Fluid Phase Equilibria 437 (2017) 118e126

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Experimental measurement and Kent-Eisenberg modelling of CO2

solubility in aqueous mixture of 2-amino-2-methyl-1-propanol and
hexamethylenediamine
Bikash K. Mondal a, Syamalendu S. Bandyopadhyay b, Amar N. Samanta a, *
a
Chemical Engineering Department, Indian Institute of Technology Kharagpur, Kharagpur 721302, India
b
Cryogenic Engineering Centre, Indian Institute of Technology Kharagpur, Kharagpur 721302, India

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

Article history: In this work, vapour-liquid equilibrium of CO2 in aqueous mixture of 2-amino-2-methyl-1-propanol
Received 9 September 2016 (AMP) and hexamethylenediamine (HMDA) is studied in the temperature and pressure range of
Received in revised form 303.15e333.15 K and 1e100 kPa respectively. Concentration of the aqueous solutions used are (5mass%
5 January 2017
HMDAþ25mass% AMP), (10 mass% HMDAþ20 mass% AMP), (15mass% HMDA þ15mass% AMP) and (20
Accepted 20 January 2017
Available online 22 January 2017
mass% HMDAþ10 mass% AMP). Density of aqueous amine solution is also measured in the same range of
temperature and concentration. Redlich-Kister equation for excess molar volume is used to model
density of the mixed solvent system. To correlate experimental CO2 solubility data, Kent and Eisenberg
Keywords:
CO2 capture
thermodynamic model is used. Equilibrium constants of bicarbamate formation reaction of HMDA and
AMP deprotonation reaction of AMP are regressed to fit experimental data with the model expression. Kent
HMDA and Eisenberg model is found to predict the CO2 solubility in aqueous (HMDA þ AMP) with good ac-
VLE curacy (AAD: 7.2%).
Kent-Eisenberg model © 2017 Elsevier B.V. All rights reserved.
Density

1. Introduction
Fossil fuel based power plants are the most CO2-intensive point
sources which contributes almost one third of the global CO2
emission. So, capturing CO2 from the power plant flue gas has major
impact on controlling CO2 emission which is the main cause of
global warming. Flue gas is usually at atmospheric pressure with
CO2 partial pressure of 3e15 kPa. Under this low CO2 partial pres-
sure condition conventional aqueous amines like Monoethanol-
amine (MEA), Diethhanolamine (DEA) are most suitable absorption
solvent [1]. However, these conventional solvents have many dis-
advantages like high degradation rate, low absorption capacity,
high regeneration energy requirement. Researchers recommend 2-
amino-2-methyl-1-propanol (AMP) based solvents to overcome the
disadvantages caused by the conventional amines because AMP
being a sterically hindered amine (SHA), forms unstable carbamate
upon reaction with CO2. For this reason AMP has high absorption
capacity [2e7] and requires less energy to regenerate the CO2
loaded solution (75 kJ/mol CO2 at 323.15 K) [8]. At 313.15 K
* Corresponding author.
E-mail address: amar@che.iitkgp.ernet.in (A.N. Samanta).
temperature and 15 kPa CO2 partial pressure 30mass% AMP shows
CO2 loading capacity [9] of 0.66 mol CO2 per mole of AMP (15%
higher than MEA). Thermal degradation temperature of AMP is also
very high (413.15 K) [10]. But CO2 absorption rate of AMP is
comparatively low (k2,AMP ¼ 740 m3kmol1s1 at 303.15 K) [11]. So,
to overcome this problem AMP is mixed with MEA [9], DEA [12e14]
and both MDEA and DEA [15]. Diamines like piperazine (PZ) [16,17]
also enhance the solvent characteristics of AMP [6,18e21] because
of their high absorption capacity as well as high reaction rate with
CO2. This is further confirmed by the solubility study of CO2 in
aqueous (AEEA þ AMP) by Guo et al. [22]. Recently, researchers
including our group recommend use of aqueous HMDA for CO2
capture because of high CO2 loading capacity [23,24] and absorp-
tion rate [25]. HMDA shows CO2 loading of 1.23 (30 mass% aqueous
HMDA) [24] at 15 kPa CO2 partial pressure and 303.15 K tempera-
ture. Second order rate constant for HMDA-CO2 reaction is 42000
m3kmol1s1 (at 303.15 K) [25].
In this work, we have investigated vapour-liquid equilibrium of
CO2 in aqueous blend of AMP and HMDA to establish this solvent
blend as a better alternative for CO2 capture and predict vapour
liquid equilibria of CO2 in aqueous amine solution using Kent and
Eisenberg model [26]. There are other models like Deshmukh-

http://dx.doi.org/10.1016/j.fluid.2017.01.020
0378-3812/© 2017 Elsevier B.V. All rights reserved.
 B.K. Mondal et al. / Fluid Phase Equilibria 437 (2017) 118e126
Mather model, Pitzer model, Electrolyte Non-Random Two Liquid
model which are also used to correlate VLE data. Although these
models give more accurate prediction than the Kent-Eisenberg's
model but they require rigorous computation, whereas Kent and
Eisenberg model is simple and yet provide a good fit between
experimental and predicted values for CO2 loading in a wide range
of conditions for single and mixed AMP based solvent [3,9,21].
2. Experimental
2.1. Materials
Reagent grade HMDA with minimum mass fraction purity of
0.99 is purchased from Sigma Aldrich India. Reagent grade AMP
with minimum mass fraction purity of 0.95 is supplied by E. Merck,
Germany. All these chemicals are used without further purification.
CO2 and N2 (minimum mole fraction purity ¼ 0.999) are procured
from Linde India Limited. Specifications of all the chemicals used in
this work are given in Table 1. For preparation of aqueous solution,
degassed double distilled water is used. A precision balance (CITI-
ZEN, CX-301 model) with an accuracy of ±0.001 g is used to mea-
sure required amount of chemicals for the preparation of aqueous
amine solution.
2.2. Density measurement
Density of aqueous amine solution is required for the conversion
of mass fraction concentration to the molar concentration. Density
is measured using 25  106 m3 (at 298.15 K) Gay-Lussac pyc-
nometer. Pycnometer filled with amine solution is immersed in a
constant temperature water bath to heat the solution at desired
temperature level. Temperature of the bath is controlled to within
±0.1 K using a refrigerated-heating circulator (Model: Julabo F32
HL). Once the solution reaches desired temperature, pycnometer is
weighted using a precision balance (CITIZEN, CX-301 model, ac-
curacy: ±0.001 g). Density of the amine solution is estimated
dividing the mass of the amine solution by standard volume of the
pycnometer (standardised previously by degassed double distilled
water at 298.15 K). Each reported density data is average of at least
three measurements. Uncertainty in the measurement of density is
±0.1%.
2.3. Carbon dioxide solubility measurement
Equilibrium solubility measurement set up (Fig. 1) and proced-
ure is same as employed in our previous works [24,27]. It is briefly
discussed here.
Solubility of CO2 in the aqueous mixed amine solvent is
measured using a high pressure stainless steel stirred equilibrium
cell (405  106 m3) which is connected to a stainless steel gas
buffer vessel (751  106 m3) through a needle valve. Both equi-
librium cell and buffer vessel are equipped with pressure trans-
mitter (Model: Rosemount 3051 TA, Accuracy: ±0.04% of the
transmitter range) and temperature sensor (Pt 100, Accuracy:
±0.1 K). The reactor is provided with the solvent inlet, gas (N2 and
CO2) inlet and purging line. The entire assembly is immersed into a
Table 1
Specifications and source of chemicals used in the experimental work.
Chemical Alias Molar mass (g/mol)
1,6-diaminohexane HMDA 116.20
2-amino-2-methyl-1-propanol AMP 89.14
Carbon Dioxide CO2 44.01
Nitrogen N2 28.01
119
water bath whose temperature is controlled by a refrigerated-
heating circulator (Model: Julabo F32 ME). A magnetic stirrer is
used to stir the liquid phase in the equilibrium cell. The buffer
vessel is used as temporary storage to supply CO2 gas at desired
temperature. A vacuum pump (INDVAC Model IV 50, India) is used
to evacuate the equilibrium cell and buffer vessel. The entire as-
sembly is tested to be leak proof.
Before starting the experimental run, equilibrium cell, buffer
vessel and all the lines are purged with N2 and then evacuated. The
buffer vessel is filled with pure CO2. The water bath is heated to
desired temperature level by setting the circulator temperature
controller. A measured amount (25  106 m3) of aqueous amine
solution heated to the desired temperature is fed to the equilibrium
cell and evacuated again so that the solution exists under its own
vapour pressure (Pv). The system is allowed to reach thermal
equilibrium. Once the temperature of the system becomes uniform
throughout, pressure data of the cell (Pv) and buffer vessel (Pb1) are
noted. Then a batch of CO2 gas from the buffer vessel is fed to the
cell by operating the needle valve. Stirrer inside the cell is switched
on. The pressure of the cell falls gradually because of the chemical
absorption of the gas. The system is allowed to reach the equilib-
rium condition. Equilibrium condition is confirmed when there is
no change in pressure in the cell for at least one hour. At this
condition pressure of the cell (Pt) and buffer vessel (Pb2) are noted.
The entire process is repeated to get equilibrium points at higher
pressure.
Partial pressure of CO2 (PCO2 ) is obtained by subtracting solution
vapour pressure (Pv) from the total pressure inside the cell at
equilibrium condition. VLE data in this work is expressed in terms
of CO2 loading (mole CO2 absorbed per mole of total amine) which
is calculated using the following expression [28].


mole CO2 absorbed in liquid phase nlCO2
aCO2 ¼
mole amine initially taken ðnam Þ
   g 
1 Vb Pb1 Pb2 V PCO2
¼   c (1)
nam RT Z1 Z2 RT ZCO2
where, Vb is the volume of buffer vessel. Pb1 and Pb2 are initial and
final buffer pressure. Z1 and Z2 are compressibility factors esti-
mated using Peng-Robinson equation of state at temperature T and
g
pressures Pb1 and Pb2 , respectively. Vc is the gas phase volume of
the cell. PCO2 and ZCO2 are partial pressure of CO2 and corresponding
compressibility factor at temperature T, respectively. nam is mole of
total amine initially introduced into the cell.
The standard uncertainty in the measurement of CO2 loading is
estimated using the law of propagation of uncertainty [29]. It is
based on the first-order Taylor series approximation. If u (xi ) is
standard absolute uncertainty associated with the input estimate xi
(i ¼ 1, 2, …), then propagated standard uncertainty in the output
estimate ‘y’ is given by the following expression.
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u N  2
uX vf
u ðyÞ ¼ ±t uðxi Þ (2)
vxi
i¼1
with,
Purity Source
>99 mass% Sigma Aldrich India
>95 mass% E. Merck, Germany
>99.9 mol% Linde India Limited
>99.9 mol% Linde India Limited
120 B.K. Mondal et al. / Fluid Phase Equilibria 437 (2017) 118e126

Fig. 1. Schematic of VLE measurement set-up: 1- VLE Cell; 2- Buffer vessel for CO2 storage; 3- Temperature sensors; 4- Liquid phase stirrer (Magnetic bar); 5- Magnetic stirrer speed
controller; 6- Pressure transducers; 7- Circulator temperature controller; 8- CO2 storage cylinder; 9- Liquid solution inlet; 10-External temperature sensor of circulator temperature
controller; 11- Thermo-stated water bath.

For ternary mixed solvent system excess molar volume is given

y ¼ fðxi Þ ; i ¼ 1; 2; …; N by the following equation.
In this work, measurement error of pressure (Pb1 ; Pb2 ; Pt ),
g
temperature (T), reactor volume (Vb ; Vc ) and solution concen- V E ¼ V12
E E
þ V13 E
þ V23 (6)
tration (nam ) are assumed to contribute in the uncertainty of CO2 Here, Ai are binary interaction parameter and are assumed to be
loading estimation. Uncertainties associated with these input es- temperature dependent. Temperature dependent expression for
timates are as follows: u(P) ¼ ±0.27 kPa, u(T) ¼ ±0.1 K, the interaction parameter used in this work is given below.
u(V) ¼ ±106 m3, u(nam) ¼ ±1.6%.
Ai ¼ ai=T (7)
3. Density model

Density of aqueous mixed solvent is correlated using Redlich-

Kister equation for the excess molar volume [30,31]. Excess molar
volume (V E ) of the liquid mixture can be calculated using the 4. Vapour-liquid equilibrium model
following expression.
X Absorption of CO2 in aqueous (HMDA þ AMP) involves both
V E ¼ Vm  xi Vio (3) phase and chemical equilibrium. Phase equilibrium is represented
i
by Henry Law Constant (HCO2) and chemical equilibrium is repre-
sented by equilibrium constants. Phase and chemical equilibrium
where, Vm and Vi0 are molar volume of mixed solvent and pure
reactions for (HMDA þ AMP þ H2O þ CO2) system can be repre-
solvent respectively. xi is mole fraction of ith component in the
sented as follows.
mixed solvent. Molar volume of the mixed solvent can be calculated
using the following expression.
 Physical solubility
P
xi Mi
i Hco2
Vm ¼ (4) CO2 ðgÞ CO2 ðaqÞ

! (8a)
rm
 Dissociation of bicarbonate ion
where xi and Mi are mole fraction and molecular mass of pure
component ‘i’ and rm is the measured density of mixed solvent. K1
HCO
3

! CO2
3 þH
þ
(8b)
Excess molar volume of a binary mixed solvent can be expressed
using Redlich-Kister expression as follows.  Formation of bicarbonate ion

. X
n
K2
E
V12 m3 :kmol1 ¼ x1 x2 Ai ðx1  x2 Þi (5) CO2 þ H2 O

! HCO
3 þH
þ
(8c)
i¼0
 Ionization of water
 B.K. Mondal et al. / Fluid Phase Equilibria 437 (2017) 118e126 121

K3
h i

H2 O ! OH þ H þ (8d) ½AMPt ¼ AMPHþ þ ½AMP (18)
 Deprotonation of HMDA  CO2 balance
K4  h i h i
HMDAHþ

! HMDA þ Hþ (8e) aCO2  ½HMDAt þ ½AMPt ¼ ½CO2  þ HCO 2
3 þ CO3
 Formation of monocarbamate h i
þ HMDACOO
K5 h
 i
HMDA þ CO2

! HMDACOO þ H þ (8f) þ 2 HMDA COO (19)
2
 Formation of bicarbamate
 Charge balance


HMDACOO þ CO2

!
K6
HMDA COO þ Hþ (8g) h i h i h i h i h i h i
2 H þ þ HMDAHþ þ AMPHþ ¼ HCO 2
3 þ 2 CO3 þ OH
h i
 Deprotonation of AMP
þ HMDACOO
K7
h
 i
AMPHþ

! AMP þ Hþ (8h) þ 2 HMDA COO
2
Kent and Eisenberg model assumes that all activity coefficients (20)
and fugacity coefficients to be unity (i.e. ideal solutions and ideal
gases). Equilibrium CO2 partial pressure (PCO2 ) is related to the Where, aCO2 is CO2 loading, ½HMDAt and ½AMPt are initial molar
physically dissolve CO2 concentration (½CO2 ) in the liquid phase by concentrations of HMDA and AMP respectively.
Henry law expression. In this work, equilibrium constants K1eK5 are taken from the
literature. Temperature dependency of these equilibrium constants
PCO2 ¼ HCO2 ½CO2  (9) is expressed as shown below.

Apparent equilibrium constant based on the chemical species

lnKi ¼ ai þ bi =T þ ci lnT (21)
concentration for the above equilibrium reactions are presented as
follows Where, ai, bi and ci are coefficients of the expression which are
h i
 given in Table 2. Deprotonation constant of HMDA (K4) is derived
CO2
3 Hþ from the pKa (¼ -log Ka) values taken from the literature [32]. This
K1 ¼ h i (10) equilibrium constant (K4) is regressed in temperature dependent
HCO3 form as shown in equation (21) and coefficients of the expressions
are shown in Table 2. The expression for the Henry constants (HCO2 )
h i
 is taken from the work of Hsu [33] as given below.
HCO
3 H
þ
K2 ¼ (11)
. 
½CO2  1:38306  104
lnHCO2 kPa:m3 kmol ¼ 20:2669 
ðT=KÞ
h ih i
K3 ¼ Hþ OH (12) 0:06913  108 0:015589  1011
þ 2

ðT=KÞ ðT=KÞ3


½HMDA Hþ 0:012  1013

K4 ¼
 (13) þ
HMDAHþ ðT=KÞ4
(22)



HMDACOO Hþ Kent and Eisenberg, in their original work, regressed some of the
K5 ¼ (14)
½HMDA½CO2  equilibrium constants as function of temperature involving main
amine reactions. Apparent equilibrium constants are expressed in

 
 different forms by different authors. In some work equilibrium
HMDA COO 2 Hþ
K6 ¼
  (15) constants are considered to be function of temperature, CO2 partial
HMDA COO ½CO2 
pressure and amine concentration [21,34,35]. In another modified

 version of the model equilibrium constants are regressed as func-
½AMP H þ tion of temperature, CO2 loading and amine concentration [36e38].
K7 ¼
 (16) In this work, equilibrium constants are regressed in term of tem-
AMPHþ
perature and CO2 loading.
Overall mass balances and charge balance equations can be
written as follows.
Table 2
Coefficients of the reaction equilibrium constants used in this work.
 HMDA balance
Ki kmol/m3 basis ai bi ci Temp range  C Ref.
h i h i
½HMDAt ¼ ½HMDA þ HMDAHþ þ HMDACOO K1 220.067 12431.7 35.4819 0e225 [39]
h
 i K2 235.485 12092.1 36.7816 0e225 [39]
þ HMDA COO (17) K3 140.932 13445.9 22.4773 0e225 [39]
2 K4 1.6664 7001.6 0 0e60 [32]
K5 7.16 4746.82 0 30e60 [24]
 AMP balance
122 B.K. Mondal et al. / Fluid Phase Equilibria 437 (2017) 118e126

Table 3 Table 4
Density of aqueous (AMP þ HMDA) and Pure HMDA at 101.3 kPa total pressure [X, T Binary parameters of the Redlich-Kister model for density deviation.
and r are the mass fraction composition of the solvent, temperature and density
respectively]a Parameter Binary Pair

H2O-AMP H2O-HMDA AMP-HMDA

X T/K r/kg.m3
A0 a0 394.525 796.675 425.213
HMDA AMP
A1 a1 940.568 917.434 36.4085
1.00 0.00 313.15 856.2 A2 a2 1299.18 1006.38 1.416343
1.00 0.00 318.15 850.0
1.00 0.00 323.15 845.3
1.00 0.00 328.15 842.3
1.00 0.00 333.15 838.1
density decreases with the increase in HMDA concentration in the
0.05 0.25 303.15 991.9 mixture keeping total amine concentration constant (30 mass %). To
0.05 0.25 313.15 984.9
correlate experimental mixed solvent density data, Redlich-Kister
0.05 0.25 323.15 978.7
0.05 0.25 333.15 972.0 excess molar volume model is used. For estimation of excess
molar volume of the mixed solvent, pure component molar volume
0.10 0.20 303.15 987.5 data is required. Molar volume of pure water and AMP are taken
0.10 0.20 313.15 981.5 from the work of Hsu and Li [30]. Since, HMDA melts at 313.15 K,
0.10 0.20 323.15 975.2
density of pure HMDA is measured in the temperature range of
0.10 0.20 333.15 968.3
313.15e333.15 K. Pure component density data of HMDA is pre-
0.15 0.15 303.15 984.0 sented in Table 3. Binary parameters of Redlich-Kister equation are
0.15 0.15 313.15 977.2 regressed to fit experimental molar volume data to that of model
0.15 0.15 323.15 970.8 expression using least square method. Regressed binary parame-
0.15 0.15 333.15 963.9 ters are presented in Table 4. Using these parameters, average ab-
solute deviation between experimental and model predicted data is
0.20 0.10 303.15 980.3
0.20 0.10 313.15 973.2
found to be 0.05%.
0.20 0.10 323.15 966.7 Vapour-liquid equilibrium of CO2 in aqueous (HMDA þ AMP) is
0.20 0.10 333.15 960.0 studied in a stirred equilibrium cell at temperatures 303.15, 313.15,
a
Standard uncertainties associated with the measured and estimated quantities: 323.15 and 333.15 K. Validation of the experimental set up is shown
u(X) ¼ ±0.00015; u(T) ¼ ±0.1 K; ur (r) ¼ ±0.1%. in our previous work [24]. To evaluate the performance of the
mixed solvent system, equilibrium CO2 solubility is measured
varying different experimental conditions (temperature, pressure,
solvent composition). Equilibrium solubility data is measured in
5. Results and discussion the CO2 partial pressure range of 1e100 kPa. Aqueous solution
concentrations of the mixed solvent used are (5mass%
Density of aqueous mixed amine solvent is required for con- HMDAþ25mass% AMP), (10 mass% HMDAþ20 mass% AMP),
version between concentration units. In this work density of (15mass% HMDAþ15mass% AMP) and (20 mass% HMDAþ10 mass%
aqueous (5mass% HMDAþ25mass% AMP), (10 mass% HMDAþ20 AMP). Measured solubility data expressed in mole CO2 per mole of
mass% AMP), (15mass% HMDAþ15mass% AMP) and (20 mass% total amine (CO2 loading) are presented in Tables 5e8 and
HMDAþ10 mass% AMP) solvent is measured in the temperature Figs. 3e6. Standard uncertainty in the estimation of CO2 loading
range of 303.15e333.15 K. Density data is given in Table 3 and data is evaluated considering all the measurement errors. Esti-
shown in Fig. 2. It is seen from the figure that density of aqueous mated maximum uncertainty in CO2 loading is found to be ±1.5%
amine solvent decreases linearly with temperature. Also, solvent considering all the data sets. Maximum standard uncertainty
associated with each data set is given in Tables 5e8 Our experi-
mental data shows that loading increases sharply in the low CO2
partial pressure range (up to 20 kPa) due to chemical absorption.
1000
5% HMDA+25% AMP-Mod
10% HMDA+20% AMP-Mod
15% HMDA+15% AMP-Mod
990 20% HMDA+10% AMP-Mod Table 5
5% HMDA+25% AMP-Exp Vapour-liquid equilibrium of CO2 in aqueous (5 %HMDAþ25%AMP) [T, PCO2 and aCO2
10% HMDA+20% AMP-Exp are the temperature, CO2 partial pressure and CO2 loading respectively]a
15% HMDA+15% AMP-Exp
20% HMDA+10% AMP-Exp T ¼ 303.15 K T ¼ 313.15 K T ¼ 323.15 K T ¼ 333.15 K
Density, kg.m-3

980
PCO2 aCO2 PCO2 aCO2 PCO2 aCO2 PCO2 aCO2
kPa mol/mol kPa mol/mol kPa mol/mol kPa mol/mol

970 1.04 0.411 1.04 0.375 1.55 0.386 3.25 0.379

7.62 0.753 3.97 0.591 7.32 0.589 13.31 0.579
22.18 0.890 12.86 0.746 19.36 0.716 26.10 0.674
44.03 0.971 25.33 0.827 41.90 0.807 36.58 0.716
960 69.53 1.016 42.81 0.886 55.09 0.840 48.07 0.749
92.39 1.045 66.02 0.933 68.39 0.865 61.25 0.781
110.76 1.064 98.60 0.975 92.43 0.901 72.43 0.804
300 305 310 315 320 325 330 335 110.57 0.994 106.58 0.918 86.23 0.827
103.80 0.845
Tempearture, K
a
Standard uncertainties associated with the measured and estimated quantities:
Fig. 2. Density of aqueous mixed amine solvents. u(P) ¼ ±0.27 kPa; u(T) ¼ ±0.1 K; ur (aCO2 ): ±1.34%.
 B.K. Mondal et al. / Fluid Phase Equilibria 437 (2017) 118e126 123

Table 6 Table 8
Vapour-liquid equilibrium of CO2 in aqueous (10 %HMDAþ20% AMP) [T, PCO2 and Vapour-liquid equilibrium of CO2 in aqueous (20 %HMDAþ10% AMP) [T, PCO2 and
aCO2 are the temperature, CO2 partial pressure and CO2 loading respectively]a aCO2 are the temperature, CO2 partial pressure and CO2 loading respectively]a
T ¼ 303.15 K T ¼ 313.15 K T ¼ 323.15 K T ¼ 333.15 K T ¼ 303.15 K T ¼ 313.15 K T ¼ 323.15 K T ¼ 333.15 K

PCO2 aCO2 PCO2 aCO2 PCO2 aCO2 PCO2 aCO2 PCO2 aCO2 PCO2 aCO2 PCO2 aCO2 PCO2 aCO2
kPa mol/mol kPa mol/mol kPa mol/mol kPa mol/mol kPa mol/mol kPa mol/mol kPa mol/mol kPa mol/mol

1.57 0.669 0.92 0.551 0.98 0.479 1.20 0.413 2.12 0.881 1.60 0.773 1.99 0.755 1.74 0.673
8.26 0.850 2.96 0.666 7.11 0.674 8.65 0.628 15.75 1.080 11.01 0.962 13.42 0.927 12.09 0.862
22.48 0.960 12.33 0.820 20.84 0.799 21.92 0.738 34.42 1.178 26.69 1.059 27.04 0.998 26.79 0.938
41.53 1.028 27.01 0.910 34.78 0.860 31.57 0.784 51.42 1.234 42.16 1.116 39.27 1.041 44.25 0.991
58.15 1.071 46.58 0.973 48.29 0.899 40.90 0.817 65.78 1.271 57.35 1.156 56.90 1.087 57.45 1.022
82.09 1.111 61.25 1.005 61.15 0.929 54.99 0.854 81.46 1.300 77.78 1.198 74.73 1.122 78.32 1.059
106.19 1.140 79.26 1.036 70.49 0.946 66.82 0.880 108.02 1.343 105.12 1.242 100.90 1.163 106.12 1.099
103.30 1.068 79.96 0.964 77.00 0.898 a
Standard uncertainties associated with the measured and estimated quantities:
99.86 0.991 98.50 0.930
u(P) ¼ ±0.27 kPa; u(T) ¼ ±0.1 K; ur (aCO2 ): ±1.50%.
a
Standard uncertainties associated with the measured and estimated quantities:
u(P) ¼ ±0.27 kPa; u(T) ¼ ±0.1 K; ur(aCO2 ): ±1.34%.
used in this work is as follows.
 
N aEx Mod 
1 X  CO2 ;i  aCO2 ;i 
But at higher CO2 partial pressure range, increase in the slope of the F¼   (23)
loading plot is slow due to stoichiometric saturation. Exothermic N i¼1  aExCO ;i

2

nature of the absorption process is indicated by the decrease in CO2

loading with increase in temperature at constant partial pressure Where, aEx
CO2 ;i
and aMod
CO2 ;i
are experimental and model predicted CO2
and composition which is also indicated by the figures (Figs. 3e6). loading data. N is the total number of data points. Along with this
In Fig. 7, CO2 loading in aqueous (HMDA þ AMP) solvent is objective function the charge balance expression is taken as the
compared with that of 30 mass% AMP data taken from the literature constraint function. Regressed coefficients of the equilibrium con-
[5,9,14] at 313.15 K. As seen from the figure, CO2 loading capacity is stants (K6 and K7) with 95% confidence limits are shown in Table 9.
enhanced significantly due to addition of HMDA. At 12 kPa CO2 Equilibrium constants (K6 and K7) expressed in terms of tempera-
partial pressure, loading is enhanced from 10% for (5mass% ture and CO2 loading are as follows.
HMDAþ25mass% AMP) solvent to 30% for (15mass%
HMDAþ15mass% AMP) compared to that in 30 mass% AMP alone. 0:0891
CO2 loading capacity of aqueous (HMDA þ AMP) solvent also in- ln K6 ¼ 33:7075  13:0445 aCO2   5:8949a2CO2
T
creases with the increase in HMDA concentration, keeping total 0:00018 aCO2
amine concentration constant. In Fig. 8, CO2 solubility in aqueous   0:0508
T2 T
(HMDA þ AMP) is compared with the conventional mixed solvents
(24)
(MEA þ AMP) [9] and (DEA þ AMP) [14] at 313.15 K. It is seen from
the figure that CO2 loading characteristics of aqueous
(HMDA þ AMP) solvent is quite higher compared to the conven- 0:0642
ln K7 ¼ 21:2358  6:1686 aCO2   2:1633a2CO2
tional mixed amine systems. T
Kent Eisenberg thermodynamic model is used to correlate and 0:00019 aCO2
  0:0186 (25)
predict CO2 solubility data in the mixed solvent system. The co- T2 T
efficients of the equilibrium constants, K6 (bicarbamate formation Kent-Eisenberg model predicted solubility data is compared
reaction constant for HMDA) and K7 (deprotonation reaction con-
stant of AMP) are regressed to fit the experimental data with the
model expression. Generalized reduced gradient nonlinear opti- 1.4
mization technique is used to minimize the error between the
experimental and model predicted data. The objective function (F) 1.2
αCΟ2/(mol CO2/ mol total amine)

1.0
Table 7
Vapour-liquid equilibrium of CO2 in aqueous (15 %HMDAþ15% AMP) [T, PCO2 and
aCO2 are the temperature, CO2 partial pressure and CO2 loading respectively]a 0.8

T ¼ 303.15 K T ¼ 313.15 K T ¼ 323.15 K T ¼ 333.15 K Mod-303.15K

0.6
PCO2 aCO2 PCO2 aCO2 PCO2 aCO2 PCO2 aCO2 Mod-313.15K
Mod-323.15K
kPa mol/mol kPa mol/mol kPa mol/mol kPa mol/mol 0.4 Mod-333.15K
0.91 0.701 1.42 0.676 1.76 0.605 1.03 0.482 Ex-303.15K
1.25 0.740 1.78 0.699 7.42 0.743 6.73 0.672 0.2 Ex-313.15K
10.18 0.939 10.13 0.863 29.64 0.901 25.71 0.819 Ex-323.15K
25.61 1.049 23.17 0.952 45.26 0.949 40.03 0.866 Ex-333.15K
43.11 1.108 38.99 1.012 55.89 0.974 49.55 0.890 0.0
59.02 1.155 52.89 1.051 64.38 1.000 61.67 0.916 0 20 40 60 80 100 120
79.02 1.191 74.73 1.094 80.61 1.027 76.96 0.945 PCO2/kPa
108.86 1.224 107.87 1.144 99.39 1.060 90.06 0.964
a
Standard uncertainties associated with the measured and estimated quantities: Fig. 3. Equilibrium solubility of CO2 in aqueous (5%HMDAþ25% AMP): Experimental
u(P) ¼ ±0.27 kPa; u(T) ¼ ±0.1 K; ur (aCO2 ): ±1.45%. and model predicted results.
124 B.K. Mondal et al. / Fluid Phase Equilibria 437 (2017) 118e126

1.4 1.5

1.4
1.2
1.3

αCO2 /(mol CO2/ mol total amine)

αCO2 /(mol CO2/mol total amine)

1.0 1.2
1.1
0.8
1.0

0.6
Mod-303.15K 0.9 Mod-303.15K
Mod-313.15K Mod-313.15K
Mod-323.15K 0.8 Mod-323.15K
0.4 Mod-333.15K 0.7 Mod-333.15K
Ex-303.15K Ex-303.15K
Ex-313.15K 0.6 Ex-313.15K
0.2
Ex-323.15K Ex-323.15K
0.5
Ex-333.15K Ex-333.15K
0.0 0.4
0 20 40 60 80 100 120 0 20 40 60 80 100 120
PCO2 / kPa PCO2 /kPa

Fig. 4. Equilibrium solubility of CO2 in aqueous (10%HMDAþ20% AMP): Experimental Fig. 6. Equilibrium solubility of CO2 in aqueous (20%HMDAþ10% AMP): Experimental
and model predicted results. and model predicted results.

with that of the experimentally measured data and are shown in The pH of CO2 loaded (5mass% HMDAþ25mass% AMPþ70%H2O)
Figs. 3e6. Average absolute deviation solution is estimated as function of temperature and loading and is
 
P aEx aMod  shown in Fig. 10. The pH values show a decreasing trend with in-
 CO2 ;i CO2 ;i 
(AAD ¼ N1 Ni¼1  aEx   100%) between the experimental and crease in temperature as well as loading. With increase in loading,
CO2 ;i 
pH of the solution moves towards the acidic range due to incor-
model predicted data is estimated to be 7.2% considering all the poration of acidic CO2. Also at higher temperature hydrogen ion
data sets. concentration in the solution increase (due to more ionization)
Applicability of the equilibrium constants (K6 and K7) are vali- which in turn decrease the pH of the solution.
dated by predicting the CO2 loading data of single amine systems
using the model developed in this work. Experimental solubility
data for 30% HMDA [24] and 30% AMP [5,9,14] at 313.15 K taken 6. Conclusion
from the literature are compared with that of model predicted data
in Fig. 9. Experimental and model predicted data for CO2 solubility Density and equilibrium CO2 solubility in aqueous
in aqueous (15%HMDAþ15%AMP) is also presented in this plot to (HMDA þ AMP) solvent system are studied in the industrially
compare model predictions of single and mixed amine solvent. It is important temperature and pressure range. HMDA behave as an
seen from the figure that the model predicted data are in good additive which enhances the loading capacity of the mixed solvent
agreement with the literature. with AMP compare to the single AMP solvent with same concen-
pH (-log [Hþ]) of the loaded solutions are estimated to check the tration. Also, aqueous (HMDA þ AMP) solvent shows better loading
validation of the model. It is expected to vary in the range of 7e12. characteristics compared to the conventional mixed solvents like

1.4
1.3
1.2
1.2
1.1
αCO2 /(mol CO2/ mol total amine)
αCO2/(mol CO2/mol total amine)

1.0
1.0
0.9
0.8 0.8
0.7 Mod-303.15K
Mod-313.15K 5% HMDA+25% AMP
0.6 Mod-323.15K 0.6 10% HMDA+15% AMP
Mod-333.15K 15% HMDA+15% AMP
0.5
Ex-303.15K 20% HMDA+10% AMP
0.4 Ex-313.15K 0.4 30% AMP (Kundu et al., 2003)
Ex-323.15K 30% AMP (Seo and Hong, 1996)
0.3
Ex-333.15K 30% AMP (Li and Chang, 1994)
0.2 0.2
0 20 40 60 80 100 120 0 20 40 60 80 100 120
PCO2 /kPa PCO2 /kPa

Fig. 5. Equilibrium solubility of CO2 in aqueous (15%HMDAþ15% AMP): Experimental Fig. 7. Comparison of CO2 loading in aqueous (HMDA þ AMP) with that of 30% AMP at
and model predicted results. 313.15 K.
 B.K. Mondal et al. / Fluid Phase Equilibria 437 (2017) 118e126 125

1.2
10.8
1.1 303K
10.4 313K
1.0
10.0
323K
0.9 333K
αCO2/(molCO2/mol total amine)

9.6
0.8
0.7 9.2

pH
0.6 8.8
0.5 8.4
0.4
8.0
5% HMDA+25% AMP (This work)
0.3
6% DEA+24% AMP (Seo and Hong, 1996) 7.6
0.2 18% DEA+12% AMP (Seo and Hong, 1996)
0.1
6% MEA+24% AMP (Li and Chang, 1994) 7.2
24% MEA+6% AMP (Li and Chang, 1994)
0.0 0.2 0.4 0.6 0.8 1.0
0.0
0 20 40 60 80 100 120 140 αCO2/(mol CO2/mol total amine)
PCO2 /kPa
Fig. 10. The pH values of CO2 loaded aqueous (5%HMDAþ25%AMP).
Fig. 8. Comparison of CO2 loading in aqueous (HMDA þ AMP) with that of aqueous
(MEA þ AMP) and (DEA þ AMP) at 313.15 K.

constant for HMDA and deprotonation reaction constant of AMP are

Table 9 regressed as function temperature and CO2 loading. Model pre-
Coefficients of regressed equilibrium constant. dicted data show good agreement with the experimental data with
an average absolute deviation of 7.2%. This indicate that the model
ln Ki ¼ ai þ bi a þ cTi þ di a2 þ Te2i þ fi aT
developed in this work is suitable for predicting CO2 solubility data
K6 K7 in aqueous (HMDA þ AMP) solvent with good accuracy.
10
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bi 13.0445 ± 1.111  1010 6.1686 ± 1.114  1002
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