Sustainable Energy Technologies and Assessments 53 (2022) 102514

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Sustainable Energy Technologies and Assessments

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CO2 solubility and thermophysical properties in aqueous mixtures of

piperazine and diethanolamine
Sami Ullah a, *, Mohamad Azmi Bustam b, Muhammad Sagir c, Mohammed Ali Assiri a,
Abdullah G. Al-Sehemi a, Muhammad Ayoub b, Abrar Inayat d, Ahmad Mukhtar e, Sidra Saqib f,
Muhammad Babar c, Khurram Shehzad Qureshi g, Su Shiung Lam h, i, *
a
Department of Chemistry, College of Science, King Khalid University, Abha 61413, Saudi Arabia
b
Department of Chemical Engineering, Universiti Teknologi PETRONAS (UTP), Seri Iskandar, Perak 32610, Malaysia
c
Department of Chemical Engineering, Khwaja Fareed University of Engineering & Information Technology (KFUEIT), Rahim Yar Khan, Pakistan
d
Department of Sustainable & Renewable Energy Engineering, University of Sharjah, Sharjah 27272, United Arab Emirates
e
Department of Chemical Engineering, NFC Institute of Engineering and Fertilizer Research, Faisalabad, Pakistan
f
Department of Chemical Engineering, COMSATS University Islamabad (CUI), Lahore Campus, Punjab 54000, Pakistan
g
Department of Chemical Engineering, Pakistan Institute of Engineering & Applied Science, Islamabad, Pakistan
h
Pyrolysis Technology Research Group, Higher Institution Centre of Excellence (HICoE), Institute of Tropical Aquaculture and Fisheries (AKUATROP), Universiti
Malaysia Terengganu, Kuala Nerus, Terengganu 21030, Malaysia
i
Sustainability Cluster, School of Engineering, University of Petroleum & Energy Studies, Dehradun, Uttarakhand 248007, India

A R T I C L E I N F O A B S T R A C T

Keywords: The population rise and economic development lead to increased energy utilization. This energy utilization is
Carbon dioxide (CO2) largely based on fossil fuel combustion and the industrial operations in oil and gas industry that result in CO2
Alkanolamines emissions. The solvent mixtures of piperazine/diethanolamine (PZ/DEA) were examined to substitute for
Thermodynamics
improved carbon dioxide (CO2) absorption from the natural gas stream. The CO2 solubility in the blends of the
Density
Refractive Index
piperazine (PZ) and diethanolamine (DEA) was evaluated at 303.2, 323.2, and 343.2 K, and partial pressures of
CO2 at (100–1000 kPa). The mixtures considered were DEA (20, 40 wt%), DEA (20 wt%) + PZ (5 wt%), DEA (20
wt%) + PZ (10 wt%), DEA (40 wt%) + PZ (5 wt%), and DEA (40 wt%) + PZ (10 wt%) aqueous solutions. The
CO2 loadings (mole CO2/mole amine) into the solutions were described concerning the equilibrium partial
pressures of CO2 at the considered temperatures. An increase in solubility of CO2 was achieved using aqueous PZ,
showing prospects to be a desirable mixture with the DEA solvent for CO2 absorption. The experimental results
showed reasonable correlations to the modified Kent-Eisenberg model. The refractive index and density data of
the alkanolamine blends were determined as a feature of temperature, demonstrating the decrement in the
thermophysical properties when the temperature of the mixtures was increased. These findings on CO2 solubility
and thermophysical properties provide key insights into the screening and practical use of next-generation
solvents for CO2 absorption.

Introduction
Environmental pollution has become a significant concern world­
wide due to the release of toxic substances from burning non-renewable
energy sources, causing air pollution and depletion of ozone. Among the
ozone-depleting gases, CO2 contributes to greenhouse gas emissions
[1–5]. When these fuels are burned, this leads to production of addi­
tional CO2, accounting for more than half of global warming caused by
greenhouse gas emissions. The concentration of this acid gas has risen
from 310 parts per million (ppm) to about 380 ppm in recent decades,
and it will continue to increase by approximately 450 ppm until year
2200 [6,7]. Researchers hypothesize that an escalation in ozone
destroyer (hydrochlorofluorocarbons, HCFCs) will increase the tem­
peratures around the world, which will result in numerous devastating
ecological impacts from human and natural activities on organisms and
their environment). In the twenty-first century, the Intergovernmental

* Corresponding authors at: Pyrolysis Technology Research Group, Higher Institution Centre of Excellence (HICoE), Institute of Tropical Aquaculture and Fisheries
(AKUATROP), Universiti Malaysia Terengganu, Kuala Nerus, Terengganu 21030, Malaysia.
E-mail addresses: samichemist1@gmail.com, samiali@kku.edu.sa (S. Ullah), lam@umt.edu.my (S. Shiung Lam).

https://doi.org/10.1016/j.seta.2022.102514
Received 24 February 2022; Received in revised form 31 May 2022; Accepted 6 July 2022
Available online 28 July 2022
2213-1388/© 2022 Elsevier Ltd. All rights reserved.
S. Ullah et al.
PVT Tank Absorption Tank
PS
Gas Regulators
Max. 20 bar
PS
TS
CO2 Gas Legends
Cylinder TS Temperature
Sensor
PS Pressure
Sensor PVT Tank
(500 mL)
Fig. 1. Experimental setup for the determination of CO2 solubility.
Panel on Climate Change (IPCC) forecasts that the earth’s climate will
increase by somewhere around 2.0 and 11.5◦ F. [8]. Consequently, CO2
should be captured and removed from the refinery off-gases, natural
gases, flue gases, synthesis gas and other gas sources, including the in­
dustrial or manufacturing, using the integrated carbon capture and
utilization (ICCU) approach [9–12].
Acid gas capturing is one of the industrial processes commonly used
in the gas and oil business to satisfy the acceptable sulfur contents in oil
and gas products. In particular, numerous advancements are being uti­
lized to isolate CO2 from the acidic flue gas, such as adsorption, physical
absorption, cryogenic methods, chemical absorption, and membrane
separation [13–21]. The chemical absorption process has advantages
over the physical absorption in terms of the chemical reaction between
the CO2 and the solvent to trap the gas in liquid form. The solvent can
then be regenerated into the desorption tower by CO2 decomposition via
heating [22]. In particular, alkanolamines are used to separate acidic
flue gases from a gas stream due to their active nature and are beneficial
for chemical absorption [23–27].
Alkanolamines are identified as primary, secondary, and tertiary
amines. Such amines are represented by diethanolamine (DEA), mono­
ethanolamine (MEA), methyldiethanolamine (MDEA), and amino­
methyl propanol (AMP) respectively. The most commonly available
system for CO2 absorption is the MEA absorption process [28–32]. There
are some drawbacks of using the MEA absorption system, namely (1)
limited capacity to load CO2, (2) strong corrosion risk, (3) amine
degradation with a strong absorbent spectrum of NO2, SO2, HF, HCl and
oxygen, and (4) high energy consumption by high-temperature absor­
bents. In addition, in comparison with the MEA liquids for CO2 ab­
sorption, the DEA solution has a lower corrosive potential. It has been
characterized for having high CO2 absorption capacity, fast reaction
kinetics, and cost-effectiveness. Herein, DEA-based mixtures appear to
be prospective solvents for absorption of CO2 in the gas treating system
[33–36]. Table S1 (supplementary materials) presents a detailed
Sustainable Energy Technologies and Assessments 53 (2022) 102514
Computer
DAQ
TS PS TS Software
PS
TS Venting
Absorption
Reactor
250 mL
Hot Plate
Stirrer
literature review of studies relevant to CO2 solubility in DEA and PZ
solutions for an extensive range of pressure, temperature and alkanol­
amine concentration.
PZ is a good promoter due to its prompt development of carbamates
with CO2 when mixed with alkanolamines [37–42]. As reported in the
homogeneous activation process, PZ could be highly efficient solvents
for CO2 removal from industrial processes [43,44]. PZ not only com­
bines with CO2 to generate carbamate under stable conditions, but it also
works as a homogeneous activator when CO2 reacts with MDEA in the
presence of PZ [45]. In the supplementary materials Table S1 that CO2
solubility in solitary diethanolamine and PZ solutions have been
extensively investigated; however, the study on carbon dioxide solubi­
lity in the solution mixtures of PZ and DEA is limited and scarcely
described in the published work [33]. The solubility of CO2 for amine
and PZ are found within the range of 2.0 M to 3.0 M at temperatures
ranging from 303.2 to 353.2 K, and 0.01 M to 0.02 M at CO2 partial
pressures range from 10.13 to 20.26 KPa. It is essential to run an opti­
mized system at specific and desirable thermodynamic, physical, and
chemical parameters to get the optimum separation outcomes. Appro­
priate variables and the choice of solvent or chemical are required.
These characteristics are then monitored on many models to reach a
specific technique for a particular system.
Therefore, the study’s objective is to thoroughly examine the solu­
bility of CO2 in the solution mixtures of DEA/PZ at different tempera­
tures (303.2, 323.2, 343.2 K) and the pressure of CO2 (100 – 1000 KPa).
Six alkanolamine proportions were studied, consisting of aqueous DEA
and DEA + PZ solutions. These concentrations were selected to ensure
an effective comparison of the influence of PZ addition on CO2 loadings
in aqueous DEA solutions. The findings on CO2 solubility and thermo­
physical properties provide essential information and understanding of
selecting suitable solvents for energy-efficient CO2 capturing.
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S. Ullah et al. Sustainable Energy Technologies and Assessments 53 (2022) 102514

Table 1
Repeated data to confirm the high-pressure VLE performance over a range of operational conditions.
Solutions Temperature (K) wamine/wt.% Reported studies This study Deviation (%) References

Pressure (KPa) α/mol.(molalk)–1

Pressure (KPa) α/mol.(molalk) –1

DEA + H2O 348.2 36.4 217.9 0.540 217.5 0.518 − 4.04 [46]
323.2 20.6 689.5 0.887 690.0 0.861 − 2.91
298.2 49.7 2179 0.919 2190 0.936 +1.11
373.2 20.6 2179 0.840 2180 0.848 +1.06

PZ + H2O 313.2 2.5 205.0 1.090 202.5 1.141 +4.72 [47]

343.2 2.5 1500 1.310 1490 1.266 − 3.35
313.2 10.1 3224 1.640 3255 1.674 +2.08
343.2 10.1 198 0.920 197.5 0.878 − 4.55

Materials and Methods: Deprotonation of DEA:

RRNH2 + ⇆RRNH + H + (1)

The chemicals used in this study are provided in Table S2 of the
supplemental materials. A balance (Mettler Toledo model AS120S, u = Carbamate reversion of DEA:
0.1 mg, analytical) was employed to synthesize the aqueous PZ and
RRNNCOO− + H2 O⇆RRNH + HCO3 − (2)
solutions of aqueous (DEA + PZ) at 298.2 K. Deionized water was used
for the preparations of all requisite solutions. All tests were done three Deprotonation of PZ:
times, and the average results were shown. The chemicals and gases
were acquired from Merck and Gas Walker, respectively. RNH2 + ⇆RNH + H + (3)
Bicarbonate formation:
Determination of thermophysical properties of aqueous DEA/PZ solutions
H2 O + CO2 ⇆HCO3 − + H + (4)

DEA/PZ solutions were weighed, and their densities were evaluated Carbonate formation:
using an Anton Parr 4500 M density meter at temperatures ranging from
HCO3 − ⇆CO3 − 2 + H + (5)
298.2 to 343.2 K. Refractive index data were measured by a digital RM
40 Refractometer from Mettler Toledo at temperatures between 303.2 Dissociation of Water:
and 343.2 K. The results were repeated three times using the fresh sol­
H2 O⇆OH − + H + (6)
vent to ensure the accuracy of data for each run, and average values
were reported. The balances governing the above equations (Eqs. (1) to (6)) are
given as follows (Eqs. (7) to (11);
Apparatus and procedure for CO2 solubility determination Alkanolamine balance:

[DEA]Total = [RRNH] + [RRNH2 + ] + [RRNNCOO− ] (7)

The Gas Solubility Cell operating at higher pressure was employed to
measure the solubility as exposed in Fig. 1. The reactor contains a cy­
lindrical stainless-steel tank having a capacity of 250 mL with a mag­
netic stirrer coupled on its top. There are liquid and gas inlet valves, and
a vacuum pump is also connected. A thermocouple is interpolated in the
cell to calculate the temperature (0.1 K accuracy). The pressure is
considered by a pressure transducer (0.14 KPa accuracy).
Firstly, approximately 50 mL of the DEA/PZ mixture was inserted
into the reaction cell. CO2 then purged the unit to eliminate oxygen
traces and heated to achieve the desired temperature. The partial CO2
pressure has been set between 300 and 1500 KPa. An Autoclave Engi­
neers temperature control device regulated the cell temperature. After
six hours of running, the cell’s average pressure remained unchanged.
Hence the equilibrium was established. It would usually take 4 h for the
reaction cell to reach equilibrium. At equilibrium, the pressure drop
reading was taken to calculate CO2 solubility. The CO2 loadings were
measured by employing the equation of the state-based material balance
method given by Suleman et al. [28]. The consistency of the reaction cell
was determined by repeating the CO2 solubility experiment three times
in the aqueous mixture of the PZ and MDEA, which was also compared
with previously published data presented in Table 1. Confidence in­
tervals at the 0.95 level are, the average uncertainties (u) is u(T) = 0.1 K
with u(P) = 1.25 kPa, u(wamine) = 0.1 wt%, whereas the extended un­
certainty Uc for the similar interval of confidence is Uc(α) = 0.078.
Thermodynamic modeling
The reaction mechanism for CO2 dispersibility in aqueous solutions
of DEA and PZ can be studied via the following equations (Eq. (1) to (6)).
[PZ]Total = [RNH] + [RNH2 + ] (8)
The reactions involving the formation of carbamate and dicarbamate
for PZ have been neglected due to lower concentrations of PZ being used
in this study [48].
Carbon dioxide balance:
( ) [ ]
α [DEA]Total + [PZ]Total = [CO2 ] + [HCO3 − ] + CO3 − 2 + [RRNNCOO− ]
(9)
[CO2] is the CO2 concentration in the liquid state and was deter­
mined by Henry’s law.
PCO2
[CO2 ] = (10)
HCO2
Where PCO2 is the pressure of CO2 and HCO2 is Henry’s constant.
Electro-neutrality balance:
[RRNH2 + ] + [RNH2 + ] + [H + ] = [HCO]3 − + 2[CO]3 − + [RRNCOO− ] + [OH − ]
(11)
The above equations were solved in line with the mathematical so­
lution given by Suleman et al. [49], and the regression parameters were
determined by Levenberg-Marquardt optimization repetitively in
MATLAB (7.14). For the solutions containing DEA (20 wt% and 40 wt%
only), the PZ equations were neglected and simplified. The model
equations for aqueous DEA solutions were solved by Suleman et al. [50].
However, the CO2 concentrations were determined by Eq. (4), and CO2
loadings are being measured at low and medium pressures [51]. The

3
S. Ullah et al. Sustainable Energy Technologies and Assessments 53 (2022) 102514

Table 2
Densities and Refractive Index of aqueous DEA and PZ solutions mixtures at various temperatures.
Mixtures (wamine/wt.%) Density (ρ, g.cm− 3) Refractive index (n, dimensionless)
1,2
Temperature (T, K) Temperature (T, K)1,2

DEA PZ 298.2 303.2 313.2 323.2 333.2 343.2 303.2 313.2 323.2 333.2 343.2

20 0 1.021 1.019 1.014 1.010 1.005 0.999 1.363 1.362 1.360 1.358 1.356
20 5 1.025 1.025 1.021 1.017 1.011 1.005 1.372 1.371 1.369 1.367 1.365
20 10 1.029 1.028 1.026 1.022 1.015 1.008 1.381 1.380 1.377 1.376 1.374
40 0 1.046 1.044 1.038 1.033 1.028 1.022 1.391 1.390 1.387 1.386 1.384
40 5 1.050 1.049 1.045 1.040 1.034 1.029 1.399 1.398 1.395 1.394 1.392
40 10 1.054 1.053 1.049 1.043 1.037 1.031 1.410 1.408 1.405 1.403 1.401
1
At confidence intervals (0.95 level), the standard uncertainties u is u(T) = 0.1 K, u(wDEA) = 0.1 wt%, u(wPZ) = 0.1 wt%, whereas for the same confidence interval,
the expanded uncertainty Uc is Uc(ρ) = 0.002 g/cm3.
2
The experimental values were measured at the pressure of 101.3 kPa with a standard uncertainty of u(P) = 0.1 kPa in its measurement.

Fig. 2. Densities of the mixtures of DEA and PZ at different compositions; (a): 20 wt% DEA with different PZ concentrations and (b): 40 wt% DEA with different PZ
concentrations.

Fig. 3. Refractive index of DEA and PZ mixtures at different compositions; (a): 20 wt% DEA with varying concentrations of PZ and (b): 40 wt% DEA with varying
concentrations of PZ.

correction parameters of the model, f11 and f22 are given in equations Results and discussions
(Eqs. (12) and (13) below.
( ) p Densities and refractive index
f11 = mln(PCO2 ) + nln [DEA]Total + ( ) (12)
[DEA]Total + PCO2
Table 2 presents the refractive index and density of various aqueous
[ (
f12 = q mln(PCO2 ) + nln [PZ]Total
)]
(13) mixtures of DEA and PZ solutions at different temperatures. Their cor­
responding graphical representation is illustrated in Figs. 2 and 3. The
The values of correction factors, m, n, p, and q for the (Eqs. (12) to density drops with an escalation in temperature, while the density es­
(13) are provided in supporting materials Table S3. calates with the increase of PZ concentration. The density shows a
positive relationship with PZ concentration, however, a negative rela­
tionship with temperature. The density of the mixture drops linearly as
the temperature of the mixture rises, indicating a weakening of the
intermolecular forces in the mixture [52]. The intermolecular in­
teractions lessen as the mixture’s temperature rises, increasing the

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S. Ullah et al. Sustainable Energy Technologies and Assessments 53 (2022) 102514

Table 3
Equilibrium loadings (α) and mole fraction (x) of CO2 in aqueous 20 wt% and 40 wt% DEA solutions at various Temperature (T) and total pressure (P) values1.
Temperature (T, K) 20 wt% DEA 40 wt% DEA

Pressure (P, KPa) Equilibrium loadings [α/mol.(molalk) ]

–1
XCO2 Pressure (P, KPa) Equilibrium loadings [α/mol.(molalk)–1] XCO2

303.2 129 0.746 0.029 102 0.696 0.066

216 0.810 0.032 422 0.812 0.076
454 0.909 0.036 613 0.846 0.079
688 0.969 0.038 785 0.869 0.081
988 1.024 0.040 991 0.891 0.083

323.2 144 0.631 0.025 122 0.581 0.056

317 0.737 0.029 270 0.649 0.062
463 0.791 0.031 494 0.705 0.067
773 0.867 0.034 783 0.749 0.071
964 0.901 0.035 978 0.771 0.073

343.2 150 0.525 0.021 127 0.472 0.046

346 0.642 0.025 331 0.560 0.054
544 0.709 0.028 622 0.622 0.060
793 0.768 0.030 822 0.651 0.062
947 0.796 0.031 986 0.670 0.064
1
At confidence intervals (0.95 level), the standard uncertainties u is u(T) = 0.1 K, u(P) = 1.25 KPa, u(wDEA) = 0.1 wt%, whereas for the same confidence interval, the
expanded uncertainty Uc is Uc(α) = 0.078 mol. (mol alk− 1).

Table 4
Equilibrium loadings (α) and mole fraction (x) of CO2 in aqueous mixtures of DEA and PZ at various temperature (T) and total pressure (P) values.1
Temperature 20 wt% DEA and 5 wt% PZ 20 wt% DEA and 10 wt% PZ 40 wt% DEA and 5 wt% PZ 40 wt% DEA and 10 wt% PZ
(T, K)
Pressure Equilibrium XCO2 Pressure Equilibrium XCO2 Pressure Equilibrium XCO2 Pressure Equilibrium XCO2
(P, KPa) loadings (P, KPa) loadings (P, KPa) loadings (P, KPa) loadings
[α/mol. [α/mol. [α/mol. [α/mol.
(molalk)–1] (molalk)–1] (molalk)–1] (molalk)–1]

303.2 134 0.725 0.039 112 0.684 0.047 107 0.662 0.076 124 0.634 0.087
227 0.786 0.042 198 0.746 0.051 322 0.784 0.089 322 0.749 0.102
463 0.882 0.047 498 0.867 0.059 624 0.817 0.093 521 0.781 0.105
674 0.948 0.050 724 0.917 0.062 741 0.821 0.093 795 0.815 0.110
992 1.004 0.053 971 0.968 0.066 956 0.824 0.093 962 0.825 0.111

323.2 152 0.611 0.033 146 0.574 0.040 152 0.567 0.066 106 0.518 0.072
322 0.718 0.038 328 0.687 0.047 285 0.624 0.072 296 0.601 0.083
471 0.770 0.041 412 0.719 0.049 465 0.665 0.077 622 0.662 0.091
782 0.845 0.045 812 0.839 0.057 742 0.708 0.081 768 0.681 0.093
947 0.880 0.047 953 0.859 0.059 924 0.717 0.082 914 0.694 0.095

343.2 141 0.501 0.027 149 0.472 0.033 138 0.425 0.050 169 0.454 0.064
226 0.574 0.031 342 0.585 0.041 396 0.545 0.064 339 0.522 0.073
478 0.688 0.037 574 0.658 0.045 584 0.586 0.068 525 0.570 0.079
696 0.747 0.040 824 0.736 0.051 804 0.609 0.071 795 0.596 0.082
941 0.775 0.041 996 0.754 0.052 992 0.624 0.072 914 0.605 0.084
1
At confidence intervals (0.95 level), the standard uncertainties u is u(T) = 0.1 K, u(P) = 1.25 kPa, u(wDEA) = 0.1 wt%, u(wPZ) = 0.1 wt%, whereas for the same
confidence interval, the expanded uncertainty Uc is Uc(α) = 0.086 mol. (mol alk− 1).

distance between the molecules due to their increased kinetic energy.
This increase in the intermolecular distance weakened the intermolec­
ular forces and increased the volume leading to the reduction in density
[53].
The refractive index reduces with an escalation in temperature,
while the refractive index escalates with the increase of PZ concentra­
tion. Refractive indices showed a positive relationship with PZ concen­
trations but a negative relationship with temperature. Similarly, the
refractive index of the mixture dropped as the temperature of the mixed
system increased [54]. This can be attributed to the increase in the
distance between the molecules of the mixture. The improved mole­
cule’s kinetic energies can explain the increase in the intermolecular
distance due to the rise in the mixture’s temperature. Hence, this
increment in the intermolecular distance led to the prevention of the
development of the compact groups composed of the molecules of the
mixture and therefore, the light from the refractometer did not strike a
huge number of the molecules of the mixture [53,55]. This leads to the
reduction in the refractive index of the mixture system. The detailed
assessment of the experimentally obtained values of density (ρ/g.cm− 3)
and refractive index (n, dimensionless) of 20, 40 wt% aqueous DEA
solutions acquired in this study with the literature at different temper­
atures (T) and pressure P = 101.3 KPa1 are provided in supplementary
materials Tables S4-S7.
CO2 solubility
Tables 3 and 4 give the experimental outcomes of CO2 solubility in
aqueous DEA/PZ solutions at various temperatures (303.2, 323.2, 343.2
K) and vapor pressure of CO2 (100 – 1000 KPa), and Fig. 4 depicts their
graphical representation with modeling results. Six alkanolamine con­
centrations were studied consisting of aqueous solutions of DEA (20 wt
%), DEA (40 wt%), DEA (20 wt%) + PZ (5 wt%), DEA (20 wt%) + PZ

5
S. Ullah et al. Sustainable Energy Technologies and Assessments 53 (2022) 102514

Fig. 4. The experimental solubility of CO2 in aqueous DEA/PZ solutions and modeling at a temperature (303.2 K 323.2 K, 343.2 K) and at partial pressure of CO2
between 100 and 1000 KPa; (a): 20 wt% DEA, (b): 40 wt% DEA, (c): 20 wt% DEA + 5 wt% PZ, (d): 20 wt% DEA + 10 wt% PZ, (e): 40 wt% DEA + 5 wt% PZ, and (f):
40 wt% DEA + 10 wt% PZ.

(10 wt%), DEA (40 wt%) + PZ (5 wt%), and DEA (40 wt%) + PZ (10 wt
%). Fig. 4 illustrates that the model correlation for equilibrium CO2
loadings for DEA (20 wt%), DEA (40 wt%), DEA (20 wt%) + PZ (5 wt%),
DEA (20 wt%) + PZ (10 wt%), DEA (40 wt%) + PZ (5 wt%), and DEA
(40 wt%) + PZ (10 wt%) solutions compared to the experimental data
obtained in this research work. The CO2 loadings increased with the rise
in pressure and reduced with temperature. This can be attributed to
carbon dioxide’s physical solubility, which upsurges by an escalation in
pressure and reduces through a temperature rise.
The CO2 absorption capability of PZ/DEA was improved (12%) than
the absorption capability of single DEA solutions determined in this
study and the data found in the published works [46,56,57]. At constant
temperature and pressure, the solubility increased as the PZ concen­
tration rose. This indicates that PZ/DEA solutions can improve CO2
separations under the same conditions. The presence of two NH-based
(amine and amide) bonds of PZ significantly increased the CO2 ab­
sorption capability, which has also been mentioned by Mondal et al.
[33], and further increased with the increase in pressure until CO2 was
absorbed chemically. Once the theoretical CO2 loadings were achieved,
the CO2 loadings were reduced.
When the concentration of diethanolamine was fixed, the addition of
PZ was identified to have high absorption rates [58,59] (as expected by
its chemical structure). When employed for molality transformation,
temperature, and molarity value modification utilizing neural network-

6
S. Ullah et al.
based analysis, their values are substantially aligned with our data [60].
The modified Kent-Eisenberg model showed a middling absolute
variance of 8.96% for aqueous DEA solutions only and an average ab­
solute variance of 21.57% for blends of DEA and PZ. The results affirmed
that the model could be effectively applied to correlate mixtures of DEA
and PZ systems. As is typical of Kent-Eisenberg type semi-empirical
models, the model correlation was over-anticipated in the decreased
pressure range (200 kPa) [51]. However, the model outcomes were well
correlated in the medium pressure region (200–1000 kPa) [53].
The DEA-PZ solvent mixture has a lot of capacity for CO2 capture.
However, other properties like corrosion, kinetics and transport char­
acteristics need to be established before proclaiming them as alterna­
tives to conventional alkanolamines used in the CO2 separation industry.
Moreover, such options also face competition from other solvent op­
tions, which include ionic liquids [61,62], amino acids [63–66] and
their mixtures with conventional alkanolamines [67–69]. The ionic
liquids-based solvent options provide a promising potential; neverthe­
less, their high solvent cost hinders their wide application. However,
amino acids and their mixtures with alkanolamines are a technically
promising area of future research, along with mixtures of alkanolamines
like the DEA-PZ system reported in this study.
Conclusions
The CO2 solubility of DEA and PZ in aqueous solutions at various
concentrations was investigated and verified experimentally throughout
a wide CO2 partial pressure and temperature. The investigation shows
that at a specific temperature and fixed concentration, CO2 solubility
decreased with increasing temperature and rose with the increased
partial pressure of CO2. The experimental findings were correlated using
a modified Kent-Eisenberg model with an average absolute deviation of
17.37 %. Moreover, refractive index and density data of the alkanol­
amine mixtures were determined over a wide temperature range. The
thermophysical characteristics of CO2 solubility in a mixture of DEA and
PZ decreased as the temperature enhanced and increased as the alka­
nolamine concentration increased. This work contributes to the selec­
tion and design of next-generation and potentially cost-effective solvents
for energy competent carbon dioxide capturing to protect the
environment.
CRediT authorship contribution statement
Sami Ullah: Writing – original draft. Mohamad Azmi Bustam:
Supervision, Project administration. Muhammad Sagir: Software.
Mohammed Ali Assiri: Writing – review & editing. Abdullah G. Al-
Sehemi: Supervision, Funding acquisition. Muhammad Ayoub: Meth­
odology. Abrar Inayat: Formal analysis, Methodology. Ahmad Mukh­
tar: Resources, Validation. Sidra Saqib: Writing – review & editing,
Investigation. Muhammad Babar: Writing – review & editing,
Conceptualization. Khurram Shehzad Qureshi: Writing – review &
editing. Su Shiung Lam: Writing – review & editing, Resources.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors would like to acknowledge the King Khalid University,
Saudi Arabia (Deanship of Scientific Research) for providing state of the
art research facilities and for financial support through the Research
Groups Project under the grant number (R.G.P.2/115/43). The authors
would like to thank The Education University of Hong Kong for financial
support under International Grant (UMT/CRIM/2-2/25/Jld.8 (49), Vot
7
Sustainable Energy Technologies and Assessments 53 (2022) 102514
53376) to perform this project.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.seta.2022.102514.
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