Fluid Phase Equilibria 550 (2021) 113235

Contents lists available at ScienceDirect

Fluid Phase Equilibria

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

New solubility and heat of absorption data for CO2 in blends of

2-amino-2-methyl-1-propanol (AMP) and Piperazine (PZ) and a new
eNRTL model representation
Ardi Hartono∗, Rafiq Ahmad1, Hallvard F. Svendsen, Hanna K. Knuutila
Department of Chemical Engineering, Norwegian University of Science and Technology, NO-7491 Trondheim, Norway

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

Article history: New data comprising CO2 partial pressure, total pressure, and the heat of absorption of CO2 for over
Received 14 June 2021 aqueous solution of 3 mol/dm3 AMP and 1.5 mol/dm3 PZ and total pressure and heat of absorption for
Revised 20 September 2021
different mol ratios of AMP/PZ (3.0/0.0, 0.0/1.5, 0.5/4.0, 1.5/3.0, 2.25/2.25, 3.0/1.5, 4.0/0.5) are presented
Accepted 22 September 2021
as functions of CO2 loading and temperature.
Available online 24 September 2021
Measured solubility data and selected data reported in the literature were used in the regression
Keywords: of binary interaction energy parameters in the quaternary system (AMP/PZ/H2 O/CO2 ) using the eNRTL
AMP model. The equilibrium constants and binary interaction energy parameters from our previous work on
CO2 solubility the ternary systems of AMP/H2 O/CO2 and PZ/H2 O/CO2 were used without refitting.
eNRTL Good agreement with the literature was observed for the total pressure data over aqueous solutions
Heat of absorption of 3.0 mol/dm3 AMP and 1.5 mol/dm3 PZ, and the CO2 partial pressure and heat of reaction data over
PZ
aqueous solutions of 3.0 mol/dm3 AMP+1.5 mol/dm3 PZ at different loadings and temperatures. The re-
Volatility
sults reflect that the new data are consistent with reported data from the literature.
The modeling results show that the eNRTL model represents the data well with AARD values of 13.1%
for total pressure and 20.9% for CO2 partial pressure. The volatility of AMP and PZ as function of load-
ing and temperature and published speciation data for AMP/AMP H + , P Z/P Z H + /P ZH22+ , P ZCO− 2
/P Z H +CO−
2
,
PZ (CO− ) and HCO−3 /CO23− were also well predicted.
2 2
Only the heat of absorption data over an aqueous solution of 3.0M AMP+1.5M PZ from this work can
be compared with literature data, and good agreement is observed. The eNRTL model also predicts satis-
factorily the experimentally obtained heat of absorption data for all different ratios of AMP/PZ. Individual
reaction contributions show that when the AMP/PZ ratio increases, the predicted total heat of absorption
goes toward the single solvent AMP system where only protonated AMP is the main contributor. When
the AMP/PZ ratio decreases, the predicted total heat of absorption also approaches the single solvent PZ
system where the protonated PZ, PZ-monocarbamate and zwitterion reactions play important roles. In
systems with high PZ-concentration, the contribution of the zwitterion, protonated PZ and PZ-carbamate
cancel each other at high loadings.
© 2021 Published by Elsevier B.V.

1. Introduction
Carbon dioxide emitted to the atmosphere through human ac-
tivity is responsible for a large part of the observed warming of
our planet [1]. In addition to the transport and domestic sectors,
fossil fuel-based power generation and CO2 -emitting industries are
the main contributors to the total CO2 emissions. Offering signifi-
∗
Corresponding author at: NTNU, Sem Saeland Vei 4, 7491 Trondheim, Norway
E-mail addresses: ardi.hartono@chemeng.ntnu.no, ardi.hartono@ntnu.no (A.
Hartono), rafiq.ahmad@umt.edu.pk (R. Ahmad).
1 orber. To reach regeneration conditions, energy must be added to
Present address: School of Food and Agricultural Science, University of Manage-
ment and Technology, Lahore 540 0 0 Pakistan
cant point sources, the latter two are attractive for CO2 emissions
reductions.
Carbon Capture and Storage is considered one of the most
promising technologies to reduce CO2 emissions and absorption
into amine solutions is today the most mature and applied tech-
nology for CO2 capture [2]. The basic concept of this technology is
a chemical solvent that reacts reversibly with CO2 . When CO2 is
absorbed, the solvent lean in CO2 approaches its equilibrium and
becomes rich in CO2 . To recycle the solvent, a regeneration process
based on temperature-swing is usually applied for low-pressure,
post combustions, releasing CO2 at elevated temperature in a des-
increase the solvent temperature, provide the heat for reversing

https://doi.org/10.1016/j.fluid.2021.113235
0378-3812/© 2021 Published by Elsevier B.V.
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 1
Experimental data available from literature and used for the AMP/PZ/CO2 /H2 O system∗ .

No Experimental type and Experiment conditions Number of Source Remarks

Collected data points

1 VLE T = 313, 333, 353K 144 [29]

PC O2 , T, [AMP/PZ ], α [AMP/PZ ]=2.0/0.5, 2.0/1.0, 2.0/1.5,
• Vapor recirculation equilibrium + Shimada GC
3.0/0.5, 3.0/1.0, 3.0/1.5M
α = 0.292 to 0.876 (<200kPa)
• Kent-Eisenberg model
PC O2 = 1.03 to 139.9 kPa

T = 303, 313, 323, 318, 328K 34 [4]

[AMP/PZ ]=3.0/1.5M
• Vapor recirculation equilibrium +NDIR CO2
α = 0.06 to 0.83
• An empirical model
PC O2 = 0.03 to 20 kPa

T = 293 to 433K 89 [6]

[mAMP /mPZ ]=5.0/2.3; 4.0/2.0
• A static VLE and Wetted wall column
α = 0.0 to 0.64
• An empirical model
PC O2 = 0.05 to 2231 kPa

2 VLE T = 313, 333, 353K 175 [30]

PT , T, [AMP/PZ ], α [AMP/PZ ] = 38/2, 35/5, 32/8, 48/2,
• SS equilibrium cell
45/4, 42/8 mass%
• An eNRTL model
α = 0.38 to 1.02
PT = 0.16 to 1418kPa
T = 313, 333, 373, 393K 91 [32]
[AMP/PZ ]=25/5, 20/10 mass%
• Static-analytic apparatus + GC
α = 0.06 to 0.83
• Kent-Eisenberg model
PT = 0.03 to 20 kPa

T = 303, 333K 112 [33]

[AMP/PZ ]=8.91/0, 8.91/1.74, 8.91/6.88,
• SS equilibrium cell
8.91/10.35; 17.82/0, 17.82/1.74,
• No modeling work
17.82/6.88, 17.82/10.35 mass%
α = >1.00 to 2.40
PT = 5 to 60 bars
T = 293, 303, 313, 323K 30 [31]
[AMP/PZ ]=13.5/0.87, 13.5/2.6,
• A glass spiral cell
8.91/1.74 mass%
• Deshmukh–Mather model
α = 0.15 to 0.94
PT = 90.66 bar
PC O2 = 18.13, 27.19, 72.52 kPa
3 Calorimetric T = 313, 333, 353K 87 [34]
HABS. , T, [AMP/PZ ], α [AMP/PZ ]=3/1.5, 3/0.5, 4/1 M
• a Differential Reaction Calorimeter (SETARAM
α = 0.1 to 0.84
PT = Not available DRC-Evolution)
• No modeling work

4 NMR speciation T = 303, 313K 25 [35]

mi. , T, [AMP/PZ ], α [mAMP /mPZ ]==4/2, 2.3/5m
• A Varian INOVA 500MHz 13C-NMR
α = 0.43 to 0.65
• An eNRTL model

α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

∗
All concentrations are given as in the original publications.

the reactions and the water vapor pressure needed. The regenera- the heat of absorption. An electrolyte NRTL (eNRTL) model, as
tion thus becomes an energy-intensive part of this technology [3]. described by Chen and Evans (1986) [11], was implemented
The search for low energy penalty solvents for CO2 capture is es- and the binary interaction parameters in the quaternary system
sential. (AMP/PZ/H2 O/CO2 ) were regressed based on all available solubil-
The EU project CESAR investigated a blend of AMP/Piperazine ity data. The binary interaction parameters for the ternary systems
at laboratory conditions [4] and demonstrated an optimized con- of AMP/H2 O/CO2 and PZ/H2 O/CO2 were taken from our previous
centration of 3.5M AMP+1.5M PZ at pilot scale [5]. Li, et al. work [10,12].
(2013) [6] also recognized aqueous AMP/PZ as an interesting sys-
tem due to its high reactivity, caused by PZ, and the relatively low
heat requirement of stripping because of AMP. As a sterically hin- 2. Theoretical background
dered amine [7], AMP has in many ways similar thermal prop-
erties as tertiary amines, but unlike tertiary amines, it can react 2.1. Chemical reaction system
with CO2 to produce both carbamate (minor product) and bicar-
bonate/carbonate (major products) [8,9]. In aqueous solution, AMP The ten equilibrium reactions describing the AMP/PZ/H2 O/CO2
has shown high CO2 equilibrium temperature sensitivity [10], and system are given below.
therefore it is a good substitute for a tertiary amine. KW
In this work, new experimental solubility, and heat of absorp- 2H2 O ↔ H3 O+ + OH − (R1)
tion data for CO2 in the quaternary system of AMP/PZ/H2 O/CO2
were generated and used together with available literature data, KHCO−
shown in Table 1, to model the vapor-liquid equilibrium and 2H2 O + C O2 ↔ H3 O+ + HCO−
3
3 (R2)

2
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 2
Number of fitted parameters in the NRTL/eNRTL models.

No. System Species NP Remark

Molecule Cation Anion∗ Total Eq. 2 ai j /bi j

1 AMP/H2 O 2 0 0 2 2 4 NRTL
2 PZ/H2 O 2 0 0 2 2 4 NRTL
3 AMP/PZ 2 0 0 2 2 4 NRTL
4 AMP/PZ/H2 O 3 0 0 3 6 12 NRTL
5 AMP/H2 O/CO2 3 2 4 9 54 108 eNRTL
6 PZ/H2 O/CO2 3 3 6 12 114 228
Zwitterion = an-
ion
eNRTL
7 4 4 7 15 236 472 eNRTL
AMP/PZ/H2 O/CO2
∗
Zwitterion is considered as an anion with zero charge.

regressed. As those parameters were kept, there remained 82 pa-

KCO2−
rameters (NP) for the parameter fitting of the quaternary system.
H2 O + HCO− ↔ H3 O+ + CO23−
3
(R3)
3 It must be noted that 12 of these parameters were set to their de-
fault values in Aspen plus® (see Table 25). The non-randomness
KPZ H + values for H2 O-salt, molecule-molecule and amine/CO2 -salt pairs
H2 O + P Z H + ↔ P Z + H3 O+ (R4)
interactions were also fixed to literature values [13].

KPZH 2+
H2 O + P ZH22+ ↔ P Z H + + H3 O+
2
(R5) 2.3. Parameter fitting

KPZCO− All the equilibrium constants needed for the quaternary system
H2 O + C O2 + P Z ↔ P ZCO− +
2
were determined in previous work (see Table 23). A gamma-phi
2 + H3 O (R6)
equation was used to solve the phase equilibrium between vapor
KPZ H + CO−
and liquid phase:
H2 O + P Z H +CO− ↔ P ZCO− +
2
2 2 + H3 O (R7) yi · P · ϕi = γi · xi · i · ψi (3)

The liquid phase activity coefficient parameters were estimated

K
( )2
PZ CO−
2  
H2 O + C O2 + P ZCO−
2
↔ P Z CO−
2 + H3 O+ (R8) using the eNRTL model [11] and in the gas phase, the Peng Robin-
2
son EoS [15] equation of state was used to calculate the fugacity
coefficients of the components: ϕi (− ). The Poynting factor, i (− ),
KAMPH +
H2 O + AMP H + ↔ AMP + H3 O+ (R9) was also considered. The reference state of species was taken as
follows:
KAMPCO− 
H2 O + C O2 + AMP ↔ AMPCO− + 2
pSi φiS , pure component re f erence state f or water and amines .
2 + H3 O (R10) i =
Hi∞ in f inite dilution re f erence state f or C O2
Altogether fifteen species are present in the system: Four
(4)
molecules (H2 O, C O2 , AMP, PZ), and cations (H3 O+ , P Z H + , AMP H + ,
P Z22+ ), six anions (OH − , HCO−
3
, CO23− , P ZCO−
2
, AMPCO−
2
, P Z (C O2 )22− ) A PSO algorithm was implemented for fitting the binary inter-
and one zwitterion (P Z H +CO− 2
) . action parameters [14] in the quaternary system whereas the pa-
rameters for the binary interaction parameters in the ternary sys-
2.2. Thermodynamic modeling tems are taken from previous work, (see [10,12]).

The local interaction energy parameters in the NRTL/eNRTL

models [11] are expressed as: 3. Materials and experimental setups

bi j 3.1. Materials
τi j = a i j + (1)
T
In any specific system, the number of interaction energy param- The purchased chemicals, as shown in Table 3, were used with-
eters needed (in eNRTL) can be calculated according to Eq. 2 (see out additional purification. Aqueous 3.0 M AMP, 1.5M PZ and the
[13,14]): five solutions with different AMP/PZ ratios, were prepared volu-
metrically and gravimetrically in 1 dm3 flasks over a scale (Met-
M!
NP = + 2 ·M ·C ·A (2) tler Toledo PM1200) at ambient temperature. All amine concentra-
( M − 2 )! tions given are for unloaded solutions. For the loaded solutions,
Where NP, M, C and A represent the number of parameters, the amine concentrations were determined by titration whereas
molecules, cations, and anions respectively. Even when only a sim- the CO2 contents were analyzed with the wet chemistry BaCl2
ple interaction parameter equation (Eq. 1) is used, this doubles the method. These two techniques are described in detail in previ-
number of parameters to be estimated. The number of interaction ous work [10,12,16–18]. The unit conversions of the prepared so-
parameters needed from the binary to the quaternary system, is lutions to molality and mass % are provided in Table 4. For conve-
given in Table 2. nience, the solution name is used in this manuscript for own work,
In the AMP/H2 O/CO2 system [10], 39 parameters (NP) were fit- whereas for the reported literature data, the original concentration
ted and in the PZ/H2 O/CO2 system[12], 100 parameters (NP) were units are used as presented in Table 1.

3
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 3
Chemicals used in this work.

Amine Abbreviation CAS number Purity Supplier

2-Amino-2-Methyl-1-propanol AMP 124-68-5 ≥0.985a Sigma Aldrich

Piperazine PZ 110-85-0 ≥0.992a Sigma Aldrich
Carbon Dioxide CO2 124-38-9 ≥0.99999 AGA Gas GmbH
a
in a mass fraction basis and taken from the Certificate of Analysis CoA from the supplier.

Table 4
The prepared solutions for experiments.

Solution Molarity (Mol per dm3 solution) Molality (Mol per kg water) Mass % (100%∗ kg/ kg total)
No. name
AMP PZ AMP PZ AMP PZ

1 3.0M AMP 3.0 0.0 4.1 0.0 26.8 0.0

2 1.5M PZ 0.0 1.5 0.0 2.1 0.0 12.8
3 3.0M AMP+1.5M PZ 3.0 1.5 5.0 2.5 26.7 12.9
4 0.5M AMP+4.0M PZ 0.5 4.0 0.8 6.1 4.2 32.8
5 1.5M AMP+3.0MPZ 1.5 3.0 2.3 4.7 12.9 25.0
6 2.25M AMP+2.25M PZ 2.25 2.25 3.6 3.6 19.8 19.2
7 4.0M AMP+0.5M PZ 4.0 0.5 6.7 0.8 35.7 4.3

Fig. 1. The CPA202 reaction calorimeter (ChemiSens AB, Sweden).

3.2. Experimental setups
3.2.1. Atmospheric pressure VLE apparatus
An atmospheric pressure VLE apparatus was used to generate
one set of partial pressures of CO2 over 3M AMP+1.5M PZ solu-
tion as function of CO2 loading and temperature. The detailed tech-
niques and procedures can be found in our previous work [18,19].
3.2.2. Medium pressure VLE apparatus
A medium pressure VLE apparatus was also used to perform
equilibrium experiments for total pressure data over 3M AMP and
1.5M PZ solutions at different CO2 loadings and temperatures. De-
tails about the techniques and procedures can be found in previous
work [18,19].
3.2.3. Reaction calorimetry experiments
A commercially available reaction calorimeter, CPA 202
(ChemiSens AB, Sweden) (see Fig. 1), was used as described
in previous work [20,21]. An experimental procedure (see Fig. 2)
similar to one described by Kim and Svendsen (2007) [22] was
used in this work: the CO2 was added in several steps to the
solution which was kept at isothermal conditions. The amount of
heat removed by the system to keep the solution at constant tem-
perature was then assumed to be equal to the heat of absorption.
The total pressure was measured and the partial pressure of CO2
above the solvent and the loading at a given temperature were
calculated according to Hartono, et al. (2008) [23].
3.2.4. Experimental uncertainties
For the atmospheric and medium pressure VLE measurements,
the uncertainties were estimated as explained in previous works
[16,18,24], whereas for the heat of absorption experiments, the es-
timation of uncertainties is given in the supporting information
(see Part A1). In the tables showing the data, some experimental
points are marked and have high uncertainty because of the small
amount of CO2 added to the reactor. This is further explained in
the supporting information. This should be considered when using
the data.

4
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 5
Measured CO2 solubility data over an aqueous solution of 3.0M AMP+1.5M PZ at different temperatures T, pressures P and
loadings α a .

313K 333K 353K

PC O2 /kPa u(PC O2 ) α u (α ) PC O2 /kPa u(PC O2 ) α u (α ) PC O2 /kPa u(PC O2 ) α u (α )

0.026 0.002 0.19 0.01 0.044 0.002 0.09 0.01 0.036 0.002 0.037 0.01
0.034 0.002 0.21 0.01 0.075 0.002 0.12 0.01 0.059 0.002 0.035 0.01
0.090 0.002 0.29 0.01 0.16 0.002 0.17 0.01 0.11 0.002 0.05 0.01
0.11 0.002 0.31 0.01 0.27 0.003 0.21 0.01 0.24 0.002 0.08 0.01
0.20 0.002 0.38 0.01 0.40 0.03 0.24 0.01 0.36 0.03 0.10 0.01
0.38 0.03 0.44 0.01 0.54 0.05 0.27 0.01 0.48 0.04 0.11 0.01
0.53 0.05 0.47 0.01 0.81 0.07 0.30 0.01 0.71 0.06 0.14 0.01
0.95 0.09 0.52 0.02 0.97 0.09 0.33 0.01 1.36 0.1 0.19 0.01
1.60 0.1 0.58 0.02 2.35 0.2 0.42 0.01 2.21 0.2 0.23 0.01
2.31 0.2 0.60 0.02 4.62 0.4 0.48 0.01 3.24 0.3 0.26 0.01
3.04 0.3 0.61 0.02 6.78 0.6 0.53 0.02 4.25 0.3 0.30 0.01
3.06 0.3 0.62 0.02 8.16 0.7 0.54 0.02 5.24 0.4 0.33 0.01
5.18 0.5 0.66 0.02 11.46 1.0 0.59 0.02 13.06 1.2 0.42 0.01
10.12 1.0 0.70 0.02 19.66 1.8 0.61 0.02 - - - -
13.32 1.2 0.729 0.02 - - - - - - - -
22.14 2.0 0.734 0.02 - - - - - - - -

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

Table 6
Measured total pressure data over an aqueous solution of 3.0M
AMP+1.5M PZ as function of temperature and loading α a .

373K 393K

PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α )

212.2 0.5 0.52 0.02 221.1 0.7 0.25 0.02

220.6 0.5 0.53 0.02 227.9 0.5 0.29 0.02
237.9 0.5 0.54 0.02 244.6 0.8 0.30 0.02
249.9 0.5 0.55 0.02 267.3 1.1 0.31 0.02
391.0 0.7 0.64 0.02 334.2 1.3 0.40 0.02
570.6 1.1 0.69 0.02 427.1 1.8 0.49 0.02
714.5 1.5 0.74 0.03 445.4 1.6 0.51 0.02
894.9 1.7 0.78 0.03 599.3 1.2 0.56 0.02
- - - - 795.4 1.6 0.60 0.02
- - - - 837.4 1.7 0.62 0.02
- - - - 934.9 1.9 0.65 0.02

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

the system go up to 934kPa and the loading covers the range from
0.25 to 0.78 mol CO2 per mol total amine.

4.3. Reaction calorimetry

4.3.1. VLE data

Fig. 2. Experimental procedure.
4. Experimental results
4.1. Atmospheric pressures VLE
The measured solubilities for CO2 in 3.0M AMP+1.5M PZ aque-
ous solution is given in Table 5. Partial pressures of CO2 ranging
from 0.026 to 22.14 kPa are reported for three temperatures (313,
333 and 353K) and loadings from 0.035 to 0.73 mol CO2 / mol total
amine.
4.2. Medium pressures VLE
In Table 6, the measured total pressures for an aqueous solution
of 3.0M AMP and 1.5M PZ are reported as function of loading at
two temperatures (373 and 393K). The measured total pressures of
New total pressure data for 3.0M of AMP are reported in Table 7
and for 1.5M PZ in Table 8. The data were obtained at five temper-
atures (313, 333, 353, 373, 393K) with total pressures up to 733
kPa and with CO2 loadings from 0.07 to 0.96 mol of CO2 per mol
of AMP and up to 843 kPa with CO2 loadings from 0.24 to 1.18 mol
of CO2 per mol of PZ.
Five blends with different mol ratios of AMP/PZ (0.5M/4M,
1.5M/3.0M, 2.25M/2.25M, 3.0M/1.5M, 4M/0.5M) were also studied
in the same temperature range. Results are shown in Tables 9-13.
The pressures cover up to 693 kPa and loadings up to 1.05 mol
CO2 / mol amine.
4.3.2. Heat of absorption data
Table 14 shows experimental results for the heat of absorption
of CO2 into 3M AMP where the values vary from 67 to 33 J/mol/K
when going from a CO2 loading of 0.2 to 0.78 mol CO2 / mol AMP.
The heat of absorption is seen to decrease slightly with increasing
temperature from 313 to 353K. As a sterically hindered amine, the
heat of absorption is seen to be lower than that of MEA [25].
Table 15 shows experimental results for the heat of absorption
of CO2 into 1.5M PZ where the values vary from 79 to 28 J/mol/K

5
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 7
Experimental total pressure data over an aqueous solution of 3.0M AMP at different temperatures T, pressures P and loadings α a .

313K 333K 353K 373K 393K

PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α )

6.8 0.15 0.07 0.01 18.8 0.15 0.07 0.01 45.7 0.20 0.07 0.01 97.9 0.20 0.07 0.01 202.1 0.20 0.07 0.01
6.9 0.15 0.13 0.01 19.3 0.15 0.14 0.01 47.9 0.20 0.13 0.01 108.6 0.20 0.14 0.01 238.0 0.20 0.14 0.01
7.0 0.15 0.20 0.01 20.2 0.15 0.21 0.01 51.5 0.20 0.20 0.01 124.6 0.20 0.21 0.01 288.6 0.20 0.20 0.01
7.2 0.15 0.26 0.01 21.4 0.15 0.28 0.01 56.4 0.20 0.26 0.01 146.4 0.20 0.27 0.01 352.8 0.20 0.26 0.01
7.6 0.15 0.33 0.01 23.2 0.15 0.35 0.01 63.2 0.20 0.33 0.01 174.9 0.20 0.34 0.01 432.4 0.20 0.32 0.01
8.1 0.15 0.39 0.01 25.8 0.15 0.42 0.01 72.6 0.20 0.40 0.01 212.5 0.20 0.40 0.01 528.1 0.20 0.38 0.01
8.9 0.15 0.46 0.01 29.7 0.15 0.49 0.01 85.3 0.20 0.46 0.01 261.1 0.20 0.47 0.01 642.1 0.20 0.43 0.01
10.2 0.15 0.52 0.02 35.6 0.15 0.56 0.02 103.0 0.20 0.52 0.02 325.0 0.20 0.53 0.02 - - - -
12.6 0.15 0.59 0.02 44.8 0.20 0.62 0.02 128.1 0.20 0.59 0.02 406.5 0.20 0.58 0.02 - - - -
16.7 0.15 0.65 0.02 59.4 0.20 0.69 0.02 163.9 0.20 0.65 0.02 510.0 0.20 0.64 0.02 - - - -
24.2 0.15 0.71 0.02 83.9 0.20 0.76 0.02 215.4 0.20 0.71 0.02 640.5 0.20 0.69 0.02 - - - -
38.7 0.15 0.78 0.02 126.8 0.20 0.82 0.02 289.9 0.20 0.76 0.02 - - - - - - - -
81.1 0.20 0.85 0.03 205.1 0.20 0.87 0.03 396.5 0.20 0.81 0.02 - - - - - - - -
174.8 0.20 0.90 0.03 341.6 0.20 0.92 0.03 542.4 0.20 0.86 0.03 - - - - - - - -
609.1 0.20 0.95 0.03 463.0 0.20 0.94 0.03 733.2 0.20 0.90 0.03 - - - - - - - -
- - - - 468.4 0.20 0.94 0.03 - - - - - - - - - - - -
- - - - 665.0 0.20 0.96 0.03 - - - - - - - - - - - -

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

Table 8
Experimental total pressure data over an aqueous solution of 1.5M PZ at different temperatures T, pressures P and loadings α a .

313K 333K 353K 373K 393K

PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α )

7.5 0.15 0.41 0.01 22.1 0.15 0.25 0.01 49.5 0.20 0.27 0.01 102.9 0.20 0.25 0.01 201.7 0.20 0.24 0.01
7.7 0.15 0.55 0.02 22.3 0.15 0.37 0.01 50.4 0.20 0.40 0.01 105.5 0.20 0.37 0.01 211.7 0.20 0.36 0.01
8.4 0.15 0.68 0.02 22.7 0.15 0.49 0.01 53.5 0.20 0.53 0.02 112.0 0.20 0.49 0.01 233.7 0.20 0.47 0.01
12.0 0.15 0.82 0.02 24.4 0.15 0.62 0.02 62.8 0.20 0.66 0.02 128.3 0.20 0.61 0.02 279.4 0.20 0.58 0.02
38.5 0.15 0.94 0.03 30.3 0.15 0.74 0.02 94.3 0.20 0.78 0.02 169.2 0.20 0.72 0.02 368.9 0.20 0.68 0.02
171.9 0.20 1.03 0.03 56.6 0.20 0.85 0.03 189.0 0.20 0.88 0.03 264.4 0.20 0.82 0.02 522.9 0.20 0.76 0.02
380.4 0.20 1.09 0.03 179.8 0.20 0.95 0.03 370.9 0.20 0.96 0.03 443.4 0.20 0.90 0.03 - - - -
607.7 0.20 1.14 0.03 400.8 0.20 1.01 0.03 610.8 0.20 1.01 0.03 699.8 0.20 0.96 0.03 - - - -
843.4 0.20 1.18 0.04 663.9 0.20 1.05 0.03 - - - - - - - - - - - -

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

Table 9
Experimental total pressure data over an aqueous solution of 0.5M AMP+4.0M PZ at different temperatures T, pressures P and loadings α a .

313K 333K 353K 373K 393K

PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α )

6.3 0.15 0.34 0.01 18.5 0.15 0.21 0.01 40.2 0.20 0.22 0.01 92.5 0.20 0.19 0.01 182.9 0.20 0.24 0.01
6.3 0.15 0.42 0.01 18.6 0.15 0.26 0.01 40.5 0.20 0.30 0.01 93.5 0.20 0.26 0.01 189.8 0.20 0.32 0.01
6.4 0.15 0.50 0.02 18.8 0.15 0.37 0.01 41.7 0.20 0.39 0.01 95.2 0.20 0.33 0.01 201.9 0.20 0.40 0.01
6.5 0.15 0.59 0.02 19.0 0.15 0.45 0.01 43.4 0.20 0.47 0.01 98.0 0.20 0.39 0.01 224.9 0.20 0.48 0.01
7.0 0.15 0.67 0.02 19.6 0.15 0.53 0.02 46.0 0.20 0.54 0.02 102.9 0.20 0.46 0.01 264.4 0.20 0.56 0.02
8.4 0.15 0.75 0.02 20.7 0.15 0.61 0.02 51.5 0.20 0.62 0.02 111.7 0.20 0.53 0.02 339.7 0.20 0.63 0.02
14.1 0.15 0.83 0.02 23.8 0.15 0.69 0.02 64.2 0.20 0.70 0.02 128.5 0.20 0.60 0.02 469.8 0.20 0.70 0.02
40.0 0.20 0.91 0.03 33.2 0.15 0.77 0.02 96.0 0.20 0.77 0.02 160.8 0.20 0.67 0.02 680.5 0.20 0.75 0.02
143.5 0.20 0.98 0.03 65.4 0.20 0.85 0.03 172.0 0.20 0.84 0.03 223.9 0.20 0.73 0.02 - - - -
373.1 0.20 1.03 0.03 166.0 0.20 0.92 0.03 337.4 0.20 0.91 0.03 - - - - - - - -
601.6 0.20 1.05 0.03 388.5 0.20 0.97 0.03 472.2 0.20 0.93 0.03 - - - - - - - -
- - - - 629.0 0.20 1.00 0.03 590.3 0.20 0.95 0.03 - - - - - - - -

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

with CO2 loadings varying from 0.4 to 1.2 mol CO2 / mol PZ. As for
AMP, the heat of absorption decreases somewhat with increasing
the temperature from 313 to 353K. As expected for a secondary
diamine, the heat of absorption is lower than that of MEA [25].
For the five blends of AMP/PZ, the heats of absorption are given
in Tables 16-20. The heat of absorption of the blends is more simi-
lar to MEA than the AMP or PZ systems. The values vary from 88 to
36 J/mol/K for CO2 loadings from 0.21 to 1.05 mol CO2 /mol amine.
The heat of absorption is seen to be relatively insensitive to both
temperature and to the blend ratio. The heats of absorption of the
individual solvents (3.0 M AMP and 1.5 MPZ) are seen to be lower
than for the blends with the same amount of each amine (3.0M
AMP+ 1.5M PZ). However, the total amine concentration is higher
which may indicate that solvation, and therefore water, plays an
important role.
5. Modeling results
The pure component properties used in this work were taken
from the DIPPR database [26] and are given in Table 21. Corre-
lations for various properties, with source reference, are given in
Table 22. The equilibrium constants for reactions R1 to R8 are
shown in Table 23.

6
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 10
Experimental total pressure data over an aqueous solution of 1.5M AMP+3.0M PZ at different temperatures T, pressures P and loadings α a .

313K 353K 373K 393K

PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α )

6.5 0.15 0.45 0.01 44.4 0.20 0.21 0.01 94.1 0.20 0.20 0.01 185.6 0.20 0.18 0.01
6.6 0.15 0.49 0.01 44.7 0.20 0.25 0.01 95.2 0.20 0.25 0.01 189.3 0.20 0.22 0.01
6.7 0.15 0.54 0.02 45.1 0.20 0.29 0.01 96.9 0.20 0.30 0.01 194.4 0.20 0.27 0.01
6.8 0.15 0.58 0.02 45.7 0.20 0.34 0.01 99.2 0.20 0.35 0.01 201.4 0.20 0.31 0.01
7.2 0.15 0.63 0.02 46.5 0.20 0.38 0.01 102.5 0.20 0.40 0.01 211.0 0.20 0.35 0.01
7.9 0.15 0.67 0.02 47.6 0.20 0.42 0.01 107.2 0.20 0.44 0.01 224.0 0.20 0.39 0.01
9.3 0.15 0.72 0.02 49.2 0.20 0.46 0.01 114.2 0.20 0.49 0.01 241.7 0.20 0.44 0.01
12.5 0.15 0.76 0.02 51.6 0.20 0.51 0.02 124.2 0.20 0.54 0.02 265.7 0.20 0.48 0.01
19.6 0.15 0.80 0.02 55.2 0.20 0.55 0.02 139.2 0.20 0.58 0.02 297.9 0.20 0.52 0.02
36.3 0.15 0.85 0.03 60.7 0.20 0.59 0.02 161.4 0.20 0.63 0.02 341.7 0.20 0.56 0.02
72.6 0.20 0.89 0.03 69.5 0.20 0.63 0.02 194.9 0.20 0.67 0.02 400.3 0.20 0.60 0.02
143.4 0.20 0.93 0.03 83.9 0.20 0.68 0.02 234.8 0.20 0.71 0.02 476.9 0.20 0.64 0.02
259.7 0.20 0.96 0.03 107.4 0.20 0.72 0.02 304.1 0.20 0.75 0.02 580.9 0.20 0.67 0.02
410.9 0.20 0.99 0.03 146.3 0.20 0.76 0.02 395.9 0.20 0.79 0.02 - - - -
- - - - 209.4 0.20 0.79 0.02 477.4 0.20 0.81 0.02 - - - -
- - - - 306.9 0.20 0.83 0.02 - - - - - - - -
- - - - 445.4 0.20 0.86 0.03 - - - - - - - -
- - - - 558.2 0.20 0.88 0.03 - - - - - - - -

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

Table 11
Experimental total pressure data over an aqueous solution of 2.25M AMP+2.25M PZ at different temperatures T, pressures P and loadings α a .

313K 333K 353K 373K 393K

PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α )

6.5 0.15 0.37 0.01 19.4 0.15 0.20 0.01 44.2 0.20 0.18 0.01 96.5 0.20 0.19 0.01 209.3 0.20 0.25 0.01
6.6 0.15 0.41 0.01 19.5 0.15 0.25 0.01 45.1 0.20 0.24 0.01 100.0 0.20 0.25 0.01 245.1 0.20 0.34 0.01
6.7 0.15 0.45 0.01 19.6 0.15 0.29 0.01 46.6 0.20 0.30 0.01 105.8 0.20 0.31 0.01 350.1 0.20 0.45 0.01
6.8 0.15 0.49 0.01 19.8 0.15 0.33 0.01 48.6 0.20 0.35 0.01 115.4 0.20 0.37 0.01 545.6 0.20 0.55 0.02
7.1 0.15 0.53 0.02 20.1 0.15 0.37 0.01 52.4 0.20 0.41 0.01 131.3 0.20 0.43 0.01 - - - -
7.6 0.15 0.57 0.02 20.5 0.15 0.41 0.01 59.2 0.20 0.47 0.01 155.4 0.20 0.49 0.01 - - - -
8.6 0.15 0.61 0.02 21.1 0.15 0.45 0.01 72.3 0.20 0.53 0.02 196.3 0.20 0.55 0.02 - - - -
10.6 0.15 0.66 0.02 22.1 0.15 0.49 0.01 98.1 0.20 0.59 0.02 267.0 0.20 0.60 0.02 - - - -
14.9 0.15 0.70 0.02 23.8 0.15 0.53 0.02 149.7 0.20 0.64 0.02 382.4 0.20 0.65 0.02 - - - -
24.4 0.15 0.74 0.02 26.5 0.15 0.57 0.02 250.4 0.20 0.69 0.02 557.2 0.20 0.70 0.02 - - - -
44.1 0.20 0.78 0.02 31.3 0.15 0.61 0.02 419.1 0.20 0.74 0.02 - - - - - - - -
60.5 0.20 0.80 0.02 40.2 0.20 0.65 0.02 - - - - - - - - - - - -
151.0 0.20 0.85 0.03 56.4 0.20 0.69 0.02 - - - - - - - - - - - -
210.4 0.20 0.87 0.03 137.3 0.20 0.76 0.02 - - - - - - - - - - - -
347.8 0.20 0.90 0.03 345.7 0.20 0.82 0.02 - - - - - - - - - - - -

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

Table 12
Experimental total pressure data over an aqueous solution of 3.0M AMP+1.5M PZ at different temperatures T, pressures P and loadings α a .

313K 333K 353K 373K 393K

PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α )

6.6 0.15 0.33 0.01 19.8 0.15 0.20 0.01 45.4 0.20 0.17 0.01 100.3 0.20 0.20 0.01 212.0 0.20 0.20 0.01
6.7 0.15 0.40 0.01 20.0 0.15 0.25 0.01 46.1 0.20 0.22 0.01 107.0 0.20 0.26 0.01 238.4 0.20 0.26 0.01
6.9 0.15 0.46 0.01 20.3 0.15 0.29 0.01 47.2 0.20 0.26 0.01 118.0 0.20 0.33 0.01 279.3 0.20 0.32 0.01
7.4 0.15 0.53 0.02 20.6 0.15 0.33 0.01 48.7 0.20 0.30 0.01 135.8 0.20 0.39 0.01 338.3 0.20 0.39 0.01
8.7 0.15 0.59 0.02 21.1 0.15 0.37 0.01 50.9 0.20 0.35 0.01 164.4 0.20 0.46 0.01 423.9 0.20 0.44 0.01
11.8 0.15 0.66 0.02 22.0 0.15 0.41 0.01 54.1 0.20 0.39 0.01 209.7 0.20 0.52 0.02 545.5 0.20 0.50 0.02
20.1 0.15 0.73 0.02 23.1 0.15 0.46 0.01 58.6 0.20 0.43 0.01 280.6 0.20 0.58 0.02 708.7 0.20 0.55 0.02
41.8 0.20 0.79 0.02 24.8 0.15 0.50 0.01 65.1 0.20 0.47 0.01 388.6 0.20 0.63 0.02 - - - -
94.4 0.20 0.85 0.03 27.5 0.15 0.54 0.02 74.4 0.20 0.52 0.02 548.4 0.20 0.69 0.02 - - - -
206.6 0.20 0.90 0.03 31.9 0.15 0.58 0.02 88.4 0.20 0.56 0.02 - - - - - - - -
315.3 0.20 0.93 0.03 38.7 0.15 0.62 0.02 109.4 0.20 0.60 0.02 - - - - - - - -
338.8 0.20 0.94 0.03 50.1 0.20 0.66 0.02 140.7 0.20 0.64 0.02 - - - - - - - -
- - - - 68.7 0.20 0.70 0.02 186.7 0.20 0.68 0.02 - - - - - - - -
- - - - 99.6 0.20 0.74 0.02 253.4 0.20 0.72 0.02 - - - - - - - -
- - - - 148.2 0.20 0.78 0.02 - - - - - - - - - - - -
- - - - 224.7 0.20 0.82 0.02 - - - - - - - - - - - -
- - - - 332.7 0.20 0.85 0.03 - - - - - - - - - - - -
- - - - 408.1 0.20 0.87 0.03 - - - - - - - - - - - -

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

7
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 13
Experimental total pressure data over an aqueous solution of 4.0M AMP +0.5M PZ at different temperatures T, pressures P and loadings α a .

313K 333K 353K 393K

PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α ) PT /kPa u(PT ) α u (α )

6.7 0.15 0.20 0.01 16.0 0.15 0.23 0.01 49.7 0.20 0.19 0.01 254.2 0.20 0.15 0.01
6.8 0.15 0.26 0.01 17.3 0.15 0.31 0.01 54.2 0.20 0.26 0.01 266.2 0.20 0.17 0.01
7.0 0.15 0.33 0.01 19.6 0.15 0.38 0.01 60.7 0.20 0.32 0.01 308.3 0.20 0.21 0.01
7.4 0.15 0.39 0.01 23.3 0.15 0.46 0.01 70.6 0.20 0.39 0.01 310.4 0.20 0.21 0.01
8.1 0.15 0.46 0.01 29.2 0.15 0.53 0.02 85.2 0.20 0.45 0.01 316.0 0.20 0.21 0.01
9.2 0.15 0.52 0.02 35.9 0.15 0.59 0.02 105.5 0.20 0.51 0.02 321.5 0.20 0.22 0.01
15.3 0.15 0.65 0.02 42.3 0.20 0.62 0.02 - - - - 322.5 0.20 0.22 0.01
22.5 0.15 0.71 0.02 - - - - - - - - - - - -
36.8 0.15 0.77 0.02 - - - - - - - - - - -
38.6 0.15 0.78 0.02 - - - - - - - - - - - -

a)α = C O2 loading = mol C O2 /(mol AMP + mol PZ )

Table 14
Measured heat of absorption data over an aqueous solution of 3.0M AMP at different temperatures T, pressures P and loadings α a a .

313K 333K 353K

−HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α )

(kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−]

67.1 4 0.20 0.01 58.3 7 0.21 0.01 53.2 4 0.20 0.01

66.4 4 0.26 0.01 57.6 7 0.28 0.01 49.1 3 0.26 0.01
63.5 4 0.33 0.01 52.6 7 0.35 0.01 43.8 3 0.33 0.01
59.8 4 0.39 0.01 51.5 7 0.42 0.01 41.6 3 0.40 0.01
56.1 4 0.46 0.01 48.0 7 0.49 0.01 37.7 3 0.46 0.01
53.7 4 0.52 0.02 48.3 7 0.56 0.02 37.6 3 0.52 0.02
48.0 3 0.59 0.02 44.7 7 0.62 0.02 34.2 2 0.59 0.02
48.7 3 0.65 0.02 39.6 7 0.69 0.02 39.1 2 0.65 0.02
41.3 3 0.71 0.02 42.1 7 0.76 0.02 55.3 2 0.71 0.02
43.1 3 0.78 0.02 50.9 8 0.82 0.02 53.6 3 0.76 0.02
33.7 ≥10b 0.78 0.02 48.1 8 0.87 0.03 50.8 4 0.81 0.02
- - - - 45.2 ≥10b 0.92 0.03 48.5 3 0.86 0.03
- - - - 45.1 ≥10b 0.94 0.03 50.0 3 0.90 0.03
a
α = C O2 loading = mol C O2 /(mol AMP + mol PZ )
b
because of small amount of added CO2 , the calculated uncertainty becomes large.

Table 15
Measured heat of absorption data over an aqueous solution of 1.5M PZ at different temperatures T, pressures P and loadings α a a .

313K 333K 353K

−HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α )

(kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−]

78.8 6 0.41 0.01 68.7 7 0.25 0.01 53.1 6 0.27 0.01

75.6 6 0.55 0.02 66.5 6 0.37 0.01 56.1 6 0.40 0.01
66.9 5 0.68 0.02 64.3 6 0.49 0.01 54.8 6 0.53 0.02
56.4 5 0.82 0.02 61.7 6 0.62 0.02 52.9 6 0.66 0.02
48.0 5 0.94 0.03 54.6 6 0.74 0.02 41.6 6 0.78 0.02
38.0 6 1.03 0.03 42.6 6 0.85 0.03 49.2 7 0.88 0.03
30.9 9 1.09 0.03 35.6 7 0.95 0.03 43.7 9 0.96 0.03
28.7 ≥10b 1.14 0.03 36.4 ≥10b 1.01 0.03 35.5 ≥10b 1.01 0.03
28.6 ≥10b 1.18 0.04 30.4 ≥10b 1.05 0.03 53.1 - - -
a
α = C O2 loading = mol C O2 /(mol AMP + mol PZ )
b
because of small amount of added CO2 , the calculated uncertainty becomes large.

5.1. The unloaded AMP/PZ and AMP/PZ/H2O systems
The binary interaction parameters for AMP/PZ should ideally
be estimated from data for the binary system. Unfortunately, no
data for the pure AMP/PZ blends were available and the inter-
action parameters for AMP/PZ were therefore indirectly obtained
from fitting of ternary data for the AMP/PZ/H2 O system while
keeping the optimum values for the binary interaction energies of
AMP/H2 O (see [10]) and PZ/H2 O (see [12]). The result for the opti-
mized binary interaction parameters for AMP/PZ were close to zero
(τAMP−PZ = τAMP−PZ = 0). A manual tuning of the obtained results,
setting (τAMP−PZ = −0.5), slightly improved the fit of the activity
coefficient model as seen in Fig. 3. The fit to the freezing point
depression data remained the same as with the original parame-
ters (τAMP−PZ = τAMP−PZ = 0 ), (see Fig. 4) where the solid line (the
original) and the improved one (dashed line) coincide.
Li, et al., [6] reported volatility data for the unloaded system of
2.3m AMP/5m PZ as a function of temperature as shown in Fig. 5.
These volatility data were not used in the parameter fitting. Still,
the model predicts well the AMP volatility but overpredicts the PZ
volatility somewhat. This may be because the PZ volatility is very
low, and therefore, difficult to measure with high accuracy. We see
that the tuning of the AMP/PZ energy interaction parameter does
not influence on the volatility predictions. No effort to improve the
volatility fit was made.

8
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 16
Measured heat of absorption data over an aqueous solution of 0.5M AMP+4.0M PZ at different temperatures T, pressures P and loadings
αa a .
313K 333K 353K

−HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α )

(kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−]

86.8 5 0.34 0.01 58.1 ≥10b 0.21 0.01 72.5 4 0.22 0.01
84.7 4 0.42 0.01 88.0 ≥10b 0.26 0.01 61.1 3 0.30 0.01
84.9 4 0.50 0.02 88.3 ≥10b 0.37 0.01 63.4 3 0.39 0.01
84.0 4 0.59 0.02 82.7 5 0.45 0.01 64.6 4 0.47 0.01
81.3 4 0.67 0.02 86.2 5 0.53 0.02 63.7 4 0.54 0.01
77.7 4 0.75 0.02 79.8 5 0.61 0.02 62.3 3 0.62 0.02
68.9 3 0.83 0.02 75.2 5 0.69 0.02 58.9 3 0.70 0.02
58.1 3 0.91 0.03 65.8 4 0.77 0.02 53.7 3 0.77 0.02
48.6 2 0.98 0.03 53.3 4 0.85 0.03 46.0 3 0.84 0.02
43.1 3 1.03 0.03 50.2 4 0.92 0.03 37.7 3 0.91 0.02
39.3 3 1.05 0.03 46.9 4 0.97 0.03 43.9 7 0.93 0.02
- - - - - - - - 36.4 8 0.95 0.03
- - - - - - - - 35.6 ≥10b 0.96 0.03
a
α = C O2 loading = mol C O2 /(mol AMP + mol PZ )
b
because of small amount of added CO2 , the calculated uncertainty becomes large.

Table 17
Measured heat of absorption data over an aqueous solution of 1.5M AMP+3.0M PZ at different temperatures T, pressures P and loadings
αa a .
313K 333K 353K

−HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α )

(kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−]

78.4 6 0.45 0.01 81.2 7 0.22 0.01 79.7 7 0.21 0.01

84.1 7 0.49 0.01 77.4 7 0.27 0.01 71.8 6 0.25 0.01
82.4 7 0.54 0.02 76.0 7 0.31 0.01 75.5 7 0.29 0.01
82.1 7 0.58 0.02 75.2 7 0.36 0.01 75.9 7 0.34 0.01
82.2 7 0.63 0.02 76.8 7 0.40 0.01 81.3 7 0.38 0.01
81.4 7 0.67 0.02 78.0 7 0.45 0.01 76.0 7 0.42 0.01
78.6 7 0.72 0.02 77.6 7 0.49 0.01 75.4 7 0.46 0.01
79.1 7 0.76 0.02 78.4 7 0.54 0.02 73.5 6 0.51 0.02
82.2 7 0.80 0.02 76.1 7 0.58 0.02 72.7 6 0.55 0.02
79.3 7 0.85 0.03 75.6 7 0.63 0.02 74.9 7 0.59 0.02
77.1 7 0.89 0.03 72.6 7 0.67 0.02 68.8 6 0.63 0.02
73.7 6 0.93 0.03 69.9 7 0.72 0.02 66.7 6 0.68 0.02
68.7 6 0.96 0.03 64.3 6 0.76 0.02 61.9 6 0.72 0.02
65.8 6 0.99 0.03 58.4 6 0.80 0.02 56.3 5 0.76 0.02
- - - - 50.4 6 0.85 0.03 50.4 5 0.79 0.02
- - - - 44.7 8 0.89 0.03 61.5 7 0.83 0.02
- - - - 48.0 7 0.93 0.03 - - - -
- - - - 45.4 7 0.96 0.03 - - - -
- - - - 36.8 ≥10b 0.99 0.03 - - - -
a
α = C O2 loading = mol C O2 /(mol AMP + mol PZ )
b
because of small amount of added CO2 , the calculated uncertainty becomes large.

Table 18
Measured heat of absorption data over an aqueous solution of 2.25M AMP+2.25M PZ at different temperatures T, pressures P and loadings
αa a .
313K 333K 353K

−HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α )

(kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−]

85.7 8 0.37 0.01 87.5 7 0.20 0.01 82.2 5 0.18 0.01

87.9 8 0.41 0.01 79.2 7 0.25 0.01 87.5 5 0.24 0.01
79.0 7 0.45 0.01 85.6 7 0.29 0.01 91.9 6 0.30 0.01
81.1 7 0.49 0.01 86.0 7 0.33 0.01 85.3 5 0.35 0.01
80.7 8 0.53 0.02 85.8 7 0.37 0.01 82.2 5 0.41 0.01
76.4 7 0.57 0.02 87.6 7 0.41 0.01 83.0 5 0.47 0.01
72.2 7 0.61 0.02 85.6 7 0.45 0.01 80.9 5 0.53 0.02
65.9 6 0.66 0.02 82.4 7 0.49 0.01 74.6 5 0.59 0.02
60.1 6 0.70 0.02 78.0 6 0.53 0.02 66.1 5 0.64 0.02
52.9 6 0.74 0.02 77.1 6 0.57 0.02 56.6 4 0.69 0.02
46.9 5 0.78 0.02 72.8 6 0.61 0.02 55.4 5 0.74 0.02
41.4 ≥10b 0.80 0.02 59.6 5 0.65 0.02 - - - -
42.5 ≥10b 0.85 0.03 60.8 5 0.69 0.02 - - - -
36.7 ≥10b 0.87 0.03 55.7 3 0.76 0.02 - - - -
33.7 6 0.90 0.03 49.4 3 0.82 0.02 - - - -
a
α = C O2 loading = mol C O2 /(mol AMP + mol PZ )
b
because of small amount of added CO2 , the calculated uncertainty becomes large.

9
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 19
Experimental values for the heat of absorption over an aqueous solution of 3.0M AMP+1.5M PZ at different temperatures T, pressures P
and loadings α a a .

313K 333K 353K

−HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α )

(kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−]

81.8 5 0.33 0.01 78.9 7 0.20 0.01 82.3 7 0.17 0.01

80.2 5 0.40 0.01 79.5 7 0.25 0.01 84.4 8 0.22 0.01
78.8 4 0.46 0.01 79.3 7 0.29 0.01 83.1 7 0.26 0.01
75.4 4 0.53 0.02 79.8 7 0.33 0.01 83.3 7 0.30 0.01
70.7 4 0.59 0.02 78.8 7 0.37 0.01 83.0 7 0.35 0.01
65.0 4 0.66 0.02 74.9 6 0.41 0.01 80.1 7 0.39 0.01
55.4 3 0.73 0.02 74.4 6 0.46 0.01 78.6 7 0.43 0.01
47.6 3 0.79 0.02 74.0 6 0.50 0.01 74.5 7 0.47 0.01
42.5 3 0.85 0.03 70.8 6 0.54 0.02 70.8 6 0.52 0.02
39.4 3 0.90 0.03 67.8 6 0.58 0.02 67.9 6 0.56 0.02
39.1 6 0.93 0.03 62.7 5 0.62 0.02 63.8 6 0.60 0.02
18.7 ≥10b 0.94 0.03 58.3 5 0.66 0.02 59.4 6 0.64 0.02
- - - - 53.3 5 0.70 0.02 55.3 5 0.68 0.02
- - - - 49.1 4 0.74 0.02 51.5 5 0.72 0.02
- - - - 44.8 4 0.78 0.02 - - - -
- - - - 42.0 4 0.82 0.02 - - - -
- - - - 43.8 5 0.85 0.03 - - - -
- - - - 40.5 9 0.87 0.03 - - - -
a
α = C O2 loading = mol C O2 /(mol AMP + mol PZ )
b
because of small amount of added CO2 , the calculated uncertainty becomes large.

Table 20
Measured heat of absorption data over an aqueous solution of 4.0M AMP+0.5M PZ at different temperatures T, pressures P and loadings
αa a .
313K 333K 353K

−HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α ) −HAbs. u(−HAbs. ) α u (α )

(kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−] (kJ/mol C O2 ) [−]

85.3 5 0.20 0.01 70.8 4 0.23 0.01 77.4 5 0.19 0.01

81.2 4 0.26 0.01 77.1 4 0.31 0.01 80.6 5 0.26 0.01
78.1 4 0.33 0.01 73.3 4 0.38 0.01 77.9 5 0.32 0.01
75.5 4 0.39 0.01 66.6 4 0.46 0.01 76.0 5 0.39 0.01
69.3 4 0.46 0.01 68.3 4 0.53 0.02 75.0 5 0.45 0.01
21.5 ≥10b 0.46 0.01 86.2 7 0.59 0.02 73.7 5 0.51 0.02
72.2 5 0.52 0.02 84.9 9 0.62 0.02 77.4 - - -
48.6 2 0.52 0.02 - - - - - - - -
31.8 1 0.65 0.02 - - - - - - - -
58.6 3 0.71 0.02 - - - - - - - -
53.1 3 0.77 0.02 - - - - - - - -
10.2 ≥10b 0.78 0.02 - - - - - - - -
a
α = C O2 loading = mol C O2 /(mol AMP + mol PZ )
b
because of small amount of added CO2 , the calculated uncertainty becomes large.

Table 21 in different apparatuses, but the results agree very well, both with
Pure component physical properties [26].
the model and earlier data, as seen in Fig. 6 for 3M AMP and Fig. 7
Species for 1.5M PZ. For 3M AMP, it is observed that the data at 313K over-
Properties lap with the data at 323K at the highest loadings, whereas for 1.5M
H2 O CO2 AMP PZ
PZ, the data at 333K are approaching the data at 353K at the high-
TC / K 647.096 304.21 619.818 638.0
est loadings but the difference between the two temperatures is
PC / kPa 22064 7383.0 4862.97 5530
VC / m3 · kmol −1 0.055947 0.0940 0.29650 0.31 still larger than the reported uncertainties (see Table 8).
ω /− 0.344861 0.223621 0.74259 0.41376

5.2.2. Heat of absorption

5.2. The ternary AMP/H2 O/CO2 and PZ/H2 O/CO2 systems
The reported parameters for both ternary systems [10,12] were
directly used in this work. It was not considered to try to im-
prove the quality of the fit with the new sets of AMP/H2 O/CO2 and
PZ/H2 O/ CO2 data for total pressure and heat of absorption from
this work.
5.2.1. Total pressure
The measured total pressures of 3M AMP and 1.5M PZ were
compared to our previous models [10,12]. The data were measured
A comparison between experimental and modelled heats of ab-
sorption for 3M AMP and 1.5M PZ at three different temperatures
(313, 333 and 353K) is shown in Figs. 8 and 9. It should be noted
that the heat of absorption data where not used in the fitting. For
both systems, it is observed that the heat of absorption seems to
decrease slightly with increasing temperature. This is in line with
earlier findings [10]. The heat of absorption results for 3M AMP at
333K and 353K are more scattered than those for 313K. The model
overpredicts the heat of absorption at 313K but predicts better at
333/353K especially at higher loadings. The heat of absorption is
seen to decrease rapidly with increasing loading. This is reason-
able, as for low loadings, carbamate formation, with the high heat

10
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 22
Correlations used in the eNRTL model.

No. Correlation Source

4 6 8
1 ln (HCO∞
2
/ MPa ) = −6.8346 + 1.2817 T
·10
− 3.7668
T2
·10
+ 2.997
T3
·10
[36]
2 ln (PHS2 O / Pa ) = 73.649 − 7258
T
.2
− 7.3037 · ln(T ) + 4.1653 · 10−6 · T 2 [26]
3 log(PAMP
S
/ kPa ) = 7.1408 − T1858
−74.9
.4
[10]a
4 log(PPZS
/ kPa ) = 5.9832 − T1215 .77
−113.56
[12]
∞
5 VAMP /cm3 · mol −1 = 84.15 − 5.887 · 10−3 · T + 1.516 · 10−4 · T 2 [37]
∞
6 VPZ /cm3 · mol −1 = 108.84 − 1.5538 · 10−2 · T + 1.8385 · 10−4 · T 2 [26]
7 εAMP = 21.0466 + 8451.2 · ( T1 − 2981.15 ) [10]
8 εPZ = 35.76 + 14836 · ( T1 − 2731.15 ) [12]
Dielectric
constantb
a
There was a typo in the original manuscript written as a logarithmic in a natural basis (ln) but it should
be in a 10 basis (log10)
b
For CO2 and H2 O are taken from Aspen plus.

Fig. 3. Activity coefficients of AMP (1) and PZ(2) in ternary AMP/PZ/H2 O at a). 313K
Fig. 5. Volatility for an unloaded aqueous solution of 2.3 m AMP and 5m PZ at
b). 333K c). 353K d). 363K and e). 373K (Points, [27]; Lines, NRTL; ✷, AMP; ✷, PZ;
different temperatures (✷, AMP; ✷, PZ; ✷, H2 O; [6]; Lines, eNRTL; —, PAMP ; —, PPZ ; —,
Solid lines, τAMP−PZ = τAMP−PZ = 0; Dashed lines, τAMP−PZ = −0.5 and τPZ−AMP = 0).
PH2 O ; Solid lines, τAMP−PZ = τAMP−PZ = 0; Dashed lines, τAMP−PZ = −0.5 and τPZ−AMP =
0).

Fig. 4. Freezing point depression in the ternary AMP/PZ/H2 O system (Points, [28];
Lines, NRTL; Solid line, τAMP−PZ = τAMP−PZ = 0; Dashed line, τAMP−PZ = −0.5 and
τPZ−AMP = 0).

of absorption, will affect the values, whereas at higher loadings
only bicarbonate/carbonate formation takes place. The contribution
of each reaction in the system is shown in different colors. The
heat of protonation of AMP is the main contributor to the total
Fig. 6. Representation of the e-NRTL model for the total pressure over an aqueous
solution of 3.0M AMP at different temperatures (Points; Exp.; Lines, eNRTL; Squares,
[10]; , 353K; , 373K; , 393K; Stars, This work; ✷, 313K; ✷, 333K; ✷, 353K, ✷,
373K; ✷, 393K).

11
A. Hartono, R. Ahmad, H.F. Svendsen et al.
Fig. 7. Representation of the e-NRTL model for the total pressure over an aqueous
solution of 1.5M PZ at different temperatures (Points; Exp; Lines, eNRTL; Squares,
[12]; , 373K; , 393K; Stars, This work; ✷, 313K; ✷, 333K; ✷, 353K, ✷, 373K; ✷,
393K).
Fig. 8. Representation of the eNRTL model predictions for the total heat of absorp-
tion and heats of each individual reaction as a function of loading over an aque-
ous solution of 3.0M AMP at different temperatures a).313K b). 333K c). 353K. (✷;
Exp.; Lines, eNRTL; ✷/—, Total; —, AMP H + diss.; —, AMPCO− f orm.; —, HCO− f orm.; —,
CO23− f orm.; —, C O2 dissol.; —, H2 O diss.)
2 3
heat of absorption up toward a loading of 1 where the dissolution
of CO2 takes over.
The experimental results for 1.5M PZ look more consistent than
those for 3.M AMP as seen in Fig. 9. The heat of absorption of
1.5M PZ decreases with increasing temperature as mentioned ear-
lier. The model predictions for the total heat of absorption are also
given in Fig. 9 and show less temperature sensitivity than indi-
cated by the experimental results. For 313K and 333K the agree-
ment is good, but at the highest temperatures the heat of absorp-
tion seems to be over-predicted by the model. PZ protonation and
PZ-monocarbamate formation give significant contributions up to a
loading of 0.6, but the zwitterion formation takes over up to load-
ing 1. After loading 1, CO2 dissolution is the most important part
in the total heat of absorption since the contributions from the
zwitterion, the protonated PZ and PZ-monocarbamate cancel each
other. Carbonate/ bicarbonate and dicarbamate play a minor role.
12
Fluid Phase Equilibria 550 (2021) 113235
Fig. 9. Representation of the eNRTL model for the total heat of absorption and
heats of each individual reactions as a function of loading over an aqueous so-
lution of 1.5 M PZ at different temperatures a).313K b). 333K c). 353K (✷; Exp.;
Lines, eNRTL; ✷/—, Total; •–•, PZ H + diss.; •–•, PZCO−2
f orm.; —, PZ H +CO−2
diss.; —,
PZ (CO− ) f orm.; —, HCO−3 f orm.; —, CO23− f orm.; —, PZH22+ diss.; —, C O2 dissol.; —,
2 2
H2 O diss.).
5.3. The quaternary AMP/PZ/CO2 /water system
Fifteen species can describe the quaternary system of
AMP/PZ/H2 O/CO2 system, i.e., the sum of species of each ternary
AMP/H2 O/CO2 and PZ/H2 O/CO2 system. No new reaction was
introduced. Although the parameters of each ternary system from
our previous work were kept, the remaining number of parame-
ters to be fitted for the quaternary system is still large (82 binary
interaction energy parameters).
Part of the VLE data in Table 1, as indicated in Table 24, and
the VLE results from this work were used in the regression of the
model parameters for the quaternary system. The heat of absorp-
tion data was not used. The model results for CO2 partial pressure,
total pressure, and heat of absorption are presented and compared
with experimental data.
The goodness of fit is presented in Table 24 as absolute average
relative deviations. We see that the fit is good with an AARD value
of 13.2 % for the total pressure measurements and 20.4% for the
CO2 partial pressure measurements. The obtained optimized pa-
rameters for the quaternary system are collected in
Table 25 where five different color backgrounds show the dif-
ferent systems. In our previous work on the ternary AMP/H2 O/CO2
system [12], unfortunately there were 6 typos in the subscript
indexes referring to the species. The corrections are shown in
Table B1 (in the supporting information). Readers should fol-
low this version and all the parameter values are the same as
reported in Hartono et al. [12]. The developed eNRTL model
is expected to valid for 4.2 ≤ [AMP ](mass % ) ≤ 35.7; 4.3 ≤
[P Z ](mass % ) ≤ 35.8; 0.04 ≤ loading ≤ 1.06; 293K ≤ T (K ) ≤ 433K;
0.03 ≤ PC O2 (kPa ) ≤ 2100. One must be careful if using the model
outside this range.
5.3.1. Partial pressure of CO2
Fig. 10 shows three sets of experimental data for the 3M AMP/
1.5M PZ solvent as function of loading and temperature. The re-
sults from this work were obtained in the same apparatus as used
by Brúder, et al. (2011) [4]. The repeatably is good as well as the
agreement between both sets of data. There is probably one out-
lier at the highest loading from the earlier work [4]. The developed
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 23
Equilibrium reaction constants on mol fraction basis used in the modeling.

ln(Ki ) = A + B
T
+ C · ln(T ) + D · T

Reaction Ki A B C D Source

1 KW 132.899 -13445.9 -22.4773 0 [38]

2 KHCO−3 231.465 -12092.1 -36.7816 0 [38]
3 KCO2− 216.049 -12431.7 -35.4819 0 [38]
3
a
4 KPZ H + -161.45575 -2.0232 25.0432 -0.0255 [12]
5 KPZH 2+ -99.65273 0.21748 14.97413 -0.00797 [12]
2
6 KPZCO−2 -2.8788 1992.1691 -2.01598 0 [12]
7 KPZ H + CO−2 -4.8766 -5864.4040 -0.2350 0 [12]
8 KPZ (CO−2 ) -5.6408 537.6375 -1.7401 0 [12]
2
a
9 KAMPH + -65.0354 -3569.787 8.8903 0 [10]
10 KAMPCO−2 -14.0057 2623.735 -1.8581 0 [10]
a
Asymmetric reference state

Table 24
Absolute average relative deviation (AARD) for the
various data sources.

PTotal

AARD/ % Source AARD/ % Source

11.5 This work 10.2 This work

23.7 [4] 24.4 [32]
22.6 [30] - -
20.9 Total 13.1 Total

Fig. 11. Representation of the eNRTL model for the CO2 partial pressure in 40 mass
% of total amine at different AMP/PZ ratio of ((a). 38/2 (b). 35/5 (c). 32/8) mass %
and at different temperatures (Points, [30]; Lines, eNRTL; ✷/—, 303K; ✷/—, 313K;
✷/—, 323K).

0.5PZ; 3M AMP/1.0M PZ) at the same three temperatures. The data

Fig. 10. Representation of the eNRTL model for the CO2 partial pressure over an
aqueous solution of 3M AMP+1.5M PZ at different temperatures (✷, [29]; ◦, This
work; , [4]; Lines, eNRTL; ✷/◦//—, 313K; ✷/◦//—, 333K; ✷/◦//—, 353K).
model works well for this blend in representing the CO2 partial
pressures and fits better with the data from this work than the
data from Brúder, et al. (2011) [4] as seen from the AARD values in
Table 24.
Yang, et al. (2010) [29] reported CO2 partial pressure data for
the same concentration. The results show that their data agree well
with our data and data from Brúder, et al. (2011) [4] only at 313K
and 333K at higher loadings. At 353K, the data show lower CO2
partial pressures than our data and data from Brúder et al. (2011)
[4] and nearly coincide with the data at 333K. The data of Yang,
et al. (2010) [29] indicate a weaker temperature sensitivity than
our data.
In addition to the concentration mentioned above, Yang, et al.
(2010) [29], also reported PC O2 data for five blends of AMP/PZ, i.e.
2.0M AMP/ 0.5PZ; 2M AMP/1.0M PZ; 2M AMP/1.5M PZ; 3.0M AMP/
from Yang, et al. (2010) [29] were not used in the fitting, but the
model still agrees well with the data, especially at 313K and 333K,
but overpredicts the PC O2 at 353K. The representation of the model
for these different blends can be seen in the supporting informa-
tion (Figures S1(a) for 2M AMP/0.5M PZ; (b) for 2M AMP/1.0M PZ;
(c) for 2M AMP/1.5M PZ; (d) for 3M AMP/0.5M PZ; (e) for 3M
AMP/1.0M PZ; (f) for 3M AMP/1.5M PZ).
Dash, et al. (2012) [30] reported data for two different to-
tal amine concentrations of 40 and 50 mass %, each concentra-
tion with three different AMP/PZ ratios. Fig. 11(a/b/c) shows the
AMP/PZ ratios (38/2, 35/5 and 32/8) with 40 mass % total amine
concentrations while Fig. 12(a/b/c) shows the AMP/PZ ratios (45/5,
48/2 and 42/8) with 50 mass % total amines.
The model represents the CO2 partial pressure data reasonably
well at both total concentrations. For the 40 mass % blends and at
higher loadings, the differences between the CO2 partial pressures
for the three blends become small and the model curves tend to
coincide. This behavior is also seen for the 50 mass % blends. This
indicates that the ratio of AMP/PZ becomes less important at very
high loadings since both AMP and PZ are not available anymore as
free amines.

13
A. Hartono, R. Ahmad, H.F. Svendsen et al. Fluid Phase Equilibria 550 (2021) 113235

Table 25
eNRTL parametersa , b , c .
Molecular Parameters
1.65 -745.70 0.00 0.00 a3,1 - b3,1 - a4,1 - b4,1 -
a1,2 3.29 b1,2 -2526.63 a2,1 3.79 b2,1 -1634.58 0.60 698.51 0.34 546.92
2.14 212.85 -2.58 0.00c
a1,3 5.32 b1,3 -1279.99 a2,3 7.84 b2,3 1024.41 a3,2 1.20 b3,2 -3016.76 a4,2 -0.36 b4,2 0.00
a1,4 4.49 b1,4 -372.03 a2,4 0.84 b2,4 0.00 a3,4 -0.50 b3,4 0.00 a4,3 0.00 b4,3 0.00
Molecule-Salt Parameters
a1,5-9 8.00 b1,5-9 0.00 a2,5-9 15.00 b2,5-9 0.00 a3,5-9 -4.09 b3,5-9 531.72 a4,5-9 -2.52 b4,5-9 0.00
a1,5-10 8.00 b1,5-10 0.00 a2,5-10 15.00 b2,5-10 0.00 a3,5-10 -1.36 b3,5-10 366.48 a4,5-10 2.35 b4,5-10 -476.75
a1,5-11 8.00 b1,5-11 0.00 a2,5-11 15.00 b2,5-11 0.00 a3,5-11 6.79 b3,5-11 1238.55 a4,5-11 0.73 b4,5-11 0.00
a1,5-12 -2.43 b1,5-12 -944.19 a2,5-12 5.66 b2,5-12 -360.92 a3,5-12 0.25 b3,5-12 2243.74 a4,5-12 -2.06 b4,5-12 313.78
a1,5-13 5.52 b1,5-13 -1295.81 a2,5-13 -1.30 b2,5-13 1493.25 a3,5-13 1.64 b3,5-13 -248.07 a4,5-13 -3.25 b4,5-13 -523.67
a1,5-14 -1.16 b1,5-14 0.00 a2,5-14 2.38 b2,5-14 -497.24 a3,5-14 5.49 b3,5-14 1078.41 a4,5-14 0.49 b4,5-14 -1498.19
a1,5-15 -7.74 b1,5-15 -314.26 a2,5-15 2.86 b2,5-15 -2851.96 a3,5-15 1.03 b3,5-15 -409.23 a4,5-15 1.42 b4,5-15 740.26
a1,6-9 1.00 b1,6-9 -2305.53 a2,6-9 -3.62 b2,6-9 1242.77 a3,6-9 -5.19 b3,6-9 1064.44 a4,6-9 -3.04 b4,6-9 -967.67
a1,6-10 6.35 b1,6-10 -1830.97 a2,6-10 -2.15 b2,6-10 207.83 a3,6-10 4.75 b3,6-10 -705.53 a4,6-10 -0.68 b4,6-10 -723.74
a1,6-11 -2.25 b1,6-11 1831.93 a2,6-11 4.12 b2,6-11 -1268.70 a3,6-11 4.12 b3,6-11 1312.84 a4,6-11 3.35 b4,6-11 0.00c
a1,6-12 -2.31 b1,6-12 -970.08 a2,6-12 2.35 b2,6-12 -1705.02 a3,6-12 3.40 b3,6-12 -327.55 a4,6-12 -1.76 b4,6-12 495.46
a1,6-13 -1.56 b1,6-13 -2188.65 a2,6-13 3.38 b2,6-13 -1170.06 a3,6-13 0.84 b3,6-13 -1913.44 a4,6-13 2.06 b4,6-13 0.00c
a1,6-14 0.18 b1,6-14 1073.67 a2,6-14 2.84 b2,6-14 580.52 a3,6-14 4.12 b3,6-14 -1618.26 a4,6-14 -2.75 b4,6-14 -232.63
a1,6-15 -1.41 b1,6-15 -3096.83 a2,6-15 -0.98 b2,6-15 -1562.34 a3,6-15 -3.27 b3,6-15 0.00 a4,6-15 -0.15 b4,6-15 0.00c
a1,7-9 3.25 b1,7-9 0.00 a2,7-9 1.88 b2,7-9 0.00 a3,7-9 3.66 b3,7-9 -716.40 a4,7-9 0.00 b4,7-9 271.95
a1,7-10 1.89 b1,7-10 0.00 a2,7-10 0.94 b2,7-10 0.00 a3,7-10 2.58 b3,7-10 -213.77 a4,7-10 2.82 b4,7-10 0.00
a1,7-11 0.13 b1,7-11 0.00 a2,7-11 3.12 b2,7-11 1394.63 a3,7-11 -0.62 b3,7-11 1425.08 a4,7-11 -2.35 b4,7-11 0.00
a1,7-12 -2.87 b1,7-12 377.05 a2,7-12 -1.82 b2,7-12 -337.01 a3,7-12 3.28 b3,7-12 853.16 a4,7-12 0.57 b4,7-12 -361.96
a1,7-13 0.25 b1,7-13 1386.49 a2,7-13 -2.33 b2,7-13 0.00c a3,7-13 4.13 b3,7-13 -151.95 a4,7-13 1.75 b4,7-13 373.82
a1,7-14 2.13 b1,7-14 -1345.70 a2,7-14 0.00 b2,7-14 0.00 a3,7-14 1.63 b3,7-14 1304.27 a4,7-14 0.00 b4,7-14 966.72
a1,7-15 3.33 b1,7-15 604.08 a2,7-15 -4.71 b2,7-15 632.00 a3,7-15 -0.19 b3,7-15 -1055.87 a4,7-15 -1.33 b4,7-15 -464.49
a1,8-9 1.48 b1,8-9 -2687.27 a2,8-9 3.78 b2,8-9 1166.13 a3,8-9 -3.64 b3,8-9 886.85 a4,8-9 1.47 b4,8-9 -219.21
a1,8-10 0.89 b1,8-10 -201.93 a2,8-10 -2.04 b2,8-10 1037.63 a3,8-10 -4.72 b3,8-10 -1892.65 a4,8-10 -0.09 b4,8-10 -523.45
a1,8-11 -0.75 b1,8-11 -1912.27 a2,8-11 -3.56 b2,8-11 0.00 a3,8-11 2.07 b3,8-11 0.00 a4,8-11 -7.53 b4,8-11 -611.22
a1,8-12 -0.14 b1,8-12 -657.51 a2,8-12 -2.32 b2,8-12 1524.71 a3,8-12 -1.30 b3,8-12 1238.20 a4,8-12 0.00c b4,8-12 396.31
a1,8-13 2.05 b1,8-13 0.00 a2,8-13 -2.59 b2,8-13 3229.01 a3,8-13 -4.18 b3,8-13 -2975.16 a4,8-13 -0.55 b4,8-13 102.57
a1,8-14 1.94 b1,8-14 -122.56 a2,8-14 -2.50 b2,8-14 384.52 a3,8-14 -5.65 b3,8-14 535.40 a4,8-14 1.79 b4,8-14 0.00c
a1,8-15 4.82 b1,8-15 -868.78 a2,8-15 -1.08 b2,8-15 -2283.28 a3,8-15 0.46 b3,8-15 2319.17 a4,8-15 3.81 b4,8-15 -608.69
Salt-Molecules Parameters
a5-9,1 -4.00 b5-9,1 0.00 a6-9,1 2.88 b6-9,1 -1349.56 a7-9,1 0.29 b7-9,1 0.00 a8-9,1 -2.76 b8-9,1 1132.73
a5-9,2 -8.00 b5-9,2 0.00 a6-9,2 -1.44 b6-9,2 878.83 a7-9,2 2.85 b7-9,2 -727.43 a8-9,2 1.39 b8-9,2 1875.27
a5-9,3 2.32 b5-9,3 299.64 a6-9,3 7.31 b6-9,3 1061.16 a7-9,3 -2.16 b7-9,3 -327.95 a8-9,3 -5.95 b8-9,3 -379.24
a5-9,4 2.89 b5-9,4 -478.94 a6-9,4 3.34 b6-9,4 -228.20 a7-9,4 -0.43 b7-9,4 0.00 a8-9,4 -4.01 b8-9,4 444.87
a5-10,1 -4.00 b5-10,1 0.00 a6-10,1 -3.29 b6-10,1 319.39 a7-10,1 0.00 b7-10,1 0.00 a8-10,1 -2.55 b8-10,1 295.13
a5-10,2 -8.00 b5-10,2 0.00 a6-10,2 2.36 b6-10,2 -1668.43 a7-10,2 1.23 b7-10,2 0.00 a8-10,2 0.55 b8-10,2 249.46
a5-10,3 -0.48 b5-10,3 -422.88 a6-10,3 -5.81 b6-10,3 -1786.29 a7-10,3 0.00c b7-10,3 0.00c a8-10,3 5.08 b8-10,3 0.00
a5-10,4 0.56 b5-10,4 -636.61 a6-10,4 3.84 b6-10,4 0.00 a7-10,4 -0.46 b7-10,4 0.00 a8-10,4 4.25 b8-10,4 704.83
a5-11,1 -4.00 b5-11,1 0.00 a6-11,1 1.02 b6-11,1 -577.30 a7-11,1 0.00 b7-11,1 0.00 a8-11,1 8.40 b8-11,1 0.00
a5-11,2 -8.00 b5-11,2 0.00 a6-11,2 5.70 b6-11,2 -652.91 a7-11,2 0.94 b7-11,2 1641.81 a8-11,2 4.92 b8-11,2 237.86
a5-11,3 -3.15 b5-11,3 304.98 a6-11,3 2.88 b6-11,3 0.00 a7-11,3 2.17 b7-11,3 0.00 a8-11,3 -1.68 b8-11,3 -219.79
a5-11,4 0.96 b5-11,4 -504.45 a6-11,4 -5.13 b6-11,4 379.28 a7-11,4 0.96 b7-11,4 0.00 a8-11,4 1.18 b8-11,4 -506.30
a5-12,1 -2.99 b5-12,1 -292.36 a6-12,1 -0.67 b6-12,1 0.00 a7-12,1 -3.95 b7-12,1 -402.65 a8-12,1 -2.48 b8-12,1 611.80
a5-12,2 3.81 b5-12,2 349.07 a6-12,2 0.08 b6-12,2 -316.18 a7-12,2 4.50 b7-12,2 -424.77 a8-12,2 1.08 b8-12,2 772.11
a5-12,3 -1.46 b5-12,3 703.19 a6-12,3 0.00 b6-12,3 -1225.12 a7-12,3 -2.91 b7-12,3 493.94 a8-12,3 -1.30 b8-12,3 -215.19
a5-12,4 -3.32 b5-12,4 330.06 a6-12,4 2.99 b6-12,4 -481.24 a7-12,4 -1.90 b7-12,4 -268.45 a8-12,4 -5.84 b8-12,4 1253.56
a5-13,1 -1.75 b5-13,1 -1618.74 a6-13,1 0.93 b6-13,1 -548.33 a7-13,1 -5.72 b7-13,1 701.64 a8-13,1 2.51 b8-13,1 -1560.58
a5-13,2 3.53 b5-13,2 0.00 a6-13,2 4.14 b6-13,2 -2895.55 a7-13,2 -0.29 b7-13,2 -350.40 a8-13,2 -6.23 b8-13,2 -319.45
a5-13,3 -1.91 b5-13,3 213.55 a6-13,3 2.96 b6-13,3 -248.20 a7-13,3 3.75 b7-13,3 1194.48 a8-13,3 0.00 b8-13,3 -1377.65
a5-13,4 -4.11 b5-13,4 399.14 a6-13,4 5.92 b6-13,4 1790.76 a7-13,4 8.57 b7-13,4 -190.58 a8-13,4 -2.21 b8-13,4 380.59
a5-14,1 0.00 b5-14,1 -1015.89 a6-14,1 2.97 b6-14,1 -567.09 a7-14,1 0.00 b7-14,1 0.00 a8-14,1 -1.92 b8-14,1 -1169.18
a5-14,2 0.00 b5-14,2 0.00 a6-14,2 -1.01 b6-14,2 0.00 a7-14,2 1.84 b7-14,2 0.00 a8-14,2 -2.23 b8-14,2 -654.28
a5-14,3 -0.21 b5-14,3 1083.10 a6-14,3 2.54 b6-14,3 1092.90 a7-14,3 -1.09 b7-14,3 117.58 a8-14,3 -2.16 b8-14,3 -2405.48
a5-14,4 1.52 b5-14,4 0.00 a6-14,4 6.36 b6-14,4 723.82 a7-14,4 0.00 b7-14,4 -406.72 a8-14,4 -0.53 b8-14,4 -520.94
a5-15,1 6.43 b5-15,1 1104.30 a6-15,1 0.11 b6-15,1 -358.58 a7-15,1 -2.29 b7-15,1 -413.55 a8-15,1 -3.14 b8-15,1 -947.06
a5-15,2 1.25 b5-15,2 0.00 a6-15,2 -2.22 b6-15,2 -912.63 a7-15,2 0.15 b7-15,2 655.41 a8-15,2 -3.01 b8-15,2 1359.43
a5-15,3 3.83 b5-15,3 -1213.89 a6-15,3 1.79 b6-15,3 -1351.47 a7-15,3 0.83 b7-15,3 711.00 a8-15,3 8.03 b8-15,3 1191.30
a5-15,4 -2.97 b5-15,4 -246.05 a6-15,4 1.59 b6-15,4 736.94 a7-15,4 -2.24 b7-15,4 864.20 a8-15,4 -3.25 b8-15,4 629.91
a
AMP/PZ/H2 O/CO2, AMP/PZ, AMP/H2 O/CO2, PZ/H2 O/CO2, Aspen plus® default value
b
Subscript: 1 = H2 O, 2 = C O2 , 3 = PZ, 4 = AMP, 5 = H3 O+ , 6 = PZ H + , 7 = AMP H + 8 = PZ22+ , 9 = OH − , 10 = HCO−
3
, 11 = CO23− , 12 = PZCO−
2
; 13 = PZ (C O2 )22− , 14 =
AMPCO−2
; 15 = (PZ H +CO−
2
)
c
Set to Zero

Li, et al. (2013) [6] reported CO2 partial pressure data for two
blends of AMP/PZ, i.e. 2.3m AMP/ 5m PZ and 4.0m AMP/ 2.0m PZ.
The experiments were performed in two different apparatuses, i.e.,
a wetted wall column and a static medium pressure VLE cell. The
wetted wall column provided data for temperatures up to 373K
while the static medium pressure VLE cell provided data from 373
to 433K. The data were not used in the modeling, but the model
agrees well with the CO2 partial pressure data generated both in
the wetted wall column and the static pressure cell. However, the
total pressure is underpredicted from the static cell total pressure
measurements for the 2.3 m AMP and 5m PZ system. The results
are shown in Fig. 13(a) for 2.3m AMP/ 5m PZ and in Fig. 13(b) for
4.0m AMP/ 2.0m PZ. The reason for the underpredictions might be
that the total pressure sensor did not provide good accuracy in the
pressure ranges reported as the data seem to give the same level
of total pressure for both ratios of PZ/AMP.
Li, et al. (2013) [6] also reported data on amine volatility in the
loaded 2.3m AMP and 5m PZ system. These data were not used in

14
A. Hartono, R. Ahmad, H.F. Svendsen et al.
Fig. 12. Representation of the eNRTL model for the CO2 partial pressure in 50 mass
% of total amine at different AMP/PZ ratio of ((a). 48/2 (b). 45/5 (c). 42/8) mass %
and at different temperatures (Points, [30]; Lines, eNRTL; ✷/—, 318K; ✷/—, 338K).
Fig. 13. CO2 solubility data for (a). 2.3 m AMP and 5m PZ (b). 4.0 m AMP and 2.0
m PZ at different temperatures (Points, [6]; Lines, eNRTL; ✷/—, 293K; ✷/—, 313K;
✷/—, 323K; ✷/—, 353K; ✷/—, 373K; ✷/—, 383K; /•–•, 393K; /•–•, 403K; /•–•,
413K; /•–•, 423K; /•–•, 433K).
the fitting, but the model works well. The results are presented in
Fig. 14 for different temperatures from 303 to 328K. The volatility
of both amines decreases with increasing loading as expected since
less and less free amine is available. The volatility increases with
temperature as also expected. AMP is more volatile than PZ as seen
by both data and model.
The reported CO2 partial pressure data of Jahangiri and
Nabipoor Hassankiadeh (2019)[31] are deemed inconsistent since
higher CO2 partial pressures were reported at lower tempera-
tures and loadings as shown in Figure S2 (see supporting informa-
tion). The reason for this might be that equilibrium was not fully
achieved.
5.3.2. Total pressure
Two different apparatuses, i.e., the medium pressure VLE
(shown as squares) and the calorimeter (shown as stars) were used
to perform total pressure measurements for the 3.0M AMP+1.5M
15
Fluid Phase Equilibria 550 (2021) 113235
Fig. 14. Volatility data for 2.3 m AMP and 5m PZ at different temperatures a). 303K
b). 308K c). 313K d). 318K e). 323K and f). 328K (Stars, [6]; Lines, eNRTL; ✷/—, PPZ ;
✷/—, PAMP ; ✷/—, PH2 O ; ✷/—, PC O2 ).
Fig. 15. Representation of the eNRTL model for the total pressure over an aque-
ous solution of 3.0M AMP+1.5M PZ at different temperatures (Squares, data from
a medium pressure; Stars, data from a calorimeter; Stars, Exp.; Lines, eNRTL; ✷/—,
313K; ✷/—, 333K; ✷/—, 353K, ✷//—, 373K; ✷//—, 393K).
PZ system at 373 and 393K. The agreement between the two data
sets obtained is reasonably good, as seen in Fig. 15. The model is
also able to represent the data satisfactorily.
For other blends, the experiments were performed in the
calorimeter and the results are shown in Fig. 16 (a). for 0.5M
AMP+4.0M PZ, (b). for 1.5M AMP+3.0M PZ, (c). for 2.0M
AMP+2.0M PZ, and (d). for 4.0M AMP+0.5M PZ respectively. The
model predicts reasonably well the total pressure of the system.
Tong, et al. (2013) [32] reported data for 30 mass % total amine
for two different ratios of AMP/PZ as seen in Fig. 17(a) for 25/5
mass % of AMP/PZ and Fig. 17(b) for 20/10 mass % of AMP/PZ. The
model agrees very well with the data at the lowest temperature
(333K) but deviates more at higher temperatures.
Murshid, et al. (2014) [33] reported total pressure data (from
0.5 to 6 MPa) for two AMP concentrations (8.9 and 17.9 mass %)
in blends with different PZ concentrations (1.74, 6.88 and 10.35
mass % PZ) and at two temperatures (318 and 338K). The reported
A. Hartono, R. Ahmad, H.F. Svendsen et al.
Fig. 16. Representation of the eNRTL model for the total pressure over aqueous so-
lutions of (a). 0.5M AMP+4.0M PZ (b). 1.5M AMP+3.0M PZ (c). 2.25M AMP+2.25M
PZ) (d). 4.0M AMP+0.5M PZ as a function of loading and temperature (Stars, Exp.;
Lines, eNRTL; ✷/—, 313K; ✷/—, 333K; ✷/—, 353K, ✷/—, 373K; ✷/—, 393K).
Fig. 17. Representation of the eNRTL model for the total pressure over aqueous so-
lutions of (a). 25 mass % AMP/ 5 mass % PZ) (b). 20 mass % AMP/ 10 mass % PZ
and at different temperatures (Stars, [32]; Lines, eNRTL; ✷/—, 313K; ✷/—, 333K; —,
353K, ✷/—, 373K; ✷/—, 393K).
loadings were very high, ranging from 1.01 to 2.66 mol CO2 per
mol amine (AMP+PZ). The data were not used in the fitting, and
the model cannot represent the reported total pressure data for
these high loadings (see Figure S3 in the supporting information).
The reported data indicate that concentration still affects the to-
tal pressure at loadings well above 1. It is expected that very little
free AMP and PZ is left in the system at this loading. When no
free amine is left, the ratio of AMP/PZ becomes less important and
the data tend to coincide, as seen earlier. Another reason for the
disagreement with the model could be that for high pressure mea-
surements, the accuracy of the pressure transducer is lower, and
the uncertainty is higher. Efforts were made to improve the fit by
using these data in the regression, but without success.
5.3.3. Heat of Absorption
For an aqueous solution of 3.0 M AMP+1.5 M PZ, the measured
heats of absorption in this work are compared with the reported
data of Xie, et al. (2013) [34] as shown in Fig. 18. The data agree
16
Fluid Phase Equilibria 550 (2021) 113235
Fig. 18. Representation of the eNRTL model for the total heat of absorption and
heats of each individual reactions as a function of loading over an aqueous solution
of 3.0M AMP+1.5M PZ at different temperatures a). 313K b). 333K c). 353K (Points,
Exp.; ✷, This work; , [34]; Lines, eNRTL; —, Total; —, AMP H + diss.; •–•, PZ H + diss.;
—, AMPCO− 2
f orm.; •–•, PZCO− 2
f orm.; —, PZ H +CO− 2
diss.; —, PZ (CO− ) f orm.; —,
2 2
HCO− 3
f orm.; —, CO23− f orm.; —, PZH22+ diss.; —, C O2 dissol.; —, H2 O diss.).
well at higher loadings but at lower loadings, but some disagree-
ment is seen for the lowest temperature at lower loadings. Xie,
et al. (2013) [34] show the same trend when presenting their 5M
MEA data with literature data. No significant effect of temperature
was found in the heat of absorption data.
The modeled total heat of absorption and the contributions of
each reaction are also given in Fig. 18. The agreement between
the model and experimental results is reasonable, but the model
shows more temperature-sensitivity than the data. Under ideal
conditions, where the excess heat of reaction can be disregarded,
a Van ’t Hoff relationship can be used to correlate the heat of ab-
sorption and the CO2 partial pressure. From Fig. 10, it is seen that
the differences in CO2 partial pressure between 333 and 353K is
smaller than between 313 and 333K at a given loading for loadings
up to 0.5 mol of CO2 / mol (AMP+PZ). This indicates that the heat
of absorption is expected to decrease with increasing temperature.
At higher loadings the differences remain almost constant but are
smaller than the differences at lower loading, implying little effect
of temperature on the heat of absorption in this range. The heat
of absorption is predicted by the model to decrease slightly with
increasing temperature. It must be noted that the reported data
were not used in the fitting. At low loadings, significant contribu-
tions from PZ-monocarbamate, protonated PZ and protonated AMP
are observed. By increasing the loading, only protonated AMP con-
tributes significantly, but at loading approaching unity, the zwit-
terion formation is a significant contributor while contributions
from PZ-monocarbamate, PZ-dicarbamate and carbonate/ bicarbon-
ate become smaller.
Measured heats of absorption for different ratios of AMP/PZ
from this work are presented together with model comparisons
in the supporting information: Figure S4 for 0.5M AMP+ 4.0M PZ,
Figure S5 for 4.0M AMP+0.5M PZ, Figure S6 for 1.5M AMP+3.0M
PZ and Figure S7 for 2.0M AMP+2.0M PZ. Furthermore, model
comparisons with the results from the work of Xie, et al. [34] are
also presented in the supporting information: Figure S8 for 3.0M
AMP+0.5M PZ and Figure S9 for 3.0M AMP+1.0M PZ. It may be
seen that the model predictions are good at 333 and 353K but ex-
ceeds the experimental values at 313K and at loadings lower than
0.5.
A. Hartono, R. Ahmad, H.F. Svendsen et al.
Fig. 19. Representation of the eNRTL model for the reported speciation of (a). 4m AMP/ 2m PZ (300K) (b). 4m AMP/ 2m PZ (313K) (c). 2.3m AMP/ 5m PZ (313K) and for the
full speciation of (d). 4m AMP/ 2m PZ (300K) (e). 4m AMP/ 2m PZ (313K) (f). 2.3m AMP/ 5m PZ (313K) (Stars, [35]; Lines, eNRTL; ✷/—/•–•, AMP/AMP H + ; —, AMPCO− 2
—/•–•, P Z/P Z H + /P ZH22+ ; ✷/—/•–•, P ZCO−
2
/P Z H +CO−
2
; ✷/—/, PZ (CO− ) ; ✷/—/, HCO−3 /CO23− ; —, C O2 ).
2 2
The model suggests that the contribution of each reaction de-
pends on the ratio of AMP/PZ. If the AMP concentration is higher
than PZ, the contribution from protonated AMP plays an important
role. In contrast, when the PZ concentration is higher, the contri-
butions of protonated PZ, PZ-monocarbamate, and the zwitterion
are important at different loadings, as in the PZ/H2 O/CO2 system.
5.3.4. Speciation
Li, et al. (2014) [35] reported speciation data for blends of 4m
AMP+2m PZ at (300K and 313K) and for 2.3m AMP+5m PZ, at
313K. A 13C-NMR method was used to measure the concentra-
tions of AMP/AMP H + , P Z/P Z H + /P ZH22+ , P ZCO−
2
/P Z H +CO−2
, P Z (CO− )
2 2
− 2−
and HCO3 /CO3 , respectively. The quality of the NMR data does
not agree well with their analytical results, since the mass bal-
ance for AMP deviates up to 25.1%, for PZ up to 23.4% and for
CO2 up to 7.6 %. These high numbers show the challenges in the
assignments and quantifications of the NMR spectra. The eNRTL
model, to some extent, predicts satisfactorily the speciation data of
AMP/AMP H + , P Z/P Z H + /P ZH22+ , P Z (CO− ) and HCO− /CO23− , but for
2 2 3
the P ZCO− 2
/P Z H +CO− , the model underpredicts the data as seen in
2
Fig. 19 (a/b/c). The full speciation model results for the considered
conditions are presented in Fig. 19 (d/e/f). The NMR data were not
used in the regression.
6. Conclusions
New data comprising CO2 partial pressure for 3.0M AMP/1.5M
PZ and total pressure and heat of absorption for different ratios
of AMP/PZ (3.0/0.0, 0.0/1.5, 0.5/4.0, 1.5/3.0, 2.5/2.5, 3.0/1.5, 4.0/0.5)
M are provided at different loadings and temperatures from three
different apparatuses, i.e. low and medium pressures VLE appara-
tuses and a CPA202 reaction calorimeter. The generated VLE data
of this work from two different apparatuses (The medium pres-
sure and the CPA reaction calorimetric) are in a good agreement.
The reported total pressure over aqueous solutions of 3M AMP and
1.5M PZ are consistent with our previous work whereas the re-
17
Fluid Phase Equilibria 550 (2021) 113235
; ✷/
ported CO2 partial pressure data heat of absorption data from this
work over an aqueous solution of 3M AMP+1.5M PZ show good
agreement with literature and indicates that both sets of data are
consistent.
The measured solubility data and selected data reported
in the literature were used in the regression to estimate bi-
nary interaction energy parameters in the quaternary system
(AMP/PZ/H2 O/CO2 ). The equilibrium constants and binary interac-
tion energy parameters from our previous works on the ternary
systems of AMP/H2 O/CO2 and PZ/H2 O/CO2 were used directly.
The results show that the model represents the data very well
and the AARD values are 13.1% for total pressure and 20.9%
for CO2 partial pressure. The volatility of AMP and PZ as func-
tion of loading and temperature and the reported speciation data
for the AMP/AMP H + , P Z/P Z H + /P ZH22+ , P ZCO−
2
/P Z H +CO−
2
, P Z (CO− )
2 2
− 2−
and HCO3 /CO3 were also well predicted. The developed eNRTL
model is expected to valid for 4.2 ≤ [AMP ](mass % ) ≤ 35.7; 4.3 ≤
[P Z ](mass % ) ≤ 35.8; 0.04 ≤ loading ≤ 1.06; 293K ≤ T (K ) ≤ 433K;
0.03 ≤ PC O2 (kPa ) ≤ 2100. One must be careful if using the model
outside this range.
The heat of absorption model predicts satisfactory the heat of
absorption data for the studied different ratios AMP/PZ. Individ-
ual reactions contributions are also presented. It is observed that
when the AMP/PZ ratio increases, the predicted total heat absorp-
tion goes toward the single amine AMP system where protonated
AMP is the main contributor. When the AMP/PZ ratio decreases,
the predicted total heat of absorption approaches the single amine
PZ system where the protonated PZ, PZ-monocarbamate and zwit-
terion reactions play important roles. The contribution of the zwit-
terion, protonated PZ and PZ-carbamate cancel each other at high
loadings.
Finally, no data for pure AMP/PZ blends were available and
the binary interaction energy parameter for AMP/PZ was fit-
ted in the ternary AMP/PZ/H2 O system using literature data. A
fine-tuning was needed to improve the fit for the AMP/PZ/H2 O
system.
A. Hartono, R. Ahmad, H.F. Svendsen et al.
Declaration of competing interest
The authors declare no competing financial or other conflict of
interest.
CRediT authorship contribution statement
Ardi Hartono: Conceptualization, Methodology, Validation, In-
vestigation, Software, Formal analysis, Resources, Data curation,
Writing – original draft, Writing – review & editing, Visualization,
Supervision. Rafiq Ahmad: Methodology, Validation, Investigation,
Resources. Hallvard F. Svendsen: Conceptualization, Methodology,
Software, Formal analysis, Writing – review & editing, Visualiza-
tion, Supervision. Hanna K. Knuutila: Writing – review & editing,
Project administration, Funding acquisition.
Acknowledgments
This work is performed under the ACT ALIGN CCUS Project No
271501. This project has received funding from RVO (NL), FZJ/PtJ
(DE), Gassnova (NO), UEFISCDI (RO), BEIS (UK) and is cofunded
by the European Commission under the Horizon 2020 programme
ACT, Grant Agreement No 691712.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.fluid.2021.113235.
References
[1] B. Metz, O. Davidson, H. de Coninck, M. Loos, L. Meyer, IPCC Special Report
on Carbon Dioxide Capture and Storage. Prepared by Working Group III of the
Intergovernmental Panel on Climate Change, Cambridge, UK, 2005.
[2] G.T. Rochelle, Amine Scrubbing for CO2 Capture, Science 325 (2009) 1652–
1654, doi:10.1126/science.1176731.
[3] H.F. Svendsen, E.T. Hessen, T. Mejdell, Carbon dioxide capture by absorption,
challenges and possibilities, Chem. Eng. J. 171 (2011) 718–724, doi:10.1016/j.
cej.2011.01.014.
[4] P. Brúder, A. Grimstvedt, T. Mejdell, H.F. Svendsen, CO2 capture into aqueous
solutions of piperazine activated 2-amino-2-methyl-1-propanol, Chem. Eng.
Sci. 66 (2011) 6193–6198, doi:10.1016/j.ces.2011.08.051.
[5] J.N. Knudsen, J. Andersen, J.N. Jensen, O. Biede, Evaluation of process upgrades
and novel solvents for the post combustion CO2 capture process in pilot-scale,
Energy Procedia 4 (2011) 1558–1565, doi:10.1016/j.egypro.2011.02.025.
[6] H. Li, L. Li, T. Nguyen, G.T. Rochelle, J. Chen, Characterization of piperazine/2-
aminomethylpropanol for carbon dioxide capture, Energy Procedia 37 (2013)
340–352, doi:10.1016/j.egypro.2013.05.120.
[7] A.K. Chakraborty, G. Astarita, K.B. Bischoff, CO2 absorption in aqueous solu-
tions of hindered amines, Chem. Eng. Sci. 41 (1986) 997–1003, doi:10.1016/
0 0 09- 2509(86)87185- 8.
[8] A.F. Ciftja, A. Hartono, H.F. Svendsen, Experimental study on carbamate forma-
tion in the AMP–CO2–H2O system at different temperatures, Chem. Eng. Sci.
107 (2014) 317–327, doi:10.1016/j.ces.2013.12.028.
[9] A.F. Ciftja, A. Hartono, E.F. da Silva, H.F. Svendsen, Study on carbamate stability
in the AMP/CO2 /H2 O system from 13 C-NMR spectroscopy, Energy Procedia 4
(2011) 614–620, doi:10.1016/j.egypro.2011.01.096.
[10] A. Hartono, R. Ahmad, M. Usman, N. Asif, H.F. Svendsen, Solubility of CO2 in
0.1M, 1M and 3M of 2-amino-2-methyl-1-propanol (AMP) from 313 to 393K
and model representation using the eNRTL framework, Fluid Phase Equilib. 511
(2020) 112485, doi:10.1016/j.fluid.2020.112485.
[11] C.-C. Chen, L.B. Evans, A local composition model for the excess Gibbs energy
of aqueous electrolyte systems, AIChE J. 32 (1986) 444–454, doi:10.1002/aic.
690320311.
[12] A. Hartono, A. Rafiq, S. Gondal, H.F. Svendsen, Solubility data for Nitrous Oxide
(N2O) and Carbon dioxide (CO2) in Piperazine (PZ) and a new eNRTL model,
Fluid Phase Equilib. 538 (2021) 112992, doi:10.1016/j.fluid.2021.112992.
[13] E.T. Hessen, T. Haug-Warberg, H.F. Svendsen, The refined e-NRTL model ap-
plied to CO2–H2O–alkanolamine systems, Chem. Eng. Sci. 65 (2010) 3638–
3648, doi:10.1016/j.ces.2010.03.010.
[14] J.G.M.S. Monteiro, D.D.D. Pinto, S.A.H. Zaidy, A. Hartono, H.F. Svendsen, VLE
data and modelling of aqueous N,N-diethylethanolamine (DEEA) solutions, Int.
J. Greenhouse Gas Control 19 (2013) 432–440, doi:10.1016/j.ijggc.2013.10.001.
18
Fluid Phase Equilibria 550 (2021) 113235
[15] D.-Y. Peng, D.B. Robinson, A new Two-constant equation of state, Ind. Eng.
Chem. Fund. 15 (1976) 59–64, doi:10.1021/i160057a011.
[16] S. Ma’mun, J.P. Jakobsen, H.F. Svendsen, O. Juliussen, Experimental and mod-
eling study of the solubility of carbon dioxide in aqueous 30 mass % 2-((2-
Aminoethyl)amino)ethanol solution, Ind. Eng. Chem. Res. 45 (2006) 2505–
2512, doi:10.1021/ie0505209.
[17] S. Ma’mun, H.F. Svendsen, K.A. Hoff, O. Juliussen, Selection of new absorbents
for carbon dioxide capture, Energy Convers. Manage. 48 (2007) 251–258,
doi:10.1016/j.enconman.20 06.04.0 07.
[18] U.E. Aronu, S. Gondal, E.T. Hessen, T. Haug-Warberg, A. Hartono, K.A. Hoff,
H.F. Svendsen, Solubility of CO2 in 15, 30, 45 and 60 mass% MEA from 40
to 120°C and model representation using the extended UNIQUAC framework,
Chem. Eng. Sci. 66 (2011) 6393–6406, doi:10.1016/j.ces.2011.08.042.
[19] S. Ma’mun, R. Nilsen, H.F. Svendsen, O. Juliussen, Solubility of Carbon Dioxide
in 30 mass % Monoethanolamine and 50 mass % Methyldiethanolamine Solu-
tions, J. Chem. Eng. Data 50 (2005) 630–634, doi:10.1021/je0496490.
[20] A. Hartono, S.J. Vevelstad, I. Kim, R. Rennemo, H.K. Knuutila, Promoted Strong
Bicarbonate Forming Solvents for CO2 Capture, Energy Procedia 114 (2017)
1794–1802, doi:10.1016/j.egypro.2017.03.1307.
[21] A. Hartono, I. Kim, H.K. Knuutila, L.V. van der Ham, E. Goetheer, Calorimetric
Studies of Precipitating Solvent System, Energy Procedia 114 (2017) 744–755,
doi:10.1016/j.egypro.2017.03.1217.
[22] I. Kim, H.F. Svendsen, Heat of absorption of carbon dioxide (CO2) in Mo-
noethanolamine (MEA) and 2-(Aminoethyl)ethanolamine (AEEA) solutions, Ind.
Eng. Chem. Res. 46 (2007) 5803–5809, doi:10.1021/ie0616489.
[23] A. Hartono, O. Juliussen, H.F. Svendsen, Solubility of N2O in aqueous solution
of diethylenetriamine, J. Chem. Eng. Data 53 (2008) 2696–2700, doi:10.1021/
je800409d.
[24] S.L.R. Ellison, A. Williams, Eurachem/CITAC guide: quantifying uncertainty in
analytical measurement, 2012.
[25] I. Kim, K.A. Hoff, T. Mejdell, Heat of absorption of CO2 with aqueous solutions
of mea: new experimental data, Energy Procedia (2014) 1446–1455.
[26] DIPPR-801, The information and data evaluation manager for design institute
for physical properties, Version 4.1.0., 2004.
[27] A. Hartono, M. Saeed, A.F. Ciftja, H.F. Svendsen, Binary and ternary VLE of the
2-amino-2-methyl-1-propanol (AMP)/piperazine (Pz)/water system, Chem. Eng.
Sci. 91 (2013) 151–161, doi:10.1016/j.ces.2013.01.015.
[28] P.L. Fosbøl, R. Neerup, M.W. Arshad, Z. Tecle, K. Thomsen, Aqueous solubility of
piperazine and 2-Amino-2-methyl-1-propanol plus their mixtures using an im-
proved freezing-point depression method, J. Chem. Eng. Data 56 (2011) 5088–
5093, doi:10.1021/je200959m.
[29] Z.Y. Yang, A.N. Soriano, A.R. Caparanga, M.H. Li, Equilibrium solubility of car-
bon dioxide in (2-amino-2-methyl-1-propanol + piperazine + water), J. Chem.
Thermodyn. 42 (2010) 659, doi:10.1016/j.jct.20 09.12.0 06.
[30] S.K. Dash, A.N. Samanta, S.S. Bandyopadhyay, Experimental and theoretical in-
vestigation of solubility of carbon dioxide in concentrated aqueous solution
of 2-amino-2-methyl-1-propanol and piperazine, J. Chem. Thermodynamics 51
(2012) 120–125, doi:10.1016/j.jct.2012.02.012.
[31] A. Jahangiri, M.Nabipoor Hassankiadeh, Effects of piperazine concentration and
operating conditions on the solubility of CO2 in AMP solution at low CO2 par-
tial pressure, Sep. Sci. Technol. 54 (2019) 1067–1078, doi:10.1080/01496395.
2018.1524907.
[32] D. Tong, G.C. Maitland, M.J.P. Trusler, P.S. Fennell, Solubility of carbon dioxide
in aqueous blends of 2-amino-2-methyl-1-propanol and piperazine, Chem. Eng.
Sci. 101 (2013) 851–864, doi:10.1016/j.ces.2013.05.034.
[33] G. Murshid, A.M. Shariff, M.A. Bustam, S. Ullah, Solubility of CO2 in Piper-
azine (PZ) activated aqueous solutions of 2-Amino-2-methyl-1-propanol (AMP)
at elevated pressures, Appl. Mech. Materr. 625 (2014) 233–236 10.4028/www.
scientific.net/AMM.625.233.
[34] Q. Xie, A. Aroonwilas, A. Veawab, Measurement of heat of CO2 absorption into
2-Amino-2-methyl-1-propanol (AMP)/Piperazine (PZ) blends using differential
reaction calorimeter, Energy Procedia 37 (2013) 826–833, doi:10.1016/j.egypro.
2013.05.175.
[35] H. Li, P.T. Frailie, G.T. Rochelle, J. Chen, Thermodynamic modeling of
piperazine/2-aminomethylpropanol/CO2/water, Chem. Eng. Sci. 117 (2014) 331–
341, doi:10.1016/j.ces.2014.06.026.
[36] J.J. Carroll, J.D. Slupsky, A.E. Mather, The solubility of carbon dioxide in water
at low pressure, J. Phys. Chem. Ref. Data 20 (1991) 1201–1209, doi:10.1063/1.
555900.
[37] K. Zhang, B. Hawrylak, R. Palepu, P.R. Tremaine, Thermodynamics of aqueous
amines: excess molar heat capacities, volumes, and expansibilities of {water+
methyldiethanolamine (MDEA)} and {water + 2-amino-2-methyl-1-propanol
(AMP)}, J. Chem. Thermodynamics 34 (2002) 679–710, doi:10.10 06/jcht.20 02.
0937.
[38] T.J. Edwards, G. Maurer, J. Newman, J.M. Prausnitz, Vapor-liquid equilibria in
multicomponent aqueous solutions of volatile weak electrolytes, AIChE J. 24
(1978) 966–976, doi:10.1002/aic.690240605.