Journal of CO₂ Utilization 33 (2019) 83–95

Contents lists available at ScienceDirect

Journal of CO2 Utilization

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

Predicting solubility of CO2 in brine by advanced machine learning systems: T

Application to carbon capture and sequestration
Nait Amar Menada, Abdolhossein Hemmati-Sarapardehb, Amir Varameshc,
Shahaboddin Shamshirbandd,e,
⁎

a
Département Etudes Thermodynamiques, Division Laboratoires, Sonatrach, Boumerdes, Algeria
b
Department of Petroleum Engineering, Shahid Bahonar University of Kerman, Kerman, Iran
c
Department of Chemical & Petroleum Engineering, University of Calgary, Calgary, AB, T2N 1N4 Canada
d
Department for Management of Science and Technology Development, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
e
Faculty of Information Technology, Ton Duc Thang University, Ho Chi Minh City, Viet Nam

ARTICLE INFO ABSTRACT

Keywords: Carbon dioxide (CO2) capture and sequestration in saline aquifers have turned into a key focus as it becomes an
CO2sequestration effective way to reduce CO2 in the atmosphere. The solubility of CO2 in brine is of vital role in monitoring CO2
CO2solubility in brine sequestration. In this study, based on molality of NaCl, pressure and temperature, modeling of CO2 solubility in
MLP brine has been carried out utilizing multilayer perceptron (MLP) and radial basis function neural network
RBFNN
(RBFNN). Levenberg-Marquardt (LM) algorithm was implemented to optimize the MLP model, while genetic
Metaheuristic algorithms
algorithm (GA), particle swarm optimization (PSO) and artificial bee colony (ABC), were applied to optimize the
RBFNN model. To this end, a widespread experimental databank including 570 data sets gathered from literature
was considered to implement the proposed models. Graphical and statistical assessment criteria were considered
to investigate the performances of these models. The obtained results revealed that all the proposed techniques
are in excellent correspondence with experimental data. In addition, the performance analyses showed that
RBFNN-ABC model exhibits the higher accuracy in the prediction of CO2 solubility in brine compared with the
other proposed smart approaches and the existing well-known models. The RBFNN-ABC model yields a root
mean square error (RMSE) value of 0.0289 and an R2 of 0.9967. Finally, the RBFNN-ABC model validity was
confirmed and a small number of probable doubtful data was detected.

1. Introduction
Carbon dioxide (CO2) is the main greenhouse gas (GHG), which is
resulted mainly from the intake of fossil fuels which represent the
primary energy source for industry and transport activities.
Indisputably, the increase in CO2 emission is related to sensible en-
vironmental issues such as the change in the climate and the increase of
the global surface average temperature [1–5]. Therefore, in the last few
decades, there has been a major area of interest within the ways to
bring down the CO2 level in the atmosphere, and one of these methods
is to capture carbon and store it in the underground. This process is
known as carbon capture and sequestration (CCS) [6].
CCS has been proven as a vital procedure to decrease the CO2 levels
in the atmosphere. Technically, the carbon capture is made by means of
cryogenic separation adsorption / absorption and membrane separation
[7], while one of the cutting-edge way that getting much attention for
the CO2 sequestration is to inject it into deep saline aquifers [8,9].
To manage the sequestration of CO2 in saline aquifers, it is required
to have accurate representation of the brine and CO2 related parameters
[10–12]. CO2 solubility in brine is considered the main parameter in the
CO2 sequestration in saline aquifers [10–12]; hence, its accurate pre-
diction is necessary. Owing the importance of CO2 solubility in brine,
numerous theoretical as well as experimental studies have been per-
formed to deepen investigate a wide variety of related topics to this
vital parameter. In short, Yan et al. [13] did experimental and modeling
researches for the solubility of CO2 in NaCl brine. In their study, CO2
solubilities were measured in 0, 1, and 5 m NaCl brines under pressure
condition varying from 5 to 40 MPa, at temperatures of 323, 373, and
413 K. Wang et al. [14] carried out measurements of the solubility of
CO2 in synthesized brine samples under intervals of 318–348 K for
temperature and 80–110 bar for pressure. Mohammadian et al. [15]
conducted experimental surveys of the solubility of CO2 in NaCl brines

⁎
Corresponding author at: Department for Management of Science and Technology Development, Ton Duc Thang University, Ho Chi Minh City, Viet Nam.
E-mail address: shahaboddin.shamshirband@tdtu.edu.vn (S. Shamshirband).

https://doi.org/10.1016/j.jcou.2019.05.009
Received 15 January 2019; Received in revised form 16 March 2019; Accepted 3 May 2019
2212-9820/ © 2019 Elsevier Ltd. All rights reserved.
N.A. Menad, et al.
Nomenclature
Acronyms
ABC artificial bee colony
AI artificial intelligence
ANN artificial neural network
BP back propagation
GA genetic algorithm
LMA Levenberg-Marquardt algorithm
MLP Multilayer perceptron
MSE mean square error
P pressure
PSO particle swarm optimization
RBFNN radial basis function neural network
RMSE Root mean squared error
R2 coefficient of determination
T temperature
in low salinity conditions (0 − 15 000 ppm) with pressures up to
25 MPa at temperatures changing from 60 to 100 °C. Mosavat et al. [16]
reported measurement tests of CO2 solubility in water, brine, and oil
mixtures at pressures ranging from 0.7–10.3 MPa and temperatures
between 21 and 40 °C. Zhao et al. [17] compared the solubility of CO2
three kinds of brine including those of natural and synthetic formations,
as well as synthetic NaCl + CaCl2 at temperatures ranged from 323 to
423 K and pressures from 100 to 200 bar. Their experimental outcomes
claimed that the solubility of CO2 in brines of the synthetic formation
can be consistently substituted by that of the synthetic NaCl + CaCl2.
In addition to the experimental investigations, the past few decades
have seen increasingly rapid advances in developing correlations and
thermodynamic paradigms to estimate properly the solubility of CO2 in
brine. In brief, the well-known thermodynamic models that were es-
tablished over the past century are Li and Nghiem [18] and Zuo and
Guo [19] models which are based on equations of state of Pen-
g–Robinson and Patel–Teja, respectively. However, these models, and
besides the limitation of their applicability domains, they fail in pro-
viding accurate values of CO2 solubility [11]. These lacks can be ex-
plained by the moderate varieties of data that were employed in the
developments of these models. Recently, some other models have been
introduced with the aim of predicting CO2 solubility in brine, such as
Sørensen et al. [20], Portier and Rochelle [21] and Duan et al. [22]. The
deep overview reported in [23] revealed that the aforementioned
thermodynamic models and the preexisting ones suffer from lack of
generalization as they are valid only within limited ranges of tem-
perature, pressure and NaCl molality. A new activity–fugacity phase
equilibrium model that outperforms the previous ones was developed
by [23]. Despite the performances shown by this model, it must be
underlined that it can be applied only when the NaCl molality does not
exceed 4.5 mol/kg. The other pragmatic model which has the ad-
vantage of calculation simplicity is the Bahadori et al. correlation [11].
Nevertheless, this correlation has not escaped criticism due to its see-
mingly intractable NaCl molality conditions (it is only valid for mNaCl
equal to 1, 2 or 4 mol/kg).
On the other hand, appraisal of modeling purposes in many en-
gineering areas using artificial neural network (ANN), which is re-
cognized as one of the principal categories of machine-learning, has
shown the high ability of this technique to provide more user-friendly,
inexpensive to apply, reliable and faster solutions to several problems
with any kind of complexity [24–30]. Multilayer perceptron (MLP) and
radial basis function neural network (RBFNN) are the common ANNs
types [31]. In addition, there are different optimization techniques to
improve the ANNs learning process by creating appropriate values for
their control parameters such as the spread coefficient and the number
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Journal of CO₂ Utilization 33 (2019) 83–95
Variables
xj position of jth particle or bee
vj velocity of jth particle
c1, c2 learning rates
rand random number
d dimension for search
Spred predicted solubility
Sexp experimental solubility
Subscripts
j particle j
Min minimum
Max maximum
t iteration
of neurons for RBFNN; biases and weights for MLP. Levenberg-Mar-
quardt (LM) algorithm [25], genetic algorithm (GA) [32,33], smart
nature-swarm algorithms such as particle swarm optimization (PSO)
and artificial bee colony (ABC) [24,34], are optimization methods
which have provided relevant results in such tasks.
In this study, several smart techniques are evolved to serve as a
rapid and accurate manner to estimate CO2 solubility in brine. These
techniques are based on MLP and RBFNN models, which are examined
to predict the solubility of CO2 in brine in terms of NaCl (mNaCl ) mol-
ality, pressure (P), and temperature (T) using extensive experimental
databank. LMA is employed to train the MLP model, while three nature-
inspired algorithms including PSO, GA and ABC are employed to opti-
mize the number of neurons as well as the spread coefficient of the
RBFNN model. Moreover, to assess the consistency of the implemented
paradigms, statistical criteria and graphical error analyses were con-
sidered, and a comparison of the accuracy is made against preexisting
models, namely those of Mao et al. [23] and Bahadori et al [11]. Fur-
thermore, to delve into the examination of the physical aspect of the
best-established model, the variations of CO2 solubility in brine were
sketched in terms of the employed variables by considering several
conditions. Finally, Leverage technique was utilized to evaluate and
examine the quality of the used-data as well as to define the applic-
ability realm of our best paradigm. The present paper differs from the
previously performed studies in literature according to: (1) the applied
techniques to model the CO2 solubility in brine, in which, MLP and
RBFNN were introduced for this purpose and they were shown to be
robust; (2) the widespread intervals of pressure (up to 1400 bar),
temperature (up to 723.15 K) and molality of NaCl (up to 6.14 mol/kg)
that were considered in the development, and this ensures an extensive
applicability domain according to the employed variables for the pro-
posed models; and (3) besides the application of PSO and GA to select
properly the RBFNN control parameters, in this study, ABC was im-
plemented for this objective and it was found that ABC outperforms the
well-known nature-inspired algorithms. The employed optimization
mechanism in ABC, which is based on three different families of bees
allowing a wealth in search process of optimal parameters is the prin-
ciple reason for choosing ABC in this study. In addition, as GA and PSO
as the well-known metaheuristic algorithms, they are selected to be
compared with ABC. Fig. 1 exhibits the problem sketch presented in this
study.
The outline of the paper is as follows. The applied data driven
techniques in the modeling, namely MLP and RBFNN are highlighted in
Section 2. Section 3 exposes briefly the optimization techniques em-
ployed in the training of RBFNN and MLP. Section 4 describes the
gathered data utilized in the implementation of the models. Section 5
N.A. Menad, et al.
Fig. 1. A schematic of the general sketch of the problem.
discloses the followed methodology, while Section 6 provides and dis-
cusses our results. Section 7 delivers some brief conclusions.
2. Modeling techniques
Artificial neural networks (ANNs) are light mathematical models for
recognizing nonlinear relationships linking inputs to outputs in com-
plex systems [35]. This class of machine learning was inspired from
human brain system mainly by adapting the conception of biological
neurons [25]. Multilayer perceptron (MLP) and radial basis function
neural networks (RBFNN) are the well-known and the most used ANN
types for modeling purposes in many complex engineering tasks. These
two kinds of ANN differ mainly in the treatment way of the information
and also in their structure [36].
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Journal of CO₂ Utilization 33 (2019) 83–95
2.1. Multilayer perceptron (MLP)
An MLP is composed of many neurons organized in three sorts of
layers: input, hidden (one or more) and output layers. The role of
hidden layer is to identify the existing relationship describing the
system inputs/outputs by means of activation functions [37]. The
numbers of neurons in the first and the last layers are equal to inputs
and outputs numbers, respectively. The proper choice of the hidden
layers’ numbers and their corresponding number of neurons is a key
aspect that affects the MLP model performances. Generally, one hidden
layer is enough to model the systems presenting moderate complexity,
while more than one hidden layer is required for highly complex sys-
tems [38]. Trial-and-error is widely run to screen suitable number of
hidden layers and their number of neurons. It consists to vary the
neurons number in each hidden layer until reaching a satisfactory
N.A. Menad, et al.
stopping criterion. The generated value from the hidden/output neu-
rons is a resultant of multiplied neurons of previous layer to their
weights added to a bias. “Sigmoid” and “Tanh” are the frequently
employed activation functions for hidden layers, while linear function
(Pureline) is mostly used for output layer [39].
Back-propagation (BP) training procedure is utilized to obtain ap-
propriate set of MLP weights and bias. Levenberg-Marquardt (LM) al-
gorithm is the most employed BP technique for MLP weights and bias
optimization thanks to its mathematical formulation and its provided
results [31]. Therefore, LM is applied in the present work for this
purpose. For a detailed description about LM, readers could refer to
[25].
2.2. Radial basis function neural network (RBFNN)
RBFNN is a branch of ANNs, which has a strong ability to categorize
highly-complex processes and capture the non-linearity describing
them. Indeed, this capacity of learning and the great generalization
anticipated are due to the data mapping in a high dimension space [40].
As in MLP, RBFNN contains the same kinds of layers, viz. input,
hidden and output. However, the main difference between the RBFNN
and MLP structures is that RBFNN have only one hidden layer, while
MLP can include more than one. The RBFNN hidden layer is formed by
nodes (hn) and biases (hb) . In addition, a specific RBF is enclosed for
each (hn) . These RBF have two main parameters, the center and the
width.
RBFNN training consists to transfer the input data introduced in the
input layer into the hidden layer, where a nonlinear transformation is
made to capture the complexity. Gaussian function is the widely em-
ployed RBF. Gaussian function is characterized by the center (ci ) and
the spread coefficient ( 2) . To calculate the position of input vector ( x )
according to the center (ci ) of the Gaussian function, the Euclidian norm
is applied:
ri =
d
(x k cki ) 2
k=1 (1)
where cki and d represent the centers and the number of variables, re-
spectively. Then, this distance is injected into the Gaussian function
that is defined as shown below:
r2
(r ) = exp ,
2 2 (2)
where the parameters , r and 2 point out the Gaussian function, the
Euclidian distance and the spread coefficient, respectively.
The generated results from the output layer are provided using the
below-shown equation:
hn
Yj = wji i (r ) + bi , i = 1, …, hn and j = 1, …, N
i=1 (3)
where N and hn stand for the training samples size and the number of
neurons in the hidden layer, respectively; Yj is the jth output of input
vector x , bj is the bias and wji denotes the weight connecting the hidden
node i to the output layer.
RBFNN performances depend greatly on the number of nodes in the
hidden layer and the Gaussian RBF spread coefficient [25]. Due to this
fact, in the present work, we propose an implantation of three meta-
heuristic algorithms, namely PSO, GA and artificial bee colony (ABC)
for the purpose of optimizing the spread coefficient and the number of
neurons in the hidden layer of the RBFNN model. MSE error function is
considered the fitness function for the aforementioned algorithms.
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Journal of CO₂ Utilization 33 (2019) 83–95
3. Optimization techniques
3.1. Genetic algorithm (GA)
GA is the earliest evolutionary algorithms which was proposed by
Holland [41] and extended later by Goldberg and Holland [42]. As its
name indicates, GA was inspired from genetic principles, and these
latter are adapted and applied as main operators while optimizing the
problems being studied. GA starts by creating an initial population of
individuals, which are encoded in form of chromosomes. A fitness
function, which is generally the objective function to minimize, is im-
plemented as a sort of index that distinguishes between the quality of
the population elements. The genetic operators applied to the popula-
tion of chromosomes guide GA iteratively towards unvisited regions in
the searching space, and hence finding better solutions. The principles
of GA operators are: selection, crossover, mutation and elitism. A full
description of these operators is given in many relevant published
sources [43–45].
These operators are repeated in each iteration while a predefined
stopping condition is not satisfied.
3.2. Particle swarm optimization (PSO)
PSO is a metaheuristic algorithm, originated from the research of
Kennedy [46], and updated and improved by Clerc [47]. The inspira-
tion of PSO algorithm was from the concept of auto-organization and
collaboration between birds (fishes) during their displacements, where
the principles of exploiting the best individual position and that of the
whole swarm are the two main rules followed to make a new move-
ment. By analogy to this, in PSO a population (swarm) of probable
solutions (particles), is displacing iteratively in the search space, ac-
cording to the objective function to be optimized. Besides the positions
x j, t , each particle is described by its velocity vj, t , which guides it through
the search steps [46,47]. For each new iteration (t + 1) , and by ex-
ploiting the gathered information from the previous iteration (t ) , pre-
processing of the velocity and the position for the particles are done
using the following formulas [47]:
vj, t + 1 = *((vj, t + c1 rand1 (pbestj, t x j, t ) + c2 rand2 (gbestt x j, t )) (4)
x j, t + 1 = x j, t + vj, t + 1 (5)
where xj, t and vj, t point out the position and the velocity for the particle
j, correspondingly; pbestj, t denotes the best position of the individual j
found up to the iteration t , while gbestt is the best global position; c1
and c2 correspond to the rates of learning, which define the impact of
social and cognitive mechanisms, respectively; rand1 and rand2 are
random from [0;1]; is equal to 0.729 .
Finally, in each iteration, the best position for the particles and for
the best elements in the population are updated basing on the following
equations which are for a minimization problem:
pbestj, t , if h (pbestj, t ) h (x j , t + 1 )
pbestj, t + 1 =
xj, t + 1, otherwise (6)
gbestt + 1 = min{ h (pbestj, t + 1)} (7)
where h means the objective function.
These steps are reiterated until satisfying stopping criterion.
3.3. Artificial bee colony (ABC)
ABC is a smart swarm optimization technique that was developed by
Karaboga [48]. This algorithm mimics the auto-organization and the
foraging behavior of the honeybees. The adaptation of these mechan-
isms in ABC algorithm for a given optimization problem is done by
N.A. Menad, et al.
initially generating a population of bees that correspond to probable
solutions. This colony is divided into three families exchanging in-
formation between them to enhance the search quality. These families
include employed, onlooker, and scout bees. In what follows, a brief
description of the ABC steps:
- Initialization: a position x j is attributed for each j employed bee. The
number of employed bees is equal to the number of onlooker bees,
which is also equal to number of solutions in the colony [49]. The
qualities of the obtained solutions for each bee are evaluated based
on the fitness function.
- Employed bees: for a new iteration (t + 1) , each bee j updates its
position using the obtained information from a previous iteration
(t ) . The following equation is applied:
x j, t + 1 = x j, t + j (x j , t x ,t ) (8)
where and j are random from {1,2, …, colony size} and [0;1], respec-
tively. must differ to j.
Afterward, the fitness value of the new position is calculated, and if
it is better than the old one, the bee considers this new position as the
current source food; otherwise it discards it.
- Onlooker bees: after the employed bees finishing their exploration,
they share their fitness performences to the onlooker bees. These
latter select solutions with a probability P, which is related to the
fitness values as shown below:
fitj
Pj = NE
j=1
fitj (9)
th
where fitj denotes the fitness value for the j bee and NE stands for the
number of employed bees. Then, the onlooker bees modify the con-
served positions in their memories following the principles described in
the employed bees phase.
- Scout Bees: an employed bee converts to scout bee if its fitness
quality stays the same after a number of iterations. In this case, its
position is replaced randomly from the search space.
The fittest bee is that which provides the best source of food, and
hence, this latter is the most qualified to be the optimum solution.
This sequence of phases is repeated in each iteration until fulfilling a
stopping condition.
4. Data acquisition and preparation
In order to develop the proposed techniques for predicting CO2
solubility in brine, we have collected 570 experimental points from
authenticated published literature [13,50–63]. A statistical overview of
the employed data is given in Table 1. Molality of NaCl (mNaCl ) , pressure
(P ) and temperature (T ) were considered the inputs for the proposed
models and the CO2 solubility in brine as the output. Before the mod-
eling phase, the data were normalized at the interval [-1,1].
Afterwards, 80% of the experimental data are chosen randomly for
developing the models and the remaining data are designated to test
them.
5. Methodology
Before presenting the outcomes of the proposed smart techniques
for predicting the solubility of CO2 in brine, it is needed to explain the
evolved procedure for each technique. As previously mentioned, the
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Journal of CO₂ Utilization 33 (2019) 83–95
data were normalized between -1 and 1, and they were split randomly
into training and testing sets.
To implement the MLP-LM model, trial and error method was ap-
plied for determination of the number of hidden layers, their corre-
sponding activation functions and their optimal number of neurons.
The most efficient choice for MLP-LM corresponds to a network with
three hidden layers having tansig as an activation function in all of
them, and pureline for the output layer. In addition, the best archi-
tecture for the MLP-LM model was 3-11−9-9-1, in which the first and
the last numbers stand for the number of inputs and output, corre-
spondingly, while the second, the third and the fourth numbers re-
present the number of neurons in each hidden layer correspondingly.
RBFNN model have two main control parameters, viz. the spread
coefficient and the number of neurons in the hidden layer. GA, PSO and
ABC algorithms were applied to optimize these parameters. During the
optimization process using the aforementioned algorithms, the control
parameters of RBFNN were represented in form of chromosomes
(binary representation) in GA, while these variables were assigned as
positions in PSO and ABC. MSE was considered the fitness function in
these algorithms.
N
i=1
(Ti Yi )2
MSE =
N (9)
where N is the number of training data, Ti and Yi are the actual and the
predicted values, correspondingly.
Fig. 2 highlights the proposed procedure of these nature-inspired
algorithms to train the RBFNN model, and Table 2 depicts their control
parameters that were obtained by mean of the tuning method. The
resulted models were denoted RBFNN-GA, RBFNN-PSO and RBFNN-
ABC, respectively. The optimum number of neurons in the RBFNN
hidden layer and the optimum spread coefficient value achieved by the
evolutionary algorithms are stated in Table 3.
6. Results and discussion
6.1. Statistical and graphical assessment
To examine the performances of the proposed models and compare
between them, statistical assessment criteria and graphical error ana-
lysis were considered. Root mean squared error (RMSE) and coefficient
of determination (R2), which are frequently used in regression analysis,
have been adopted in our study. The mathematical expressions of these
statistical criteria are specified in Appendix A.
A detailed comparison between the performances of the proposed
models using the above-mentioned criteria is reported in Table 4. To get
a visual verification of the models accuracy, cross plots of the predicted
CO2 solubility in brine against the corresponding experimental mea-
surements for the established models are depicted in Fig. 3, where in
this type of plot, accumulation of points nearby the unit slope line in-
dicates the high accommodation between the model predictions and the
real data. In addition, for a better visual comparison, bar plots of RMSE
and R2 are depicted in Fig. 4(a) and (b), respectively. Fig. 3 exhibits that
Table 1
Statistical description of the input/output data.
Max Min Mean SD
−1
Output Solubility (mol·Kg ) 12.35 0.0106 0.27 0.39
Input Temperature (°K) 723.15 273.15 379.5 97.6
Pressure (bar) 1400 0.98 153.41 272.39
mNaCl (mol·Kg−1) 6.14 0.016 1.69 1.91
N.A. Menad, et al. Journal of CO₂ Utilization 33 (2019) 83–95

Fig. 2. Flowchart of the proposed RBFNN model optimized by GA, PSO and ABC.

Table 2 Table 3
Evolutionary algorithms setting parameters used in the study. Key parameters of the established RBFNN models for CO2 solubility in brine.
Algorithms Parameters Value/setting RBFNN-GA RBFNN-PSO RBFNN-ABC

GA Population size 60 Number of Nodes 167 182 206

Crossover’s probability 90 % Spread coefficient 11.8452 14.2156 14.3946
Mutation’s probability 15 %
Elitism 10 %
Type of selection Linear ranking
Table 4
Max number of generation 100
Coding Binary
Statistical indexes of the established models for CO2 solubility in brine.
PSO Size of the Swarm 60 RBFNN-ABC RBFNN-PSO RBFNN-GA MLP-LM
Max number of iteration 100
C1 2.05 Training RMSE 0.0218 0.0240 0.0243 0.0472
C2 2.05 (456 points) R2 0.9984 0.9981 0.9980 0.9926
0.729 Test RMSE 0.0572 0.0597 0.0925 0.0304
ABC Number of employer bees 10 (114 points) R2 0.9896 0.9887 0.9724 0.9968
Number of onlooker bees 10 All RMSE 0.0289 0.0311 0.0380 0.0439
Maximum number of iteration 30 (570 R2 0.9967 0.9962 0.9929 0.9934
Number of iterations to scout bees 4 points)

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Fig. 3. Cross plots of the established RBFNN models (CO2 solubility in brine).

majority of the data points predicted by all the implemented smart
techniques are very close to the unit slope line proving their high
prediction ability. Deepen analyses of the reported statistical criteria in
Table 4 confirms the high degree of performances for all the proposed
techniques. Moreover, and according to Table 4 and Fig. 4, RBFNN-ABC
is the most reliable model thanks to its lower overall RMSE value of
0.0289 and its high R2 value of 0.9967. It can also be underlined from
Tables 4 and Fig. 4 that our proposed models for predicting CO2 solu-
bility in brine follow the accuracy ranking shown below:
RBFNN-ABC > RBFNN-PSO > RBFNN-GA > MLP-LM
In order to get a deep insight into the quality of the RBFNN-ABC
predictions, Fig. 5 illustrates a comparison between the esteemed CO2
solubility in brine using RBFNN-ABC and the experimental data for
training (Fig. 5(a)) and testing (Fig. 5(b)) phases. In addition, histogram
plots representing the frequency of error distribution for train and test
dataset are shown in Fig. 6. As it can be seen from the two subplots of
Fig. 5, an excellent agreement between experimental and RBFNN-ABC
predicted data is achieved in both training and testing phases. More-
over, Fig. 6 reveals that RBFNN-ABC model shows normal distribution
near zero mean in both train and test sets, indicating therefore, the
excellent performance of this model.
6.2. Comparison of RBFNN-ABC model with existing models
Being the most performant model that leads to accurate predictions
of the CO2 solubility in brine, RBFNN-ABC was further compared with
two new approaches, namely the activity–fugacity phase equilibrium
model introduced by Mao et al. [23] and Bahadori et al [11] correla-
tion. For this purpose, the accompanied “executable program” with
Mao et al. [23] model was utilized to predict the corresponding values
of the employed data when these latter were within the applicability
domain of Mao et al. approach. To ensure the fairness of the comparison
with the Bahadori et al [11] correlation, it should be noted that we have
considered only the points respecting the NaCl molality conditions from
the employed data. Statistical comparison between RBFNN-ABC and

Fig. 4. Comparison of RMSE and R2 of the established models.

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N.A. Menad, et al.
Fig. 5. The comparison between RBFNN-ABC outcomes and real values of CO2 solubility for each sample of dataset (a) training data and (b) testing data.
these models is reported in Table 5. In addition, for better readily ob-
serve the comparison, Fig. 7(a) and (a) display, respectively, RMSE and
R2 bar plots for the evaluated models. It can be said from the statistical
criteria stated in Table 5 and the graphical comparison shown in Fig. 6
that Mao et al. [23] model has satisfactory predictions compared to
Bahadori et al [11] correlation, which shows the worst performance.
This bad performance may be explained by the fact that the correlation
was established using data with modest varieties in the conditions. In
addition, it can obviously be seen that RBFNN-ABC model results in the
lowest value of RMSE and the highest coefficient of determination, and
it outperforms significantly the considered pre-existing models.
To testify the performances of RBFNN-ABC in the prediction of the
solubility of CO2 in brine compared to Mao et al. model according to a
wide ranged temperature and pressure conditions, trend analyses of
these two models are depicted in Fig. 8. As it is shown, the immitted
outputs by RBFNN-ABC follow better the real variation compared to the
generated outputs by Mao et al. model.
6.3. RBFNN-ABC model validity in terms of the employed variables
To check the behavior of the RBFNN-ABC predictions in terms of the
employed variables, trend analyses that compare the results of our best
model for estimating the CO2 solubility in brine with the reported ex-
perimental data for extended variety of the NaCl molality, pressure and
temperature conditions, are presented in Figs. 8 and 9. Closer inspec-
tion of this figure shows that RBFNN-ABC is highly reliable and
90
Journal of CO₂ Utilization 33 (2019) 83–95
accurate in predicting the solubility of CO2 in brine with variations of
mNaCl , P and T.
6.4. Applicability domain of the RBFNN-ABC model
As experimental measurements reported in the literature may be
related to some uncertainties, ascertaining the validity of these data and
identifying the RBFNN-ABC realm of application are worthwhile. To do
so, Leverage approach, was considered. From this method, the Williams
plot that shows the applicability realm of the model, is obtained by
sketching the residual R values versus the hat vector that corresponds to
the diagonal elements of the so-called Hat matrix [64,65]. The com-
putational procedure for the Leverage technique can be found else-
where [66]. Fig. 10 depicts the Williams plot for the RBFNN-ABC
model. As it can be observed from this figure, the large part of the data
are in the ranges of 0 H 0.0211 and 3 R 3, signifying there-
fore the high trustworthiness of the RBFNN-ABC model and its statis-
tical validity. In addition, it should be noted that only 22 points are
detected as outliers from the feasibility domain of the RBFNN-ABC
model, and their associated parameters are reported in Table 6. It must
be noted that this number of suspected data is equivalent to only 3.86%
of the whole data points.
Finally, it is needed to mention that the established RBFNN-ABC
paradigm should be applied to predict the solubility of CO2 in brine
when P, T and mNaCl fall within the ranges of application. Indeed, this
model can be applied for situations out-side of this region with care as
N.A. Menad, et al. Journal of CO₂ Utilization 33 (2019) 83–95

Fig. 6. Histogram plot for the datasets applied in constructing RBFNN-ABC: (a) train and (b) test.

Table 5 its accuracy is not ensured since it can provide accurate predictions for
Statistical parameters of various models for CO2 solubility in brine. given values of the employed variables, as well as inaccurate predic-
Model/correlation RMSE R2 tions for some other values. Nevertheless, as widespread P, T and mNaCl
conditions were included when the RBFNN-ABC model was established,
Bahadori et al. (2009) (124 data points) 6.4255 0.1354 it can be applied for many cases having proprieties located within the
Mao et al. (2013) (457 data points) 0.2442 0.9301
range of the aforementioned inputs.
RBFNN-ABC 0.0289 0.9967
(570 data points)

Fig. 7. Comparison of RMSE and R2 for RBFNN-ABC and existing models for predicting CO2 solubility in brine.

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N.A. Menad, et al. Journal of CO₂ Utilization 33 (2019) 83–95

Fig. 9. CO2 solubility in brine based in several conditions: a comparison be-

tween RBFNN-ABC and experimental data.

Fig. 8. CO2 solubility in brine based in several conditions: a comparison be- Fig. 10. The Williams plot of the utilized dataset for RBFNN-ABC model.
tween predictions of RBFNN-ABC and those of Mao et al. (2013) model against
experimental data.

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N.A. Menad, et al. Journal of CO₂ Utilization 33 (2019) 83–95

Table 6
Experimental data which are out of the applicability domain of the proposed RBFNN-ABC.
No T(K) P(bar) mNaCl (mol·Kg−1) Solubility (mol·Kg−1) Ref.

1 313.38 56.2470 0.52 0.92167 [62]

2 313.38 67.7630 0.52 1.04611 [62]
3 353.08 5.4726 0.52 0.05611 [62]
4 353.08 83.3480 0.52 0.83722 [62]
5 352.77 83.5410 4.34 0.39056 [62]
6 303.15 1.0132 0.2 0.029 [51]
7 308.15 1.0132 0.2 0.0259 [51]
8 473.15 1000 1.09 2.568 [56]
9 623.15 1400 4.28 3.8605 [56]
10 473.15 200 1.09 1.091 [56]
11 473.15 300 1.09 1.439 [56]
12 673.15 400 1.09 1.973 [56]
13 298.15 1.01325 5.096 0.0106 [50]
14 308.15 1.01325 0.449 0.0246 [50]
15 308.15 1.01325 0.88 0.0223 [50]
16 308.15 1.01325 1.438 0.0197 [50]
17 323.15 1.0132 1 0.0158 [51]
18 283.15 1.0132 3 0.0277 [51]
19 288.15 1.0132 3 0.0241 [51]
20 308.15 1.0132 3 0.0151 [51]
21 323.15 1.0132 3 0.0111 [51]
22 298.15 3.95 3 0.0008 [63]

7. Conclusions predicting the solubility of CO2 in brine.

In this investigation, four smart techniques were proposed to de-
velop easy-to-use, extended and reliable models to predict the solubility
of CO2 in brine basing on two machine-learning techniques, namely
MLP and RBFNN. LMA was implemented in the optimization of the
weights and the bias of the MLP model, and three evolutionary algo-
rithms including GA, PSO and ABC were considered in the optimization
of the RBFNN control parameters. Based on the achieved outputs, the
following important conclusions can be drawn:
1 The implemented smart models showed satisfactory performances in
the prediction of CO2 solubility in brine.
2 RBFNN-ABC model is found as the most reliable model for
3 RBFNN-ABC exhibited very small RMSE value of 0.0289 and high
coefficient of determination (0.9967).
4 Comparison of the RBFNN-ABC predictions against pre-existing
models in the literature highlighted its superiority compared to
these latter.
5 Trend analyses demonstrated that the generated outputs by RBFNN-
ABC model follow the expected variations in terms of the in-
dependent variables.
6 The application of Leverage approach affirmed that the im-
plemented RBFNN-ABC model is reliable and statistically valid, and
less than 4% of the data may be outliers.
7 The constructed RBFNN-ABC tool can be used by mean of the pro-
vided excel macro to predict the CO2 solubility in brine.

Appendix A. Statistical formulas

The statistical indexes employed in the evaluation of the implemented models are defined as follows:
N
1
RMSE = (Siexp Si pred ) 2
N i=1 (A.1)
N
i=1
(Siexp Si pred )2
R2 = 1 N
i=1
(Si pred S¯ )2 (A.2)
where S denotes the CO2 solubility in brine; subscripts exp and pred point out the experimental and predicted values, correspondingly; S̄ stands for
average solubility and N is the number of data.

Appendix B. RBFNN-ABC generated model

To use the model, please open the macros titled "CO2_solubility_in_brine_Calculator.xltm".

Note: The macros must be activated in your Excel. The program generates the CO2 Solubility in brine by introducing values for NaCl molality
(mol/kg), pressure (bar) and temperature (K) and clicking in the calculate button.

Appendix C. Supplementary data

Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.jcou.2019.05.009.

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