Chemical Engineering Science 174 (2017) 174–188

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Chemical Engineering Science

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

Computationally based analysis of the energy efficiency of a CO2 capture

process
Bojan Vujic, Alexander P. Lyubartsev ⇑
Stockholms University, Department of Materials and Environmental Chemistry, Division of Physical Chemistry, Stockholm University, SE 106 91 Stockholm, Sweden

h i g h l i g h t s g r a p h i c a l a b s t r a c t

A model for thermodynamic

evaluation of the energy efficiency of
CO2 capture.

Accounting for the working capacity,
regenerability and purity of the
captured CO2.

Determination of the most efficient
desorption conditions for CO2
capture.

Grand Canonical Monte Carlo
simulations for more than 1000
zeolite structures.

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

Article history: We propose a model for thermodynamic evaluation of the energy efficiency of a CO2 capture in a
Received 4 October 2016 temperature-pressure swing adsorption. Major parts of this model are computational prediction of the
Received in revised form 8 August 2017 adsorbed gas loading as a function of temperature and partial CO2 pressure, evaluation of the energy
Accepted 1 September 2017
expenses under specified conditions for the working capacity, regenerability of the sorbent and purity
Available online 7 September 2017
of the captured CO2, as well as determination of the most optimal desorption conditions in terms of des-
orption pressure and temperature. The proposed model can be applied for fast evaluation of the energy
Keywords:
costs of the CO2 capture process with the use of both experimental or simulation adsorption data with
Gas separation
Adsorption
respect to pressure and temperature. We tested this model analyzing data obtained from Grand
Carbon capture and storage Canonical Monte Carlo simulations for more than thousand different zeolite structures. Within our
Monte Carlo simulations approach it is possible to evaluate a theoretical limit of the energy expenses for each specific material
Pressure-temperature swing adsorption and to use the proposed method in screening different structures for the most efficient sorbent material
from the energy efficiency point of view under specified requirements for the working capacity of the
process, regenerability and purity of captured CO2. We show that setting realistic from the industrial
point of view parameters of the CO2 capture cycle leads to substantial reduction of the number of suitable
zeolite structures, and to increase of the energy penalty of the CO2 capture compared to evaluations based
on minimization of the parasitic energy only.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction special emphasis is placed particularly on carbon dioxide, as the

One of the major problems the modern era is facing is a rapid
increase of greenhouse gases concentration in the atmosphere. A
⇑ Corresponding author.
E-mail address: alexander.lyubartsev@mmk.su.se (A.P. Lyubartsev).
main greenhouse gas. Increasing concentration of CO2 in the atmo-
sphere leads to global warming, and may also have a negative
impact on human health (Patz et al., 2005; Milly et al., 2005;
McMichael et al., 2006). Because of this reason, science and tech-
nology are facing a problem of finding new ways to fast and yet
efficiently reduce CO2 emission. Carbon capture and storage

http://dx.doi.org/10.1016/j.ces.2017.09.006
0009-2509/Ó 2017 Elsevier Ltd. All rights reserved.
 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188
(CCS) technology (Bacsik et al., 2016; Hedin et al., 2013; Xu and
Hedin, 2016) is expected to play an important role in the reduction
of greenhouse gases emissions into the atmosphere (Miles and
Kapos, 2008; Paustian et al., 1998; Choi et al., 2009; Ming et al.,
2016; Songolzadeh et al., 2012; Smit et al., 1986).
CCS can be defined as the separation and capture of CO2 pro-
duced at stationary sources, followed by transport and storage in
geological reservoirs or in the ocean (Damen et al., 2006). Carbon
dioxide can be captured directly from industrial sources by one
of three main methods: pre-combustion capture (via oxygen-
blown gasification), post-combustion capture, and oxyfuel process
(Songolzadeh et al., 2012; D’Alessandro et al., 2010; Benson and
Orr, 2008). Post-combustion capture in power plants involves the
separation of CO2 from flue gas mixtures, followed by its compres-
sion and sequestration in geological formations (Metz et al., 2005;
Massood et al., 2007).
There are several techniques for separation of carbon dioxide
from flue gas mixture, such as adsorption (Martin-Calvo et al.,
2014; Sethia et al., 2010; Maurin et al., 2005; Hedin et al., 2013;
Akhtar and Bergström, 2011), absorption (Yan et al., 2008;
Conway et al., 2015), cryogenic membrane (Pfaff and Kather,
2009; Ye et al., 2014) and micro algal bio-fixation (Pellerano
et al., 2009). Practical choices can vary, but in general, adsorption
can be a very good choice in terms of efficiency, possibility of
large-scale applications and recycling of the adsorbent material.
Considering the overall cost of CO2 capture, adsorption process in
comparison with other methods is the most efficient one
(Pellerano et al., 2009; Liu et al., 2010).
Adsorption relates to uptake of sorbate molecules onto the sur-
face or in pours of a solid adsorbent, to which they adhere via two
types of forces, weaker van der Waals and dipole forces in the case
of physisorption, or stronger covalent bonding in the case of
chemisorption (Hedin et al., 2013). Absorption in contrasts with
adsorption is the process where sorbate molecules dissolve into
the bulk of the material itself (Bhown and Freeman, 2011). The most
used physisorbents, such as active carbon (Ribeiro et al., 2008;
Berlier, 1997), metal-organic frameworks (MOFs) (Bastin et al.,
2008; Bao et al., 2015; Lee et al., 2015; McDonald et al., 2015;
Verdegaal et al., 2016) and zeolites (Liu et al., 2010; Cheung et al.,
2012; Siriwardane et al., 2005; García-Pérez et al., 2007; García-
Sánchez et al., 2009), are better options than chemisorbents, such
as amine-modified mesoporous silica (Bacsik et al., 2010; Hedin
et al., 2010) due to relatively easy regeneration of the sorbent mate-
rial by the change of temperature or pressure.
Whatever technique is used for CO2 capture, it inevitably
requires certain amount of energy, which exert an additional load
on the power plant and which is called for this reason parasitic
energy. Within existing techniques parasitic energy can account
for about 30% of the total energy produced by a power plant
(Bhown and Freeman, 2011; Lin et al., 2012) and reducing this
energy cost is of primary importance for further development of
CCS technology. Not surprisingly, much effort in recent years, in
both experimental (Jensen et al., 2012; Harlick and Tezel, 2004)
and computational (Gomez-Alvarez et al., 2016; Babarao and
Jiang, 2008; Deroche et al., 2008; Krishna and Long, 2011;
Yazaydin et al., 2009; Kim et al., 2012; Hasan et al., 2013;
Matito-Martos et al., 2014; Matito-Martos et al., 2015) studies have
been devoted to investigation of the adsorption properties of vari-
ous materials like zeolites and MOFs, as well as the energy costs
and efficiency of CCS.
In recent computational studies (Lin et al., 2012; Berger and
Bhown, 2013; Huck et al., 2014) a model for computation of para-
sitic energy in a typical temperature–pressure swing process has
been suggested which included two main contributions: thermal
energy to desorb CO2 and thus regenerate the adsorbent, and com-
pression energy to compress captured CO2 to the transportation
175
pressure (conventionally 150 bar). These energy contributions
can be evaluated from the adsorption isotherms determined in
computer simulations of considered materials. By varying thermo-
dynamic conditions of the desorption state, a minimum of the par-
asitic energy (per mol or per gram of the captured CO2) can be
found. The most optimal desorption conditions are defined by
the minimum of the parasitic energy. Computations can be done
for any material with known atomic structure, thus the method
becomes suitable for screening many possible candidates for effi-
cient CO2 adsorbents.
The model described in works (Lin et al., 2012; Huck et al.,
2014) predicted the theoretical minimum of the parasitic energy
from the basic relationships of thermodynamics. However, that
methodology does not consider several important parameters of
the adsorption-desorption cycle which are important from the
industrial applications point of view: working capacity (which is
defined as the difference between adsorption and desorption load-
ings and equals to amount of CO2 captured in a single cycle), purity
of the captured CO2 and regenerability (percent of CO2 remaining
in the sorbent). Our computations show that in many cases work-
ing conditions defined by the minimum of the parasitic energy
alone correspond to a very small working capacity (which would
require many adsorption/desorption cycles for the same amount
of CO2 captured and thus make the whole capturing process slow
and expensive), to a low regenerability of the sorbent framework
and to poor purity of the captured CO2. Amount of the parasitic
energy related to the realistic working conditions can thus be
highly underestimated. We therefore propose in this work to com-
plement the search of the optimal conditions for the minimum of
the parasitic energy by additional conditions for the minimal
acceptable working capacity, purity and regenerability.
Another problem we address to is how to make the computer
search for the most suitable adsorbents more efficient. For precise
computation of the parasitic energy, it is required to have a large
number of fugacity steps (desorption points) for each adsorption
isotherm, as well as a large number of adsorption isotherms in a
reasonable temperature range. Such computations require hun-
dreds of simulations for each considered material which makes
the screening process expensive in terms of CPU time. Here we pro-
pose a thermodynamical model (based on the Langmuir adsorption
model), which expresses the adsorption load of CO2 and N2 as a
function of partial gas pressures and temperature. Parameters of
this function can be fitted by running simulations for about ten
temperature–pressure points, which allows reducing the number
of computations (relative to the computation of the whole set of
adsorption isotherms) by more than one order of magnitude. Fur-
thermore, within the model the parasitic energy itself is expressed
as an analytical function of the parameters which facilitates evalu-
ation of the parasitic energy, and makes it possible to use the model
for experimental data. Using this methodology we are able to fast
and yet accurately evaluate the minimum of the parasitic energy
and thus find the most optimal desorption conditions (in terms of
desorption temperature and pressure) for working capacity, regen-
erability and purity of captured CO2 specified in advance.
2. Materials and computational methods
2.1. Zeolites as CO2 adsorbents
Among many materials which can be used as adsorbents (Hedin
et al., 2013; Ribeiro et al., 2008; Cheung et al., 2012; Hedin et al.,
2010; Xu and Hedin, 2016), zeolites have shown promising results
for separating carbon dioxide from flue gas mixtures in the pres-
sure swing adsorption (PSA) (Chue et al., 1995), temperature swing
adsorption (TSA) (Merel et al., 2008; Ntiamoah et al., 2016) as well
176 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188
as in the combined techniques. Zeolites are three-dimensional
microporous materials which are built from tetrahedral blocks.
Central atoms (T-atoms) in these blocks are silicon, but quite often
aluminum and/or phosphorus. Depending on the composition of T
atoms inside a zeolite structure, zeolites can be divided in general
into three main groups: alumino-silicates, alumino-phosphates
and silico-alumino-phosphates.
At some point in the zeolite framework, Al3+ ion can replace Si4+
and thus the framework becomes negatively charged (Čejka et al.,
2007) For each Si4+ replaced by Al3+ the charge must be balanced
by other positive ions such as Na+, K+ and Ca2+, or with protons,
H+. According to Löwenstein’s rule (Löwenstein, 1954), the distri-
bution of aluminum-oxygen tetrahedra is such that they tend to
connect to four silicon-oxygen tetrahedra. In another words, oxy-
gen bridges between two aluminum atoms (Al–O–Al) are forbid-
den. This leads to the conclusion that in zeolites, the minimal Si:
Al ratio is equal to one. Still, in some zeolites, depending on the
space group of the crystal system, it is not possible to create a
structure with Si:Al = 1 without violation of the Löwenstein’s rule.
Thus in zeolite structures the minimal Si:Al ratio is often greater
that 1.
Since carbon dioxide emissions are frequently associated with
large amounts of other gases such as nitrogen, an adsorbent selec-
tivity for one of these compounds is required. These adsorbents
should also be selective even at high temperatures, i.e., tempera-
tures typical of carbon dioxide emission sources (Dantas et al.,
2012). In principle, a carbon dioxide adsorbent must have a high
adsorption capacity, high selectivity, adequate adsorption/desorp-
tion kinetics, and possess good thermal and mechanical stability,
remaining stable after several adsorption/desorption cycles
(Helwani et al., 2012). Besides all these requirements which should
be fulfilled by a perspective adsorbent material, the requirement of
an acceptable energy cost for the adsorption/desorption cycle
should also be satisfied in practical use. Thus an adsorbent material
needs to provide economically efficient adsorption with a good
working capacity, high purity of captured CO2, high regenerability,
as well as low cost energy requirements. In this work we concen-
trate on equilibrium thermodynamic properties of adsorption
which determine the theoretical limit for the energy cost of CO2
capture, leaving issues related to adsorption kinetics and frame-
work stability for future studies.
A total number of theoretically predicted zeolite framework
types is enormously large (Pophale et al., 2011) compared to pre-
sently known 225 zeolite frameworks (Baerlocher et al., 2007). In
this work we consider only known IZA zeolite structures, noting
that only few of them are so far industrially commercialized
(Čejka et al., 2007). With varying composition of Si and Al atoms
we screen each of IZA zeolite frameworks with 8 different Si:Al
ratios (2, 3, 5, 7, 10, 20, 40 and all silica structures), resulting with
1800 structures in total.
2.2. Energy expenses in CCS process
Flue gas produced in power plants is often a mixture of nitro-
gen, carbon dioxide, water and other gases. Partial pressure (con-
centration) of some components can vary, but frequently the
composition of flue gas is as follows: 70–75% N2, 10–15% CO2,
8–10% H2O, 3–4% O2, with traces of SOx, NOx and other compounds
(Bhown and Freeman, 2011; Feron, 2010). Flue gases are normally
at atmospheric pressure (1 bar), but the temperature can vary from
30° up to a 100 °C (303–373 K). Following previous works (Lin
et al., 2012; Huck et al., 2014), we in this paper assume a flue
gas as a mixture of nitrogen and carbon dioxide in a molar ratio
85:15, and temperature 40 °C.
Among the three parts of CCS, the separation and capture pro-
cess of carbon dioxide from flue gas mixtures is the most expensive
(Metz et al., 2005; Bhown and Freeman, 2011). While it can be dif-
ficult to affect the cost of transport and storage, there can exist
good possibilities to significantly reduce the cost of capture by a
proper choice of adsorbent.
Following previous works, (Lin et al., 2012; Huck et al., 2014)
we distinguish three energy components needed to arrange a full
adsorption-desorption cycle in a combined pressure–temperature
swing capture process: (1) energy to heat the material to the des-
orption temperature; (2) energy to supply the heat of desorption
(equal to the minus enthalpy of adsorption); (3) energy required
to pressurize captured CO2 to 150 bar. We modified approach
accepted in the previous works by providing a more realistic com-
putation of energy required to perform the compression part by
considering separately ranges of pressure below and above 1 atm
and taking into account the degree of purity of captured CO2 as
well as considering a multistage compression train.
The first two parts of the energy requirements represent ther-
mal energy (Q), which can be obtained in a power plant diverting
steam from a turbine. Since not the whole thermal energy is con-
verted to the output mechanical work, the parasitic load on the
power plant caused by diverting the steam can be evaluated by
multiplication of the thermal energy by the efficiency of turbine
(e) and Carnot efficiency (g) (Lin et al., 2012). The total parasitic
energy (Ep ) will be then
Ep ¼ egQ thermal þ W comp: þ W v acuum ð1Þ
where W v acuum is the vacuum work to create a low pressure for the
desorption process, W comp is the compression work to pressurize
captured CO2 ; e is the efficiency of turbine (taken to be equal to
0.75). Carnot efficiency (g) is determined by the temperature ratio:
T ads
g¼1 ð2Þ
T des
where T ads and T des denote the adsorption and desorption tempera-
tures, respectively.
The thermal work (thermal energy expenses) is determined by
the temperature difference and amount of the adsorbed gases (CO2
and N2)


cp msorbent ðT des  T ads Þ þ DnCO2 DhCO2 þ DnN2 DhN2
Q thermal ¼ ð3Þ
mCO2
where cp and msorbent are the heat capacity and mass of the sorbent,
respectively; DhCO2 and DhN2 are the heats of adsorption of the flue
gas components; DnCO2 and DnN2 are the amount (in mol) of the des-
orbed (captured in one adsorption/desorption cycle) gas; mCO2 is the
amount of captured CO2 in kg per 1 kg of adsorbent
(mCO2 ¼ DnCO2  MCO2 ). In practical computation we assume ‘‘aver-
1
age” heat capacity of the zeolite framework C p ¼ 1 kJkg K1
(Hemingway and Robie, 1984; Deem et al., 2009; Čejka et al., 2007)
According to Eqs. (2) and (3), if there is no change in tempera-
ture of a flue gas (DT ¼ T des  T ads ¼ 0 which corresponds to pres-
sure swing adsorption cycle), thermal work ðQ Þ will be equal to
zero. The parasitic energy evaluated in that way depends only on
the vacuum and compression works.
The amount of captured CO2 and N2 (in moles) is determined as
the difference in the load at the adsorption and desorption points
DnCO2 ¼ nads and DnN2 ¼ nads
CO2  nCO2 N2  nN2 ð4Þ
des des
The difference between adsorption and desorption loading
defines the working capacity, that is the amount of CO2 or N2 cap-
tured in a single adsorption–desorption cycle and given usually in
terms of mol of the captured gas per unit mass of the sorbent
framework. The adsorption point is determined by the physical
properties (pressure and temperature) of the flue gases in the tur-
bine outlet. Typically, pads and T ads , are 100 kPa (1 bar) and 40 °C
 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188
respectively (Bhown and Freeman, 2011; Lin et al., 2012) which is
also accepted in this work. Unlike the adsorption point, thermody-
namic conditions at the desorption point can vary. The subsequent
desorption can be achieved by decreasing the pressure (Pressure
Swing Adsorption, or PSA), by increasing the temperature (Temper-
ature Swing Adsorption, or TSA) or by simultaneous change of tem-
perature and pressure which is called hybrid temperature/pressure
swing adsorption (TPSA). Partial contributions from all compo-
nents of the parasitic energy depend on the equilibrium adsorption
load at the adsorption and desorption conditions. Thus for calcula-
tion of the parasitic energy the most important data are the
adsorption isotherms, which together with the isosteric heat of
adsorption provide all necessary data to compute the parasitic
energy.
Regarding the compression work in Eq. (1), we first note that
compression of the desorbed CO2 from the desorption point (which
is typically below the atmospheric pressure) to the atmospheric
pressure (1 bar) does not in fact require energy expenses, and in
further calculations we assume the compression work starting
from 1 bar pressure in cases when the desorption pressure is below
1 bar. Further, the work to compress the captured gas to the stor-
age pressure can be evaluated, in the first approximation, for a
closed system at constant temperature determined in the ideal
gas approximation:
 
RT ads p sion composed of 7 stages with efficiency of heat-exchanger in the
W isothermal
comp: ¼ ln 2
0:85M gas p1
where p1 and p2 are inlet and outlet pressure respectively; Mgas is an
average molar mass of the captured gas (given in kgmol1); R is the
1
gas constant (8.314 Jmol K1) and factor 0.85 takes into account
the average efficiency of the compression process (Lin et al., 2012)
A typical industrial compression is usually an open flow system
with increase of temperature from an inlet pressure to an outlet
pressure, which can be approximated by adiabatic compression:
" c1 #
RT ads c p2 c
W adiabatic ¼ 1
comp:
0:85M gas c  1 p1
where c is the average ratio between molar heat capacities
(c ¼ Cp=C v ). The average molar mass of the captured gas is calcu-
lated according to the expression:
M gas ¼ Pr  MCO2 þ ð1  Pr Þ  MN2
where MCO2 and MN2 are molar masses of CO2 and N2, taken to be 44
and 28 gmol1, respectively; Pr is the purity of captured CO2 given
as
DnCO2
Pr ¼
DnCO2 þ DnN2
An average ratio of heat capacities c is evaluated as:
Cpgas
cgas ¼
C v gas
where
Cpgas ¼ Pr  CpCO2 þ ð1  Pr Þ  CpN2
ð10Þ
C v gas ¼ Pr  C v CO2 þ ð1  Pr Þ  C v N2
In industrial conditions compression is usually decomposed
into several stages of adiabatic compression with subsequent cool-
ing, creating so called single compression train. A typical 6 stage
compression train (Vermeulen, 2011) shown in Fig. 1 requires
around 378 kJ(kg CO2)1 of energy to compress captured CO2 to
123 bar. We have computed the work to compress 1 kg CO2 gas
from 1 bar to 150 bar using a 7 stage compression train shown in
Fig. 1 by black line and using numerical values for pressure–en-
177
thalpy isotherms, C p and C v of gases downloaded from the NIST
database (Linstrom and Mallard, 2005) (summarized and available
from the authors upon request). Thus, real gas properties have
been used in all calculations regarding the compression work.
Assuming that the efficiency of the compression process is 0.85,
amount of work required for compression of captured gas from
1 bar to 150 bar, including 0.2 bar pressure loss and 5% heat-
exchanger loss between subsequent stages, is equal to 406 kJ(kg
CO2)1. For comparison, ideal compression under single-stage
isothermal conditions computed by Eq. (5) is equal to 337 kJ(kg
CO2)1. Assuming instead that the efficiency of isothermal com-
pression process is equal to 70.55% (instead of 85%), W isothermal
comp:
becomes equal to W adiabatic
comp: .
Regardless of which compression method is used, for an ideal
case when the purity of the captured CO2 is equal to 100%, the dif-
ference between any two specific compression pathways is a con-
stant which can be of order of several tens of kJ(kg CO2)1.
Therefore, deviation in the computed compression work from com-
pression work in real industrial applications will be the same for
any adsorbent material and not important solely for comparison
of different zeolite structures in the process of screening zeolites
for gas separation. We argue that for the screening purposes it is
not essential which compression method will be used. We note
further that in all our calculations we assumed adiabatic compres-
ð5Þ
interstage cooling process equal to 95% and a pressure drop of
0.2 bar between subsequent compression stages.
As we already noted, compression of the captured CO2 from the
desorption point (below the atmospheric pressure) to the atmo-
spheric pressure does not require energy expenses. On the other
hand, certain energy is required for generating low pressure (work
against atmospheric pressure to create vacuum). We therefore pro-
pose a model for calculation of the amount of work to create low
(under 1 bar) pressure needed to put adsorbent framework with
ð6Þ
ð7Þ
ð8Þ
ð9Þ
Fig. 1. Schematic presentation of a typical 6 stage-compression of CO2, and
compression train assumed in this work are shown on a pressureenthalpy
diagram. Horizontal lines represent interstage cooling when compressed gas is
cooled back to the inlet temperature (in our study 40  C). Efficiency of the heat
exchanger in interstage cooling was assumed to be 95% and a pressure drop of
0.2 bar between subsequent compression stages is included in the calculations.
Tabulated pressure–enthalpy isotherms are downloaded from the NIST database
(Linstrom and Mallard, 2005).
178 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188

adsorbed CO2 for gas desorption and sorbent regeneration. Given

the fact that for low pressures under 1 bar the gas state is well
described by the ideal gas equation, and that due to low heat
capacity of rarefies gas an isothemic process can be a more appro-
priate way of description, we compute the ”vacuum” work assum-
ing isothermic process and ideal gas equation of state. Denoting p1
as desorption pressure and p0 ¼ 1bar, we have for 1 mol of gas:
Z V1 Z V1
W v acuum ¼ DpðVÞdV ¼ ðp0  pðVÞÞdV
V0 V0
Z V1  
RT ð11Þ
¼ p0  dV
V0 V
V1
¼ p0 ðV 1  V 0 Þ  RT ln
V0
By using V 1 ¼ V 0  p0 =p1 , we have
p0 V 0 p0 V1 Fig. 2. Schematic presentation of adsorption and desorption stages.
W v acuum ¼  p0 V 0  RT ln ð12Þ
p1 V0
Taking p0 V 0 ¼ RT, for vacuum work (for 1 mol of captured gas) In the calculations, adsorbed loadings of each particular gas are
finally we have: determined by the partial pressure of the given gas and adsorption
  isotherms. Desorption loading, however, is predicted by the Ideal
p0 V1
W v acuum ¼ RT  1  RT ln Adsorbed Solution Theory (IAST), where the molar ratio of CO2
p1 V0
  ð13Þ and N2 molecules is assumed to be equal to that in the adsorbed
p0 p0
¼ RT  1  ln phase. By taking desorption pressure (pdes ) as a sum of partial
p1 p1 CO2 and N2 pressures
Taking the efficiency of the vacuum process to be equal to 0.75,
pdes ¼ ppartial
CO2 þ ppartial
N2 ð15Þ
vacuum work for 1 kg of captured gas can be estimated as follows:
  we assume that partial pressures of CO2 and N2 are equal to
RT des pads p
W v acuum ¼  1  ln ads ð14Þ
0:75M gas pdes pdes ppartial
CO2 ¼ xCO2  pdes and ppartial
N2 ¼ xN2  pdes ð16Þ
Thus instead of using only compression work, we introduce two where xCO2 and xN2 are the mole fractions of each gas, given as
separate functions: vacuum work, Eq. (13) is used for flue gas pres- follows:
sures below 1 atmosphere (in general below adsorption pressure)
and compression work, Eq. (5) for pressurization of captured gas nads
CO2 nads
N2
xCO2 ¼ and xN2 ¼ ð17Þ
from atmospheric pressure to 150 bar. nads
CO2 þ nads
N2 nads
CO2 þ nads
N2

2.3. Adsorption – desorption cycle The amount of adsorbed CO2 and N2 molecules remaining in the
sorbent framework under the desorption pressure (ndes des
CO2 and nN2 )

Adsorption and desorption processes are assumed as follows.
Composition of the flue gas is assumed as a mixture of CO2 and
N2 in molar ratio 15:85, respectively. Adsorption takes place at flue
gas temperature (T ads ¼ 313 K and atmospheric pres-
surepads ¼ 100 kPa). During the adsorption (Fig. 2) valves 1 and 2
are kept open, while valve 3 is closed. Due to the different break-
through curves of CO2 and N2 (Dantas et al., 2009; Ye et al.,
2013; Liu et al., 2011) valve 2 is kept open until CO2 molecules
reach this valve, after which it becomes closed. After the adsorbent
reaches the saturation uptake the bed inlet (valve 1) is closed. The
amount of adsorbed CO2 and N2 (nads ads
CO2 and nN2 ) is defined by com-
puted adsorption isotherms of the given gas mixture. A pressuriza-
tion stage used sometimes in PSA is not assumed in this work. We
can argue that pressurizing CO2/N2 mixture would require more
work than for (almost) pure captured CO2.
The next step is the desorption process in which the adsorbed
gas is extracted from the sorbent framework and the sorbent is
regenerated. In the hybrid temperature-pressure swing process
the adsorption bed is first heated to the desorption temperature
(T des ). Upon the heating, adsorbed molecules start to desorb, which
is allowed by connecting the outlet bed (opening valve 3) with the
vacuum pump. The vacuum pump decreases the pressure to the
desorption value P des , and the process of desorption goes until a
thermodynamic equilibrium is reached between the extracted
gas at temperature and pressure, and the remaining gas in the
adsorption bed.
was then computed using the fitting Eq. (25) (see details in the sec-
tion below), for partial pressures of each given gas and applying the
IAST model (Myers and Prausnitz, 1965; Walton and Sholl, 2015;
Simon et al., 2016; Kadoura et al., 2016). To test the validity of
the IAST model versus competitive adsorption of a binary gas mix-
ture, we performed a test simulations on randomly chosen 50 zeo-
lite structures. Only in a few cases the estimated error in parasitic
energy calculated as
jEpðcompetitiv eÞ  EpðIASTÞ j
Eperror ¼  100% ð18Þ
Epðcompetitiv eÞ
was more than 1%, but always below 2.5%.
2.4. Monte Carlo calculation of adsorption isotherms
Adsorption isotherms in this work are computed by the Grand
Canonical Monte Carlo (GCMC) (Stenqvist et al., 2013; Purton
et al., 2013; Martin, 2013; Yiannourakou et al., 2013; Morales
et al., 2013) simulation method as implemented in the package
RASPA (Dubbeldam et al., 2013, 2016; Dubbeldam and Snurr,
2007). We also used Materials Studio Accelrys (Materials Studio,
2013; Akkermans et al., 2013) for preparation of input files and
Music (Gupta et al., 2003; Chempath et al., 2013) software package
for some of production runs. In GCMC simulations, alongside with
Monte Carlo steps moving the gas molecules, steps with insertion
and deletion of a single molecule are performed with probabilities
 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188 179

determined by the given chemical potential (Leach, 2001). In this
work we used the Peng–Robinson equation of state (Peng and
Robinson, 1976) for conversion between gas pressure and fugacity.
The result of a CGMC simulation is the average number of mole-
cules in the simulation cell. Other thermodynamic parameters of
the system, such as adsorption enthalpy, are also determined from
the simulations.
We have carried out CGMC simulations of CO2/N2 gas mixture
in a large number of zeolite-like frameworks available from the
Zeolite data base (Baerlocher et al., 2007). For each structure the
unit cell was repeated periodically several times so that the system
size was always above 24 Å in each direction. Further, in each of
the framework types a part of T-atoms (which by default represent
Si) were substituted in a random manner by Al atoms to have
desirable composition. The position of Al3+ ions in the zeolite
framework are usually unknown, that is why in our study we used
a random method for distribution of Al3+ under the only condition
that Löwenstein’s rule is satisfied. After that, Na+ counter-ions
were added to neutralize the charge. Gas phase molecules (CO2
and N2) were treated in the frame of a grand-canonical ensemble.
Transferable force field for adsorption of CO2, N2, O2 and Ar in zeo-
lites (Vujić and Lyubartsev, 2016), recently developed in our group,
was used in the simulations. This force field was optimized to
reproduce CO2 and N2 (among other gases) experimental adsorp-
tion isotherms of a large set of zeolite structures. Electrostatic
interactions were treated by the Ewald summation method
(Frenkel and Smit, 2002; Leach, 2001; Karasawa and Goddard,
1989). Van der Waals interactions where treated with the 12–6
Lennard-Jones potential. The potential was truncated at the cut-
off distance of 12 Å and long range tail correction was used. Zeolite
framework atoms were fixed at their initial crystallographic
coordinates and sodium ions were allowed to move during the
simulations. CO2 and N2 molecules were treated as flexible. A typ-
ical simulation consisted of 3  105 MC cycles (one MC cycle con-
sists of attempts to move in average each molecule in the system)
where initial one third of cycles was used for equilibration and the
rest of simulation for collecting the averages. We found that the
average number of adsorbed molecules in zeolite unit cell usually
does not change significantly after about 105 MC cycles indicating
that convergence was reached.
In all of the adsorption isotherms, loading of CO2 and N2 mole-
cules in the zeolite framework is given in the unit mmolg1. Since
GCMC simulations provide results as number of guest molecules
per unit cell, we convert it into mmolg1 by using expression
nCO2 Nmolecules=cell Nmolecules=cell  103
nmmol=g ¼ ¼ ¼ ð19Þ
mcell M cell  Da  N A M cell
where Mcell is mass of the simulation cell framework in atomic
units; Da is unified atomic mass (equal to 1:66  1027 kg) and NA
is the Avogadro number (equal to 6:022  1023 mol1).
3. Results and discussion
3.1. Minimization of the parasitic energy
In a typical zeolite framework and partial gas pressure below
100 kPa one can generally distinguish three categories of adsorp-
tion isotherms depending on the value of Henry coefficient (Lin
et al., 2012). In adsorption isotherms of category one (Fig. 3a,
SAO zeolite), the Henry coefficient has the highest value in com-
parison with two other zeolite frameworks, JSR and SAS. Thus,

Fig. 3. (a) Three categories of adsorption isotherms represented by adsorption of CO2 in SAO (red), JSR (blue) and SAS (green) zeolites. (b–d) Plots of the parasitic energy
(hexagons: 313 K blue, 333 K red and 353 K green) and working capacity (stars: 313 K blue, 333 K red and 353 K green) versus desorption pressure (as given by Eq. (15)). For
each graph (b–d), working capacity is given on the secondary, and parasitic energy on the primary y-axes. Si:Al ratio in all three zeolites (SAO, JSR, SAS) is equal to 2. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
180 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188
the adsorption isotherm can be described by the Henry law in a
very low pressure range, after which the loading reaches the satu-
ration point. The amount of captured carbon dioxide in this cate-
gory of adsorption isotherms is usually high and saturation
loading is reached faster than in two other categories of adsorption
isotherms. Regeneration of the sorbent may require in this case
rather high temperatures and/or low pressures, that is why para-
sitic energy can be relatively high, as demonstrated in Fig. 3b.
In the second category of adsorption isotherm, represented by
the JSR zeolite, the amount of adsorbed gas at the adsorption point
(1 bar) is still high, but amount of the adsorbed gas is decreasing
with a pressure drop faster than in the adsorption isotherm of cat-
egory 1. This means that regeneration of the material can be done
at lower temperatures (T des P T ads ) or higher pressures (pdes < pads )
compared with isotherm of category 1, which as a result may have
lower parasitic energy for the same working capacity, as demon-
strated in Fig. 3c.
The adsorption isotherm of category three (Fig. 3a, SAS zeolite)
follows the Henry law in a wide pressure range. The amount of
captured CO2 with respect to the partial CO2 pressure is typically
lower than in the first two examples, and thus the working capac-
ity is low. To reach acceptable working capacity (if possible at all),
a very low desorption pressure or a high desorption temperature is
required, which would lead to a higher value of the parasitic
energy, as shown in Fig. 3d. From these simple observations we
can conclude that the optimal performance in terms of parasitic
energy can be expected for materials showing adsorption iso-
therms of category two.
Another observation from Fig. 3 is that the graphs for parasitic
energy as a function of desorption pressure look similar, since in
the case of PSA the parasitic energy is determined only by the des-
orption pressure and purity of captured CO2. However, working
capacities of these three cases are different (note also different
scale of the axes). We demonstrate also in Fig. 3 that the minimum
of parasitic energy is achieved when the desorption point
approaches the adsorption point (15 kPa CO2, 85 kPa N2 and
313 K, in the present case). At the same conditions, the working
capacity tends to zero, which means that only a minor part of
the adsorbed CO2 become captured. Same conclusion can be made
from the analysis of the parasitic energy and working capacities for
other zeolite structures, examples of 24 of which are presented in
the Supplementary Information, Figs. S1 and S2. As another conse-
quence this leads to a low regenerability of CO2, given as
DnCO2 ndes
CO
Rg ¼ ¼ 1  ads2
ads
nCO2 nCO2
Low regenerability from the perspective of large-scale industrial
applications is not economical, because it is directly related to the
amount of remaining (not captured) CO2. The trend that conditions
leading to the lowest parasitic energy lead to lower working capac-
ity and low regenerability holds in all three presented cases.
The parasitic energy computed within the present approach is
the theoretical minimum implying establishment of the thermody-
namic equilibrium both at the adsorption and at the desorption
points, which requires a certain amount of time depending on
the adsorption kinetics. Too small working capacity would require
too many adsorption-desorption cycles. That is why it seems rea-
sonable to set an acceptable minimum of the working capacity,
and after that define conditions of the parasitic energy minimum
according to this constraint. Moreover, besides setting a minimum
of the working capacity, it is even more important from the envi-
ronmental point of view to set an acceptable minimum for the
regenerability, as well as the purity of captured CO2. In the follow-
ing, we will define a series of the working capacities, starting from
0.25, up to 4.0 mmolg1 and for each given working capacity cal-
culate the minimum of the parasitic energy within the constraints
that purity and regenerability have to be larger than 95 and 90%,
respectively. Theoretical minimum of the parasitic energy, within
these constraints, can be used as a reliable indicator of zeolite per-
formance as a CO2 adsorbent in the CCS process.
3.2. Predicting the adsorption isotherms of CO2 and N2
To reduce the time for calculation of the adsorption isotherms
in GCMC simulations, we have developed a simple Langmuir-like
model which expresses the adsorption load as a function of gas
pressure and temperature. There are several methods for fitting
data from adsorption isotherms with respect to pressure (Čejka
et al., 2007). According to the commonly used Langmuir model,
amount of adsorbed gas (loading) can be described using single
ði ¼ 1Þ or dual binding site ði ¼ 2Þ Langmuir isotherm
X
2
Kic
ni ¼ ni;mono ð21Þ
i¼1
1 þ Kic
where ni is loading of flue gas component at concentration
ðc ¼ p=RTÞ; ni;mono is the saturation loading (called also monolayer
capacity); and K i is the adsorption coefficient, related also to the
adsorption Henry law constant and adsorption free energy.
Previous works (Lin et al., 2012; Hasan et al., 2013) have used
two states Langmuir model to describe adsorption loading. Here
we have employed both, a single site Langmuir model for struc-
tures which show this type of adsorption isotherms, as well as dual
site for other structures. Furthermore, in contrast to previous stud-
ies we complemented the Langmuir adsorption model by a tem-
perature dependence of the monolayer capacity.
For a constant temperature we describe adsorption load of CO2
as a function of pressure by
X i
2
nimono kCO2 pCO2
CO2 ¼
nads ð22Þ
i
i¼1 1 þ kCO2 pCO2
i
where kCO2 is adsorption Henry coefficient, nimono is the monolayer
capacity (saturation loading), and pCO2 is the partial pressure of car-
bon dioxide.
For each adsorption isotherm, the monolayer capacity and
Henry coefficient can be obtained by fitting the computed data
points to the expression (22). For a temperature dependency of
the Henry coefficient, we used a known relationship relating the
latter to the excess molar Gibbs free energy (chemical potential
ð20Þ
l) in the limit of low concentration:
 l
kCO2 ¼ c  exp  ð23Þ
RT
where c and l are fitting parameters.
There are a number of different flexible functions which we
tested for evaluation of dependency of saturation capacity with
respect to temperature, and in the end a simple exponential form
similar to that used for the Henry coefficient was found to provide
good results for various categories of adsorption isotherms
 
b
nmono ¼ a  exp ð24Þ
T
where a and b are fitting parameters. Since the first fitting parame-
ter ðaÞ has the unit of mmol=g, it can be interpreted as a monolayer
(saturation) capacity of material at infinite temperature. Physical
meaning of the parameter b can be interpreted then as a chemical
potential (divided by the gas constant R) corresponding to a satu-
rated state of the adsorbed monolayer.
Combining Eqs. (22)–(24), a final expression for the single site
loading nðp; TÞ function can be presented as follows:
 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188 181

 
l
b c exp  RT pCO2 an analytical approach from the fitted data can be found in the
nCO2 ðpCO2 ; TÞ ¼ a exp
l ð25Þ
T 1 þ c exp  RT pCO2 Supplementary Information.
Examples of fitting simulation adsorption isotherm of CO2 by
In cases when single site Langmuir equation did not provide a using Eq. (25) for the three categories of adsorption isotherms
good fitting of the adsorption isotherms, a dual-site Langmuir are shown in Fig. 4. Fitting lines show generally a very good agree-
model was used with two additional fitting parameters (b and l0 ):
0
ment with the simulation points in the whole considered range of
2 0  3 pressures and temperatures. Some deviations between fitted and

b l  l0
exp  exp bT  RT simulation results can be seen for adsorption isotherms of category
n00CO2 ¼ acpCO2 4 T
RT 
l þ
l0  5 ð26Þ
1 þ c exp  RT pCO2 1 þ c exp  RT pCO2 one (zeolites showing a large Henry coefficient value). Although
some errors in the calculated parasitic energy with the use of fitted
where n00CO2 (as a function of pCO2 and T) indicates that the dual site isotherms thus can appear, they would be noticeable mostly for
low desorption pressures, much below 2 kPa, which are of less
Langmuir equation is used.
interest because of large parasitic energy corresponding to such
To determine whether we should use a single or a dual site
desorption points due to large vacuum work. From our experience,
Langmuir model we compared the errors of both models:
most zeolites have shown the minimum of parasitic energy for
N  2
1X nj  nsim;j capturing at least 1 mmol/g of CO2 at partial CO2 desorption pres-
erri ¼ ð27Þ sures above 1 kPa. Nonetheless, these deviations in predicted par-
N j¼1 nsim;j
asitic energy appears only for zeolites with a large Henry
coefficient, while in other cases Eq. (25) provides a good agreement
where erri is the error of dual or single Langmuir model, N is num-
ber of data points included, nj is loading predicted using dual or sin- between GCMC simulations and fitted results.
Eq. (25) can be used not only for fitting of simulated adsorption
gle model and nsim;j is the gas loading obtained directly from
isotherms, Fig. 4, but also for analyses based on experimental data.
molecular simulation. We have used the single site expression in
An example of fitting experimental adsorption isotherms of CO2 in
cases when dual site fitting did not provide better than 5% improve-
ment compared to the single site model.
In all considered cases, N2 adsorption isotherms were found to
be of category 3 (Henry-like). That is why the nitrogen loading as a
function of N2 partial pressure was described by the Henry law
equation

nN2 ðpN2 ; TÞ ¼ kN2  pN2 ð28Þ

where kN2 is the Henry coefficient of nitrogen adsorption, pN2 is par-

tial pressure of nitrogen, and nN2 is loading of nitrogen at adsorption
or desorption point. As in the case of CO2 adsorption, here we
implemented the temperature dependency of kN2 in the form of
 
0 T
kN2 ¼ kN2 exp  ð29Þ
dN2

where kN2 ¼ 1 mmolg1 kPa1 is a constant ensuring the correct

0

units and being the same for all zeolite structures, and dN2 is a fit-
ting parameter. Thus, loading of nitrogen at any temperature and
partial N2 pressure below 85 kPa is predicted with only two fitting
Fig. 5. An example of fitting experimental (Ohlin et al., 2013) adsorption isotherms
parameters.
of CO2 in Na-ZSM-5, measured at 308, 323, 358 and 393 K. The fitting lines were
An example of evaluation of the fitting parameters of the single- obtained with fitting parameters in Eq. (25): a ¼ 5:0  102 [mmolg1],
site model for NES zeolite, and evaluation of the parasitic energy by b ¼ 1234:39 [K], c ¼ 5:0  107 [kPa1], l ¼ 25:65 [kJmol1].

Fig. 4. Examples of fitting simulation adsorption isotherm of CO2 using the proposed model, for the three categories of adsorption isotherms. Representative zeolites have the
following framework code: JOZ, NES and SAS. Si:Al ratio in all three cases were around 2. For JOZ zeolite a dual site adsorption isotherm is used, were for other two structures
a single site isotherm was used instead. Markers: GCMC simulation results, lines: fitting according to Eq. (25).
182 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188
Na-ZSM-5 shown in Fig. 5 demonstrates almost perfect matching
to the experimentally measured data.
Besides the given example, we also tested the fitting model on
experimental data from other works (Moura et al., 2015; Cheung
and Hedin, 2014). In overall the fitting model was found to be very
well applicable. The fitted adsorption isotherms together with the
heat of adsorption, measured in experiments, can also be used for
evaluation of the parasitic energy. This can be used as a further val-
idation of the adsorbents which were found to be efficient from the
computer screening point of view.
3.3. Working capacity and purity of captured CO2
The first step in the process of screening zeolite frameworks is
to make a selection of zeolite structures based on a required work-
ing capacity. Theoretically the maximal working capacity achiev-
able for a given structure is equal to the amount of adsorbed gas
at the adsorption point. Since the vacuum work given in Eq. (14)
exponentially increases with respect to decrease in desorption
pressure, the total parasitic energy related to the maximal working
capacity becomes significantly high. Thus, in the process of selec-
tion of potentially good CO2 adsorbents, working capacity is an
important parameter determining on the one hand the amount
of the captured gas, and on the other hand strongly affecting the
parasitic energy. A screening of zeolite structures is made for work-
ing capacities of CO2 in steps of 0.25 mmolg1, Fig. 6.
Our computations show that a rather high percentage of zeolite
structures within a given Si:Al ratio are able to capture at least
0.25 mmolg1 of CO2. As the working capacity increases, it inevita-
bly leads to decrease in the number of zeolites that can achieve this
working capacity. From Fig. 6 a conclusion can be drawn, that the
higher the Si:Al ratio is, the lower is the number of zeolite struc-
tures for a given working capacity. One can also see in Fig. 6 that
for intermediate range of working capacities (0:5 6 DnCO2 6
1:0 mmolg1), zeolites with Si:Al = 7 have the highest number of
structures. Structures with Si:Al = 5 performs better for working
capacity in the range of 1.25–1.75 mmolg1. For even higher
working capacity, zeolites with Si:Al = 3 and less performs best.
In other words, the higher the aluminum content, the higher the
maximal working capacity which can be achieved with a given
structure. Thus, if we need to achieve a working capacity of
4 mmolg1, the only choice would be Si:Al = 2, since there are four
zeolite structures with Si:Al = 2 which can achieve this working
capacity.
Another important factor to consider in CCS is the purity of cap-
tured CO2. If the purity of captured CO2 at certain working condi-
tions (desorption pressure and temperature) is poor the process
Fig. 6. Number of zeolite structures within a given Si:Al ratio, which are able to
capture a certain amount of CO2. The total number of zeolites within each Si:Al ratio
is equal to 225.
can not be considered as efficient, even though parasitic energy
might have a low value at that specific point.
In the next selection we have analyzed available zeolite struc-
tures with respect to the minimum of the parasitic energy at a
given working capacity (1, 2 and 3 mmolg1) and the purity of
the captured CO2, and displayed the statistics on Fig. 7a. Data for
other working capacities are given in Figs. S3–S7 of the Supple-
mentary Information. Each point in Fig. 7a represents the mini-
mum of the parasitic energy obtained by a given zeolite at
condition of the given working capacity, relative to the purity of
captured CO2 when the desorption conditions correspond to the
minimum of the parasitic energy. As the required working capacity
increases (from 1 up to 3 mmolg1), the number of zeolite struc-
tures is decreasing. Another observation is that purity of captured
CO2 at the minimum of parasitic energy for a certain working
capacity is increasing as the Si:Al ratio decreases. Therefore, con-
sidering parasitic energy with two additional constraints, working
capacity and the purity of captured CO2, zeolites with Si:Al ratio of
2 perform best.
In the following we accept the purity of 95% (meaning that 95%
of captured gas is CO2 and only 5% of the N2) to be an acceptable
level.
3.4. Parasitic energy and regenerability of CO2
One more important aspect in the process of defining the opti-
mal CO2 capture working condition is to include regenerability as
an additional constraint. Regenerability of CO2, calculated accord-
ing to Eq. (20), is a direct measure of the amount CO2 left not cap-
tured, and from the environmental point of view it is of primary
importance to have a good regenerability. Here we assume the
minimum of Rg being equal to 90%, which means that at least
90% of CO2 from flue gases has to be captured.
Fig. 7b presents the minimum of the parasitic energy for each
specific zeolite structure as a function of the corresponding Rg at
a given minimum value of the working capacity. Additional plots
can be found in the Supplementary Information, Figs. S8–S12.
The evaluated minimum of Ep clearly increases with increase in
Rg . The lowest unconstrained parasitic energy within the consid-
ered model is around 540 kJ(kg CO2)1. However, the minimum
of Ep within constraints DnCO2 P 2:0 mmolg1 and Rg P 90% is
about 770 kJ(kg CO2)1, which is ca. 230 kJ(kg CO2)1 higher than
the theoretical minimum.
Fig. 8 shows histograms of the number of zeolite structures
with respect to P r of captured CO2 for zeolites with working capac-
ity above 1.5 mmolg1 (a detailed procedure of the selection of
structures and extended data for other working capacities are pre-
sented in Section S6, Figs. S13–S28 of the Supplementary Informa-
tion). The number of zeolites within each selection satisfying also
criteria Rg 6 90% is given on each plot. The previously made selec-
tion of zeolite structures shown in Fig. 6 changes in such a way that
the number of zeolites within a given Si:Al ratio decreases with
each additional constraint (Pr and Rg ). To demonstrate our reason-
ing we give Si:Al = 5 as an example, Fig. 8. The number of zeolites
within this particular Si:Al ratio that are able to capture at least
1.5 mmolg1 of CO2 is equal to 122. 23 of them satisfy condition
for the purity Pr 6 95%. Yet, there are only five zeolites having
Emin:
p 6 1000 kJ(kg CO2)1 and Pr P 95%, and none if condition
for the regenerability Rg 6 90% is also included.
To illustrate further the relation between Rg and Pr for the cor-
responding minimum of Ep at a specified working capacity, we pre-
sent statistics in Fig. 9. Data for other minimal working capacities
are given in the Supplementary Information, Figs. S29–S44. Each
specific point on a graph is colored according to the actual value
of parasitic energy (Emin:
p ) computed at the only constraint of work-
 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188 183

Fig. 7. (A) Minimum of parasitic energy (Ep ) in relation to purity (P r ) of captured CO2 for three working capacities. For more data refer to SI related with this article. (B) The
minimum of parasitic energy in relation to regenerability of CO2 for three working capacities is presented.

Fig. 8. Histogram of distribution of zeolite structures within a certain Si:Al ratio versus purity of captured CO2, for DnCO2 P 1:5 mmolg1 and Rg P 90%. Value for P r relates to
the working condition (pdes ; T des ) at which Ep have a minimum for a given working capacity. Dark blue areas correspond to the number of zeolites within additional condition
Ep 6 1000 kJ(kg CO2)1.

ing capacity. The minimum of parasitic energy for a given working
capacity does not necessarily provide acceptable values of Rg and
P r for CO2 capture. Inevitably, increased requirements of regenera-
bility and purity of captured CO2 decrease substantially the num-
ber of suitable structures.
3.5. Procedure for evaluation of the most efficient adsorbents for
industrial applications
In the previous subsections we evaluated, for each structure, the
minimum of Ep under constraint of a given working capacity, and
then excluded structures which, for the desorption conditions cor-
responding to the minimum of parasitic energy did not provide
requirements for the minimal purity of captured CO2 and/or regen-
erability. Still, for many structures the last two criteria can be sat-
isfied by choosing other desorption conditions with expense of the
parasitic energy. From the point of view of industrial applications,
all four criteria are important: working capacity, regenerability,
purity of captured CO2 and finally the parasitic energy. We there-
fore made selection of the most efficient adsorbents according to
the following procedure. For each zeolite structure, we generated
about 105 desorption conditions, considering pdes from 0.1 kPa to
184 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188

Fig. 9. Relation between regenerability and purity of CO2 for DnCO2 P 1:5 mmolg1. Within a given Si:Al ratio, each scatter point represents one zeolite structure. Points are
colored according to the corresponding value of the minimum parasitic energy for a given working capacity (see secondary axis).

a point at which DnCO2 tends to zero (maximum 100 kPa), and T des
in a slightly wider range from 313 up to 473 K (previously given
from 313 to 413 K). Among all the desorption points for each zeo-
lite framework, we selected only those that satisfied given require-
ments in terms of DnCO2 ; P r and Rg . Then the parasitic energy was
calculated for the remaining set of desorption points and the min-
imum of Ep was determined.
An example of two-dimensional maps showing dependences of
the parasitic energy, working capacity, regenerability and purity on
the desorption pressure and temperature for a FAU zeolite is
shown in Fig. 10. One can see that fulfilling of the condition for a
low parasitic energy requires lower desorption temperatures while
conditions for high working capacity, regenerability and purity
require higher desorption temperatures. Furthermore, the lines Fig. 11. Number of zeolite structures within given Si:Al ratio, able to capture a
with equal parasitic energy in Fig. 10a reach maximum tempera- certain amount of CO2 satisfying requirements for the purity P r P 95% and
ture in the desorption pressure range 10–20 kPa. This mean that regenerability Rg P 90%.
the desorption conditions providing minimum parasitic energy
under specified constraint conditions correspond to the partial Rg P 90% for different values of working capacity is shown in
pressure which is similar to that at the adsorption point, and Fig. 11. One can note considerable decrease of the number of struc-
higher temperature. This observation, made for the case of FAU tures compared with data in Fig. 6 where conditions for the purity
zeolite, holds also for other structures showing good adsorption and regenerability were not set.
properties: the minimum of parasitic energy determined in this The minimum of the parasitic energy for CCS in the current
approach tends towards higher desorption temperature and higher state of art industrial applications gives an estimate of 1060 kJ
pressure, ultimately to TSA. per kg CO2 (Lin et al., 2012; Huck et al., 2014; Berger and Bhown,
The total number of zeolite frameworks within each Si:Al ratio 2013). Previous works reported possibility of many hundreds
that satisfied conditions for the purity Pr P 95% and regenerability structures within this energy penalty. The number of zeolites with

Fig. 10. Two-dimensional maps of parasitic energy (A), working capacity (B), purity (C) and regenerability (D) as functions of the desorption temperature and desorption
pressure, for CO2 capture in FAU zeolite with Si:Al = 2.
 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188
Fig. 12. Zeolite structures which provide the lowest parasitic energy under
requirements for the minimal working capacity (3.5 mmolg1), purity 95% and
regenerability 90%. Exact values of the parasitic energy, working capacity, purity
and regenerability for these four zeolites are given in Table 1. Na+ ions are omitted.
Figure created using VMD (Humphrey et al., 1996; Stone et al., 2001; Varshney
et al., 1994; Sanner et al., 1995) (IRR, JSR) and Materials Studio Accelrys (Materials
Studio, 2013) (RWY, NPT) software.
different Si:Al ratios, which exhibits the minimum of Ep 6 1060 kJ
(kg CO2)1 under conditions Pr P 95%; Rg P 90%, is given in the
Figs. S45–S60 of the Supplementary Information. In comparison
to the total number of zeolites within a given Si:Al ratio, only a
small portion is capable of capturing CO2 under the specified
conditions.
All 225 known zeolite framework types, each with several com-
positions (resulting with 1800 structures in total), have been tested
in GCMC simulations to determine parameters for computation of
adsorption isotherms and parasitic energy. According to our find-
ings, the number of the most efficient structures is ultimately less
than 1% of the total number of structures within each Si:Al ratio.
Examples of zeolite structures which have shown the lowest para-
sitic energy under the given constraints of the working capacity,
purity and regenerability are presented in Fig. 12, whereas the
exact values of the desorption conditions and parameters
DnCO2 ; Pr and Rg are summarized in Table 1.
Surprisingly, a commonly used FAU zeolite is not found in the
top of the most optimal structures since its lowest parasitic energy
is 1070 kJ per kg of captured CO2 for DnCO2 ¼ 3 mmolg1 ;
Table 1
Zeolite structures heaving the lowest parasitic energy for working capacity of at least 3.5 mmolg1 CO2, purity 95% and regenerability 90%.
Zeolite framework Si:Al ratio Ep
[kJ(kg CO2)1]
RWY 2 856.4
JSR 2 875.4
IRR 2 915.5
NPT 5 955.9
185
Pr ¼ 97% and Rg ¼ 91%. The reason is because FAU zeolite shows
isotherm of category 1 for CO2 adsorption, meaning that although
the amount of adsorbed CO2 at the adsorption conditions is high, it
is rather difficult and energy demanding to regenerate the material
after the adsorption, and thus met required conditions in working
capacity and regenerability, as presented in Fig. 10. The parasitic
energy value associated with the three examples on Fig. 12 is in
the range  860—960 kJ(kg CO2)1, which in complement to previ-
ously reported values (Lin et al., 2012; Berger and Bhown, 2013)
gives a realistic estimate of the minimal energy penalty in the
CCS process.
4. Conclusion
In this work we have developed a new method for thermody-
namic evaluation of the theoretical minimum of the energy
expenses in the CCS process under realistic industrial conditions.
The method provides a fast evaluation of the amount of captured
CO2 and N2, as well as the energetically optimal adsorption and
desorption conditions under specified requirements for the work-
ing capacity, regenerability of he sorbent framework and purity
of captured CO2. The minimum of thermodynamic energy expenses
in a hybrid pressure–temperature swing CO2 capture process (or in
a pure pressure or temperature swing process) thus can be evalu-
ated within the given constraints. Mechanical and thermal stability
of a zeolite framework, energy losses of non-thermodynamics ori-
gin, as well as kinetics of the adsorption and sorbent regeneration
were out of the scope of this work.
For a fast evaluation of adsorption isotherms in a temperature
range of interest we have developed a fitting model with four
parameters for CO2 (or six using the dual site Langmuir model)
and two parameters for N2, which can be optimized from a small
number of Grand Canonical Monte Carlo calculations. The model
was tested on a large number of zeolite structures by comparing
fitted data with detailed computation of adsorption isotherms by
Grand Canonical Monte Carlo simulations. It can be applied also
for fitting of experimental adsorption data enabling evaluation of
the energy expenses in CCS using data from laboratory experimen-
tal measurements.
Within our approach, it is possible to evaluate the theoretical
limit of the energy expenses for each specific material which can
be used as an adsorbent in the CCS process, under specified in
advance requirements for the working capacity, regenerability
and purity, and use the proposed method for screening of various
structures for the most efficient adsorbent. For this purpose we
performed adsorption calculations for 225 known zeolite frame-
work types varying composition in each of them, and created a
short list of the structures with could be potentially good adsor-
bents, which can be used for further analysis. It follows from our
observations that when conditions for the working capacity, regen-
erability and purity are set, the optimal from the equilibrium ther-
modynamics point of view desorption conditions tend towards
higher desorption temperature and higher pressure, ultimately to
TSA.
T des pdes DnCO2 Pr Rg
[K] [kPa] [mmolg1] [%] [%]
440 14.30 4.39 96.05 90.06
472 10.10 4.41 96.91 90.02
479 10.05 4.17 97.93 90.04
492 20.10 3.55 95.79 90.00
186 B. Vujic, A.P. Lyubartsev / Chemical Engineering Science 174 (2017) 174–188
The development method can be further extended for studies of
water effect on CO2 capture by generalizing the model to ternary
mixtures CO2/N2/H2O, to other sorbent materials such as metallo-
organic frameworks, or for separation of other gas mixtures such
as CO2/CH4.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.ces.2017.09.006.
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