Journal of Cleaner Production 176 (2018) 704e715

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Journal of Cleaner Production

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

Design of energy efficient reactive solvents for post combustion CO2

capture using computer aided approach
Muhammad Zulhilmi Ahmad a, b, Haslenda Hashim a, b, Azizul Azri Mustaffa a, b,
Hasmerya Maarof c, Nor Alafiza Yunus a, b, *
a
Process Systems Engineering Centre (PROSPECT), Research Institute for Sustainable Environment, Universiti Teknologi Malaysia, 81310 Johor Bahru, Johor,
Malaysia
b
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310 Johor Bahru, Johor, Malaysia
c
Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 Johor Bahru, Johor, Malaysia

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

Article history: The reduction of CO2 emissions has become a challenge due to rapid economic growth all over the world.
Received 13 April 2017 Growing concerns on this issue have led the researcher to develop and implement several strategies
Received in revised form including one very promising strategy involving CO2 capture from power plants. This paper presents a
29 October 2017
Computer Aided Molecular Design (CAMD) technique to design new alternative solvents as replacements
Accepted 30 November 2017
for commonly used solvents during the post combustion carbon capture process in power plants, which
Available online 19 December 2017
is often costly and energy intensive. The CAMD technique can quickly identify the most suitable solvents
and avoid spending resources on infeasible solvent replacements. In this study, the reverse design
Keywords:
Reactive solvent
approach is used where, first, the criteria of the targeted solvents are identified and then the desired
Amine-based solvent solvent candidates generated. The methods for this work consists of five steps: 1) Problem formulation,
Computer-aided molecular design 2) Generation of single reactive solvent candidate using ProCAMD tools in ICAS software, 3) Prediction of
Post combustion CO2 capture the reaction mechanism between the potential amine solvent candidate and CO2 using the zwitterion
Chemical absorption mechanism and base-catalysed hydration mechanism, 4) Evaluation of process performance by calcu-
Regeneration energy lating the heat required for the solvent regeneration process, and 5) Selection of the best solvent
candidate based on its desired process performance. The result of this study reveals that 25 amine-based
solvents for the chemical absorption process were successfully generated from the amine and alcohol
functional groups. By using the proposed solvent, significant savings on regeneration energy, up to 31.4%,
could be achieved compared to the conventional solvent, MEA. The percentage average absolute devi-
ation (AAD) of the property prediction model that this study used to estimate the value of heat of for-
mation is 4.67%. This finding is important to further reduce the regeneration energy, which makes the
CO2 capture process costly, and achieve a more sustainable and cleaner environment.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction economies, and limited alternatives sources of energy, fossil fuels

The power generation sector (e.g. fossil fuels and coal-fired
power plants) is one of the main contributors of CO2 emission in
the atmosphere. As reported in the IPCC report (2014), the power
generation sector accounts for 35% of total greenhouse gases (GHG)
emissions, in which CO2 is one of the main GHG emitted. Due to an
increase in energy demands and world population, the growth of
* Corresponding author. Faculty of Chemical and Energy Engineering, Universiti
Teknologi Malaysia, 81310 Johor Bahru, Johor, Malaysia.
E-mail address: alafiza@utm.my (N.A. Yunus).
will continue to contribute a major proportion of future energy
worldwide, especially in developing countries (IEA, 2013). Based on
this scenario, it is expected that the concentration of CO2 in the
atmosphere will keep increasing if no action is taken to mitigate the
CO2 emission in the atmosphere. This will have an adverse effect on
the environment and contribute towards increasing global warm-
ing effects. A short-term approach is required to alleviate the
emission of CO2 into the atmosphere, whilst other alternative
sources of green energy (e.g. renewable energy and low carbon
fuels) are commercialised to replace the use of fossil fuels in the
power generation sector. This can be realised through the imple-
mentation of Carbon Capture Storage (CCS) in the power generation

https://doi.org/10.1016/j.jclepro.2017.11.254
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715
sector since CCS helps to produce energy with near-zero CO2
emissions. As stated by Leung et al. (2014), CCS can capture up to
90% of CO2 from the point of emission source in the power gener-
ation sector.
There are three main types of CO2 capture technologies associ-
ated with different combustion processes, which are post com-
bustion, pre-combustion, and oxyfuel combustion (Leung et al.,
2014). Post combustion carbon capture (PCCC) technology in-
volves the separation process of CO2 from the flue gas after the
combustion of fossil fuels and before its emission into the atmo-
sphere. In pre-combustion carbon capture, the fuel is pre-treated
with air and steam through the gasification reaction and water
gas shift reaction before the combustion process. This process is
most suited for application in coal gasification plants. Meanwhile,
in oxyfuel combustion technology, during the combustion process,
the fuel is reacted with pure oxygen gas instead of air. The nitrogen
gas is separated and removed from the air at the early stages in
order to facilitate the capture process by producing high concen-
trations of CO2. This study focuses on PCCC since it is the best and
most mature technology for capturing CO2 from flue gas emissions
of fossil fuel power plants. Besides, PCCC technology can easily be
integrated or retrofitted to any existing power plant.
Several methods have been proposed by previous researchers to
separate CO2 from flue gas based on PCCC technology including
absorption using physical or chemical solvents (Wu et al., 2014),
adsorption onto solid sorbents (Zhao et al., 2007), cryogenic
distillation (Tuinier et al., 2010), and membrane separation
(Khalilpour et al., 2015). The selection of the method of separation
depends on the concentration of CO2 emissions. Since flue gas has a
low concentration of CO2, which is around 4e14 w/w% (Olajire,
2010), chemical absorption by solvents is considered to be the
most promising method. Chemical absorption is highly selective
with very high carbon capture efficiency even at low CO2 concen-
trations and low CO2 partial pressure. This is due to the addition of
reaction driving force between CO2 and solvents, which help to
increase the absorption capacity of CO2. The current commercial-
ised solvent used in this process is monoethanolamine (MEA).
However, despite all the advantages of this technology, chemical
absorption PCCC processes are still recognised as economically
unattractive (Wang et al., 2011). This is due to the characteristics of
the solvent used in the chemical absorption process. As reported in
a previous study, although MEA is a cheap solvent, has a high
reactivity rate towards CO2 and a high absorbing rate (Rao et al.,
2004), it still possesses some disadvantages. For example, high
energy is required during the regeneration process of the MEA
solvent, which contributes to a high energy penalty (Han et al.,
2013). Besides, MEA is a volatile solvent that can easily degrade at
high operating temperatures with detrimental effects on human
health and the environment (Mertens et al., 2013). The chemical
degradation of the MEA solvent also occurs in the presence of ox-
ygen (Zaman and Lee, 2013) and contributes to the increase in
equipment corrosion rate (Yu et al., 2012). All these disadvantages
of MEA solvents inadvertently lead to an increase in capital and
operating cost for CCS (Hasaneen et al., 2014). This hinders the
commercialisation of large-scale application of chemical absorption
PCCC plants (Bandyopadhyay, 2011).
Therefore, to ensure PCCC is competitively placed as one of the
cost effective options for CO2 emissions mitigation measures, the
solvent used in the process needs to be improved or replaced with
other potential solvents. The search for, and development of new
alternative solvents have gained more attention in recent years,
mostly through experimental studies. For example, Goto et al.
(2009) developed three high performance and low cost amine-
based solvents for the carbon capture process. The three designed
solvents have different criteria: Solvent A had a high CO2
705
absorption capacity, Solvent B had low regeneration energy, and
Solvent C had a high absorption/desorption rate. Chowdhury et al.
(2011) synthesised and selected new hindered amine to reduce the
regeneration energy and cost of the CO2 capture process. The au-
thors found two hindered secondary amines (2-
isopropylaminoethanol (IPAE) and 2-isobutylaminoethanol
(IBAE)) and two hindered tertiary amines (1-Methyl-2-
piperidineethanol (1M-2PPE) and 2-isopropyldiethanolamine
(IPDEA)) as promising solvent candidates. Van Der Ham et al.
(2014) evaluated the performance of concentrated aqueous piper-
azine as the CO2 captured solvent. Several studies were also con-
ducted on the design of blended aqueous amines solvents. Singh
et al. (2013) conducted an experimental pilot plant study to syn-
thesise energy efficient amine-based solvent blends. Two new
promising solvent blends were introduced in their study (e.g.
Blends of 2-amino-2-methyl-1-propanol
(AMP) þ hexamethyldiamine þ H2O). Conway et al. (2015) syn-
thesised a blended aqueous amine solvent from a combination of
primary amine solvents (e.g. MEA) with tertiary or sterically hin-
dered amine solvents (e.g. AMP). El Hadri et al. (2015) performed an
experimental study to design a novel solvent to replace MDEA as
the co-solvent in a blended aqueous amine solution.
Besides the amine-based solvents, other examples of alternative
chemical solvents that have been introduced for absorption of CO2
are ammonia (Molina and Bouallou, 2015), potassium carbonate
(Jayaweera et al., 2014), and recently, the ionic liquid solvent
(Ozkutlu et al., 2016). Unfortunately, the disadvantages in designing
new solvents using purely experimental work is that it is time
consuming and would use up resources if the experimental work
were not systematically planned. Apart from this, an experimental
approach cannot handle a large amount of solvent candidates since
it is cost intensive and it is almost impossible to run experiments
for all solvent candidates. Therefore, a more efficient solution
strategy is needed to overcome these drawbacks. The CAMD
approach is an alternative method that can be applied at the early
stages of solvent design, to narrow down the search region,
resulting in focused experimental work on promising solvent
candidates only (Hashim et al., 2017).
The CAMD approach can predict the nature and properties of
molecules or mixtures, which will later perform the desired ac-
tivities. From the definition of Achenie et al. (2003), CAMD can be
recognised as a reversed engineering approach where a set of target
properties are specified, following which the molecular structure
that meets the targeted properties are determined. The advantage
of using the CAMD technique is that it can quickly identify the
potential molecular structures (Eslick et al., 2011) and eliminate all
the infeasible alternatives at the early stage of design based on the
defined target properties. Furthermore, by applying this CAMD
technique, a large number of potential candidates can be consid-
ered in the design process (Achenie et al., 2003). Another advantage
of the CAMD technique is that it can reduce the required number of
experiments, since CAMD has already performed the screening
process, experimental work will be conducted on potential candi-
dates only (Yunus et al., 2014). As a result, CAMD will help save
resources, minimize the cost for experimental work, and reduce the
time to market the product.
Several studies have successfully applied the CAMD technique to
develop novel material based on the given desired target proper-
ties. For example, CAMD was used as a systematic and powerful tool
for the design of refrigerant mixtures (Churi and Achenie, 1997),
solvents and extractants (Wang and Achenie, 2002), skin care
cream (Cheng et al., 2009), paint and insect repellent (Conte et al.,
2012), gasoline blends and lubricant base oil (Yunus et al., 2014),
tailor-made biofuel blend from palm biomass (Hashim et al., 2017)
and ionic liquids as an energy efficient entrainer in the separation
706 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715
process (Kulajanpeng et al., 2016). The CAMD approach was also
employed in the development of solvent for the carbon capture
process. Qadir et al. (2014) used the CAMD framework to simulta-
neously design an optimal solvent and optimal process conditions
for the pre-combustion carbon capture process. The aim of their
study was to formulate a solvent that can minimize the energy
requirement in the pre-combustion carbon capture process. They
developed an optimal pure and binary solvent blend in their study
through solving a MINLP optimization problem. Another work that
used the CAMD approach in the development of solvents for the
pre-combustion process is that of Pereira et al. (2011) in which the
author integrated the development of a solvent with process design
for the high pressure separation process of CO2 from methane using
a SAFT-VR thermodynamic model.
Recently, the CAMD technique has been extended to include the
designing of solvents in the PCCC process. Chong et al. (2015)
applied the CAMD framework to design ionic liquid as a solvent
for enhanced post combustion carbon dioxide capture. Group
contribution and a UNIFAC model was used in their study to esti-
mate the properties of ionic liquids and the solubility of CO2 in the
ionic liquids. Valencia-Marquez et al. (2016) used CAMD to obtain
the optimal molecular structure for ionic liquids as potential sol-
vents for CO2 capture and integrated with a multi-objective opti-
mization framework to deal with conflicting design objectives
related to process economics and sustainability issues. Zarogiannis
et al. (2016) also developed a systematic framework for the selec-
tion of mixtures as a post combustion solvent candidate using the
CAMD approach. The authors identified the solvents from a large
pool of potential candidates. A simple property model was used for
screening potential solvent candidates at the early stages of design
and a SAFT equation of state model was used as a rigorous evalu-
ation to predict the non-ideal interaction between CO2, water, and
solvent.
However, the mechanism of reaction that occurs between
reactive solvents and solute (unknown reaction stoichiometry) has
not been addressed in previous studies associated with the mo-
lecular design approach. Most research only consider the physical
absorptive contribution of the solvent and assume that no reaction
will occur between solvent and solute (Chong et al., 2015). This will
lead to difficulty in evaluating the chemical absorption process
performance of the reactive solvent, in which information on re-
action stoichiometry is essential for the evaluation of the energy for
solvent regeneration, chemical absorption rate and chemical ab-
sorption capacity of the reactive solvent. This study addresses this
limitation by considering both reactive and physical absorptive
contributions of the solvent in order to design an energy efficient
reactive solvent for the chemical absorption PCCC process through
the CAMD approach.
2. Methodology
An overview of the systematic method used in this study for the
design of an energy efficient reactive single solvent is illustrated in
Fig. 1. This study utilised the advantages of the CAMD approach in
order to speed up the process of finding feasible solvent candidates
and reliably reduce the search space through the screening process.
This has helped reduce the required number of experiments since
the experiments will focus on promising solvent candidates only.
The systematic method consists of five main steps, which are: 1)
Problem formulation; 2) Generation of single reactive solvent
candidate using ProCAMD tool in ICAS software. In this second step,
the proposed solvent candidates are generated using CAMD
approach by specifying the targeted properties; 3) Prediction of
reaction stoichiometry between potential amine solvent and CO2
either using zwitterion mechanism or base-catalysed hydration
Step 1: Problem formulation
Step 2: Generation of feasible solvent
candidates
Has a feasible
No
solvent been
generated?
Yes
Step 3: Prediction of reaction between potential
solvent candidate and CO2
Step 4: Evaluation of process performance
Step 5: Selection of solvent candidate
Fig. 1. Systematic method for the design of an energy efficient reactive solvent using
the CAMD approach.
mechanism; 4) Evaluation of process performance by calculating
energy required for the solvent regeneration process; and 5) Se-
lection of the best solvent candidate based on the lowest energy
needed for the regeneration process. In this study, the most
commonly used aqueous MEA solvent is used as the reference
solvent for performance comparison.
2.1. Step 1: problem formulation
Problem formulation is a step to establish user attributes and
needs. In this step, the functionality of solvents in the chemical
absorption process is determined. Based on the functionality of the
solvent, several performance criteria of the desired reactive solvent
are listed. These performance criteria indicate the specific charac-
teristic that the solvent should have in order to capture CO2 through
the chemical absorption process. It also covers detailed knowledge
of the overall process such as the desired physical and chemical
properties of reactive solvents, the physical and chemical proper-
ties of the solute (CO2), and the performance of the chemical ab-
sorption process.
The important performance criteria that have been listed are
translated into physicochemical target properties. Table 1 sum-
marises all the performance criteria and target properties that are
considered in this study on the design of an energy efficient reac-
tive solvent for the PCCC process. Then, all the listed target prop-
erties are specified with the desired range of values taken from the
literature study and from the best properties of the conventional
solvent. This step is done to ensure that the values of target prop-
erties for newly designed solvents are within the desired range. The
range of constraint value for each target property used in this study
is obtained from Ahmad et al. (2015).
Some of the performance criteria must first be translated into a
selection of suitable chemical databases. For example, only solvents
 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715
Table 1
Performance criteria and target properties for the designed solvents.
Performance criteria Physicochemical target properties
Solvent performance i. Solubility parameter (MPa1/2)
ii. Density (g/cm3)
iii. Viscosity (cP)
iv. Normal boiling point (K)
v. Normal melting point (K)
vi. Surface tension (dynes/cm)
Safety and environmental i. Flash point (K)
ii. Vapour pressure (kPa)
Process performance Energy needed for solvent regeneration
that can react with CO2 through reversible reaction are considered
since this is the main solvent criteria for the chemical absorption
process. The CO2 non-reactive solvents are eliminated from the
chemical database. This step involves the elimination of infeasible
chemicals based on the performance criteria at an early stage of the
design.
2.2. Step 2: generation of feasible reactive solvent candidates
Once the solvent design problem has been formulated, the next
step is to generate the feasible solvent candidates that have all the
desired target properties using ProCAMD tools. The input data
required by ProCAMD tools to generate the solvent are the type of
functional group that is represented in the molecular structure,
type of chemical compounds (either acyclic, cyclic or aromatic
compounds), size and complexity of molecular structure (mini-
mum and maximum number of functional groups present in the
molecular structure), and most importantly, the target property
value defined in Step 1. Once the entire input data has been
transferred to ProCAMD, the software will generate all the feasible
solvent candidates. If no feasible candidates are generated, the
design specifications specified in Step 1 will be revised and
adjusted. This step is done repeatedly until a feasible solvent
candidate is generated.
2.3. Step 3: prediction of reaction stoichiometry between solvent
and solute
The purpose of this step is to identify the reaction mechanism
and to predict the product of the reaction between potential solvent
candidates and solute (CO2). The reaction mechanism is important
in order to evaluate the performance of the solvent in the chemical
absorption process, the calculation of the enthalpy of reaction be-
tween solvent and CO2 (energy required for regeneration process)
being one example.
In order to predict this reaction stoichiometry, information on
reaction mechanism from the experimental study is needed.
Therefore, this study only focuses on potential solvent candidates
from the amine functional group since only amine-based solvents
have the required information based on experimental studies.
There are two assumptions made for this step, which are specified
based on the literature study:
1) Only the main reaction is considered in this study; all side re-
actions are neglected.
2) If the potential amine solvent has more than one amine group
(e.g. diamine or triamine), only one amine group is considered
to react with CO2 since the reaction of the second or third amine
group only occurs at high CO2 loading (Ciftja et al., 2013). Be-
sides, even at high CO2 loading, the formation of dicarbamate
from the reaction between CO2 with the second amine group in
707
a diamine solvent is much smaller compared to the formation of
carbamate (Ciftja et al., 2013).
Range
13.6e25.0
The step-by-step procedure to predict the reaction stoichiom-
1.0e1.5 etry for the reaction between amine-based solvent and CO2 is
<3.0 explained in Sections 2.3.1e2.3.3.
>400.0
<293.0
25.0e60.0 2.3.1. Perform literature search for the reaction between amine-
>313.0 based solvent and CO2
<7.0 The general chemical reaction stoichiometry between amine-
e based solvents and CO2 is identified from previous experimental
studies. Based on the literature study conducted, the reaction be-
tween an amine-based solvent and CO2 can be categorised into
three categories, which are primary amine, secondary amine and
tertiary amine.
For the primary and secondary amine category, the solvent will
react with CO2 through the zwitterion mechanism (Vaidya and
Kenig, 2007). The zwitterion mechanism consists of two re-
actions. In the first reaction, the amine will react with CO2 to form a
zwitterion (RNHþ 
2 COO ) as an intermediate. Then, in the second
reaction, this zwitterion will undergo a deprotonation reaction by a
base to form carbamate (RNHCOO). Usually, the base in the second
reaction is the amine itself. The chemical equation for the first and
second reaction is shown in Eqs. (1) and (2) below. The overall
reaction for the zwitterion mechanism is the sum of Eqs. (1) and (2),
as shown in Eq. (3) for the primary amine solvent and Eq. (4) for the
secondary amine solvent.
RNH2 þ CO2 ! RNH2þ COO (1)
RNH2þ COO þ RNH2 ! RNHCOO þ RNH3þ (2)
2RNH2 þ CO2 ! RNHCOO þ RNH3þ (3)
2R1 R2 NH þ CO2 ! R1 R2 NCOO þ R1 R2 NH2þ (4)
For the tertiary amine solvent category, the solvent will react
with CO2 through a based-catalysed hydration mechanism (Vaidya
and Kenig, 2007). This mechanism is a single-step reaction, as
shown in Eq. (5) below. In this reaction, the tertiary amine will react
with CO2 and water (H2O) to produce a bicarbonate ion (HCO 3)
instead of carbamate.
R1 R2 R3 N þ CO2 þ H2 O ! R1 R2 R3 NH þ þ HCO
3 (5)
where the R1, R2 and R3 groups in the chemical reaction stoichi-
ometry above represents the unreactive sites of the amine solvent
(e.g. alkyl group), which are the structures that remain the same in
the reactant and product.
2.3.2. Classification of amine-based solvent into primary, secondary
or tertiary amines
In order to identify the reactive site of potential amine solvents
(which is the part of the amine solvent that reacts with CO2), the
potential amine solvent needs to be classified into three categories
of amines, which are the primary amine, secondary amine and
tertiary amine. This classification is made based on the molecular
structure of potential amine solvent candidates. Fig. 2 summarises
the step-by-step process to classify the potential amine solvents
into primary, secondary, or tertiary amine groups.
For single amine solvent candidates (solvents that only have one
amine functional group) the classification of the potential solvent is
very straightforward, based on the position of the amine functional
group in the molecule. This is shown in the left hand side of Fig. 2.
708 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715
Potential amine solvent candidate
Is there only one
Yes
amino group present
in the molecule?
Single amine solvent
Primary Yes
Is the -NH2 grou
group
amine
t?
present?
No
Yes
Secondary Iss the -NH grou
group
amine present?
No
Tertiary amines
Fig. 2. Step-by-step procedure for the classification of amine-based solvent into primary, secondary, or tertiary amines.
For example;
1) Case 1: If the amine functional group is attached to two
hydrogen atoms and one carbon atom (RNH2), the solvent is
categorised as a primary amine. An example of a primary amine
is MEA (OHCH2CH2NH2).
2) Case 2: If the amine functional group is attached to one
hydrogen atom and two carbon atoms (R1R2NH), the solvent is
categorised as a secondary amine. An example of a secondary
amine is Ethyl butyl amine (CH3CH2CH2CH2NHCH2CH3).
3) Case 3: If the amine functional group is attached to three carbon
atoms (R1R2R3N), the solvent is categorised as a tertiary amine.
An example of a tertiary amine is MDEA (CH3N(CH2CH2OH)2).
For diamine or triamine solvent candidates (solvents that have
more than one amine functional group in their molecular struc-
ture), only one amine group is considered as reactive and the other
is considered unreactive based on the second assumption stated in
Section 2.3. The right hand side of Fig. 2 shows the step-by-step
process to determine the reactive site of diamine- or triamine-
based solvents. This depends on the selectivity of amines towards
CO2. As reported in a previous study, the selectivity of amine to-
wards CO2 follows the sequence of primary amine, secondary
amine, and lastly, tertiary amine (Ciftja et al., 2013). This means that
the primary amine has the highest reactivity while the tertiary
amine has the lowest reactivity towards CO2. For example if the
solvent has both primary and tertiary amine groups in their mo-
lecular structure, the solvent is thus classified as a primary amine
since the primary amine has a high selectivity towards CO2.
2.3.3. Generation of reaction stoichiometry for each solvent
candidate
Once all the potential solvent candidates are categorised into
No
Diamine/triamine solvent
Yes Primary
Is the-NH2 group
amine
present?
No
Yes
Secondary
Is the-NH group
present? amine
No
Tertiary amines
primary, secondary, and tertiary amines, the reaction stoichiometry
for all the solvent candidates are generated. The generation is based
on the general reaction stoichiometry of amine-based solvent with
CO2, as established in Section 2.3.1.
2.4. Step 4:Evaluation of process performance
2.4.1. Energy required for solvent regeneration
In this study, the evaluation of process performance only focuses
on the energy required for solvent regeneration since this is the
main energy penalty in the carbon capture process. The total en-
ergy required for solvent regeneration is determined by the sum-
mation of three primary components, which are the enthalpy of
reaction, sensible heat, and stripping heat, as shown in Eq. (6)
(Hopkinson et al., 2014).
Ereg ¼ QDHr þ QSH þ QST (6)
where, Ereg (kJ/mol) is the total energy required for solvent
regeneration, QDHr (kJ/mol) is the enthalpy of reaction between
solute and solvent, QSH (kJ/mol) is the sensible heat, and QST (kJ/
mol) is the stripping heat. Sensible heat is the heat required to
increase the temperature of the inlet stream of the stripping col-
umn to the desired operating temperature for the regeneration
process. Meanwhile, stripping heat is the latent heat of water
vapour that is needed to create desorption driving force at the top
of the stripping column. The contribution of sensible heat and
stripping heat to the overall energy required for solvent regenera-
tion will not be considered in this study since this study is a pre-
liminary design study and the operating condition of the
regeneration process is still unknown. Therefore, the total energy
required for solvent regeneration in this study is equal to the
enthalpy of reaction between reactive solvent and CO2.
 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715 709

The enthalpy of reaction is the heat required to break the

chemical bond between solute (CO2) and solvent in the stripping
column. The enthalpy of reaction is calculated using Eq. (7) based
on the chemical reaction stoichiometry defined in Step 3 (Section
2.3).
X  X  eCl, eOH, eCH3, eCOH, eCOOH, eNO2, and eCN. In Eq. (8), the
QDHr ¼ DHf product  DHf reactant
DHf (kJ/mol) in Eq. (7) is the heat of formation for the product and
reactant in kilojoule per mol. In this research, the value of heat of
formation for the product and reactant is estimated using quantum
mechanics calculation and isodesmic reaction since ionic com-
pounds (carbamate and RNHþ 4 are formed as products from the
reaction of amine-based solvent and CO2) are involved. The ProPred
tool does not have the necessary features for the prediction of heat
of formation for ionic compounds.
2.4.2. Property prediction method for heat of formation using the
quantum mechanics approach
The first step in estimating the heat of formation using a
quantum mechanics approach is to determine the sum of electronic
and thermal enthalpies, Ho, for each chemical structure using
Gaussian09 software. The Gaussian09 software performs quantum
mechanics calculations to generate thermochemistry data based on
molecular structure. The detail input data needed for the
Gaussian09 software is shown in Table 2 below.
In Table 2, the theoretical model represents the method used to
model the system with a specific set of approximations. The basis
set represents a set of wave functions, which describe the shape of
atomic orbitals. Molecule specification is required to specify the
type of atoms and their coordinates in the molecule structure (also
known as the Z-matrix coordinate). In this study, Chemdraw soft-
ware is used to generate the Z-matrix coordinate for each chemical
structure.
The value of Ho is extracted from the thermochemistry data
generated by the Gaussion09 software. After Ho has been deter-
mined, the isodesmic reaction is constructed for each chemical
structure. The isodesmic reaction is the reaction that contains the
same number and same kind of chemical bond in the reactant and
product. The rule for constructing the isodesmic reaction is given by
Khrapkovskii et al. (2013), as shown in the chemical equation (Eq.
(8)) below.
XCH2 CH2 Y þ CH4 / XCH3 þ CH3 CH2 Y (8)
where XCH2CH2Y is the desired chemical (from which the required
heat of formation will be estimated), while X and Y in the above
equation represent other functional groups such as NH2e, eH, eF,
(7) number and type of bond in the reactant and product are the same.
One important thing that needs to be considered in the con-
struction of an isodesmic reaction is that the experimental heat of
exp
formation, DHf , data for all other chemicals involved in the re-
action stoichiometry of isodesmic reaction, must be available. This
is because the DHfexp value will be required in order to estimate the
heat of formation of the desired chemicals and to provide accurate
results for the heat of formation (Chen and Hamilton, 1999).
After the isodesmic reaction has been constructed, the heat of
formation of the desired chemical will be estimated using Table 3,
Eqs. (9) and (10). Subscripts i and j in Eqs. (9) and (10) represent the
number of reactant and product in the isodesmic reaction.
X X
DHR ¼ Hoj  Hoi (9)
j i
X X
DHf ;A ¼ DHfexp
j
 DHfexp
i
 DHR (10)
j i¼2
First, the enthalpy of reaction, DHR, will be calculated using Eq.
(9) based on the value of Ho of each product and reactant. Then, the
value of heat of formation of the desired chemical will be estimated
using the calculated DHR and experimental heat of formation,
DHexp
f
value, as shown in Eq. (10). The advantage of using isodesmic
reaction is that the accuracy of the estimation result will be
improved since the computational errors associated with reactants
and products will tend to cancel out due to the similarity in
bonding (Saraf et al., 2003).
2.5. Step 5: selection of the best solvent candidate
The reactive solvent candidate, which has the lowest energy
required for the regeneration process, is selected as the most
promising solvent, since the objective of this study is to design an
energy efficient reactive solvent for the chemical absorption PCCC
process. The performance of the selected solvent is compared with
the performance of a conventional solvent.

3. Results and discussions

Table 2
Input data required for Gaussian09 software.
3.1. Generation of feasible solvent candidate
Parameter Input data

Type of calculation Frequency calculation with optimised structure In this work, the feasible solvent candidates for PCCC were
Theoretical models Ground state, density functional theory (DFT), B3LYP
generated using ProCAMD software. Since the method is consid-
(Method) model
Basis sets 6-311G (d, p): 6 Gaussian Type Orbitals (GTOs) for core ered to be a new approach for PCCC, there is a need to prove that it
orbital, 3 GTOs for inner valence, 2 difference GTOs for can generate a feasible solvent for CO2 capture. In order to prove the
outer balance method, a base case study was used where the result of the solvents
Molecule Z-matrix coordinate generated from the base case study are compared with a previous
specification
study. In the base case study, the search for feasible solvents was

Table 3
Estimation of heat of formation using quantum mechanics and the isodesmic reaction approach.

Isodesmic reaction Reactant 1 Reactant 2 / Product 1 Product 2

Chemical A (desired chemical) B C D

Sum of electronic and thermal enthalpies (kJ/mol) Ho, A Ho, B Ho, C Ho, D
Experimental value of heat of formation (kJ/mol) DHf, A DHexp
f ;B
DHexp
f;C
DHexp
f ;D
710 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715

Table 4 ProCAMD software was 1.07 s. Of these 571 chemical structures,

Summary of the feasible solvent candidates generated in this study based on only 29 chemicals were available in the ICAS database and
functional group.
considered in this study as feasible solvents for the chemical ab-
Functional group Number of feasible reactive solvent candidates generated sorption process. The rest of the generated structures were not in
Amine 17 the chemical database with some possibly not even available in the
Amine and alcohol 8 market (must be synthesised from other chemicals). Due to this
Alcohol 4 limitation, the rest of the generated structures were eliminated in
Total 29
this study. Table 4 summarises the result according to the func-
tional group of the reactive solvent generated. Out of 29 feasible
reactive solvent candidates generated, 17 reactive solvents con-
done for commonly employed solvent, which is the acyclic com- tained the amine functional group, 8 reactive solvents contained a
pound from amines and alcohol functional groups only. However, combination of amine and alcohol functional groups, and the rest
once the method is proven, then the application could be extended only contained the alcohol functional group. A list of reactive sol-
to include other groups of chemicals including cyclic amines. vents generated in this study is shown in Table 5.
The result of the base case study shows that 571 chemical Some of the 29 solvents listed in Table 5 was also found in
structures (including isomers) have been generated from the Pro- previous studies. For example, the tertiary amine solvent, 2-
CAMD software based on the design specification defined in Step 1 propanol, 1-(dimethylamino)-, was found in a study by Zhang
(Section 2.1). The total time required to generate the result using et al. (2016). Another secondary amine solvent, which is ethanol,

Table 5
List of feasible generated solvents.

Name of solvent candidate Chemical structure Functional group

1,2-Ethanediamine, N-methyl- Amine

1,3-Propanediamine Amine

1,2-Ethanediamine, N-ethyl- Amine

1,2-Ethanediamine, N,N0 -dimethyl- Amine

1,4-Butanediamine Amine

1,2-Ethanediamine, N,N,N0 -trimethyl- Amine

1,3-Propanediamine, N,N-dimethyl- Amine

Pentane-1,5-diamine (Cadaverine) Amine

1,2-Ethanediamine, N,N-diethyl- Amine

N,N-dimethyl diethylenetriamine Amine

1,2-Ethanediamine, N0 -ethyl-N,N-dimethyl- Amine

1,3-Propanediamine, N-(3-aminopropyl)- Amine

1-butamine, N-ethyl Amine

1-Propanamine, N-propyl- Amine

1,6-Hexanediamine Amine

1-Hexanamine Amine
 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715
Table 5 (continued )
Name of solvent candidate Chemical structure
4-methylpentanamine
Ethanol, 2-(ethylamino)-
Ethanol, 2-(propylamino)-
4-Aminobutanol
5-Aminopentanol
Ethanol, 2-(dimethylamino)-
1-Propanol, 2-(dimethylamino)-
2-Propanol, 1-(dimethylamino)-
1-Propanol, 3-(dimethylamino)-
2-Butanol, 3-methyl
1-Butanol, 2-methyl
1-Butanol, 3-methyl
1-Pentanol
2-(ethylamino)-, was found in a study by Hwang et al. (2017), and
three primary amine solvents (1,3-propanediamine; 1,6-
hexanediamine; 1,3-propanediamine, N,N-dimethyl-), one sec-
ondary amine solvent (ethanol, 2-(ethylamino)-) and three tertiary
amine solvents (ethanol, 2-(dimethylamino)-; 2-propanol, 1-
(dimethylamino)-;1-propanol, 3-(dimethylamino)-) were found in
the study conducted by El Hadri et al. (2017). These results prove
that the method used in this study can generate feasible solvents
for CO2 capture similar to the experimental approach. Furthermore,
some solvents generated in this study have not been found in the
literature (to the best of the authors’ knowledge). These solvents
might be one of the potential novel solvents for CO2 capture in the
future (e.g., the primary amine solvent 1,2-ethanediamine, N,N-
diethyl-). The other advantages of the approach proposed in this
work are that it helps to reduce the time to generate feasible sol-
vents and saves on resources and cost since experimental works
will only be conducted for promising solvents only.
3.2. Classification of reactive solvent and prediction of reaction
stoichiometry
The reaction of each potential solvent candidate with CO2 was
predicted using the method proposed in Step 3 (see Section 2.3).
711
Functional group
Amine
Amine and alcohol
Amine and alcohol
Amine and alcohol
Amine and alcohol
Amine and alcohol
Amine and alcohol
Amine and alcohol
Amine and alcohol
Alcohol
Alcohol
Alcohol
Alcohol
Based on the literature study, only amines were found to react with
CO2; no information has been found regarding the reaction be-
tween alcohol and CO2. Therefore, four potential solvents that
contain only the alcohol functional group were eliminated at this
stage since it is assumed that no reaction will happen between
alcohol and CO2.
In order to identify the reaction mechanism of each potential
amine-based solvent with CO2, all 25 potential candidates were
classified based on their reactive sites; either primary, secondary, or
tertiary amines. The result of amine solvent classification is shown
in Table 6 below.
The reaction stoichiometry for potential solvent candidates with
CO2 from the primary and secondary amine category is generated
using the zwitterion mechanism (see Eqs. (3) and (4)). Meanwhile,
for the tertiary amine category, the reaction stoichiometry of the
potential solvent with CO2 is generated using a base-catalysed
hydration mechanism (See Eq. (5)).
3.3. Evaluation of energy required for solvent regeneration
In this stage, the performance of the solvent regeneration pro-
cess will be evaluated and ranked for all 25 potential solvents. The
performance evaluations were performed based on enthalpy of
712 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715

Table 6 reaction stoichiometry generated for each solvent candidate and

Result of amine solvent classification.
Potential amine solvent candidate
1-Hexanamine
4-methylpentanamine
4-Aminobutanol
5-Aminopentanol
1,2-Ethanediamine, N-methyl-
1,3-Propanediamine
1,2-Ethanediamine, N-ethyl-
1,4-Butanediamine
1,3-Propanediamine, N,N-dimethyl-
Pentane-1,5-diamine
1,2-Ethanediamine, N,N-diethyl-
1,6-Hexanediamine
N,N-dimethyl diethylenetriamine
1,3-Propanediamine, N-(3-aminopropyl)-
1-butamine, N-ethyl
1-Propanamine, N-propyl-
Ethanol, 2-(ethylamino)-
Ethanol, 2-(propylamino)-
1,2-Ethanediamine, N,N0 -dimethyl-
0
1,2-Ethanediamine, N,N,N -trimethyl-
1,2-Ethanediamine, N0 -ethyl-N,N-
dimethyl-
1-Propanol, 3-(dimethylamino)-
1-Propanol, 2-(dimethylamino)-
Ethanol, 2-(dimethylamino)-
2-Propanol, 1-(dimethylamino)-
Number of amino Category of
groups present amine
1 Primary amine
1 Primary amine
1 Primary amine
1 Primary amine
2 Primary amine
2 Primary amine
2 Primary amine
2 Primary amine
2 Primary amine
2 Primary amine
2 Primary amine
2 Primary amine
3 Primary amine
3 Primary amine
1 Secondary
amine
1 Secondary
amine
1 Secondary
amine
1 Secondary
amine
2 Secondary
amine
2 Secondary
amine
2 Secondary
amine
1 Tertiary amine
1 Tertiary amine
1 Tertiary amine
1 Tertiary amine
heat of formation predicted using the quantum mechanics
approach. Tables 7 and 8 show the results of the enthalpy of
desorption reaction for primary/secondary amines and tertiary
amines respectively, which were calculated at standard condition, a
temperature of 298.15 K, and a pressure of 1 atm. The results in
Tables 7 and 8 are arranged in the form of increasing order of
enthalpy of desorption reaction (from the lowest enthalpy values to
the highest enthalpy values). The enthalpy of desorption reaction
for the conventional solvent, MEA, with CO2 was calculated using
the same approach, yielding a value of 97.43 kJ/mol.
In this study, the value of enthalpy of desorption represents the
energy required for the solvent regeneration process in the stripper
column. Based on the result in Table 7, it is shown that amongst all
the primary and secondary amine solvent candidates generated in
this study, 1,2-ethanediamine, N,N-diethyl- (primary amine) and 1-
propanamine, N-propyl- (secondary amines) have the lowest
enthalpy of desorption value, which are 101.07 kJ/mol and
101.37 kJ/mol respectively. On the other hand 1,5-pentanediamine
(primary amine) has the highest value of enthalpy of desorption,
which is 130.71 kJ/mol. The results in Table 7 also indicate that most
secondary amine solvents have an enthalpy of desorption value
that is lower than that of primary amine solvents. This result is due
to the weak formation of carbamate (unstable) in the reaction be-
tween secondary amine solvents with CO2 (Hwang et al., 2017).
Therefore, less energy is required in the desorption process of
secondary amines.
Meanwhile, in Table 8, from four tertiary amine solvent candi-
dates generated in this study, 2-propanol, 1-(dimethylamino)- has
the lowest value of enthalpy of desorption, which is 66.85 kJ/mol.
The range of enthalpy of desorption for all tertiary amine solvents
generated in this study is between 66.85 kJ/mol to 83.78 kJ/mol.

desorption between the potential amine solvent and CO2 only. The
contribution of sensible heat and stripping heat to the overall en- Table 8
ergy required for solvent regeneration has not been considered in Results of enthalpy of desorption for tertiary amine solvents with CO2.
this study since this is a preliminary study and the optimum
Potential tertiary amine solvents Enthalpy of desorption (kJ/mol)
operating condition of the regeneration process for each solvent
has not been established yet. The enthalpy of desorption is equal to 2-Propanol, 1-(dimethylamino)- 66.85
1-Propanol, 2-(dimethylamino)- 79.94
the negative value of enthalpy of absorption. The enthalpy of
1-Propanol, 3-(dimethylamino)- 82.98
desorption was calculated using Eq. (7) based on the reverse Ethanol, 2-(dimethylamino)- 83.78

Table 7
Result of enthalpy of desorption for primary and secondary amine solvents with CO2.

Potential primary and secondary amine solvents Category of amine Enthalpy of desorption (kJ/mol)

1,2-Ethanediamine, N,N-diethyl- Primary amine 101.07

1-Propanamine, N-propyl- Secondary amine 101.31
Ethanol, 2-(propylamino)- Secondary amine 103.27
Ethanol, 2-(ethylamino)- Secondary amine 104.06
1-butamine, N-ethyl Secondary amine 104.55
1,2-Ethanediamine, N0 -ethyl-N,N-dimethyl- Secondary amine 105.17
1,2-Ethanediamine, N,N0 -dimethyl- Secondary amine 105.41
N,N-dimethyl diethylenetriamine Primary amine 107.72
4-Aminobutanol Primary amine 108.64
1,3-Propanediamine, N-(3-aminopropyl)- Primary amine 108.84
1,3-Propanediamine, N,N-dimethyl- Primary amine 109.18
5-Aminopentanol Primary amine 109.86
1,3-Propanediamine Primary amine 111.80
1,6-Hexanediamine Primary amine 113.26
1,2-Ethanediamine, N-methyl- Primary amine 113.48
1,2-Ethanediamine, N,N,N0 -trimethyl- Secondary amine 115.37
1,2-Ethanediamine, N-ethyl- Primary amine 118.62
1,4-Butanediamine Primary amine 119.91
4-methylpentanamine Primary amine 120.83
1-Hexanamine Primary amine 122.85
1,5-Pentanediamine Primary amine 130.91
 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715
This result indicates that the enthalpy of desorption for all tertiary
amine solvents are lower than that of primary and secondary amine
solvents. The reason for tertiary amine solvents having a lower
enthalpy of desorption compared to primary and secondary amine
solvents is the different types of reaction mechanism, as stated in
Eqs. (1)e(5). The reaction between tertiary amine and CO2 follows
the base-catalysed hydration mechanism, which forms bicarbonate
ions as a product instead of carbamate ions. The advantage of the
formation of bicarbonate ions is that it helps reduce the enthalpy of
desorption since bicarbonate ions are easily decomposed by heat.
As stated by Zhang et al. (2016), breaking CeO bonds in bi-
carbonates ions to release CO2 requires less energy compared to
breaking CeN bonds in carbamates.
When comparing the performance of the solvent generated in
this study with the conventional solvent, MEA, all four tertiary
amines solvents showed a lower enthalpy of desorption value
(which is between 66.85 kJ/mol to 83.78 kJ/mol) compared to the
MEA solvent (97.43 kJ/mol). Therefore, by using the tertiary amine
solvents proposed in this study, significant savings on regeneration
energy, up to 31.4%, could be achieved as compared to using the
conventional solvent MEA. This result indicates that the proposed
tertiary amine solvent can help reduce the cost of carbon capture by
reducing the energy requirement for the solvent regeneration
process.
The enthalpy of desorption for all primary and secondary amine
solvents generated in this study are found to be higher than that of
MEA. However, one primary amine solvent (1,2-ethanediamine,
N,N-diethyl-) and six secondary amine solvents (1-propanamine,
N-propyl-; ethanol, 2-(propylamino)-; ethanol, 2-(ethylamino)-; 1-
butamine, N-ethyl; 1,2-ethanediamine, N0 -ethyl-N,N-dimethyl-;
1,2-ethanediamine, N,N0 -dimethyl-) show an enthalpy of desorp-
tion value nearer to the value of enthalpy of desorption for MEA (in
the range of 10 kJ/mol of the enthalpy of desorption for MEA, which
is 97.43 kJ/mol). Therefore, these four tertiary amine solvents, one
primary amine solvent, and six secondary amine solvents should be
considered for further study as promising solvent candidates for
CO2 capture.
The accuracy of the result in this study (enthalpy of desorption
reaction) really depends on the accuracy of the property prediction
model used to estimate the value of heat of formation for each
product and reactant. As mentioned in the method of Section 2.4.2,
the heat of formation is estimated using a quantum mechanics
approach and isodesmic reaction. Table 9 shows the comparison of
heat of formation value calculated from three different approaches,
which are the quantum mechanics approach (this work), ProPred
tools, and experimental approach. However, this comparison does
not involve the heat of formation value from the ionic compound
due to the absence of experimental data on heat of formation for
ionic compounds from previous studies, and because the ProPred
tool cannot predict the properties for ionic compounds. The per-
centage of average absolute deviation (%AAD) for each method is
calculated using Eq. (11), as shown below.
Table 9
Comparison of heat of formation value estimated using different approaches.
Potential amine solvent Heat of formation (kJ/mol)
Quantum mechanics (This work)
MEA 206.25
1,6-Hexanediamine 93.51
1-Hexanamine 121.32
Ethanol, 2-(dimethylamino)- 193.66
AAD (%) 4.67
713
 
1 XXEst  XExp 
%AAD ¼  X   100 (11)
n Exp
where n is the available data point for heat of formation, XEst is the
value of heat of formation estimated using a property prediction
model, and XExp is the experimental value of heat of formation
taken from previous studies. The result of %AAD for the heat of
formation estimate using the quantum mechanics approach and
ProPred tool are tabulated in Table 9.
The results in Table 9 show that the accuracy of the result in this
study is still tolerable with a percentage of AAD of around 4.67%.
The use of isodesmic reactions has helped improve the accuracy of
the result (estimation of heat of formation) since the computational
errors associated with the reactants and products will tend to
cancel out due to the similarity in number and type of bonding
(Saraf et al., 2003). The trend of the result obtained in this study is
also in line with that of previous studies. This trend is shown by the
value of enthalpy of reaction for tertiary amine solvents, which is
lower than the value of enthalpy of reaction for primary and sec-
ondary amine solvents (Liang et al., 2016).
4. Conclusions and further recommendations
In this study, an integrated molecular and process level
approach was used for the design of energy efficient reactive sol-
vents for the chemical absorption PCCC process. The systematic
method applied the CAMD approach in order to speed up the
process of finding and generating feasible solvent candidates. This
study reveals that 25 reactive single solvent candidates for the
chemical absorption process were successfully generated from the
amine and alcohol functional groups based on specified target
properties. In addition, some of the amine solvents generated in
this study were also found in previous studies. This proves that the
approach used in this study can generate feasible solvents for CO2
capture.
The performance of all potential amine solvents was evaluated
based on the energy required for solvent regeneration. In order to
evaluate the process performance, the reaction stoichiometry for
each potential amine solvent with CO2 was generated using the
prediction of reaction method introduced in this work. This reac-
tion stoichiometry is needed for the calculation of enthalpy of
desorption. In this study, the value of enthalpy of desorption rep-
resents the amount of energy required for the solvent regeneration
process. Based on the process performance result, it is found that all
four tertiary amines solvents generated in this study have a value of
enthalpy of desorption (range from 66.85 kJ/mol to 83.78 kJ/mol),
which is lower than that of the conventional solvent, MEA (97.43 kJ/
mol). These results show a significant reduction of regeneration
energy of up to 31.4% that could be achieved with the new proposed
reactive amine solvent. This proposed reactive solvent can help
reduce carbon capture cost by reducing the energy requirement for
the regeneration process.
In future works, additional process performance criteria will be
ProPred tool (ICAS software) Experimental approach
213.51 206.70
98.80 98.80
133.38 133.30
202.25 202.00
0.87 e
714 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715
considered in order to select the best reactive solvent with high CO2
capture efficiency, low regeneration energy, low degradation rate,
and minimised cost of the capture process. It is also recommended
that the experimental work be conducted and high priority be
given to the promising solvent suggested in this study. This work
will also be extended to include the design of reactive solvent
blends for the chemical absorption process.
Acknowledgements
This study was supported by the Research University Grants,
RUG (Vote number: Q.J130000.2544.10H67 and
Q.J130000.2546.14H46) Universiti Teknologi Malaysia, and the
Ministry of Higher Education, Malaysia.
References
Achenie, L.E.K., Gani, R., Venkatasubramanian, V. (Eds.), 2003. Computer Aided
Molecular Design: Theory and Practice, Computer Aided Chemical Engineering.
Elsevier. https://doi.org/10.1016/S1570-7946(13)70754-5.
Ahmad, M.Z., Hashim, H., Yunus, N.A., Muis, Z., 2015. Optimal solvent design for CO2
capture process. Chem. Eng. Trans. 1135e1140. https://doi.org/10.3303/
CET1545190.
Bandyopadhyay, A., 2011. Amine versus ammonia absorption of CO2 as a measure of
reducing GHG emission: a critical analysis. Clean Technol. Environ. Policy 13,
269e294. https://doi.org/10.1007/s10098-010-0299-z.
Chen, Z., Hamilton, T.P., 1999. Ab initio calculation of the heats of formation of
nitrosamides: comparison with nitramides. J. Phys. Chem. 103, 11026e11033.
https://doi.org/10.1021/jp991735x.
Cheng, Y.S., Lam, K.W., Ng, K.M., Ko, R.K.M., Wibowo, C., 2009. An integrative
approach to product development-A skin-care cream. Comput. Chem. Eng. 33,
1097e1113. https://doi.org/10.1016/j.compchemeng.2008.10.010.
Chong, F.K., Foo, D.C.Y., Eljack, F.T., Atilhan, M., Chemmangattuvalappil, N.G., 2015.
Ionic liquid design for enhanced carbon dioxide capture by computer-aided
molecular design approach. Clean Technol. Environ. Policy 17, 1301e1312.
https://doi.org/10.1007/s10098-015-0938-5.
Chowdhury, F.A., Okabe, H., Yamada, H., Onoda, M., Fujioka, Y., 2011. Synthesis and
selection of hindered new amine absorbents for CO2 capture. Energy Procedia
201e208. https://doi.org/10.1016/j.egypro.2011.01.042.
Churi, N., Achenie, L.E.K., 1997. The optimal design of refrigerant mixtures for a two-
evaporator refrigeration system. Comput. Chem. Eng. 21, S349eS354. https://
doi.org/10.1016/S0098-1354(97)87526-6.
Ciftja, A.F., Hartono, A., Svendsen, H.F., 2013. Carbamate formation in aqueous -
diamine - CO2 systems. Energy Procedia 1605e1612. https://doi.org/10.1016/
j.egypro.2013.06.036.
Conte, E., Gani, R., Cheng, Y.S., Ng, K.M., 2012. Design of formulated products:
experimental component. AIChE J. 58, 173e189. https://doi.org/10.1002/
aic.12582.
Conway, W., Bruggink, S., Beyad, Y., Luo, W., Melia n-Cabrera, I., Puxty, G., Feron, P.,
2015. CO2 absorption into aqueous amine blended solutions containing mon-
oethanolamine (MEA), N,N-dimethylethanolamine (DMEA), N,N-
diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) for
post-combustion capture processes. Chem. Eng. Sci. 126, 446e454. https://
doi.org/10.1016/j.ces.2014.12.053.
El Hadri, N., Quang, D.V., Abu-Zahra, M.R.M., 2015. Study of novel solvent for CO2
post-combustion capture. Energy Procedia 2268e2286. https://doi.org/10.1016/
j.egypro.2015.07.414.
El Hadri, N., Quang, D.V., Goetheer, E.L.V., Abu Zahra, M.R.M., 2017. Aqueous amine
solution characterization for post-combustion CO2 capture process. Appl. En-
ergy 185, 1433e1449. https://doi.org/10.1016/j.apenergy.2016.03.043.
Eslick, J.C., Shulda, S.M., Spencer, P., Camarda, K.V., 2011. Optimization-based ap-
proaches to computational molecular design. In: Process Systems Engineering.
Wiley-VCH Verlag GmbH & Co. KGaA, pp. 173e193. https://doi.org/10.1002/
9783527631315.ch5.
Goto, K., Okabe, H., Shimizu, S., Onoda, M., Fujioka, Y., 2009. Evaluation method of
novel absorbents for CO2 capture. Energy Procedia 1083e1089. https://doi.org/
10.1016/j.egypro.2009.01.143.
Han, K., Ahn, C.K., Lee, M.S., Rhee, C.H., Kim, J.Y., Chun, H.D., 2013. Current status and
challenges of the ammonia-based CO2 capture technologies toward commer-
cialization. Int. J. Greenh. Gas Control 14, 270e281. https://doi.org/10.1016/
j.ijggc.2013.01.007.
Hasaneen, R., Elsayed, N.A., Barrufet, M.A., 2014. Analysis of the technical, micro-
economic, and political impact of a carbon tax on carbon dioxide sequestration
resulting from liquefied natural gas production. Clean Technol. Environ. Policy
16, 1597e1613. https://doi.org/10.1007/s10098-014-0735-6.
Hashim, H., Narayanasamy, M., Yunus, N.A., Shiun, L.J., Muis, Z.A., Ho, W.S., 2017.
A cleaner and greener fuel: biofuel blend formulation and emission assessment.
J. Clean. Prod. 146, 208e217. https://doi.org/10.1016/j.jclepro.2016.06.021.
Hopkinson, D., Luebke, D., Li, Z., Chen, S., 2014. Solvent optimization of conventional
absorption processes for CO2 capture from postcombustion flue gases. Ind. Eng.
Chem. Res. 53, 7149e7156. https://doi.org/10.1021/ie403869y.
Hwang, S.J., Kim, J., Kim, H., Lee, K.S., 2017. Solubility of carbon dioxide in aqueous
solutions of three secondary amines: 2-(butylamino)ethanol, 2-(iso-
propylamino)ethanol, and 2-(ethylamino)ethanol secondary alkanolamine so-
lutions. J. Chem. Eng. Data 62, 2428e2435. https://doi.org/10.1021/
acs.jced.7b00364.
IEA, 2013. Redrawing the Energy-Climate Map: World Energy Outlook Special
Report. France, Paris.
IPCC, 2014. Climate Change 2014: Mitigation of Climate Change: Working Group III
Contribution to the Fifth Assessment Report of the Intergovernmental Panel on
Climate Change. Cambridge University Press, New York. https://doi.org/10.1017/
CBO9781107415416.
Jayaweera, I., Jayaweera, P., Elmore, R., Bao, J., Bhamidi, S., 2014. Update on mixed-
salt technology development for CO2 capture from post-combustion power
stations. Energy Procedia 640e650. https://doi.org/10.1016/
j.egypro.2014.11.070.
Khalilpour, R., Mumford, K., Zhai, H., Abbas, A., Stevens, G., Rubin, E.S., 2015.
Membrane-based carbon capture from flue gas: a review. J. Clean. Prod. 103,
286e300. https://doi.org/10.1016/j.jclepro.2014.10.050.
Khrapkovskii, G.M., Sharipov, D.D., Shamov, A.G., Egorov, D.L., Chachkov, D.V.,
Tsyshevsky, R.V., 2013. Enthalpies of formation of mono substituted nitroben-
zenes: a quantum chemistry study. Comput. Theor. Chem. 1011, 37e43. https://
doi.org/10.1016/j.comptc.2013.02.005.
Kulajanpeng, K., Suriyapraphadilok, U., Gani, R., 2016. Systematic screening meth-
odology and energy efficient design of ionic liquid-based separation processes.
J. Clean. Prod. 111, 93e107. https://doi.org/10.1016/j.jclepro.2015.07.052.
Leung, D.Y.C., Caramanna, G., Maroto-Valer, M.M., 2014. An overview of current
status of carbon dioxide capture and storage technologies. Renew. Sustain.
Energy Rev. 39, 426e443. https://doi.org/10.1016/j.rser.2014.07.093.
Liang, Z., Fu, K., Idem, R., Tontiwachwuthikul, P., 2016. Review on current advances,
future challenges and consideration issues for post-combustion CO2 capture
using amine-based absorbents. Chin. J. Chem. Eng. 24, 278e288. https://doi.org/
10.1016/j.cjche.2015.06.013.
Mertens, J., Lepaumier, H., Desagher, D., Thielens, M.-L., 2013. Understanding
ethanolamine (MEA) and ammonia emissions from amine based post com-
bustion carbon capture: lessons learned from field tests. Int. J. Greenh. Gas
Control 13, 72e77. https://doi.org/10.1016/j.ijggc.2012.12.013.
Molina, C.T., Bouallou, C., 2015. Assessment of different methods of CO2 capture in
post-combustion using ammonia as solvent. J. Clean. Prod. 103, 463e468.
https://doi.org/10.1016/j.jclepro.2014.03.024.
Olajire, A.A., 2010. CO2 capture and separation technologies for end-of-pipe appli-
cations - a review. Energy 35, 2610e2628. https://doi.org/10.1016/
j.energy.2010.02.030.
Ozkutlu, M., Orhan, O.Y., Ersan, H.Y., Alper, E., 2016. Kinetic performance of ionic
liquid e diethanolamine system for CO2 absorption. Chem. Data Collect 2,
25e35. https://doi.org/10.1016/j.cdc.2016.05.001.
Pereira, F.E., Keskes, E., Galindo, A., Jackson, G., Adjiman, C.S., 2011. Integrated sol-
vent and process design using a SAFT-VR thermodynamic description: high-
pressure separation of carbon dioxide and methane. Comput. Chem. Eng. 35,
474e491. https://doi.org/10.1016/j.compchemeng.2010.06.016.
Qadir, A., Chiesa, M., Abbas, A., 2014. In silico design of solvents for carbon capture
with simultaneous optimisation of operating conditions. Int. J. Greenh. Gas
Control 30, 179e187. https://doi.org/10.1016/j.ijggc.2014.08.023.
Rao, A.B., Rubin, E.S., Berkenpas, M.B., 2004. An Integrated Modelling Framework for
Carbon Management Technologies. Pittsburgh, Pennsylvania.
Saraf, S.R., Rogers, W.J., Mannan, M.S., Hall, M.B., Thomson, L.M., 2003. Theoretical
thermochemistry: ab initio heat of formation for hydroxylamine. J. Phys. Chem.
107, 1077e1081. https://doi.org/10.1021/jp026027h.
Singh, P., Van Swaaij, W.P.M., Brilman, D.W.F., 2013. Energy efficient solvents for CO2
absorption from flue gas: vapor liquid equilibrium and pilot plant study. Energy
Procedia 2021e2046. https://doi.org/10.1016/j.egypro.2013.06.082.
Tuinier, M.J., Van Sint Annaland, M., Kramer, G.J., Kuipers, J.A.M., 2010. Cryogenic
CO2 capture using dynamically operated packed beds. Chem. Eng. Sci. 65,
114e119. https://doi.org/10.1016/j.ces.2009.01.055.
Vaidya, P.D., Kenig, E.Y., 2007. CO2-Alkanolamine reaction kinetics: a review of
recent studies. Chem. Eng. Technol. 30, 1467e1474. https://doi.org/10.1002/
ceat.200700268.
Valencia-Marquez, D., Flores-Tlacuahuac, A., Vasquez-Medrano, R., 2016. An opti-
mization approach for CO2 capture using ionic liquids. J. Clean. Prod. https://
doi.org/10.1016/j.jclepro.2016.11.064.
Van Der Ham, L.V., Romano, M.C., Kvamsdal, H.M., Bonalumi, D., Van Os, P.,
Goetheer, E.L.V., 2014. Concentrated aqueous piperazine as CO2 capture solvent:
detailed evaluation of the integration with a power plant. Energy Procedia
1218e1222. https://doi.org/10.1016/j.egypro.2014.11.131.
Wang, Y., Achenie, L.E.K., 2002. Computer aided solvent design for extractive
fermentation. Fluid Phase Equil. 201, 1e18. https://doi.org/10.1016/S0378-
3812(02)00073-0.
Wang, M., Lawal, A., Stephenson, P., Sidders, J., Ramshaw, C., 2011. Post-combustion
CO2 capture with chemical absorption: a state-of-the-art review. Chem. Eng.
Res. Des. 89, 1609e1624. https://doi.org/10.1016/j.cherd.2010.11.005.
Wu, X., Yu, Y., Qin, Z., Zhang, Z., 2014. The advances of post-combustion CO2 capture
with chemical solvents: review and guidelines. Energy Procedia 1339e1346.
https://doi.org/10.1016/j.egypro.2014.11.143.
Yu, C.H., Huang, C.H., Tan, C.S., 2012. A review of CO2 capture by absorption and
adsorption. Aerosol Air Qual. Res. 12, 745e769. https://doi.org/10.4209/
 M.Z. Ahmad et al. / Journal of Cleaner Production 176 (2018) 704e715
aaqr.2012.05.0132.
Yunus, N.A., Gernaey, K.V., Woodley, J.M., Gani, R., 2014. A systematic methodology
for design of tailor-made blended products. Comput. Chem. Eng. 66, 201e213.
https://doi.org/10.1016/j.compchemeng.2013.12.011.
Zaman, M., Lee, J.H., 2013. Carbon capture from stationary power generation
sources: a review of the current status of the technologies. Kor. J. Chem. Eng. 30,
1497e1526. https://doi.org/10.1007/s11814-013-0127-3.
Zarogiannis, T., Papadopoulos, A.I., Seferlis, P., 2016. Systematic selection of amine
mixtures as post-combustion CO2 capture solvent candidates. J. Clean. Prod.
715
136, 159e175. https://doi.org/10.1016/j.jclepro.2016.04.110.
Zhang, R., Liang, Z., Liu, H., Rongwong, W., Luo, X., Idem, R., Yang, Q., 2016. Study of
formation of bicarbonate ions in CO2-loaded aqueous single 1DMA2P and
MDEA tertiary amines and blended MEAe1DMA2P and MEAeMDEA amines for
low heat of regeneration. Ind. Eng. Chem. Res. 55, 3710e3717. https://doi.org/
10.1021/acs.iecr.5b03097.
Zhao, Z., Cui, X., Ma, J., Li, R., 2007. Adsorption of carbon dioxide on alkali-modified
zeolite 13X adsorbents. Int. J. Greenh. Gas Control 1, 355e359. https://doi.org/
10.1016/S1750-5836(07)00072-2.