapor liquid equilibria
Alkanolamine
DebyeHuckel formula suitable for mixed solvent, water and alkanolamines. Adjustable parameters of
ElectrolyteUNIQUAC the electrolyteUNIQUAC equation, representing short range interactions, were determined by orthogonal
Carbon dioxide distance regression technique using a large and wide range of experimental VLE data. Earlier extensions of
Hydrogen sulde UNIQUAC to handle electrolyte solutions are ion-specic. In this work, the adjustable parameters were
setup to use the ion-pair interaction approach and satisfy both the principle of like-ion repulsion and local
electroneutrality. Eight different systems were considered in this work. The model predictions were in
excellent agreement with the experimental measurements and the speciation results are useful to be used
in mass transfer models to represent the CO2 and H2S absorption process using alkanolamine solutions.
2012 Elsevier B.V. All rights reserved.

1. Introduction
In many industrial gas treating processes, the sour gas contains
substantial amounts of both CO2 and H2S. A high clean up is neces-
sary for CO2 and H2S to avoid catalyst poisoning, corrosion, and
equally importantly, to meet the increasingly strict environment
regulations to reduce greenhouse gas emissions, which are the main
cause of global climate change. Therefore, the need for effective and
economical clean up becomes imperative. Various processes could
be used for the removal of CO2 and H2S from sour gases, but absorp-
tion by alkanolamines is generally the most economical [1].
Amines are classied as primary, secondary, or tertiary depend-
ing on the group attached to the nitrogen atom. Tertiary amines
react instantaneously with H2S by the same proton transfer mecha-
nism of primary and secondary amines. Therefore, in addition to the
single aqueous solution alkanolamine, mixed amines are also used,
especially; if selective removal of H2S from CO2 containing gases is
required. Mixed amine systems are typically composed of a tertiary
amine which reacts relatively slowly with CO2, and a primary or sec-
ondary amine which reacts much faster. By varying the composition
Corresponding author. Tel.: +965 24985599; fax: +965 24839498.
E-mail address: osama.alrashed@ku.edu.kw (O.A. Al-Rashed).
1
Corresponding author last name has been changed as of January 2008 from
Al-Bofersen to Al-Rashed.
of these amines, one can adjust the CO2 removal in a sour gas
stream. Selective H2S absorption is economically very attractive.
Increasing the selectivity reduces the solvent circulation rate and
therefore the steam consumption in the regenerators and moreover,
reduces the dimension and the capital cost of the sulfur recovery
unit. A blend of diethanolamine (DEA), which is a secondary amine,
and methyldiethanolamine (MDEA), which is a tertiary amine, is
one of the most widely used blends in the gas processing industry,
therefore; it is considered in this study.
The design and operation of an amine plant is most complete
when a computer simulator is available to provide guidelines for
grass root design, process optimization, and assistance in trouble-
shooting. Two design approaches are in common use; the equilib-
rium-based model and the rate-based model. These models are
well known, details regarding these models can be found in [2].
The rate-based design approach is more suitable, especially for
reactive systems. Development of a reliable vaporliquid equilib-
rium model is essential for rate-based design model which requires
accurate representation of activity coefcients as well as speciation
of all molecular and ionic species in the solution.
Several attempts have been made in the development of gener-
alized correlations for predicting phase equilibrium data for CO2
and H2S in aqueous amines solutions. Early thermodynamic mod-
els adopted empirical approaches that did not account for physical
interactions. Danckwerts and McNeil [3] were the rst to model

1383-5866/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2012.04.007
72 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183

Nomenclature

CO2 carbon dioxide R2NCOO DEA carbamate

CO 3 carbonate R2NH diethanolamine
DEA diethanolamine R2 NH 2 protonated diethanolamine
DEACOO DEA carbamate RR0 R00 N methyldiethanolamine
+
DEAH protonated diethanolamine RR0 R00 NH+ protonated methyldiethanolamine
Psw
Hi;w Henrys constant for molecular solute i (CO2 or H2S) in rk UNIQUAC pure component volume parameter
pure water at the system temperature and the vapor S= sulde
pressure of water T temperature in Kelvin
H2O water v lw molar volume of pure water at the system temperature
H3O+ hydronim v i;w
1
partial molar volume at innite dilution
H2S hydrogen sulde xi liquid phase mole fraction
HCO 3 bicarbonate yi vapor phase mole fraction
HS bisulde Z lattice coordination number
Im ionic strength on the molality scale (mol/kg) zi charge number of ion i
Ki equilibrium reaction constant aCO2 CO2 loading (mole CO2/mole amine)
Mk molecular weight of component k aH2 S H2S loading (mole H2S/mole amine)
MW molecular weight of water ci activity coefcient
MDEA methyldiethanolamine e dielectric constant
MDEAH+ protonated methyldiethanolamine Hk UNIQUAC average area fraction
mDEA molality of DEA (mole DEA/kg H2O) qk density of the pure solvent k
mi molality of an ion i qs density of the mixed-solvent mixture
mMDEA molality of MDEA (mole MDEA/kg H2O) ski UNIQUAC interaction parameter
nT total mole of mixture Uk UNIQUAC average segment fraction
nw total moles of water (reacted plus unreacted) in solution /i fugacity coefcient of solute i
OH hydroxide /sw fugacity coefcient of saturated water at the system
P system pressure temperature
Psw vapor pressure of water at the system temperature Wki UNIQUAC interaction function
qk UNIQUAC pure component area parameter
R gas constant

the CO2aminewater system using an empirical approach origi-
nally proposed by Van Krevelen and co-workers [4]. Apparently
their model is not capable of accounting properly for the nonideal-
ities caused by the many ionic species in the system. The rst prac-
tical and widely used model was proposed by Kent and Eisenberg
[5]. Although the KentEisenberg model has some deciencies, the
model has the important advantage of computational simplicity.
Following the Kent and Eisenberg model, a more rigorous models
and therefore more generally applicable model based on sound
thermodynamic principles were proposed in the literature. The
DeshmukhMather model [6], electrolyteNRTL model [7], electro-
lyte EOS model [8], and CleggPitzer model [9] are among the most
widely used models to analyze the solubility of CO2 and H2S in
aqueous amine solutions.
Several studies [1014] used an electrolyte equation of state
model rst proposed by Frst and Renon [8] to represent VLE data
for CO2H2Samine systems. In this model an equation of state ap-
proach is used instead of the excess Gibbs energy approach. Wei-
land and co-workers [15] used the DeshmukhMather model to
correlate CO2 and H2S equilibrium for MEA, DEA, DGA, and MDEA.
Benamor and Aroua [16] also utilized the DeshmukhMather model
[6] with new available experimental data and a new estimated car-
bamate reversion equilibrium reaction constant to model the solu-
bility for DEAMDEACO2H2O systems. Kundu and co-workers
[17] modied the CleggPitzer model [9] to correlate VLE data for
DEAMDEACO2H2O systems. Probably the most accurate model
available at this time for predicting phase equilibrium of the acid
gasalkanolamineswater system is the electrolyteNRTL of Aust-
gen and co-workers [7]. This model is a modication of the electro-
lyteNRTL model of Chen and Evans [18]. The model is based on
combining the DebyeHuckel theory to account for long range elec-
trostatic interactions between ions and NRTL local composition
theory, Renon and Prausnitz, [19], to account for short range inter-
actions between all liquid phase species, molecular and ionic. The
model is thermodynamically rigorous, but computationally com-
plex. The electrolyteNRTL model has been widely used in the liter-
ature for different kind of amine systems by several studies
[7,20,21,39]. A similar model, the electrolyteUNIQUAC model,
was proposed by our group [22]. Our model retained the Debye
Huckel term to account for ionion long range interactions and re-
placed the NRTL expression by a UNIQUAC expression, Abrams and
Prausnitz [23], to account for short range interactions of all kinds.
The CO2H2SH2Oalkanolamines system is comprised of mole-
cules and ions which differ appreciably in both size and shape. This
is taken into account in the electrolyteUNIQUAC model through
structure parameters. Furthermore, in the electrolyteUNIQUAC
model, it is assumed that short range interactions occur between
ionpairs (rather than ions) with surface area fractions properly
distributed relative to those of the individual ions (as will be dis-
cussed later). This greatly simplies the resulting activity coef-
cient expressions compared to the electrolyteNRTL model.
Earlier extensions of UNIQUAC to handle electrolyte solutions, such
as the one by Sander and co-workers [24], are ion-specic and they
satisfy the ion repulsion assumption, however, they do not satisfy
the local electroneutrality concept. In our model the adjustable
parameters are setup to use the ionpair interaction approach
and satisfy both the principle of like-ion repulsion and local
electroneutrality.
Therefore, the electrolyteUNIQUAC model will be used to de-
scribe the thermodynamic equilibrium of the mixed acid gases
CO2 and H2S in mixed DEA/MDEA alkanolamine solutions. The
following eight systems will be considered: (CO2DEAH2O),
(CO2MDEAH2O), (H2SDEAH2O), (H2SMDEAH2O), (CO2
H2SDEAH2O), (CO2H2SMDEAH2O), (CO2DEAMDEAH2O),
 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183 73

and (H2SDEAMDEAH2O). These eight systems are sub-systems xH3 O xHCO3 cH3 O cHCO3
K CO2 10
of the general ninth system consisting of mixed acid gases and x2H2 O xCO2 c2H2 O cCO2
mixed amine solutions i.e. CO2H2SDEAMDEAH2O. Therefore,
the following model derivation will be based on this general sys- xH3 O xCO3 cH3 O cCO3
tem. For other sub-systems such as single acid gas or single amine, K HCO3 11
xH2 O xHCO3 cH2 O cHCO
the procedure will remain the same but the equations for the 3

unconsidered components need to be omitted.

xH3 O xHS cH3 O cHS
 
K H2 S 12
2. Model development for CO2H2SDEAMDEAH2O system xH2 O xH2 S cH2 O cH2 S

xH3 O xS cH3 O cS
 
The thermodynamic framework for calculating VLE for the CO2
K HS 13
H2SDEAMDEAH2O system is based on two types of equilibria: xH2 O xHS cH2 O cHS


chemical reaction/dissociation equilibria in the liquid phase and

xH3 O xR2 NH cH3 O cR2 NH

vaporliquid phase equilibria for molecular species.
The vapor phase contains molecular solutes CO2 and H2S in K DEA 14
xH2 O xR2 NH cH2 O cR NH
2 2
addition to water. The molecular solutes CO2 and H2S dissolve into 2

the liquid and react partially with the amines to produce a number
xH3 O xRR0 R00 N cH3 O cRR0 R00 N

of ionic species. The unreacted CO2 and H2S in the liquid phase are K MDEA 15
in physical equilibrium with their corresponding partial pressures xH2 O xRR0 R00 NH cH2 O cRR R NH
in the vapor phase. Similarly, the partial pressure of water in the
vapor phase is also in equilibrium with the water in the liquid xHCO3 xR2 NH cHCO3 cR2 NH
K DEACOO 16
phase. Ionic species are treated as nonvolatile and the vapor pres- xH2 O xR2 NCOO cH2 O cR2 NCOO
sures of amines are assumed negligible in the temperature range
under considerations. The solution is treated as a mixed solvent where xi and ci are the mole fraction and activity coefcient of spe-
system (wateralkanolamines). All other species are considered cies i. Innite dilution expressions of the equilibrium constants as a
to be molecular or ionic solutes. function of temperature are reported in the literature [7,20,25] as:
C2
2.1. Liquid phase equations ln K C 1 C 3 ln T C 4 T 17
T
Activity coefcients of all species are assumed to be indepen-
When CO2 and H2S dissolved in aqueous solution of DEA and
dent of pressure. The superscript on the activity coefcients of
MDEA, the following equilibrium reactions exist in solution:
the solutes and ions indicate that they are normalized according
to the unsymmetric convention. This means that the activity coef-
 Ionization of water
cient of each solute approaches unity as the corresponding mole
KH
2O fraction approaches zero in pure water. On the other hand, the
2H2 O $ H3 O OH 1
activity coefcients of the solvents (amines and water) approach
 Ionization of carbon dioxide unity as the corresponding mole fraction approach unity.
K CO Also from reactions (1)(8) the following conservation relations
CO2 2H2 O $ HCO3 H3 O
2
2 may be obtained:
 Dissociation of bicarbonate
(i) DEA mole balance:
K HCO
HCO3
CO3 nW M W =1000
3
H2 O $ H3 O 3 xR2 NH xR2 NH xR2 NCOO mDEA 18
2 nT
 Dissociation of hydrogen sulde
(ii) MDEA mole balance:
KH
2S
H2 S H2 O $ H3 O HS 4 nW M W =1000
xRR0 R00 N xRR0 R00 NH mMDEA 19
 Dissociation of bisulde nT
K HS (iii) CO2 mole balance:
HS H2 O $ H3 O S 5
xCO2 xHCO3 xCO3 xR2 NCOO
 Dissociation of protonated DEA
nW M W =1000
K DEA aCO2 mDEA mMDEA 20
R2 NH2 H2 O $ R2 NH H3 O 6 nT
 Dissociation of protonated MDEA (iv) H2S mole balance:
K MDEA nW MW =1000
RR0 R00NH H2 O $ RR0 R00N H3 O 7 xH2 S xHS xS aH2 S mDEA mMDEA 21
nT
 DEA carbamate reversion to bicarbonate
(v) H2O mole balance: To derive a water mass balance, we rst
K DEACOO write an atomic hydrogen balance, then use Eqs. (18)(20)
R2 NCOO H2 O $ R2 NH HCO3 8
to eliminate mDEA, mMDEA, and H2S loading. The result is:

From these reactions, the following equilibrium relations can be 2xH2 O xR2 NH xRR0 R00 NH  xR2 NCOO xHCO3 3xH3 O
2
written as:
xOH  xHS  2xS
xH3 O xOH cH3 O cOH
 
K H2 O 9 2nW
2
xH2 O cH2 O
2 22
nT
74 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183

(vi) Charge balance: as the sum of two terms, one related to long-range forces between
ions and the other to short-range forces between all species.
xR2 NH xRR0 R00 NH xH3 O xR2 NCOO xHCO3 2xCO3 The DebyeHuckel formula is used to represent the contribu-
2

xOH xHS 2xS 23 tion from long-range ionion interactions, which are most impor-
tant at low concentrations, while an extended UNIQUAC equation
(vii) Mole fraction balance: is used to account for short-range interactions of all kinds, which
are most important at higher concentrations. Hence the excess
xH2 O xR2 NH xRR0 R00 N xCO2 xH2 S xR2 NH xRR0 R00 NH
2 Gibbs energy can be written as:
xR2 NCOO xHCO3 xCO3 xH3 O xOH xHS xS 1   
g ex g ex ;dh g ex UNI
24 28
RT RT RT
Expressions for the activity coefcients are obtained by differ-
So far we have derived 15 equations for the liquid phase. These entiation of excess Gibbs functions with respect to component
equations are, 8 reaction equilibrium relations given by Eqs. (9) mole number at constant pressure and temperature, this leads to:
(16), and 7 conservation equations given by Eqs. (18)(24). In a
typical problem, the total molality of the amines, mDEA and ln cn ln cdh UNI
n ln cn for solvent component n 29a
mMDEA , and the CO2 and H2S loadings, aCO2 and aH2 S , are given.
We assume further that the activity coefcients are known func- ln cm ln cdh ;UNI
m ln cm for molecular solutes m 29b
tions of the mole fraction of the various species in the liquid phase.
Under these conditions, a glance at the liquid phase equations ln ci ln cdh
i ln c;UNI
i for ionic component i 29c
shows that these equations constitute a set of 15 non-linear equa-
tions in 15 unknowns. The unknowns are the mole fractions of the
various species in the liquid phase, ionic and molecular, and the ra- 2.3.1. Long range interaction contribution (DebyeHuckel expression)
tio (nw/nT), the initial moles of water before ionization to the total Since many DebyeHuckel type expressions have been pro-
number of moles. A NewtonRaphson method is used to solve the posed to represent the long-range contribution, the formula rst
15 non-linear liquid phase equations for the 15 unknowns. proposed by Fowler and Guggenheim [29] and then modied by
Macedo and co-workers [30] to account for multisolvent mixtures
will be used. The DebyeHuckel activity coefcient of solvent n and
2.2. Vapor phase equations molecular component m is given by:
 p  p
Once the liquid phase equations have been solved for the mole 2AMk qs 1
ln cdh
k 3
1 b Im  p  2 ln 1 b Im
fraction of each species in the liquid phase, the vapor phase com- b qk 1 b Im
position for molecular solutes CO2 and H2S can be obtained from k n; m 30
the vaporliquid equilibrium relation:
! where
P sw v 1i;w P  Psw
yi /i P xi i Hi;w
c exp 25 q1=2
s
RT A 1:327757  105 31
eT 3=2
For water, VLE may be expressed by:
  q1=2
v lw P  Psw b 6:359696
s
32
yH2 O /H2 O P xH2 O H2 O /sw Psw
c exp 26 eT 1=2
RT
Note that the subscripts H2O and w are used in Eq. (26) to N
1X ion

distinguish between the properties of water in a mixture and water Im mi z2i 33

2 i1
as a pure component, respectively. Expressions for the mole-frac-
tion based Henrys constants as a function of temperature for The DebyeHuckel activity coefcient of an ion i is given by:
CO2 and H2S are provided in [20]. Also expressions for the partial p
molar volume of CO2 and H2S are available in [26]. The vapor pres- ;dh Az2i Im
ln c i  p 34
sure of water as a function of temperature are given in [27]. 1 b Im
The vapor phase fugacity coefcients in Eqs. (25) and (26) are
Expressions for dielectric constants as a function of temperature
calculated using the SoaveRedlichKwong (SRK) equation of state
for H2O, DEA, and MDEA are provided in [31,32,7] respectively. The
[28]:
densities of pure solvent H2O, DEA, and MDEA expressed as a func-
    
bi PV PV b tion of temperature are given by [33].
ln /i  1  ln 1
b RT RT V
" #   2.3.2. Short range interaction contribution (extended UNIQUAC
aa bi 2 X b
 yj aaij ln 1 27 equation)
bRT b aa j V The short-range interaction contribution was accounted for
using the local composition concept. Among the various models
incorporating the local composition concept for short-range interac-
2.3. Activity coefcient model tions, the UNIQUAC equation described by Abrams and Prausnitz
[23] was adopted for the following reasons. The CO2H2Swater
By examining the liquid phase equations, expressions for the alkanolamine system is comprised of molecules and ions that differ
activity coefcients of the various species in the liquid phase are appreciably in both size and shape. The UNIQUAC model has the dis-
needed, the electrolyteUNIQUAC model will be used to calculate tinct advantage of giving consideration to molecular size and shape
these activity coefcients. The basic postulate of the electrolyte through structural parameters. Deviations from random mixing are
UNIQUAC model is that the excess Gibbs energy can be considered accounted for through application of the local-composition concept.
 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183 75

In addition, the resulting UNIQUAC equation is algebraically simple Observation of the activity coefcients equations indicate that
while applicable to systems composed of strong electrolytes, multi- these equations are functions of the mole fractions xi of the various
ple solvents, molecular solutes, and weak electrolytes. Cristensen species in the liquid phase. In addition, they also depend on the en-
and co-workers [34] followed by Sander and co-workers [24] were ergy interaction parameters ski , the volume parameters rk, and the
the rst to use a modied UNIQUAC model for electrolyte systems. surface area parameters qk. The volume and surface area parame-
They showed that the UNIQUAC equation is capable of correlating ters are pure component structural quantities that can be esti-
and predicting the salt effect on vaporliquid equilibria in mixed- mated from Van der Waals volumes and areas of the molecules
solvent solutions. Earlier extensions of UNIQUAC to handle electro- and ion present in solution [23]. For ions, r and q are not available;
lyte solutions are ion-specic and they satisfy the ion repulsion however, these may be approximated to the values of the closest
assumption, however, they do not satisfy the local electroneutrality molecules. The parameters for molecular component can be ob-
concept. In this work the adjustable parameters are setup to use the tained from Aspen Plus software [35]. Table 1 provides the param-
ionpair interaction approach and satisfy both the principle of like- eters used in this study.
ion repulsion and local electroneutrality.
In the UNIQUAC equation, the symmetric activity coefcient is 2.3.3. The Energy Interaction Parameters
calculated as a sum of a combinatorial term and a residual term gi- Calculations of the activity coefcients require determination of
ven as: the energy interaction parameters. This can be achieved by adjust-
ln cUNI ln cCk ln cRk 35 ing these parameters to give the best t of the experimental VLE
k
data. Usually solubility data of CO2 and H2S in DEA/MDEA aqueous
The two parts are given for solvent k by: solutions are reported in the literature as loadings (aCO2 , aH2 S )
 
Uk Uk z Uk Uk verses partial pressures (PCO2 , PH2 S ) at a given temperature and ini-
ln cCk ln 1  qk ln  1 36 tial molality of the amines. Therefore, in doing the regression, the
xk xk 2 Hk Hk
same vapor and liquid phases equations, as discussed earlier, are
ln cRk qk 1  ln Sk  Ak  37 used. However, instead of calculating the equilibrium partial pres-
sure as before, the partial pressures of the acid gases are known,
where and hence the only unknowns are the interaction parameters
X which can be determined by adjusting them to match the VLE data.
Sk Hi Wik 38
i
The interaction parameters are of different types: molecule
molecule, moleculeion, ionmolecule, and ionion. To satisfy
X Hi Wki the local composition theory in electrolyte system, the interactions
Ak 39 take place among molecules and ion pairs rather than molecules
i
Si
and ions [18,36]. Formation of ion pairs is based on two
q xk assumptions:
Hk Xk 40
q i xi
(1) Like ion repulsion assumption: due to large repulsive forces
i
between ions of the same charge, ion pairs or ion triplets
r xk cannot form among ions of the same charge.
Uk Xk : 41
(2) Local electroneutrality assumption: local electroneutrality
r i xi
i requires that the local net ionic charge be zero in solution.
This implies that cations and anions may form ion pairs or
 ski 
Wki exp  42 ion triplets in such a way that their net charge is zero.
T
where ski is an interaction parameter. Accordingly, the general formula for an ion pair is given by:
P
The i in the above relations means summation over all com-
za c; zc a 47
ponents in the liquid mixture.
The UNIQUAC unsymmetric activity coefcient of molecular where c and a stand for cations and anions, respectively, and zc and
solutes and ionic components is given by: za are the absolute charge on the cations and anions, respectively.
For the CO2H2SDEAMDEAH2O system, the ion pairs which
ln c;UNI
l ln cUNI
l  ln c1;UNI
l 43 are considered to form at signicant levels are: (DEAH+, DEACOO),
where

ln c1;UNI
l lim ln cUNI
l 44 Table 1
xw !i;xk !0 Volume and surface area parameters.
xi !0
Component r q
Here, the subscript w refers to water, the subscript l refers to molec- H2O 0.92 1.4
ular solutes and ionic components, and the subscript k refers to all DEA 2.5735 2.36
components except water. MDEA 4.2624 3.42
Hence the UNIQUAC unsymmetric activity coefcients of CO2 0.92 1.4
H2S 0.92 1.4
molecular solutes and ionic components:
DEAH+ 2.5735 2.36
MDEAH+ 4.2624 3.42
UlUl rl rl
ln c;C
l ln   ln DEACOO 3.4935 3.76
xl xl rw rw HCO3 0.92 1.4
 
z Ul Ul rl q rl q CO3 0.92 1.4
 ql ln   ln w  w 45 HS 0.92 1.4
2 Hl Hl rw ql rw ql S=
0.92 1.4
H3O+ 0.92 1.4
ln c;R
l ql  ln Sl  Al ln Wwl Wwl  46 OH 0.92 1.4
76 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183

 
(DEAH+, HCO +  + 
3 ), (DEAH , HS ), (MDEAH , DEACOO ), (MDEAH ,
+ xDEAH
 HDEAH ;HCO3 HHCO3
HCO3 ), and (MDEAH , HS ). Other ion pairs among the ions DEAH+,
+ 
xDEAH xMDEAH
MDEAH+, H3O+, OH, CO = " #
3 , and S can also formed. For example, xHCO3

(DEAH , OH ), (2DEAH , CO3 ), (2DEAH+, S=), (MDEAH+, OH),
+  +
HDEAH 53
xHCO3 xDEACOO xHS
(2MDEAH+, CO + = +  +
3 ), (2MDEAH , S ), (H3O , OH ), (2H3O , CO3 ),

+ =
(2H3O , S ). However, for the CO2H2SDEAMDEAH2O system,  
the concentration of H3O+, OH, CO = xDEAH
3 , and S ions are so small that HDEAH ;HS HHS
ion pairs associated with these species may be neglected [6]. Hence xDEAH xMDEAH
" #
our new system in terms of ion pairs consists of: xHS
HDEAH 54
xHCO3 xDEACOO xHS
Molecular components: H2O, DEA, MDEA, CO2, H2S
Ion pairs: (DEAH+, DEACOO), (DEAH+, HCO +
3 ), (DEAH , HS ),

 
(MDEAH+, DEACOO), (MDEAH+, HCO ), and (MDEAH +
, HS
) xMDEAH
3 HMDEAH ;DEACOO HDEACOO
Neglected ion pairs: (DEAH+, OH), (2 DEAH+, CO + = xDEAH xMDEAH
3 ), (2DEAH , S ), " #
+  + + = + 
(MDEAH , OH ), (2MDEAH , CO3 ), (2MDEAH , S ), (H3O , OH ), xDEACOO
(2H3O+, CO + = HMDEAH 55
3 ), (2H3O , S ).

xHCO3 xDEACOO xHS

In the new system interactions take place among ion pairs  

xMDEAH
rather than the ions, however, a glance at the liquid phase equa- HMDEAH ;HCO3 HHCO3
tions, particularly the reaction equilibrium relations given by Eqs.
xDEAH xMDEAH
" #
(9)(16), indicate that the activity coefcients of the single ions xHCO3
forming the ion pairs are needed. Thus, we will calculate the activ-
HMDEAH 56
xHCO3 xDEACOO xHS
ity coefcients of ion pairs themselves and then relate these coef-
cients to the activity coefcients of the corresponding ions.  
xMDEAH
According to the activity coefcients Eqs. (29) and (35), we see HMDEAH ;HS HHS
xDEAH xMDEAH
that these equations present explicit expressions for the activity " #
coefcients of the solvent n, the molecular solute m, and the ionic xHS
HMDEAH 57
species i. Each equation contains a DebyeHuckel term, a combina- xHCO3 xDEACOO xHS
torial term, and a residual term. A close examination of each term
shows that only the residual term contains the interaction param- The surface area fraction conservation Eq. (51) yields the fol-
eters ski . Hence, in calculating the activity coefcients of ion pairs, lowing equation for our ion pairs:
only the residual part needs to be addressed. The DebyeHuckel
and the combinatorial parts of these equations remain unaltered HDEAH ;DEACOO HDEAH ;HCO3 HDEAH ;HS HMDEAH ;DEACOO
and apply directly to the ions forming the ion pairs. HMDEAH ;HCO3 HMDEAH ;HS
Calculations of the residual activity coefcients require surface
area parameters of the ion pairs qZa c;Zc a , which is readily calculated HDEACOO HHCO3 HHS HDEAH HMDEAH 58
from the following simple relation:
The residual activity coefcients of ion pairs are readily calcu-
lated using Eq. (46) with the surface area parameter q and the sur-
qZa c;Zc a za qc zc qa 48
face area fraction h for the ion pairs known from Eqs. (49) and (50)
Applying this equation for example to the (DEAH ; DEACOO ) respectively.
ionpair we get: As discussed earlier the activity coefcients of the single ions
forming the ion pairs are needed in Eqs. (9)(16). The residual
qDEAH ;DEACOO qDEAH qDEACOO 49 activity coefcients of the ions, that forms the ion pairs, can be re-
lated to the corresponding residual activity coefcients of ion pairs
Also the local electroneutrality assumption maybe achieved by via the relation:
demanding that the surface area fraction of an ion pair to satisfy
the following equation h
Z a
Zc iZa Z
1
c
c;R
za ;c;zc ;a c;R
c c;R
a 59
z c xc z a xa
HZa c;Zc a Ha P Hc P 50 Or in logarithmic form
z x
c c0 c0
0 a0 za0 xa0

P P za zc
where c0 and a0 mean summation over all cations and anions, ln c;R
za ;c;zc ;a ln c;R
c ln c;R
a 60
za zc za zc
respectively. Notice that Eq. (50) conserves the surface area fraction
on all ion pairs relative to the individual ions, that is Eq. (59) is identical to the familiar relation relating the mean
activity coefcient of a strong electrolyte to the activity coefcients
XX X X of the corresponding ions [37]. Applying Eq. (60) to the CO2H2S
HZa C;Zc a Ha HC 51
a c a C DEAMDEAH2O system gives:

Applying Eq. (50) to the six ion pairs introduced earlier, we 1  ;R  1  
ln c;R
DEAH ;DEACOO
ln cDEAH ln c;R
DEACOO 61
obtain: 2 CRBM 2 DEA

  1  ;R  1  
xDEAH ln c;R ln cDEAH ln c;R 62
HDEAH ;DEACOO HDEACOO DEAH ;HCO 2 bicarbonate 2 HCO3 DEA
xDEAH xMDEAH 3

" #
xDEACOO 1  ;R  1  
HDEAH 52 ln c;R ln cDEAH ln c;R
HS 63
xHCO3 xDEACOO xHS DEAH ;HS 2 bisulfide 2 DEA
 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183 77

1  ;R  1  ;R 
Application of Eqs. (73)(75) to the ion pairs in our system give
ln c;R
MDEAH ;DEACOO
ln cMDEAH ln cDEACOO  64
2 CRBM 2 MDEA the relationships between residual activity coefcients of ion pairs
to the corresponding ions, for example, protonated DEA residual
1  ;R  1  
activity coefcient will be:
ln c;R
MDEAH ;HCO
ln cMDEAH ln c;R
HCO 65
3 2 bicarbonate 2 3 MDEA
D E HDEAH ;DEACOO
    ln c;R
DEAH

1 1 HDEAH
;DEACOO HDEAH ;HCO
 HDEAH ;HS
ln c;R
MDEAH ;HS
ln c;R
MDEAH
ln c;R
HS 66 3
2 bisulfide 2 MDEA
 ln c;R
DEAH ;DEACOO
Note that the residual activity coefcient of DEAH + ion associ-
HDEAH ;HCO3
ated with (DEAH+, DEACOO) ion pair is different from the residual
activity coefcient of DEAH + ion associated with(DEAH+, HCO HDEAH  HDEAH ;HCO3 HDEAH ;HS
3)
;DEACOO

ion pair which is also different from the residual activity coefcient  ln c ;R
DEAH ;HCO
of DEAH + ion associated with (DEAH+, HS) ion pair. The distinc- 3

tion is made clear by introducing the subscripts CRBM, bicar- HDEAH ;HS

bonate, and bisulde. The same remark can be drawn for the HDEAH
;DEACOO  HDEAH ;HCO3 HDEAH ;HS
residual activity coefcients of MDEAH+. Furthermore, the residual ;R
 ln c DEAH ;HS
76
activity coefcient of HCO + 
3 ion associated with (DEAH , HCO3 ) ion
pair is different from the residual activity coefcient of HCO 3 ion And the residual activity coefcient of HCO
3 is:
associated with(MDEAH+, HCO 3 ) ion pair. The distinction is made D E HDEAH ;HCO3
clear by introducing the subscripts DEA and MDEA. The same ln c;R ln c;R
HCO DEAH ;HCO
remark can be drawn for the residual activity coefcients of DEA- 3 HDEAH ;HCO3 HMDEAH ;HCO3 3

COO and HS. HMDEAH ;HCO3

With the residual activity coefcients of the ion pairs known, ln c;R
MDEAH ;HCO
77
HDEAH ;HCO3 HMDEAH ;HCO3 3
from equation (46) accompanied by Eqs. (49) and (50), Eqs. (61)
(66) contain 12 unknowns. To accomplish a solution to these equa- In a similar manner the rest of all ions/cations residual activity
tions, it is reasonable to assume for each equation (i.e. for each ion coefcient are obtained from their corresponding ion pairs.
pair) that c;R
c is equal to c;R
a [18,36], then Eqs. (61)(66) become: All of the above discussion is for the system: mixed acid gases-
    mixed amines, i.e. CO2H2SDEAMDEAH2O. However, for other
ln c;R
DEAH
ln c;R
DEACOO ln c;R
DEAH ;DEACOO
67 subsystem such as single acid gas or single amine, the vapor phase
CRBM DEA
equation and the liquid phase equation for the unconsidered com-
    ponent are omitted and the procedure remains the same.
ln c;R
DEAH ln c;R
HCO ln c;R
DEAH ;HCO
68
bicarbonate 3 DEA 3

    3. Results
ln c;R
DEAH
ln c;R
HS ln c;R
DEAH ;HS
69
bisulfide DEA
A large number of experimental VLE data have been collected
    and were used to obtain optimum interaction parameters for the
ln c;R
MDEAH
ln c;R
DEACOO ln c;R
MDEAH ;DEACOO
70 electrolyteUNIQUAC model which best represent the solubility
CRBM MDEA
of CO2 and H2S in aqueous solutions of DEA/MDEA. In this work
    a total of 2854 experimental data points were considered. Litera-
ln c;R
MDEAH
ln c;R
HCO ln c;R
MDEAH ;HCO
71
bicarbonate 3 MDEA 3 ture source of these data is provided in Table 2. A close examina-
tion of the experimental data available in the literature showed
   
ln c;R ln c;R ln c;R 72 some discrepancy between different investigators, especially at
MDEAH HS MDEAH ;HS
bisulfide MDEA low acid gas loadings where the measurement is very sensitive.
Or generally these equations can be written as: This discrepancy maybe also due to the different techniques used
to measure the VLE data. However, we decided to include all avail-
ln c;R ;R ;R
za ;c;zc ;a ln cc ln ca 73 able VLE data in this study.
Eq. (73) represents the relationship between the residual activ-
3.1. Parameters estimation results
ity coefcient of an ion pair and those of the individual ions. Since
an ion or a cation can associate with more than one ion pair, its
The electrolyteUNIQUAC interaction parameters skis can be
residual activity coefcient varies depending on the ion pair
determined by regression of experimental VLE data. Many of the
formed. However, a single value of residual activity coefcient of
investigators in the literature use the conventional least square
the ion/cation is needed. This can be obtained by averaging its val-
regression technique to regress the VLE experimental data to their
ues obtained from all ion pairs. The average will be performed
based on surface area fraction according to:
0 1 Table 2
  XB HZ c;Z a C
Literature source of experimental data.
ln cc;R
BX a c C ln c;R 74
@ H 0
A c a System Data Source
a Z a0 c;Z c a
a0 CO2DEAH2O [3946]
H2SDEAH2O [39,44,4650]
0 1 CO2MDEAH2O [7,42,43,5163]
  XB HZ c;Z a C
H2SMDEAH2O [52,55,57,61,62,64]
ln ca;R
BX a c C ln c;R 75 CO2H2SDEAH2O [46,65,66]
@ H 0 A a c
c Z a c ;Z c0 a CO2H2SMDEAH2O [67,68]
c0 CO2DEAMDEAH2O [16,17,43,69,70]
H2SDEAMDEAH2O [71]
where the angular bracket imply average.
78 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183

models. This technique assumes that only the measured response expected, the concentration of H3 O , OH , CO 3 , and S

ions are
variable contains error. However the weighted orthogonal distance found to be very small. Hence, ion pairs associated with these spe-
regression technique considers all measured variables (explana- cies were neglected. In addition, it is found that some other inter-
tory and response) to have some measurement errors. In our case actions are not important and can be set equal to zero without
the explanatory variables are loadings and temperature whereas affecting the results. Furthermore, the interaction parameter func-
the response variables are acid gas partial pressures. All these vari- tion s contains three terms. The regression results showed that one
ables are associated with experimental measurement error. Among or two of the three terms can be set to zero without affecting the
the available software for data regression, ODRPACK95 data maxi- results. The important electrolyteUNIQUAC interaction parame-
mum likehood regression system, Zwolak et al. [38], is used. This ters and the required terms in each function are shown in Table 3.
code is designed to solve weighted orthogonal distance regression
problems for multi dimensional data. In performing the regression, 3.2. Result analysis
all experimental data are equally weighted and the interaction
parameters are assumed to be temperature dependent and were Since weighted orthogonal distance regression technique is
tted to the following function: used in this work, the Root Mean Square Deviation (RMSD%) is
based on all measured variables:
b 100
s a cT 78 RMSD%
T n
v
!2  !2
u 2
The interaction parameters are obtained according to the fol- uX n
Pexp:  Pcal: aexp:  acal: T exp:  T cal:
 t i i
i i
i i
lowing manner: moleculemolecule binary parameters were rst Pexp: aexp: T exp:
i1 i i i
adjusted on experimental binary system data reported in the liter-
ature. Best values of moleculeion pair and ion pairmolecule 79
interaction parameters were then determined by xing the mole- Among all eight systems studied in this work, the maximum
culemolecule parameters at previously estimated values and t- RMSD% is found to be 9.21% in CO2H2SDEAH2O system. In addi-
ting moleculeion pair parameters on ternary systems data tion, the average value of RMSD% for all eight systems is found to be
reported in the literature. Similarly, ion pairion pair interaction 6.73%.
parameters were next determined by xing moleculemolecule ElectrolyteUNIQUAC model predictions of acid gas partial
and moleculeion pair parameters at previously estimated values pressures (P CO2 , PH2 S ) and loadings (aCO2 , aH2 S ) compared to their
and tting ion pairion pair parameters on quaternary system data corresponding experimental values are shown in Figs. 19 for all
and so on. eight systems considered in this work. With exception of few data
The number of interaction parameters is si,j is high. Some sim- points, these gures reveal that the electrolyteUNIQUAC thermo-
plications are clearly required in order to reduce the interaction dynamic model represent nearly all experimental data fairly well.
parameters to a reasonable number. Hence, sensitivity analysis In designing or simulating absorption processes using the rate-
has been conducted to see the effect and importance of each inter- based approach, detailed speciation of all species in the liquid phase,
action parameter on the solubility prediction of each system. As including ions are required in addition to their activity coefcients.

Table 3
Binary interaction parameters, sij aij bTij cij T.*
Binary component i,j ai,j bi,j ci,j aj,i bj,I cj,i
H2ODEA 80.69 245.33 48.96 406.14
H2OMDEA 714.14 2.93 2477.48 7.56
H2OCO2 10926.25 3274442.31 554.08 166018.51
H2OH2S 545.8 176181.73 172.3 88010.7
H2ODEAH+, HCO 3 33.43 19.98 17.74 399.53
DEADEAH+, HCO 3 62.76 0.0 19.67 0.0
+
DEADEAH , DEACOO 21.44 0.0 19.64 0.0
H2ODEAH+, DEACOO 214.91 20.01 18.8 20.14
H2ODEAH+, HS 0.0016 0.0 0.004 3109.59
DEADEAH+, HS 0.011 1994.34 0.0004 492.51
H2SDEAH+, HS 0.098 37068.28 0.045 115.59
H2OMDEAH+, HCO 3 928.126 1.723 366.16 0.366
MDEAMDEAH+, HCO 3 3762.27 11.96 0.96 150.65
+ 
CO2MDEAH , HCO3 138.49 1.29 953.72 3.77
MDEACO2 511.74 0.844 1047.2 2.7
H2OMDEAH+, HS 8621.66 28.19 656.59 0.956
MDEAMDEAH+, HS 764.024 0.0026 28.59 0.00094
H2SMDEAH+, HS 47.44 0.1 87.0 178.1
MDEAH2S 1133.325 0.00024 341.22 0.016
DEAH+, HSDEAH+, DEACOO 64.56 182.69 328.52 214.81
DEAH+, HSDEAH+, HCO 3 164.99 120.86 5.54 211.9
H2SMDEAH+, HCO 3 1402.5 4.33 1037.47 0.6
+  +
MDEAH , HCO3 MDEAH , HS 495.67 1.712 205.8 1.11
MDEADEA 169.26 52.44 361.8 1.33
DEAMDEAH+, HCO 3 121.45 0.36 476.86 0.0
DEAH+, HCO +
3 MDEAH , DEACOO

53.15 0.0 49.61 0.0
DEAH+, HCO 3 MDEAH +
, HCO 
3 211.05 1.36 671.21 9196.65
DEAMDEAH+, HS 18.36 74.87 3355.23 121.35
+ 
MDEADEAH , HS 4427.46 0.0 0.617 86.86
DEAH+, HSMDEAH+, HS 2842.84 0.0 28.3 13.82
*
T is the temperature in K.
 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183 79

100000 100000

Pi Cal. (i= CO2 or H2S) (mmHg)

8M 2M 0.5 M
System: CO2-H 2S-DEA-H2O

10000 10000
CO2
PCO2 (mmHg)

H2S
1000 System: CO2-DEA-H2O 1000
T = 323 K

100 M ason et al. [40] 100

Lee et a.l [41]
Barreau et a.l [39] 10
10
M odel
1
1
1 10 100 1000 10000 100000
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Loading (mole CO2/mole DEA) Pi Exp. (i=CO2 or H2S) (mmHg)

Fig. 1. Comparison of model predictions (line) with experimental data (symbols) Fig. 3. Comparison between the calculated and the experimental partial pressures
for CO2DEAH2O system at T = 323 K and at different DEA concentrations. of CO2 and H2S considering all experimental data used to model the system CO2
H2SDEAH2O.

100000.0
System: H2S-DEA-H2O 1.2
2M DEA System: CO2-H2S-DEA-H2O

(mole gas/mole DEA) Calc.

1
Leibash et al. [48]
1000.0 CO2
Lal et al. [44]
0.8 H2S

Loading
Lee et al. [49]
PH2S (mmHg)

Model 0.6
10.0
0.4

T = 298 K 0.2
T = 373 K T = 323 K
0.1
0
0 0.2 0.4 0.6 0.8 1 1.2

0.0 Loading (mole gas/mole DEA) Exp.

0.001 0.01 0.1 1 10
Fig. 4. Comparison between the calculated and the experimental loadings of CO2
Loading (mole H2S/mole DEA) and H2S considering all experimental data used to model the system CO2H2S
DEAH2O.
Fig. 2. Comparison of model predictions (line) with experimental data (symbols)
for H2SDEAH2O system at 2 M DEA and at different temperatures.

The developed electrolyteUNIQUAC model can be used to compute 100000

the liquid phase composition and activity coefcients, Figs. 10 and 10000
11 show the mole fraction variation of all species (ionic and molec-
1000
ular) as a function of loading for the system CO2DEAH2O at a tem-
P CO 2 (mmHg)

System: CO2-MDEA-H 2O
perature of 348 K and 2 M DEA. At low loadings less than about 0.5, 100 30 wt% MDEA
CO2 reacts with the amine to produce carbamate and protonated Jou et al [62]
10
amine. Little bicarbonate forms in this loading range from hydroly-
sis and dissociation of absorbed CO2. As the loading increases be- 1 T=353.15 K
T=393.15 K
yond 0.5 the carbamate concentration decreases and bicarbonate
0.1 T=313.15 K
begins to form mainly through reversion of carbamate to bicarbon-
T=298.15 K
ate and slightly due to hydrolysis and dissociation of absorbed CO2. 0.01
Model
The protonated amine continues to rise since it is also produced by 0.001
the carbamate reversion reaction. The maximum concentration of 0 0.2 0.4 0.6 0.8 1 1.2 1.4
carbamate occurs at CO2 loading of approximately 0.5 correspond-
Loading (mole CO2 / mole MDEA )
ing to nearly complete consumption of the amine. Little carbonate
forms throughout the whole loading range. Also we can see from
Fig. 5. Comparison of model predictions (line) with experimental data (symbols)
Fig. 11, the concentration of the proton and hydroxide ions are neg- for CO2MDEAH2O system at 30% weight MDEA and at different temperatures.
ligible for all loadings. This support our assumptions of neglecting
ionpairs associated with these ions. and bicarbonate. However, at high temperature, chemical equilib-
The appreciable concentration of molecular CO2 as a function of rium favors molecular CO2 rather than carbamate or bicarbonate.
loading varies with temperature. Fig. 12 shows the CO2 mole frac- To study the H2S behavior, electrolyteUNIQUAC model specia-
tion prole as a function of loading at different temperatures for tion plots for the system H2SDEAH2O at 298 K and 2 M DEA are
2 M DEA in the system CO2DEAH2O. The concentration of CO2 be- shown in Figs. 13 and 14. These Figures show that the only ionic
come appreciable at loadings of 0.8, 0.5, 0.4 and 0.3 corresponding species present in the solution at appreciable levels are the proton-
to temperatures of 298, 373, 393, and 413 K, respectively. The dif- ated amine and the bisulde. The concentrations of both ions are
ferent behavior of CO2 concentration curves is due to the phenom- approximately the same at all H2S loadings. On the other hand,
ena that permit aqueous alkanolamine solutions to be used in the concentration of H3 O , OH and S ions are negligible at all
absorption/stripping processes for gas treating. At low temperature, loadings. This again supports our assumption of neglecting ion
chemical equilibrium favors the conversion of CO2 to carbamate pairs associated with these ions.
80 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183

100000 9000
System: H2S-MDEA-H2O System: H2S-DEA-MDEA-H2O
8000
4.1 M MDEA 12.5 w t% DEA, 32.5 w t% MDEA
10000
Jou et al. [57] 7000 Libreros et al. [71]

6000 T=313 K

PH2S (mmHg)
1000
PH2S (mmHg)

T=343 K
5000
T=393 K
100 4000 Model
T=298 K
T=313 K 3000
10
T=343 K 2000
T=373 K
1 1000
Model
0
0.1
0 0.2 0.4 0.6 0.8 1 1.2 1.4
0 0.2 0.4 0.6 0.8 1 1.2
Loading (mole H2S/total mole amines)
Loading (mole H2S / mole MDEA)

Fig. 9. Comparison of model predictions (line) with experimental data (symbols)

Fig. 6. Comparison of model predictions (line) with experimental data (symbols) for H2SDEAMDEAH2O system at 12.5 wt.% DEA and 32.5 wt.% MDEA with
for H2SMDEAH2O system at 4.1 M MDEA and at different temperatures. different temperatures.

100000
System: CO2-H2S-MDEA-H2O 0.045
Pi Cal. (i = CO2 or H2S) (mmHg)

10000
System: CO 2 -DEA-H 2 O
0.04
CO2 2M DEA, T=348 K
1000 H2S 0.035

Mole Fraction 0.03 DEAH+ HCO3-

100
DEA
0.025
10
0.02
1
0.015
CO2
0.1 0.01 DEACOO-
0.1 1 10 100 1000 10000 100000
0.005
Pi Exp. (i = CO2 or H2S) (mmHg)
0
Fig. 7. Comparison between the calculated and the experimental partial pressures 0 0.2 0.4 0.6 0.8 1 1.2
of CO2 and H2S considering all experimental data used to model the system CO2
Loading (mole CO2 /mole DEA)
H2SMDEAH2O.

Fig. 10. Variation of the mole fraction of the species present in the solution vs.
loading for the CO2DEAH2O system at 2 M DEA and T = 348 K.

40000
System: CO2-DEA-MDEA-H 2O
35000 0.8 M DEA , 3.4 M MDEA 1.0E+00
Dawodu et. al. [43]
1.0E-01 System: CO 2 -DEA-H 2 O
30000 T= 433 K T= 413 K
T= 393 K T= 373 K T= 343 K CO2
1.0E-02 2M DEA, T=348 K
PCO2 (mmHg)

25000
1.0E-03
Mole Fraction

20000 1.0E-04
CO3=
1.0E-05
15000
1.0E-06
10000 OH -
1.0E-07
5000 1.0E-08
1.0E-09
0 H3O+
1.0E-10
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1.0E-11
Loading (mole CO2/total mole amines) 0.0 0.2 0.4 0.6 0.8 1.0 1.2

Fig. 8. Comparison of model predictions (line) with experimental data (symbols) Loading (mole CO2/mole DEA)
for CO2DEAMDEAH2O system at 0.8 M DEA and 3.4 M MDEA with different
temperatures. Fig. 11. Variation of the mole fraction of the species present in the solution vs.
loading for the CO2DEAH2O system at 2 M DEA and T = 348 K.

For amine blends, we can observe the competition of both

amines to react with CO2 from the electrolyteUNIQUAC speciation of CO2 with MDEA and also, but with less extent, due to the rever-
plot shown in Fig. 15 for the blend amine system CO2DEAMDEA sion reaction of carbamate to produce DEAH+ and bicarbonate. To
H2O which consist of 12.5 wt.% DEA and 32.5 wt.% MDEA at 313 K. further examine the competition of both amines to react with
At low loading the concentration of carbamate is more than the CO2, Fig. 16 compares the solubility of CO2 in a single 2 M DEA, sin-
concentration of bicarbonate, indicating that the fast reaction of gle 2 M MDEA, and (1:1) 2 M DEA/MDEA blend all at 313 K. At low
CO2 with DEA to produce carbamate is most signicant than the to moderate loadings up to 0.6 the solubility of CO2 is the highest
reaction of CO2 with MDEA which is relatively very slow. As the in DEA followed by DEA/MDEA blend and then MDEA. Above a
loading increases, most of DEA consumed and hence, the concen- loading about 0.6 the phenomena is reversed where the solubility
tration of bicarbonate becomes higher due mainly to the reaction of CO2 is the highest in MDEA followed by DEA/MDEA blend and
 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183 81

9.0E-03 900
298 K
8.0E-03 System: CO2-DEA-H2O 393 K T = 313 K 1
2 M DEA 800 2
CO2 Mole Fraction

413 K 373 K 1: Single 2 M DEA 3

7.0E-03
700 2: Blend 1 M DEA & 1 M MDEA
6.0E-03
3: Single 2 M MDEA

PCO2 (mmHg)
5.0E-03 600
4.0E-03 500
3.0E-03
400
2.0E-03
1.0E-03 300
0.0E+00 200
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 3
100
Loading (mole CO2/mole DEA) 2
1
0
Fig. 12. Effect of temperature on CO2 liquid concentration. 0 0.2 0.4 0.6 0.8 1
Loading (mole CO2/total mole amines)

0.040 Fig. 16. CO2 solubility in different amine blend at T = 313 K and a total amine
0.036 concentration of 2 M.
DEA + -
DEAH and HS
0.032
Mole Fraction

0.028
0.024 0.08
System: H2S-DEA-MDEA-H2O
0.020 0.07 HS-
H2S 12.5 wt% DEA, 32.5 wt% MDEA
0.016 0.06 T=313 K
MDEAH+

Mole Fraction
0.012
System: H2S-DEA-H2O 0.05
0.008
2M DEA, T=298 K 0.04
0.004 MDEA
0.000 0.03 H2S
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 DEAH+
0.02
Loading (mole H2S/mole DEA) 0.01
DEA
0
Fig. 13. Variation of the mole fraction of the species present in the solution vs. 0 0.2 0.4 0.6 0.8 1 1.2 1.4
loading for the H2SDEAH2O system at 2 M DEA and T = 298 K.
Loading (mole H2S/total mole amine)

Fig. 17. Variation of the mole fraction of the species present in the solution vs.
1.0E+01 loading for the H2SDEAMDEAH2O system at T = 313 K and a blend of 12.5 wt.%
DEA and 32.5 wt.% MDEA.
System: H2S-DEA-H2O
1.0E-01 2M DEA, T=298 K

1.0E-03
Mole Fraction

1.0E-05
1.0E-05 OH- System: H2S-DEA-MDEA-H 2O
12.5 wt% DEA, 32.5 wt% MDEA
1.0E-06 T=313 K
1.0E-07
S= OH-
Mole Fraction

1.0E-07
1.0E-09
H3O+ S=
1.0E-11 1.0E-08

1.0E-13 1.0E-09
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
1.0E-10 H3O+
Loading (mole H 2S/mole DEA)
1.0E-11
Fig. 14. Variation of the mole fraction of the species present in the solution vs. 0 0.2 0.4 0.6 0.8 1 1.2 1.4
loading for the H2SDEAH2O system at 2 M DEA and T = 298 K.
Loading (mole H2S/total mole amine)

Fig. 18. Variation of the mole fraction of the species present in the solution vs.
loading for the H2SDEAMDEAH2O system at T = 313 K and a blend of 12.5 wt.%
0.09 DEA and 32.5 wt.% MDEA.
System: CO 2 -DEA-MDEA-H 2 O
HCO3-
0.08 T=313 o K
0.07
Mole Fraction

12.5 wt% DEA , 32.5 wt% MDEA

MDEAH+
0.06
0.05 MDEA lowest in DEA. This happens because as the loading increase most
0.04 of DEA is consumed and the carbamate reversion reaction take
0.03 place to produce DEAH+ and bicarbonate, and since MDEA does
DEAH+
0.02 not form carbamate, it continues to absorb CO2 in a higher rate.
DEACOO- CO2
0.01 Speciation plots for the system CO2DEAMDEAH2O have
DEA
0.00 been analyzed in the literature using different thermodynamic
0.0 0.2 0.4 0.6 0.8 1.0 1.2
models. Among them are the plots of Austgen and co-workers [7]
Loading (moleCO2/total mole amines) using the electrolyteNRTL, the plots of Benamor and co-workers
[16] using the DeshmukhMather model, and the plots of Kundu
Fig. 15. Variation of the mole fraction of the species present in the solution vs.
loading for the CO2DEAMDEAH2O system at T = 313 K and a blend of 12.5 wt.% and co-workers [17] using the modied CleggPitzer model.
DEA and 32.5 wt.% MDEA. Although different amine concentrations and temperatures were
82 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183

3.5 3.8
3.4

Activity Coefficient
DEA DEA
3.0
Activity Coefficient

3
2.5 System: CO 2 -DEA-MDEA-H 2 O
MDEA 2.6 System: H2S-DEA-MDEA-H2O
T = 343 o K
12.5 wt% DEA, 32.5 wt% MDEA
2.0 0.8 M DEA , 3.4 M MDEA 2.2 T= 313 K
1.8
1.5 CO2
H2O 1.4 H2O
1.0 1
0.6
0.5
HCO3- 0 0.2 0.4 0.6 0.8 1 1.2 1.4
0.0
Loading (mole H 2S/total mole amines)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Loading (mole CO2/total moles amines) Fig. 22. Variation of the Activity coefcients of the species present in the solution
vs. loading for the H2SDEAMDEAH2O system at T = 313 K and a blend of
Fig. 19. Variation of the Activity coefcients of the species present in the solution 12.5 wt.% DEA and 32.5 wt.% MDEA.
vs. loading for the CO2DEAMDEAH2O system at T = 343 K and a blend of 0.8 M
DEA and 3.4 M MDEA.
and a blend of 0.8 M DEA and 3.4 M MDEA are shown in Figs. 19
and 20. Similar plots for H2SDEAMDEAH2O consists of
0.7 12.5 wt.% DEA and 32.5 wt.% MDEA at T = 313 K are shown in
System: CO 2 -DEA-MDEA-H 2 O
Figs. 21 and 22. Clearly, the strong variation of activity coefcients
0.6 T = 343 o K
with respect to loading and their deviation from ideality indicates
Activity Coefficient

0.8 M DEA , 3.4 M MDEA

0.5 H3O+ and OH- how important to get accurate model when dealing with such
0.4 systems.

0.3 DEAH+ DEACOO-

4. Conclusion
0.2
MDEAH+
0.1 An electrolyteUNIQUAC model is developed to represent the
CO3=
0.0 solubility of CO2 and H2S in single and blend of aqueous solutions
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 of DEA and MDEA. The model accounts for physical equilibrium be-
tween the vapor and the liquid phases using the SRK equation of
Loading (mole CO2/total moles amines)
state. The chemical equilibrium in the liquid phase between
Fig. 20. Variation of the Activity coefcients of the species present in the solution molecular as well as ionic species is accounted by two terms. A De-
vs. loading for the CO2DEAMDEAH2O system at T = 343 K and a blend of 0.8 M byeHuckel term is used to account for long range ionion interac-
DEA and 3.4 M MDEA. tions while an extended UNIQUAC term to handle electrolyte
solution is used to account for short range interactions of all kinds.
The system CO2H2SDEAMDEAH2O comprised of molecule and
0.8 ions which differ appreciably in both size and shape. Unlike other
0.7 local composition models, such as NRTL, the UNIQUAC model has
HS -
Activity Coefficient

0.6 the distinct advantage of giving consideration to molecular size

+
H3O and OH -
and shape through structural parameters. Earlier extensions of
0.5
System: H 2S-DEA-MDEA-H2O UNIQUAC to handle electrolyte solutions are ion-specic and they
0.4 12.5 wt% DEA, 32.5 wt% MDEA DEAH +
T= 313 K
satisfy the ion repulsion assumption, however, they do not satisfy
0.3 MDEA the local electroneutrality concept. Our extension of UNIQUAC is
0.2 MDEAH + setup to use the ionpair interaction approach, rather than ion-
H2S
0.1 = specic approach, and hence, satisfy both the principle of like-ion
S
0
repulsion and local electroneutrality concepts. This was achieved
0 0.2 0.4 0.6 0.8 1 1.2 1.4
by formulating the appropriate ionpairs with surface area frac-
tions properly distributed relative to those of the individual ions.
Loading (mole H 2S/total mole amines)
This in turn makes the model thermodynamically consistent. Large
Fig. 21. Variation of the Activity coefcients of the species present in the solution and wide ranges of experimental VLE data were used to obtain the
vs. loading for the H2S DEAMDEAH2O system at T = 313 K and a blend of electrolyteUNIQUAC interaction parameters using orthogonal dis-
12.5 wt.% DEA and 32.5 wt.% MDEA. tance regression technique. The results of all eight systems consid-
ered in this project show an improved representation of the
used by the different authors, the speciation trends obtained by the solubility of CO2 and H2S in single and blend of aqueous solutions
electrolyteUNIQUAC are in excellent agreement with the litera- of DEA and MDEA. The analysis of the results shows the capability
ture ones. of the electrolyteUNIQUAC model to represent the concentrations
Very limited experimental VLE data are available in the open lit- and activity coefcients of all species, molecular and ionic, pre-
erature for the solubility of H2S in DEA/MDEA blend amine system. sented in the highly non-ideal system composed of CO2H2S
Figs. 17 and 18 show the electrolyteUNIQUAC speciation plots for DEAMDEAH2O.
the system H2SDEAMDEAH2O consists of 12.5 wt.% DEA and There are no experimental VLE data in the open literature for
32.5 wt.% MDEA at T = 313 K. mixed acid gases and mixed amine solutions i.e. CO2H2SDEA
As mentioned earlier, activity coefcient representations are MDEAH2O system. As a result, some interaction parameters pre-
needed for rate-based model used to design or simulate absorp- sented in this system could not be determined for our model or
tion/stripping processes. The electrolyteUNIQUAC activity coef- any other models. So research is needed to measure the solubility
cient plots for all species presented in the blend amine system of mixed acid gases in mixed amine solutions. Meanwhile, the
CO2DEAMDEAH2O as a function of CO2 loading at T = 343 K undetermined values of the interaction parameters presented in
 O.A. Al-Rashed, S.H. Ali / Separation and Purication Technology 94 (2012) 7183
mixed gases and mixed amine system could be approximated with
the ones which have similar molecular structure and are previ-
ously estimated in lower systems.
Acknowledgment
This work was supported by Kuwait University, Research Grant
No. EC 03/07. The authors are also grateful to PRP research center
[GE03/08] at the faculty of Engineering and Petroleum in Kuwait
University for computational facilities.
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