Chemical Engineering Science 91 (2013) 151161

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Binary and ternary VLE of the 2-amino-2-methyl-1-propanol

(AMP)/piperazine (Pz)/water system
Ardi Hartono, Muhammad Saeed, Arlinda F. Ciftja, Hallvard F. Svendsen n
Department of Chemical Engineering, Norwegian University of Science and Technology, N-7491 Trondheim, Norway

H I G H L I G H T S
c
c
c
c
c

Binary VLE data of aqueous 2-amino-2-methyl-1-propanol (AMP) solution was measured.

Binary VLE data of aqueous piperazine (Pz) solution was measured.
Ternary VLE data of aqueous AMP/Pz solution was reported.
A combination of titration and a 1H-NMR techniques was successfully carried out.
The NRTL, Wilson and UNIQUAC models were tested and the parameters are suggested.

a r t i c l e i n f o

abstract

Article history:
Received 27 September 2012
Received in revised form
18 December 2012
Accepted 6 January 2013
Available online 16 January 2013

New VLE ebulliometric data for binary aqueous 2-amino-2-methyl-1-propanol (AMP) and piperazine
(Pz) solutions and ternary aqueous AMP/Pz solutions are reported at different temperatures and
concentrations. A proposed combination of titration and a 1H-NMR technique was developed and
determination of the composition of the ternary system was successfully carried out. Results show that
AMP is more volatile than commercial solvents such as MEA and MDEA whereas Pz is observed to be
less volatile than that of MEA and MAPA. Three thermodynamic models (NRTL, Wilson and UNIQUAC)
were used to correlate the data and the determined interaction parameters for both the binary and
ternary VLE systems are given. New binary interaction parameters for (AMP(1) and Pz(2)) are also
proposed. However, the parameters have no statistical signicance which indicates that the activity
coefcients for the species in the ternary system in general are similar to the activity coefcients
obtained from the corresponding binary mixture. More data may be required for ternary VLE
estimation, especially at higher amine concentrations.
& 2013 Elsevier Ltd. All rights reserved.

Keywords:
VLE
NMR
AMP
Pz
Absorption
Modeling

1. Introduction
A remaining challenge for the amine based CCS technology is
to reduce the regeneration energy requirement. One alternative is
to nd better solvents with improved mass transfer, higher
stability toward thermal and oxidative degradation, lower heat
of absorption, high equilibrium temperature sensitivity and high
cyclic capacity while still being environmental friendly.
AMP (2-amino-2-methyl-1-propanol) as a sterically hindered
amine has been studied with regard to the low carbamate
stability (Ciftja et al., 2011; Chakraborty et al., 1986). Low
carbamate stability can be associated with formation of predominantly carbonate/bicarbonate and thereby a reduction in

Corresponding author. Tel.: 47 73594100; fax: 47 73594080.

E-mail addresses: hallvard.svendsen@chemeng.ntnu.no,
hartono@nt.ntnu.no (H.F. Svendsen).
0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.01.015

regeneration energy requirement may be possible. Piperazine

(Pz), as a cyclic diamine, has also been studied due to its fast
mass transfer compared to most alkanolamines (Derks et al.,
2006; Sun et al., 2005) and has been considered as a promoter
(Xu et al., 1998; Bishnoi and Rochelle, 2000). Bruder et al. (2011)
reported that the 3 M AMP and 1.5 M Pz system could be a very
strong contender to the 5 M MEA system due to the large cyclic
capacity, comparable heat of absorption and good equilibrium
temperature sensitivity.
To better understand this system, fundamental data such as
binary and ternary VLE (vaporliquid equilibrium) are essential
for designing the gas treating process. These properties are also
crucial when developing rigorous thermodynamic models (e.g.,
e-NRTL or e-UNIQUAC).
Binary VLE data for the AMP/H2O system can be found in the
literature (Pappa et al., 2006 and Belabbaci et al., 2010). Contrary
to binary VLE for the AMP/H2O system, binary VLE for the Pz/H2O
system could not be found in the literature. Hilliard (2008)

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A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

reported some binary VLE data for this system but only the total
pressure above the Pz/H2O solution. These data were regressed to
determine binary interaction parameters in the Aspen Plus
simulator, the average absolute relative deviation (AARD)
reported was 13% and the maximum AARD was 29%. No data
could be found for the ternary system of AMP/Pz/H2O.
In this work, the binary (AMP/H2O and Pz/H2O) and ternary
(AMP/Pz/H2O) systems were studied in a modied Swietoslawski
ebulliometer. The compositions of the liquid and vapor phases
of the binary systems were determined with a titration method
while for the ternary system the phases were analysed using
1
H-NMR. The gathered data were then model to determine the
binary interaction parameters.

2. Experimental section
2.1. Material
All chemicals used were reagent grade. Both 2-amino-2methyl-1-propanol (AMP) with purity 498.5% and piperazine
(Pz) with purity 99% supplied by Sigma-Aldrich, were used without any further purication. The solutions were prepared gravimetrically by dissolving the chemical in deionized water.
About 10 wt% of deuterium oxide (D2O) solution with 99.98%
purity supplied by Sigma-Aldrich was added as locking agent for the
NMR experiments. All NMR samples were prepared gravimetrically
using an analytical balance (Mettler AE163 digital analytical) with
accuracy of 70.0001 g. Total alkalinity was determined experimentally by acid-base titration with 0.1 M H2SO4 for liquid phase and
0.01 M H2SO4 for vapor phase condensate.
2.2. Binary VLE measurements of AMP(1)H2O(3)
and Pz(2) H2O(3)
The PTxy data for the binary systems AMP/H2O and Pz/H2O
at different temperatures and concentrations were generated in a
modied Swietoslawski ebulliometer (see Fig. S1, Supplementary
material). Detailed experimental procedures can be found in
previous work (Kim et al., 2008). A gravimetrically prepared,
65 wt% solution of AMP/H2O was initially fed to the ebulliometer.
During the experiment, after each equilibration, the initial solution was diluted gradually to achieve high dilution at the end. No
problems were encountered during the experiments since the
initial solutions were always in liquid phase. On the other hand,
the binary Pz/H2O system tended to solidify at room temperature
due to the solidliquid equilibrium (Kim et al., 2011; Fosbl et al.,
2011). Therefore the initial solution was prepared at 40 wt% and
kept at 45 1C. The warm liquid was then fed into the ebulliometer and left until equilibrium was established. Both liquid and
vapour samples were collected and the amine content quantied
with the titration method.
2.3. Ternary VLE measurements of AMP(1)Pz(2) H2O(3) system
Ternary solutions containing different concentrations of AMP/
Pz were prepared gravimetrically and fed into the ebulliometer.
When equilibrium was established at specic temperature, samples of liquid and vapour phase were collected. Two parallel
samples were analysed with titration to quantify total amine and
1
H-NMR was used to quantify the ratio between AMP and Pz.

concentrations for the binary systems. The concentration of each

amine in the ternary system could not be quantied by titration
only. Therefore for the ternary system, a combination of titration
(total alkalinity) and the 1H-NMR was employed to quantify the
amount of each amine.
The spectra for these systems were acquired by a Bruker
Avance DPX 400 MHz NMR spectrometer (Bruker BioSpin GmbH)
with a 5 mm DUAL 1H/13C probe head. 1H-NMR spectra were
recorded at 25 1C and were processed and plotted by MestReNova
V.8.0.1 Software. The 1H-NMR spectra were collected using the
following parameters: pulse duration, p1 10.50 ms, acquisition
time, AQ3.96 s, delay time between two transitions, D1 2 s and
number of scans, NS 128 resulting in a total acquisition time of
12 min for each 1H-NMR experiment. The areas under the signal
peaks were integrated and the concentration of each amine and
water present in the samples determined. The accuracy of the
NMR experiments was tested by running parallel samples several
times and the uncertainty was found to be less than 2%. The
detection limit for the 1H-NMR measurements was found to be
70.0001 mol fraction for both amines.
3. Determination of experimental activity coefcient gExp

i
The ebulliometer experiment provides PTxy data for both
the binary and ternary systems and experimental activity coefcients gExp
for each amine were determined according to Eq. (1)
i
(Van Ness, 1995).

gExp

yi  P
 Fi
xi  P3i

here xi, yi, P, P3i and Fi are liquid mole fraction, vapor mole
fraction, total pressure of solution, saturation pressure of pure
substance, and the poynting factor, respectively. Eq. (1) is developed for molecular systems and in this work we assume that the
protonation of amine can be disregarded and that the amine itself
is the main contributor in the speciation. The [Amine]/[AmineH ]
ratio is related to the difference between the actual pH of the
solution and the amine pKa value. A typical value for the
difference between pH and pKa is about 1.11.2 (for both AMP
and Pz) at innite dilution. This implies that that the contribution
of protonated amine is less than 68% for innite dilution. For
more concentrated solutions the pH will increase and the contribution of protonated amine will be even lower (see Fig. S2).
Since the measurements were performed at or below atmospheric
conditions, the poynting factor (Fi) could be set to one. The
saturation pressures of the pure substances were, for water and
Pz, taken from the DIPPR 801 (2004) and, since Pz is a solid at
room temperature, extrapolated from the data (DIPPR) at higher
temperatures. In previous work (Hilliard, 2008; Nguyen et al.,
2010) reported that an extrapolation of the DIPPR correlation
could be done with good accuracy. The reported saturation
pressure data of AMP (Pappa et al., 2006; Belabbaci et al., 2010
and Klepacova et al., 2011) were regressed in this work using an
Antoine equation, according to Eq. (2):
ln P 3AMP 15:80973986:86067=T 189:9303

where and T represent the saturation pressure of AMP (kPa) and

temperature (K), respectively. Eq. (2) is valid for temperature
ranges from 20 1C to 165 1C with an AARD of 3.5%.
4. The activity coefcient model gcalc

2.4. Liquid (x) and vapor (y) phase analyses

The collected liquid and vapor solutions were examined with
amine titration (Metler Toledo G20) to determine the amine

In this work three different thermodynamic models based on

the excess Gibbs energy were used (Wilson, NRTL and UNIQUAC).
The Wilson (1964) and NRTL (Renon and Prausnitz, 1968) models

A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

153

Table 1
Thermodynamic models.
Model

Correlation

NRTL

PN
tij Gij xj
P
xj Gij
Pj N 1
N
lngNRTL
j i PN
i
k 1

Gki xk

tii tjj tkk 0;

WILSON

lngWilson
1ln
i

PN

ji

k i

xk Gkj

k 1

xj  Gji 

PN

PN j

xk Gkj



vj
Gij  exp lij =T ;
vi

UAC
ln Fxii 2z  qi  ln Fyii li  Fxii 
lngUNIQ
i

qi  ln

yi  tji qi qi

X
j



z
li   r j qj  rj 1 ;
2

Gij expaij  tij

x Gij

ji

Gii Gjj Gkk 1;

Gkj xk

Gii Gjj Gkk expaii  tii 1;

k i

UNIQUAC



PN
t Gkj xk
k 1 kj
 tij  P
N

vi

ri
Mi

xj  lj

y  tij
P j
k yk  tkj
q  xi
;
j qj  xj

yi P i

r  xi
;
j r j  xj

Fi P i

tij exp aij =T ;

aij u0ij uTij  T298:15

for multi component mixtures were implemented and summarized in Table 1.

The densities (ri) of the pure Pz and H2O were taken from the
DIPPR 801 (2004) while the density (ri) of AMP was taken from
Henni et al. (2003). As we can see, the Wilson model only requires
two interaction parameters (lij) for a binary system.
Based on the work of Posey (1996) for amine/alkanolamine
systems, the non-randomness parameter (aij) was specied to be
a xed value of 0.2 and tij aij bij/T was the recommended
correlation. The NRTL model requires 4 parameters (aij,bij) to be
calculated when the non-randomness parameter (aij) is set to a
xed value.
The equation for the activity coefcient in the UNIQUAC model
was originally developed by Abrams and Prausnitz (1974) and is
given in Table 1.
The values of the van der Waals volume parameter (r) and area
parameter (q) are summarized in Table 2.
These values were adopted in the present regression and only
4 parameters u0ij ,uTij needed to be determined during the parameter estimation.
In addition to calculating the excess enthalpy of solution (HE),
the derivation of an excess enthalpy for the Wilson (1964) model,
the NRTL model (Posey, 1996 and Schmidt et al., 2007) and the
UNIQUAC model (Thomsen and Rasmussen, 1999) were
implemented.

5. Regression
The parameters of the three different thermodynamic models
were determined by using an in-house Matlab code for multiresponse parameter estimation, Modt (Hertzberg and Mejdell,
1998), with the objective function (F) as given by Eq. (3).
!2
!2
n
n
X
X
PExp
P calc
gExp
gcalc
Sol
Amine
Amine
Sol
F

gExp
P Exp
i1
i1
Amine
Amine
!2
!2
n
n
X
X
HESol Exp HESol calc
YFSol Exp YFSol calc

3
HESol Exp
YFSol Exp
i1
i1
The deviations of the model results from the experimental
data are expressed as absolute average relative deviations (AARD)

Table 2
r and q values for the selected systems.
Compound

Source

AMP
Pz
H2O

3.92
3.73
0.92

3.44
2.95
1.44

Pappa et al. (2006)

Ermatchkov and Maurer (2011)
Abrams and Prausnitz (1974)

according to Eq. (4).



n 
Rmodel Rexp 
1X
AARD
ni1
Rexp

where R is the activity coefcient, total pressure of solution,

excess enthalpy and freezing point depression, respectively
The experimental activity coefcient gExp
was taken from this
i
work. The total pressure of solution P Exp
, excess enthalpy HESol
Sol
and the freezing point depression YFSol were all taken from the
literature. For the AMP system all three selected responses were
available in the literature but for the Pz system no reported data
for excess enthalpy were found. The freezing point depression of
this system was estimated with the method developed by Ge and
Wang (2009).

6. Results and discussion

6.1. Binary VLE of AMP(1)H2O(3) system
VLE for the AMP/H2O system was measured in the ebulliometer for three temperatures and the results are shown in
Table 3 together with the k-value. The k-values increase with
increasing temperature which indicates that the volatility of AMP
increases more than that of water with temperature. The k-values
decrease with concentration showing that the activity coefcient
decreases with concentration. It is also observed that AMP is more
volatile than the most commonly used amine MEA at a same
concentration and temperature (Kim et al., 2008).
The volatility of AMP can also be evaluated by the experimental activity coefcient gExp
. The reported values in this work
i

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A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

Table 3
VLE data for AMP(1) H2O(3) system at different temperatures.
t (1C)

P (kPa)

x1

y1

k1 y1/x1

59.97
60.03
59.98
60.04
59.97
60.00
59.97
60.00
60.00
80.01
79.98
79.99
80.00
80.02
80.02
100.02
100.01
100.00
100.00
100.02
100.02
100.01
100.01
100.01
100.02
100.00

19.2
19.1
19.0
18.9
18.6
18.3
17.6
16.5
15.1
46.1
45.6
45.5
43.5
41.5
37.1
98.9
97.4
96.8
96.8
96.0
95.0
93.5
91.6
89.2
85.4
78.0

0.0370
0.0442
0.0528
0.0638
0.0783
0.0968
0.1185
0.2092
0.2946
0.0297
0.0353
0.0408
0.1040
0.1626
0.2757
0.0228
0.0385
0.0460
0.0555
0.0675
0.0834
0.1039
0.1317
0.1621
0.2177
0.3023

0.0023
0.0027
0.0031
0.0038
0.0045
0.0052
0.0063
0.0108
0.0149
0.0034
0.0036
0.0040
0.0092
0.0129
0.0200
0.0040
0.0062
0.0069
0.0078
0.0095
0.0112
0.0133
0.0155
0.0181
0.0234
0.0309

0.0622
0.0611
0.0587
0.0596
0.0575
0.0537
0.0532
0.0516
0.0506
0.1145
0.1020
0.0980
0.0885
0.0793
0.0725
0.1754
0.1610
0.1500
0.1405
0.1407
0.1343
0.1280
0.1177
0.1117
0.1075
0.1022

are found to be high, starting from 1.5 to 2 at low concentrations

(x1 r0.2), see Fig. 1. This is much higher than MEA which
typically has a low activity coefcient at low concentrations, in
the range 0.20.5 (Kim et al., 2008). The experimental data were
regressed using the models described earlier and the experimental and predicted activity coefcients gExp
and gCalc
, can be seen
i
i
in Fig. 2ac for different temperatures. The obtained binary
interaction parameters from the model regression and the standard deviations of the parameters are summarized in Table 4. It is
seen that the parameter standard deviations are the lowest for the
Wilson model, mainly because only two parameters are tted.
For the two others the UNIQUAC model has somewhat lower
parameter standard deviations but the difference is small. The
absolute average relative deviations (AARD) of the t are shown
in Table 5.
It is seen that both the NRTL and UNIQUAC models give a
better t than the Wilson model. However, all the models can
represent the experimental data with reasonable accuracy. It is
also observed that the three models give a quite different value of
the activity coefcient of AMP at innite dilution. If more data
were available at low concentration this could be improved
signicantly.
The predicted liquid and vapor phase concentrations at the
different temperatures are showed in Fig. S3, it is seen that the
obtained parameters are also capable of representing the experimental data. However, it seen that the Wilson model tends to

Exp
Calc
Calc
Fig. 1. Experimental AMP activity coefcients gExp
and the model representation at 60 1C (a) 80 1C (b) and 100 1C (c) (J,gExp
1 ; &, g3 ; Solid lines, g1 ; Dashed lines, g3 ;
i
Blue, NRTL; Red, Wilson; Green, UNIQUAC). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

155

Fig. 2. Experimental PTxy data and the predicted models (a) this work (J, 60 1C; &, 80 1C; B, 100 1C); (b) Pappa et al. (2006) (J,66.7 kPa; &, 80.0 kPa; B, 101.3 kPa);
(c) Belabbaci et al. (2010) (J,20 1C; &, 30 1C; B, 40 1C; , 50 1C; A, 60 1C; x , 70 1C; n, 80 1C; D, 90 1C); (c) AMP vapor pressure at 0.29 molality (m) and 4070 1C (Nguyen
et al., 2011); (Solid lines, models; Blue, NRTL; Red, Wilson; Green, UNIQUAC). (For interpretation of the references to color in this gure legend, the reader is referred to the
web version of this article.)

over-predict the concentration at higher concentrations

( 40.2 mol fraction).
The collected total pressure of solution data from a static
ebulliometer apparatus (Belabbaci et al., 2010), where only PTx
data were gathered (Fig. 2c), were taken into the parameter
regression. Fig. 4ac, shows that the model also represents
successfully the experimental points from this work (Fig. 2a)
as well as the work done in the same type of ebulliometer in
an isobaric experiment (Pappa et al., 2006) (Fig. 2b). In Fig. 2d

reported AMP vapor pressures (Nguyen et al., 2010) are plotted

together with the three models. All models work satisfactorily but
the UNIQUAC model gives the best representation of the data.
The excess enthalpy of AMP solution data (Mathonat et al.,
1997) was also used in the parameter estimation as shown in
Fig. 3. The models give a reasonable representation of the excess
enthalpy data. It predicts well for both low and high AMP
concentrations, but in the middle concentration range the models
under-predict the experimental values.

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A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

Freezing point data (Fosbl et al., 2011) were also used in the
regression. To estimate freezing point depression a method based
on the modied three-characteristic-parameter correlation model
for electrolyte solutions (Ge and Wang, 2009) was implemented.
Fig. 4 shows the freezing point depression data and the prediction
models. It can be said that the models predict well for only low
AMP concentrations, but in the high concentration range the
three models over-predict the experimental values. This may be
explained by the used model (Ge and Wang, 2009) being

Table 4
Binary interaction parameter of AMP(1) H2O(3) for NRTL, Wilson and UNIQUAC
models.
NRTL
a13
b13

 0.73 70.3
 399.977 135

a31
b31

5.737 0.9
 845.19 7355

 6995.157 44

l31

9446.107 143

 50.26 716
 1.19 70.2

u331

 63.00 7 16
2.3840 70.3

WILSON

l13
UNIQUAC
u313
uT13

uT31

Table 5
Absolute average relative deviations (AARD) of models for AMP(1) H2O(3)
system.
Number of points (N)

NRTL

HESol ,%

26
80
16

3.5
5.8
6.1

7.5
7.4
8.8

3.5
6.4
7.5

YFSol ,%

14

9.5

10.7

5.1

gi,%
PSol,%

Wilson

UNIQUAC

developed for strong electrolyte solutions and the fact that AMP
is a weak base and in solution dissociates as a weak electrolyte.

6.2. Binary Pz(2) H2O(3) system

New experimental data at three different temperatures were
obtained in the ebulliometer and the results are shown in Table 6.

Table 6
VLE data for Pz(2) H2O(3) system at different temperatures.
t (1C)

P (kPa)

x2

y2

k2 y2/x2

60.00
59.96
59.95
60.04
60.00
60.07
59.97
60.05
79.99
79.99
79.99
80.00
79.97
79.99
80.04
79.99
79.99
80.00
100.00
100.02
100.00
100.02
100.02
100.03

19.2
19.0
18.8
18.6
18.2
17.9
17.0
16.3
45.9
45.8
45.4
45.1
44.8
44.2
43.5
42.6
41.3
39.2
98.5
98.1
95.9
94.9
89.3
86.1

0.0324
0.0390
0.0469
0.0569
0.0677
0.0808
0.0991
0.1168
0.0251
0.0297
0.0347
0.0408
0.0472
0.0564
0.0652
0.0794
0.0957
0.1177
0.0237
0.0279
0.0454
0.0536
0.0937
0.1136

0.0004
0.0004
0.0004
0.0005
0.0007
0.0011
0.0017
0.0025
0.0004
0.0005
0.0005
0.0008
0.0020
0.0011
0.0014
0.0020
0.0031
0.0051
0.0006
0.0008
0.0017
0.0018
0.0043
0.0067

0.0123
0.0103
0.0085
0.0088
0.0103
0.0136
0.0172
0.0214
0.0159
0.0168
0.0144
0.0196
0.0424
0.0195
0.0215
0.0252
0.0324
0.0433
0.0253
0.0287
0.0374
0.0336
0.0459
0.0590

Fig. 3. Experimental excess enthalpy of AMP solution and the predicted model at 35 1C ( , Mathonat et al. (1997); Solid lines, models; Blue, NRTL; Red, Wilson; Green,
UNIQUAC). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

Fig. 4. Experimental freezing point depression of AMP solution and the predicted model (J, Fosbl et al. (2011); Solid lines, models; Blue, NRTL; Red, Wilson; Green,
UNIQUAC). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

157

Exp
Calc
Calc
Fig. 5. Experimental and predicted activity coefcients for Pz at 60 1C (a) 80 1C (b) and 100 1C (c). (J, gExp
2 ; &, g3 ; Solid lines, g2 ; Dashed lines, g3 ; Blue, NRTL; Red,
Wilson; Green, UNIQUAC). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

The k-values increase with increasing temperature and concentration indicating that Pz becomes more volatile with increasing
concentration. It is also seen that Pz is less volatile than AMP and
MEA and diamine (MAPA) but it is found to be more volatile than
that of MDEA at a similar concentration and temperature (Kim
et al., 2008).
The volatility of Pz in aqueous solution is partly seen from the
experimental activity coefcients gExp
. The reported values in
i
this work are found to be very low as seen in Fig. 5. The data
experimentally obtained and literature data found were tted
using the models presented earlier. Fig. 5ac show the experimental and predicted activity coefcients, gExp
and gCalc
, for
i
i
different temperatures. The obtained binary interaction parameters from the regression, and the standard deviations of the
parameters, are summarized in Table 7 along with the absolute
average relative deviations (AARD) of the tting in Table 8. For the
Pz/H2O system the UNIQUAC model has signicantly lower
parameter standard deviations than the NRTL. However, the
number of data points is much lower for this system than for
AMP/H2O.
It is seen from Table 8 that both the NRTL and UNIQUAC
models give much better ts than that of the Wilson model. It is
observed that the three models give a similar value of the activity

Table 7
Binary interaction parameter of Pz(2) H2O(3) for NRTL, Wilson and UNIQUAC
models.
NRTL
a23
b23

0.95 7 1.5
 1208.627 531

a32
b32

4.95 7 3.4
 1315.657 1180

 9482.177 172

l32

4902.517 484

 398.737 36
3.68 7 0.7

u332

 222.147 23
 1.14 7 0.4

WILSON

l23
UNIQUAC
u323
uT23

uT32

Table 8
Absolute average relative deviations (AARD) of models for Pz(2) H2O(3) system.

gi,%
PSol,%

YFSol ,%

Number of points (N)

NRTL

Wilson

UNIQUAC

24
35
12

7.9
7.9
9.1

15.3
24.3
15.4

7.9
6.5
9.7

158

A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

Fig. 6. Experimental PTxy data and the predicted model (a) this work ( / ,60 1C; / , 80 1C; / , 100 1C); (b) Wilson and Wilding (1994)( / , 112.9 1C; / ,
198.8 1C); Solid lines, models; Blue, NRTL; Red, Wilson; Green, UNIQUAC; , Hilliard (2008); (c) Vapor pressure of Pz (Hilliard, 2008/Nguyen et al., 2010) ( , 0.9 m; ,
1.8 m; , 1.95 m; , 2.5 m; , 3.6 m; , 5.0 m; Solid line, NRTL; Dash-dot line; Wilson; Dash line, UNIQUAC; , e-NRTL (Hilliard, 2008). (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of this article.)

Fig. 7. Experimental and predicted freezing point depressions for the Pz/H2O system (J, Fosbl et al. (2011); Solid lines, models; Blue, NRTL; Red, Wilson; Green,
UNIQUAC). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

coefcient of Pz at innite dilution even though little data were

provided at low concentrations.
The predicted liquid and vapor phase concentrations at different temperatures are shown in Fig. S4, it is seen that the obtained
parameters are able to represent the experimental data well.
However it is noted that the Wilson model shows an over-

prediction at lower temperatures and an under-prediction at

higher temperatures.
Since only few reports on the binary Pz/H2O solution exist, the
collected total pressure of solution data (Wilson and Wilding,
1994), were taken into the parameter regression. It is seen in
Fig. 6a and b, that the NRTL and UNIQUAC models predict well the

A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

experimental points from this work (Fig. 6a) as well as the work
at higher pressure (Fig. 6b) (Wilson and Wilding, 1990). The
Wilson model was off at higher mole fractions and under-predicts
the y-values at higher temperature and pressure. It is also seen
that the extrapolation of the saturation pressure of Pz down to
room temperature works ne.
Hilliard (2008) reported parameters for the binary Pz/H2O
system using the e-NRTL model in Aspen Plus. He tted the
parameters based on the available data at that time, such as: the
total pressure of pure amine, VLE and heat capacity. The Hilliard
model is plotted in Fig. 6a and it is seen that the suggested
parameters t the total pressure data for Pz mole fractions,
x2 o0.05, but unfortunately shows an azeotrope at x2  0.8. We
cannot rule out the existence of an azeotrope based on the data
from the present work but it can be seen that this is unlikely for
the system at higher temperature (see Fig. 6b) based on data of
Wilson and Wilding (1994). In addition, the partial pressures of Pz
measured by Hilliard (2008) and Nguyen et al. (2010) for different
molalities and temperatures are shown in Fig. 9c. It is seen that
the models developed in this work only represent the data
satisfactorily at higher concentrations, whereas at lower concentrations the model under-predicts the vapor pressures. The
Hilliard (2008) model, black lines, works better for this set of
amine vapor pressure data. It should be noted that these data may
not be absolutely accurate as it is seen that some points at
different concentrations have about the same partial pressure of
Pz at the same temperature. The reason may be a low sensitivity
of the FTIR used for this system and it is suggested that new
parameters could be re-evaluated in Aspen Plus.

159

Freezing point data (Fosbl et al., 2011) were also used in the
regression and the freezing point depression predictions were
done as for AMP by the method of Ge and Wang (2009). Fig. 7
shows the freezing point depression data and the model. The
experimental data seem to be more scattered than those of
AMP. Both the NRTL and UNIQUAC models gave good ts. The

Table 9
Ternary VLE data for AMP(1) Pz(2) H2O(3) system at different temperatures.
t (1C)

P (kPa)

x1

y1

k1 y1/x1

x2

y2

k2 y2/x2

60.04
60.01
60.02
60.05
60.01
60.00
59.96
70.03
70.04
70.01
70.04
69.98
69.97
69.99
70.03
80.00
79.98
80.00
80.02
79.98
80.01
80.03
90.00
90.02
90.01
90.00
90.02
90.01
90.00
100.00
100.02
99.99
100.00
100.01
100.00
100.00

19.0
18.5
18.7
18.3
17.9
17.8
17.0
29.8
30.4
29.7
29.4
28.9
27.9
28.6
27.3
45.3
45.8
45.4
44.8
44.0
43.8
41.7
67.2
68.0
67.1
66.5
65.2
63.9
62.1
97.3
98.5
97.0
96.5
94.4
90.8
93.0

0.0132
0.0221
0.0262
0.0367
0.0793
0.0840
0.0910
0.0121
0.0212
0.0224
0.0250
0.0358
0.0655
0.0789
0.0908
0.0117
0.0210
0.0218
0.0228
0.0351
0.0768
0.0877
0.0132
0.0200
0.0211
0.0227
0.0746
0.0794
0.0830
0.0116
0.0200
0.0210
0.0224
0.0570
0.0816
0.0992

0.0009
0.0027
0.0027
0.0022
0.0041
0.0042
0.0070
0.0009
0.0022
0.0014
0.0019
0.0036
0.0050
0.0053
0.0070
0.0014
0.0022
0.0029
0.0025
0.0068
0.0098
0.0078
0.0015
0.0024
0.0023
0.0036
0.0085
0.0083
0.0095
0.0016
0.0033
0.0040
0.0039
0.0089
0.0077
0.0114

0.0682
0.1222
0.1031
0.0599
0.0517
0.0500
0.0769
0.0744
0.1038
0.0625
0.0760
0.1006
0.0763
0.0672
0.0771
0.1197
0.1048
0.1330
0.1096
0.1937
0.1276
0.0889
0.1136
0.1200
0.1090
0.1586
0.1139
0.1045
0.1145
0.1379
0.1650
0.1905
0.1741
0.1561
0.0944
0.1149

0.0362
0.0231
0.0395
0.0353
0.0139
0.0280
0.0474
0.0367
0.0107
0.0228
0.0384
0.0370
0.0340
0.0133
0.0474
0.0345
0.0106
0.0220
0.0350
0.0359
0.0129
0.0449
0.0336
0.0103
0.0217
0.0345
0.0128
0.0261
0.0430
0.0329
0.0101
0.0208
0.0345
0.0192
0.0422
0.0167

0.0007
0.0004
0.0014
0.0010
0.0001
0.0007
0.0014
0.0005
0.0004
0.0006
0.0006
0.0013
0.0006
0.0001
0.0009
0.0008
0.0003
0.0005
0.0007
0.0043
0.0008
0.0011
0.0009
0.0008
0.0009
0.0011
0.0005
0.0007
0.0013
0.0014
0.0004
0.0007
0.0013
0.0003
0.0011
0.0015

0.0193
0.0173
0.0354
0.0283
0.0072
0.0250
0.0295
0.0136
0.0374
0.0263
0.0156
0.0351
0.0176
0.0075
0.0190
0.0232
0.0283
0.0227
0.0200
0.1198
0.0620
0.0245
0.0268
0.0777
0.0415
0.0319
0.0391
0.0268
0.0302
0.0426
0.0396
0.0337
0.0377
0.0156
0.0261
0.0898

Fig. 8. Experimental and predicted activity coefcients for AMP(1) and

Pz(2) without binary interaction for AMP/Pz at 60 1C (a), 70 1C (b), 80 1C (c),
Exp
Calc
Calc
90 1C (d) and 100 1C (e) (J, gExp
1 ; &, g2 ; Solid lines, g1 ; Dashed lines, g2 ; Blue,
NRTL; Red, Wilson; Green, UNIQUAC). (For interpretation of the references to color
in this gure legend, the reader is referred to the web version of this article.)

160

A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

Fig. 9. Experimental freezing point depression for the ternary system and the predicted model without binary interaction for AMP/Pz (J, Fosbl et al. (2011); Solid lines,
models; Blue, NRTL; Red, Wilson; Green, UNIQUAC). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this
article.)

suggested method (Ge and Wang, 2009) seems work better here
than for AMP in spite of Pz only being a slightly stronger base
than AMP. The Wilson model under-predicts the freezing point
depressions.

Table 10
The AARD value of the ternary VLE data for AMP(1) Pz(2) H2O(3) system for
different models without introducing the binary interaction of AMP(1) and Pz(2).

6.3. Ternary AMP(1)Pz(2) H2O(3) system

g1,%
g2,%

Ternary VLE experiments at ve different temperatures and for

different AMP/Pz ratios were performed in the ebulliometer. To
quantify the concentrations of the individual amines 1H-NMR
acquisitions were carried out as shown in Fig. S5. The NMR
method used in this work is a promising method as it separates
the signals for AMP, Pz, and H2O and is relatively fast (12 min.).
Results show that AMP gives two singlet signals, at 0.9 ppm
(6 protons of 2 methyl groups) and at  3.2 ppm (2 protons of
ethyl group) whereas Pz only gives one singlet signal at  2.6 ppm
(8 protons of 4 ethyl groups). Both liquid and vapor phase show
similar spectra but water is always dominant. The AMP/Pz ratio
can be determined by the ratio of the integral peaks of the
corresponding signals. A full set of experimental data for the
ternary system is given in Table 9.
Results in Table 9 show that at constant Pz concentration,
when the AMP concentration increases, the change in volatility of
Pz is not signicant. The same thing occurs for AMP when the Pz
concentration varies. This might indicate that the activity coefcients for the species in the ternary system are in general similar
to the activity coefcients obtained from the corresponding
binary mixture.
Fig. 8 shows experimental and predicted activity coefcients
only using the calculated binary interaction parameters without
any new binary interaction parameter for AMP(1) and Pz(2). First
it is seen that the data are quite scattered, particularly for the
vapor phase. The model predictions of the ternary VLE
AMP(1)Pz(2)H2O(3) system are quite reasonable for both
AMP and Pz, but the scatter in the Pz data give higher AARD for
the Pz t. The freezing point depression data (Fosbl et al., 2011)
for the ternary system are plotted together with the model
predictions in Fig. 9. The results show that the NRTL and
UNIQUAC models predict accurately the freezing point depression
whereas the Wilson model slightly over-predicts the effect. The
quality of the t can be seen in Table 9.
Table 10 A binary interaction parameter for AMP(1)Pz(2) was
introduced and the results are given in Table 11 along with the
AARD values given in Table 12. The binary interaction parameters
for AMP(1)H2O(2) and Pz(1) H2O(3) were kept as determined
from the binary systems, and the activity coefcient of water
gExp
3 was selected as an objective function. It is seen that a slight
improvement is obtained in the NRTL and UNIQUAC models for
the activity coefcients for AMP (Fig. S6), but the accuracy of the
activity coefcient for Pz are reduced. The opposite behavior was
observed for the Wilson model. No improvement by introducing

YF,%

NRTL

Wilson

UNIQUAC

18.5
42.8
2.9

17.3
40.9
8.0

17.2
44.0
2.1

Table 11
Binary interaction parameter of AMP(1) Pz(2) for NRTL, Wilson and UNIQUAC
models.
NRTL
a12
b12

7.0567
4.1687

a21
b21

 2.4095
1.8764

58,053.35

l21

63,032.90

3.0
 1.43

u321
uT21

3.0
 1.49

WILSON

l12
UNIQUAC
u312
uT12

Table 12
The AARD value of the ternary VLE data for AMP(1) Pz(2) H2O(3) system for
different models with a new binary interaction of AMP(1) Pz(2).

g1,%
g2,%
F

Y ,%

NRTL

Wilson

UNIQUAC

15.9
46.3
2.9

22.8
43.7
8.0

15.4
46.8
2.1

the new binary interaction parameter was observed for the three
models in predicting freezing point depression (Fig. S7). From
Table 11 it can be seen that the suggested parameter has no
statistical signicance. This implies that there is no signicant
effect of tting to the ternary system and that the binary
interaction parameters with water are sufcient for describing
also the ternary system.

7. Conclusion
New ebulliometric VLE data for the binary AMP/H2O and Pz/
H2O systems and the ternary AMP/Pz/H2O system were obtained
for different temperatures and amine concentrations. A combined
titration and 1H-NMR technique to quantify the composition of
the individual amine concentrations in the ternary system was
proposed and successfully used in this work. Results show that
AMP is more volatile than some of commercial solvents such as

A. Hartono et al. / Chemical Engineering Science 91 (2013) 151161

MEA and MDEA whereas Pz is observed to be less volatile than

MEA and MAPA but it is more volatile than of MDEA.
Three thermodynamic models (NRTL, Wilson and UNIQUAC)
were tested as to their ability to represent the data. The results
show that all three models gave a good correlation with the
experimental data for the binary VLE data. However, the NRTL
and UNIQUAC models performed better than the Wilson model.
The obtained binary interaction parameters for amine and water
from the three models were used successfully to predict the VLE
in the ternary VLE solutions. New binary interaction parameters
between the two amines (AMP(1) and Pz(2)) was proposed, but
introduction of this parameter gave no improvement of the t and
the parameters have no statistical condence. This indicates that
the activity coefcients for the species in the ternary system are
in general similar to the activity coefcients obtained from the
corresponding binary mixtures. More data are needed to support
the modelling of ternary VLE, especially at higher amine
concentrations.

Acknowledgment
Direct nancial support from DNV (Det Norske Veritas AS) and
the CCERT project is greatly appreciated. The CCERT project is
supported by the Research Council of Norway (NFR 182607), Shell
Technology Norway AS, Metso Automation, Det Norske Veritas AS,
and Statoil AS.

Appendix A. Supporting information

Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.ces.2013.01.015.

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