Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417

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Chemical Engineering Research and Design

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

Efficient hybrid modeling of CO2 absorption in

aqueous solution of piperazine: Applications to
energy and environment

Amir Dashti a , Mojtaba Raji b , Amir Razmi c , Nima Rezaei d ,

Sohrab Zendehboudi d,∗ , Morteza Asghari b
a Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran
b Separation Processes Research Group, Department of Engineering, University of Kashan, Kashan, Iran
c Biological & Ecological Engineering, Oregon State University, Corvallis, OR, USA
d Faculty of Engineering and Applied Science, Memorial University, St. John’s, NL, Canada

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

Article history: Carbon dioxide (CO2 ) considerably contributes to the greenhouse effects and consequently,
Received 9 May 2018 to the global warming. Thus, reduction of CO2 emissions/concentration in the atmosphere is
Received in revised form 22 an important goal for various industrial and environmental sectors. In this research work, we
December 2018 study CO2 capture by its absorption in mixtures of water and piperazine (PZ). Experimental
Accepted 21 January 2019 techniques to obtain the equilibrium data are usually costly and time consuming. Ther-
Available online 29 January 2019 modynamic modeling by Equations of State (EOSs) and connectionist tools leads to more
reliable and accurate results, compared to the empirical models and analytical modeling
Keywords: strategies. This research work utilizes Genetic Programming (GP) and Genetic Algorithm-
CO2 absorption Adaptive Neuro Fuzzy Inference System (GA-ANFIS) to estimate the solubility of CO2 in
Piperazine mixtures of water and piperazine (PZ). In both methods, the input parameters are temper-
Solubility ature, partial pressure of CO2 , and concentration of PZ in the solution. A total number of
Deterministic tools 390 data points is collected from the literature and used to develop GP and GA-ANFIS mod-
Accuracy els. Assessing the models by the statistical methods, both models are found to acceptably
Environmental implication predict the CO2 solubility in water/PZ mixtures. However, the GP exhibits a superior perfor-
mance, compared to GA-ANFIS; the values of Average Absolute Relative Error (AARD) are
5.3213% and 9.7143% for the GP and GA-ANFIS models, respectively. Such reliable predictive
tools can assist engineers and researchers to effectively determine the key thermodynamic
properties (e.g., solubility, vapor pressure, and compressibility factor) which are central to
design and operation of the carbon capture processes in a variety of chemical plants such
as power plants and refineries.
© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Although fossil fuels such as coal and petroleum are used as the
main sources of energy supply, they raise environmental concerns. For
instance, burning fossil fuels emits carbon monoxide (CO), carbon diox-
ide (CO2 ), and potentially a small amount of hydrogen sulfide (H2 S),
leading to acid rains and global warming. Water, methane, nitrous
oxide, and ozone are other greenhouse gases found in the atmosphere
(Crutzen et al., 2016; Wallington et al., 2009). The combustion of fos-
sil fuels, destruction of forests, use of chlorofluorocarbons (CFCs) in
refrigeration systems, and utilization of CFCs and halons in firefight-
ing systems increase the concentration of greenhouse gases in the

∗
Corresponding author.
E-mail address: szendehboudi@mun.ca (S. Zendehboudi).
https://doi.org/10.1016/j.cherd.2019.01.019
0263-8762/© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
406 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417

estation, land use change, and agricultural operations (Anderson et al.,

2016; Bolin et al., 1986; Kirk-Davidoff, 2017). Continuing the greenhouse
Nomenclature
gas emissions at the present rate would be harmful to the ecosys-
Acronyms tem, biodiversity, and livelihoods of the human and animal species
AARD Average Absolute Relative Error across the world. It is estimated that at the current emission rates, the
AdaBoost-CART Adaptive Boosting-Classification and upper limit to reach dangerous global warming stage is by 2036 (Doshi,
Regression Tree 2016). Hence, developing new methods to capture the greenhouse gases
appears to be of critical importance to academia, research centers, and
AI Artificial Intelligence
industries (Saeidi et al., 2014). Several techniques including membrane
ANFIS Adaptive Neuro-Fuzzy Inference System
separation, adsorption, and absorption were introduced to remove the
ANN Artificial Neural Network
greenhouse gases (Aghaie et al., 2018, 2019; Dashti and Asghari, 2015;
CFCs Chlorofluorocarbons
Dashti et al., 2018a; Ho, 2006; Raji et al., 2016; Rezakazemi et al., 2017;
CHPSO Conjugate Hybrid Particle Swarm Optimization Rezakazemi et al., 2018; Sodeifian et al., 2018; Yang et al., 2008; Zargar
CMIS Committee Machine Intelligent System et al., 2015). The membrane separation method offers benefits such
CO2 Carbon Dioxide as low energy consumption, high mass transfer, high separation effi-
CPZ Concentrated Piperazine ciency, and simple operation. However, chemical incompatibilities with
CSA Coupled Simulated Annealing the process fluids, long processing time, fouling, temperature limi-
exp Exponential tation, and non-selectivity are considered among disadvantages of
FIS Fuzzy Inference System the membrane processes (Nath, 2017; Padaki et al., 2015). Adsorption
is widely employed in industrial processes such as H2 , natural gas,
GA Generic Algorithm
and synthesis gas production systems with elevated CO2 concentra-
GP Genetic Programming
tions (Olajire, 2010). There are several commercial processes including
LSSVM Least Square Support Vector Machine ® ® ® ®
SelexolTM , Rectisol , Purisol , Morphysorb , and Fluor to separate
MEA Monoethanolamine gases such as carbon dioxide from other gaseous components (Yu et al.,
MLP Multi Layer Perceptron 2012; Yong et al., 2002). However, adsorption methods face various con-
MFs Membership Functions cerns such as regeneration operation and high capital and operating
MSE Mean Squared Error costs. Absorption is another common mechanism of CO2 removal in
NMP N-Methylpyrrolidone which CO2 is separated from gas stream by using chemical or phys-
PSO Particle Swarm Optimization ical solvents (absorbents) during the removal operation (Wang et al.,
PZ Piperazine 2015). Among different CO2 removal methods, the absorption using
amine solvents has been widely implemented in the recent years. Due
R2 Squared Correlation Coefficient
to low mass transfer of CO2 in amines, the primary, secondary, and
RBF Radial Basis Function
tertiary alkanolamines are employed due to their high chemical reac-
STD Standard Deviation
tivity. The main limitations of the alkanolamines are high regeneration
energy, chemical instability, and corrosion. The tertiary alkanolamines
English letters
feature a better absorption capacity, though the reaction rate between
A ANFIS Layer 1 Constant Parameter the tertiary alkanolamines and CO2 is slow (Chakravarty et al., 1985;
B ANFIS Layer 1 Constant Parameter Sartori and Savage, 1983). An improvement in the absorption capacity
n Number of Data Points can be attained by mixing different grades of alkanolamines (Derks
Oi Membership Function of a Fuzzy Set et al., 2006). BASF developed a process based on activated methyl-
p ANFIS Structure Constant Parameter dientanolamine (MDEA) in 1970. For the first time, this process was
q ANFIS Structure Constant Parameter commercialized in 1982 (Headley et al., 2012). Nowadays, this technol-
r ANFIS Structure Constant Parameter ogy is the most common solvent-based strategy for CO2 removal. One
of the key alkanolamines components to remove CO2 from natural gas
rk Relevancy Factor
streams is piperazine (PZ) (Khan et al., 2016). Several research stud-
w̄i Normalized Firing strength
ies were conducted on the CO2 absorption using the PZ solution. For
Xk,i Input Parameter
instance, the absorption rate of CO2 in the aqueous solutions of PZ in
X¯k Average Value of the kth Input the temperature range of 298–333 K was investigated by Bishnoi and
Y ith Output Value Rochelle (2000) under various pressures and PZ concentrations. CO2
absorption in the PZ aqueous solution was also studied by Freeman
Greek letters et al. (2010a) and Freeman et al. (2010b); they found the rate of CO2
␮ Membership Function absorption in the PZ solution to be more than double of that with 7 m
(molal) monoethanolamine (MEA) at a temperature of 40 ◦ C and a sol-
Subscripts vent concentration of 11–21 ppm (Freeman et al., 2010b). Derks et al.
exp Experimental Value (2005) reported experimental data for the CO2 solubility in the PZ solu-
sim Simulation Value tions. The data were modeled using a thermodynamic model based on
the electrolyte Equation of State (EOS). The effect of PZ (as an additive
to various amine solutions) on the CO2 absorption has been recently
atmosphere. Greenhouse gases from the industry and agriculture have studied (Dash et al., 2011b; Du et al., 2013; Mazari et al., 2014; Seo and
raised the concern of the society and public environmental agencies Hong, 2000).
(Burney et al., 2010). Among the greenhouse gases, CO2 has the largest Considering the cost, difficulty, and time-consuming nature of the
share in the global warming. The presence of CO2 in a variety of chem- laboratory methods, the use of empirical methods and deterministic
ical and energy industries also results in various problems such as connectionist tools seems essential to estimate various physical, chem-
corrosion (of process equipment), reduction of the heating value of the ical, and thermodynamic properties (Dashti et al., 2018b). To attain an
natural gas, and a decrease in the pipeline transport capacity (Tatar optimal design of the CO2 absorption process at an industrial scale,
et al., 2016a). Since the industrial revolution in 1750, the CO2 concen- proper simulation and optimization strategies are needed. The first
tration in the atmosphere has increased from 280 ppm to 406 ppm in step in computer-aided process design is to develop a reliable model
2017, implying a significant increase in the total emissions (Edenhofer of the CO2 solubility in the PZ aqueous solution. In thermodynamic
et al., 2011; Shakun et al., 2012; Voigt et al., 2017). This increase is mainly modeling context, the physicochemical properties such as activity coef-
due to the human activities such as combustion of fossil fuels, defor- ficients, chemical reaction extent, equilibrium constants (of ionic and
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417 407

molecular components in the solution), long- and short- range binary

and ternary interaction parameters, Henry’s constant, and fugacity
coefficients are required (Tatar et al., 2016a). Determination of these
parameters requires reliable experimental and modeling tools that
cover a wide range of operating conditions. Soft computing techniques
are powerful alternatives for the thermodynamic, phenomenologi-
cal, and conventional modeling approaches. They possess advantages
such as high flexibility, noise reduction potential, and high precision
(Haykin and Network, 2004). Recently, several smart models includ-
ing Artificial Neural Network (ANN), Adaptive Neuro-Fuzzy Inference
System (ANFIS), and Least Square Support Vector Machine (LSSVM)
were employed to study the solubility of gases in a variety of solvents
(Baghban et al., 2015, 2017a; Baghban et al., 2017b). The solubility of CO2
in the mixture of water and PZ was estimated using Conjugate Hybrid
Particle Swarm Optimization-Adaptive Neuro-Fuzzy Inference System
(CHPSO-ANFIS) and Coupled Simulated Annealing-Least Square Sup-
port Vector Machine (CSA-LSSVM) (Tatar et al., 2016a), where the
reliability and accuracy of the CHPSO-ANFIS model was found superior
to the CSA-LSSVM. CO2 absorption was modeled at various composi-
tions of amine aqueous solutions, using MLP-ANN, RBF-ANN, LSSVM,
and ANFIS where LSSVM model was found more accurate, compared to
the other methods (Baghban et al., 2017a). To estimate the solubilities of
CO2 and H2 S in various ionic liquids and amine solutions, ANN model
was utilized (Hamzehie et al., 2015). The results demonstrated capabil- Fig. 1 – Simple schematic of chemical structure of PZ.
ities of the ANN technique to accurately estimate the solubility of these
acidic gases in different solutions. Tatar et al. (2016a) predicted the CO2
absorption in various solutions (e.g., MDEA and N-methylpyrrolidone
(NMP)) using hybrid mathematical models including MLP-ANN, GA-RBF,
LSSVM, Hybrid-ANFIS, PSO-ANFIS, and CMIS; based on their study, the
model predictions were in agreement with the experimental data (Tatar
et al., 2016c). Hamzehie et al. (2014) introduced an ANN model to deter-
mine the CO2 solubility in aqueous amine solutions. Babamohammadi
et al. (2018) used ANN to estimate the CO2 solubility in aqueous solu-
tions of glycerol and MEA. Norouzbahari et al. (2015) developed an ANN
model to obtain the CO2 loading in aqueous PZ solutions. To forecast the
CO2 solubility in the aqueous PZ solutions, four models including ANN,
ANFIS, LSSVM, and Adaptive Boosting-Classification and Regression
Tree (AdaBoost-CART) were utilized by Yarveicy et al. (2017). AdaBoost-
CART model was found more accurate than the other models employed
in their work.
Fig. 2 – Representative schematic of function sin (X2 ) − log
To the best of our knowledge, no research study has been conducted
using GA-ANFIS and Genetic Programming (GP) techniques to model (X − 9) in GP model.
the CO2 solubility in PZ solutions yet. The main advantage of the GP
method is that it offers an empirical mathematical model to determine ahydrate salt, C4 H10 N2 ·6H2 O (Mao et al., 2016). It has a melting
an objective function, where the input parameters are given. Hence, point of 44 ◦ C and a boiling point of 125–130 ◦ C (Haramoto et al.,
the current research focuses on the applicability of the GA-ANFIS and 2002; Khan et al., 2017; Yokozeki and Kuchitsu, 1971). The solu-
GP for the prediction of the CO2 solubility in aqueous mixtures of PZ bility of PZ in water and ethylene glycol is unlimited; however,
and water. We use 390 experimental data points to develop appro- its solubility in diethyl ether is zero. A 10% PZ aqueous solu-
priate deterministic models. The ANFIS is coupled with the GA as an tion results in a pH in the range of 10.8–11.8, implying it is a
optimization algorithm to improve its prediction accuracy. Important weak base. PZ is known for its applications to absorb carbon
variables such as temperature, partial pressure of CO2 , and the PZ con-
dioxide and water from air (Dash and Bandyopadhyay, 2016;
centration in the solution are considered as the input parameters and
Mumford et al., 2015; Zhang et al., 2018).
the accuracy of the GA-ANFIS and GP models is assessed by a statistical
PZ naturally exists as alkaline crystals, and is obtained
analysis. The structure of this paper is as follows: in Section 2, the theo-
retical background on PZ is given; Section 3 summarizes the theoretical through three reaction pathways, including: 1) reaction of
frameworks of ANFIS, GA, and GP; Section 4 gives details of data acqui- alcoholic ammonia with 1,2-dichloroethane, 2) reaction of
sition on vapor–liquid phase equilibria related to CO2 /PZ/H2 O system; sodium and ethylene glycol with ethylene diamine hydrochlo-
Section 5 includes results and discussions; and Section 6 provides the ride, and 3) reduction of pyrazine with sodium in ethanol
conclusion remarks. (Chetan et al., 2010; Gettys et al., 2017; Chaudhary et al., 2006;
Takai et al., 2015; Waszkielewicz et al., 2015).
2. Characteristics and applications of PZ is the main functional group of a wide range of phar-
piperazine maceuticals, which are usually in the citrate forms. Other
industries such as polymer (plastics and resins), agriculture
Piperazine is the IUPAC preferred name for 1,4-diazinane, also (pesticides), and chemical/petrochemical also use PZ in their
known as hexahydropyrazine. As shown in Fig. 1, its chemical processes (Das et al., 2013; Tan et al., 2016; Zhou et al., 2017).
structure is composed of a six-carbon benzene ring with two PZ solubility in amines is generally low such that it is often
N H groups on atoms 1 and 4. Piper, which is the Latin word for used in small amounts to make an amine solvent. The low
pepper, is its original name, while it has never been extracted concentration of PZ decreases its performance in terms of
from the pepper plant. PZ is commercially available as a hex- absorption capacity. The rate of CO2 absorption, solvent capac-
408 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417

ity, and heat of absorption are increased by adding PZ to the 1, where j = 1, node i refers to an adaptive node with the input
amine gas purification solvents (Lepaumier et al., 2009; Li et al., of x (or y). Ai (or Bi−2 ) represents a linguistic label attributed
2013). The absorption processes with the amine solutions are to this node. Hence, the membership function for this node is
usually conducted at the temperature range of 45 ◦ C–55 ◦ C. expressed as follows:
The carbon capture capacity of the PZ is significant at this
temperature condition. PZ is distilled and recycled to the pro- O1i = Ai (x) , i = 1, 2 (1)
cess after the flash distillation at temperatures up to 150 ◦ C.
PZ is a cyclic diamine, which is promising in absorbing CO2 or
due to the rapid formation of CO2 from carbonates (Freeman
et al., 2010b; Rochelle et al., 2011). The amine groups on the PZ O1i = Bi−2 (y) , i = 3, 4 (2)
molecule promptly react with CO2 to create the PZ carbamate
(at the reduced loading) and PZ bicarbamate at an opera- Thus, O1i denotes the membership function of a fuzzy set A
tional condition of 0.31–0.41 mol CO2 /equiv PZ, improving the (A1 , A2 , B1 , or B2 ) and it determines the level to which the input
rate of CO2 solubility. As a result, there is not a significant x (or y) correlates to the quantifier A. The Membership Func-
amount of free PZ in the solvent that causes a reduction in tions (MFs) for A and B can be represented by the generalized
the volatility and precipitation rates through formation of bell functions, as given below:
PZ.6H2 O (Rochelle et al., 2011). Concentrated piperazine (CPZ)
is a novel absorbent that has a higher CO2 absorption capacity, 1
Ai (x) =  x−r 2q (3)
compared to MEA (Freeman et al., 2010b). CPZ is more reac- 1+ p i i
i
tive and thermally more stable (compared to MEA), which is
expected to reduce the capital and operation costs of the CO2 In Eq. (3), pi , qi , and ri resemble the parameter sets. Through
capture based on the CSIRO pilot plant tests (Cottrell et al., changing these parameters, the function shape is altered. In
2013; Li et al., 2013). the next layer, where j = 2, the inputs are multiplied using the
nodes such that their product is expressed by the following
3. Mathematical modeling approach relationship:

Model selection is normally based on the knowledge about the O2i = wi Ai (x) Bi (y) , i = 1, 2 (4)
problem and set objectives. There are advantages and draw-
backs with any model (Rodrigues and Minceva, 2005). Physical Every node product demonstrates the rules firing strength.
and chemical phenomena/behaviors to describe the process In layer 3, which is called the normalization layer, the ratio of
form the foundations of theoretical models. In general, the firing strength of node i to sum of all rules’ firing strengths is
main governing equations to simulate the process behav- calculated as follows:
iors are obtained from the conservation laws of momentum, wi
mass, and energy. The complex (and nonlinear) mathemati- O3i = w̄i = , i = 1, 2 (5)
w1 + w2
cal algebraic equations need proper tools to attain solutions.
A majority of the solution methods may encounter serious In layer 4, node i calculates the portion of the ith rule to the
issues such as lack of proper curve fitting and convergence. total output as given below:
Artificial Intelligence (AI) models have a capability to offer
effective models when they learn and simulate processes O4i = w̄i zi = w̄i (ai x + bi y + ci ) , i = 1, 2 (6)
(Zendehboudi et al., 2018; Kamari et al., 2015a,b; Chamkalani
et al., 2014). They appear to be a good choice when it is difficult in which, w̄i denotes the normalized firing strength (layer 3
to find physical or chemical concepts/phenomena to describe output) and ai , bi , and ci represent the set of parameters, which
a system, or when the model formulation is not feasible by are called the consequent parameters.
existing knowledge, experience, and data. Previous studies In layer 5, the ultimate output is computed by summation
show high capabilities of ANN approaches to obtain appro- of the entire incoming signals in a node as follows:
priate formulations and solutions for complex and nonlinear

systems/ problems (Azizi et al., 2017; Zendehboudi et al., 2018). wi zi
In this section, the modeling tools are briefly described.
i
O5i = w̄i zi =  (7)
i wi
3.1. Adaptive Neuro-Fuzzy Inference System (ANFIS) i

The modeling approach of Adaptive Neuro-Fuzzy Inference
System (ANFIS) was initially proposed by Jang (1993); it
hybridizes ANN and Fuzzy Inference System (FIS) to compen-
sate for the drawbacks of the stand-alone ANN and FIS models.
ANFIS is a class of adaptive multi-layer feed forward network
that is used to forecast the target parameters in nonlinear sys-
tems (Ying and Pan, 2008). Given its structure comprises of
nodes formed in five different layers (Yun et al., 2008), ANFIS
is a fuzzy logic-based model with the fuzzy rules, which are
obtained during the training step (Kamari et al., 2015a). Each
node is described by its membership function. The output
j
from the ith node of layer j is shown by Oi . For instance, in layer
In this study, the GA approach is applied to optimize the
values of the membership function variables in the ANFIS
algorithm.
3.2. Genetic algorithm
The concept and capability of Genetic Algorithm (GA) in solv-
ing the science and engineering optimization problems were
first explored by John Holland in 1975. More applications of the
GA were discussed in several research studies (Houck et al.,
1995). Generic Algorithm (GA) finds the best criteria for the fit-
ness function. The algorithm is made of chromosomes, which
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417 409

are the strings of genes. The optimal criteria in GA are obtained dard Deviation (STD), and Mean Squared Error (MSE) to check
through the fitness functions that can be either maximized the reliability of the GP and GA-ANFIS models. The definitions
or minimized. The genetic operators are subsequently repro- of these statistical criteria are given below (Arabloo et al., 2015;
duced, mutated, migrated, and crossed over, starting from an Ghiasi et al., 2014).
initial population of chromosomes to upgrade their quality.
The single point and matrix crossover are the common oper-
1  exp
n
2
ators in the GA (Goldberg, 1989). MSE = yi − ysim
i
(8)
n
i=1

3.3. Genetic programming


n

n
 2 exp
Koza (1992) proposed Genetic Programming (GP) for the  (ysim − ym ) yi
 i
first time, which can be considered as the first evolution- i=1 i=1
STD = , ym = (9)
ary algorithm in mathematical modeling (Bäck et al., 1997). n−1 n
GP represents a strategy to find a solution for a problem
by a computer through automatic generation of algorithms
100 
n
ysim
exp
− yi
i
and expressions, which are based on the natural evolu- % AARD = exp (10)
n yi
tion. This method can be expressed as a tree whose nodes i=1
are functions and leaves are the terminals. GP is imple-
mented by function construction, which contains a set of n exp 2
√  (ysim − yi )
mathematical operations including (+, −, ∗, /, ∧, , log, exp, i=1
i
sin, and arcsin). The GP model resembles natural selection R2 = 1 − n
(11)
exp 2
 (yi − ym )
through operators such as crossover and mutation to the i=1
“children”. The selection process means to retain the best per-
forming parents from one generation to the next. Through exp
yi refers to the ith measured solubility data; ysim
i
represents
applying an operator such as crossover in the GP model-
the modeling result for the ith data point; ym is the average
ing program, the new generation (called children) imitates
value of solubility from experiential data; and n is the total
the natural selection to maintain identical features from one
number of data points.
generation to another. Mutation is another operator that
makes random changes. The initial population of models
(which is a random population) affects the program solution 5. Results and discussion
where a relationship between the independent and depen-
dent parameters is being exploited. The population resulted The GA-ANFIS and GP are proposed to predict the solubility of
from the optimal selection of fitness criterion and replace- CO2 in the PZ solutions. This section presents and discusses
ment leads to a better performance. Fig. 2 displays a schematic the results obtained from the modeling approaches.
of the function sin(X2 ) − log (X − 9) in the GP, as an exam-
ple.
5.1. GA-ANFIS results

4. Data acquisition and analysis
The accuracy, robustness, and reliability of any model have to
be checked with the actual data and behavior trends through
employing statistical tools (Dadkhah et al., 2017; Nasery et al.,
2016; Tatar et al., 2016b; Kamari et al., 2014a,b,c). For each
model, there are always independent input parameters that
considerably influence the output parameter(s). In our study,
temperature, partial pressure of CO2 , and concentration of PZ
are considered as the independent input parameters and the
CO2 solubility in aqueous PZ solution, which is defined as mole
CO2 /mole PZ, is an output parameter. In data selection pro-
cess, it is important to have reliable data points to train and
to evaluate the model. We gathered 390 experimental data for
the solubility of CO2 in PZ solution from the previously pub-
lished works, as listed in Table 1 (Bishnoi and Rochelle, 2000;
Dash et al., 2011a; Derks et al., 2005). Data points are randomly
divided into two categories such that 70% are used at the train-
ing stage and the remaining data points are utilized at the
testing phase.
In the training stage, the model is developed and in the
testing stage, its performance is evaluated with quantifying
the objective function(s). To check the model reliability, a para-
metric sensitivity analysis is conducted. In this research work,
we use four statistical parameters including Average Absolute
Relative Error (AARD), coefficient of determination (R2 ), Stan-
First, the ANFIS model whose structure is optimized by GA
is developed. The maximum number of generations, size of
population, mutation (%), crossover (%), selection pressure,
and mutation rate are the parameters of the GA algorithm for
®
which their optimal values are determined. We use MATLAB
to develop the GA-ANFIS model. The GA role is to effectively
relate the model inputs to the output through a proper opti-
mization scheme. Finding the optimal parameters of the GA
is vital in the development of a robust smart model. Trial and
error procedure is employed to tune the GA parameters. The
GA is also used to optimize the ANFIS structure, as depicted
in Fig. 3.
Temperature (in K), partial pressure of CO2 (in kPa), and
the PZ concentration (in mol/L) are considered as impor-
tant factors, affecting the solubility of CO2 in the PZ/H2 O
solutions. The MFs in the fuzzy sub-domain are of general-
ized Gaussian type, as recommended by the previous studies
(Ganjidoost et al., 2016; Ghasemi et al., 2016; Ghiasi et al., 2016;
Hasanipanah et al., 2016; Tatar et al., 2016a, c). The GA-ANFIS
related MFs for estimation of solubility of CO2 in solutions of
PZ/H2 O are illustrated in Fig. 4. Table 2 also lists the properties
of the GA-ANFIS model used for determination of CO2 solubil-
ity in the solutions. According to Table 2, the optimal values of
the maximum generation number, maximum population size,
mutation (%), crossover (%), selection pressure, and mutation
rate are obtained at 100, 1000, 0.7, 0.65, 8, and 0.05, respectively.
410 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417

Table 1 – Ranges of temperature (T), partial pressure of CO2 (PCO2 ), and concentration of PZ (CPZ ) of the collected data
points (n).
PCO2 (kPa) T (K) CPZ (mol/L) CO2 solubility (mol CO2 /mol PZ) n References

0.032–40 313–343 0.2, 0.6 0.16–0.96 17 Bishnoi and Rochelle (2000)

0.083–1487 298–328 0.2–4.5 0.263–2.956 315 Dash et al. (2011a)
0.45–111.37 298–343 0.2–0.6 0.36–1.23 58 Derks et al. (2005)

Table 2 – Characteristics of the GA-ANFIS approach to

estimate the solubility of CO2 in solutions of PZ and H2 O.
Parameter Value

Population size 100

Iteration or generation size 1000
Mutation (%) 0.7
Crossover (%) 0.65
Selection pressure 8
Mutation rate 0.05
Number of fuzzy rules 10

Table 3 – Properties of the GP model for prediction of CO2

solubility in PZ/H2 O solutions.
Variable Value

Number of population 100

Maximum generation 1000
Maximum depth of trees 7
Selection type Tournament
Terminals (x1 , x2 , x3 )
Functions (+, −, ×, /, exp, 2 )

lows:
 x2
2
0.006072 9.89314484 − ex2
y = 0.0001494x1 −
19.937466+ex3
x2 + x1 +1
 x3

0.0001494 11.872896 − x2 0.0001494x2
+ +
x3 x3
 x2

0.0006357 0.006072 x2 − x3 − x12 + x3
− +
x2 x1
0.0001494 (x2 − 2x1 + 2.942727)
Fig. 3 – Schematic diagram of combined GA and ANFIS −
0.3469x3 − 2.883
model.
0.0001494 (2x3 + 18.122610)
+ + 2.816 (12)
5.2. GP results x1 x32

The maximum generations of 1000, 100 populations, the max-
imum depth of trees of 7, and the tournament selection
approach are taken into account in the GP algorithm. The best
value for the tree depth is selected to be 7 after the mag-
nitudes of 6–12 trees were tested so that the runtime and
error percentage hold the minimum values at the depth of
trees of 7. To generate proper mathematical models using
the GP, the function set of (+, −, ×, /, and exp) is chosen.
An independent variable (X) or an integer is considered as
the terminal. As mentioned earlier, temperature (in K), par-
tial pressure of CO2 (in kPa), and PZ concentration (in mol/L)
are the independent input variables, and the CO2 solubility is
the objective function. To evaluate the fitness function perfor-
mance, the Mean Squared Error (MSE) of the GP, representing
the difference between the predictions and experimental val-
ues, is used. Table 3 presents the specifications of the GP
model.
Employing the GP model, the best correlation to determine
the CO2 solubility in the PZ/H2 O solutions is obtained as fol-
where x1 , x2 , and x3 stand for the temperature (K), par-
tial pressure of CO2 (kPa), and concentration of PZ (mol/L),
respectively. The evolutionary algorithm for this deterministic
®
approach is performed by the GPTIPS toolbox in the MATLAB
software.
The model results (for both deterministic tools) are com-
pared against the actual values and this comparison is
depicted in Fig. 5, showing a slope near one. It implies that
the predictions and experimental data are in a good match.
The coefficient of determination (R2 ) of the GA-ANFIS model
is 0.9531, while the R2 of the GP approach is 0.9735. Therefore,
both methods are successful in explaining a major part of cor-
relation in the data, though the GP model shows a slightly
better performance.
Fig. 6 illustrates the experimental data and model estima-
tions versus the data index to examine the accuracy of both
models. As it is clear, there is a very good agreement between
the estimated magnitudes of solubility and the experimental
data within a wide range of operating conditions. It can be con-
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417 411

Fig. 4 – The Membership Functions (MFs) for (a) temperature, (b) partial pressure of CO2 , and (c) concentration of PZ in
prognostication of solubility of CO2 in PZ/water solutions on the basis of the GA-ANFIS model.

cluded that both GA-ANFIS and GP result in accurate values for
the target parameter (e.g., CO2 solubility in PZ solutions). His-
tograms of the model errors are shown in Figs. 7 and 8. For
both GA-ANFIS and GP models, the histogram for the training
and testing phases is presented. The results of error distri-
bution confirm that the models follow relatively the normal
distribution curves.
The relative error (%) in the model outputs compared to
the experimental data is demonstrated in Fig. 9. Except for
the lower range of pressure (P < 0.5 MPa), the errors are ran-
412 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417

Table 4 – Statistical values while estimating the CO2 solubility in mixture of PZ and H2 O through utilization of various
models in this study.
Parameter GA-ANFIS GP

Train Test Total Train Test Total

R2 0.9587 0.9418 0.9531 0.9762 0.9679 0.9735

MSE 0.0061 0.0100 0.0073 0.0035 0.0055 0.0041
STD 0.3773 0.4042 0.3864 0.3786 0.4076 0.3883
Error percentage range [−22.81, 170.99] [−21.96, 119.75] [−22.81, 170.99] [−15.57, 35.24] [−15.89, 80.7] [−15.57, 80.7]
%AARD 8.9340 11.5351 9.7143 5.1251 5.7790 5.3213

Fig. 6 – Experimental and estimated values for various

models against data index: (a) GA-ANFIS and (b) GP.

Fig. 5 – Predicted CO2 solubility results versus

experimental data for two models: (a) GA-ANFIS and (b) GP.

domly distributed. In the pressure range below 0.5 MPa, both

GA-ANFIS and GP tend to overestimate the solubility of CO2
in the piperazine solution. However, the errors are small in
the upper pressure range such that the values of MSE in the
upper pressure range are less than 0.007% and 0.004% with the
GA-ANFIS and GP models, respectively. According to Fig. 9, the
data points very close to the x-axis exhibit very low (near zero)
relative deviation with respect to the real data. The AARD for Fig. 7 – Histogram of training and testing stages with
the GA- ANFIS and GP models are 9.71% and 5.32%, respec- GA-ANFIS model while estimating the CO2 solubility in the
tively. The magnitudes of the maximum error percentage and solutions of PZ/H2 O.
STD for the GA-ANFIS model are 170.99 and 0.3864, respec-
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417
Fig. 8 – Histogram of training and testing stages with GP
model while obtaining CO2 solubility in PZ/H2 O mixtures.
Fig. 9 – Relative deviations of the deterministic tools for: (a)
GA-ANFIS and (b) GP.
tively; while the corresponding values for the GP model are
80.7 and 0.3883, respectively (see Table 4).
A successful mathematical model should be able to accu-
rately predict the behaviors/trend of the target parameter(s) as
a function of input variables. In this study, the experimental
and predicted values of CO2 solubility in piperazine solution
versus partial pressure of CO2 at different temperatures are
plotted in Fig. 10 using a part of the experimental data. The
413
GP model outputs (CO2 solubility) follow experimental solu-
bility data better, compared to the GA-ANFIS model when the
variations of the input factors such as temperature and partial
pressure of CO2 are considered. In addition, the GP capability
is higher than the GA-ANFIS model due to its greater flexibil-
ity and training strategy that allow to cover wider ranges of
operating and thermodynamic conditions.
Table 4 summarizes the statistical performances of the GA-
ANFIS and GP models in estimating the solubility of CO2 in
piperazine solution. The more precise model features lower
AARD, MSE, and STD, but a higher value of R2 . According to
Table 4, the values of AARD for the GA-ANFIS model are higher
than those for the GP, meaning that the latter technique is
more accurate. On the other hand, higher value of R2 and lower
MSE for the GP model reveal that the GP model exhibits a bet-
ter performance, although there are small differences between
these two models in terms of R2 and MSE. The statistical mea-
sures for both models clearly indicate an excellent prediction
performance in estimating the solubility of CO2 in piperazine
aqueous solution. No significant differences between the GP
and GA-ANFIS in terms of performance and applicability are
noticed.
There are adjustable connecting parameters between the
input and output parameters in a developed connectionist
model. To quantify the influence of the inputs variables on the
output, a sensitivity analysis is conducted. The input parame-
ter with the largest effect on the CO2 solubility in PZ solutions
has the highest relevancy factor (r) as defined below (Arabloo
et al., 2015; Ghiasi et al., 2014):

n
(xk,i − xk · m )(yi − ym )
i=1
rk = (13)

n
2

n
2
(xk,i − xk · m ) (yi − ym )
i=1 i=1
where rk is the relevancy factor for input k where k = 1, 2, and
3; xk,i denotes the ith data point for kth input; xk,m represents
the average (considering all data points) for the kth input; yi is
the ith output data point; ym is the average of the output data
points; and n stands for the number of data points.
An input parameter with a higher absolute value of rk
shows a greater impact on the output. In addition, a posi-
tive value for the relevancy factor means that the output will
increase with an increase in the input variable, and a nega-
tive value for rk means that the output will decrease with an
increase in the kth input variable.
As depicted in Fig. 11, the CO2 solubility is affected by the
partial pressure of CO2 (PCO2 ) the most, following the system
temperature (T), and the PZ concentration (CPZ ). The relevancy
factor is only positive for the partial pressure of CO2 , mean-
ing that increasing the partial pressure of CO2 will increase
the CO2 solubility, while it is negative for the temperature and
the concentration of piperazine as observed in Fig. 11. The rel-
evancy factor is 0.6948 for the partial pressure of CO2 , it is
−0.3075 for the temperature, and its magnitude is −0.2278 for
the PZ concentration.
As the connectionist models are developed based on the
input data, there are no limitations for this type of determin-
istic tools, similar to those for empirical models and EOSs (e.g.,
need of comprehensive knowledge of the targeted process
to develop a predictive model and applicable/valid for more
specific conditions in terms of process/thermodynamic behav-
414 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417

Fig. 10 – Objective function determined by the GA-ANFIS and GP models versus temperature and partial pressure of CO2 :
T = 313 K & PZ concentration = 0.6 M (Bishnoi and Rochelle, 2000); T = 343 K & PZ concentration = 0.6 M (Bishnoi and Rochelle,
2000); and T = 298 K & PZ concentration = 0.2 M (Dash et al., 2011a). The solid and dashed lines show the GP and GA-ANFIS
model estimates, respectively, and the scatter points represent the experimental data.

2004; Bishnoi and Rochelle, 2000; Dash et al., 2011a,b; Derks

et al., 2005; Dugas and Rochelle, 2009; Ermatchkov et al., 2006;
Nguyen et al., 2010). The equilibrium data for mixtures of
CO2 , PZ, and H2 O for process engineering and thermodynamic
modeling are necessary; however, it is a difficult task to obtain
them within broad intervals of temperature, pressure, and
composition through experiments and thermodynamic mod-
els. To determine the thermodynamic data in non-linear cases
such as multiphase equilibrium, the smart models appear to
be efficient. GP and GA-ANFIS tools are explicit and relatively
problem independent approaches where detailed information
and knowledge about the targeted processes are not required
for various process engineering purposes.

6. Conclusions

CO2 capture is considered as an efficient strategy to lower

Fig. 11 – Relative significance of input parameters
employed to predict CO2 solubility. Partial pressure of CO2
is shown in red; temperature is shown in blue; and the
concentration of PZ appears in green. (For interpretation of
the references to colour in this figure legend, the reader is
referred to the web version of this article).
iors). Thus, they are able to handle all ranges of the input data.
For instance, they can accurately estimate the phase behaviors
at high temperatures and pressures and critical conditions as
long as they are trained with an adequate number of experi-
mental data at these conditions. Indeed, selection of suitable
input parameters considerably improves the model accuracy.
The number of data points in training and testing phases will
affect the accuracy of the model. All efforts for the reduction
of uncertainties during the model development increase the
performance and accuracy of the model.
Predicting the CO2 solubility in amine solutions is the
primary stage in the design and optimization of industrial
amine absorption/desorption processes. There have been sev-
eral research works in this field (Aroua and Mohd Salleh,
CO2 emissions to the atmosphere. There are several methods
for capturing/absorbing CO2 originated from various chemi-
cal processes and operations. CO2 absorption by amines is
a common technology for carbon management. Considering
the high absorption potential of of the piperazine (PZ), it is
vital to obtain the process and thermodynamic characteris-
tics of CO2 /H2 O/PZ through proper laboratory and modeling
tools. As the experimental trials are normally expensive and
lengthy in terms of time, the connectionist models can be an
appropriate alternative for determination of CO2 absorption
equilibrium data in CO2 capture plants. This paper intro-
duces two powerful deterministic methodologies including
Genetic Programming (GP) and Genetic Algorithm-Adaptive
Neuro Fuzzy Inference System (GA-ANFIS) to obtain solubil-
ity of CO2 in the solutions of PZ/H2 O where the temperature,
partial pressure of CO2 , and concentration of PZ are the inde-
pendent input parameters. Statistical and graphical analysis
show that both models lead to an acceptable accuracy within
wide ranges of operational conditions. It is concluded that the
outcomes of the proposed GP model are closer to the exper-
imental values, compared to the GA-ANFIS model, though
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 405–417
the GA-ANFIS model results exhibit a very good match with
the real data, as well. The GP model can be used by various
researchers, who are not familiar with artificial intelligence
science to predict the CO2 solubility. The sensitivity analysis
shows that the partial pressure of CO2 has the highest influ-
ence on the CO2 solubility in the PZ solution.
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