Materials Today: Proceedings xxx (xxxx) xxx

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Simulation of CO2 capture for amine impregnated activated

carbon - palm kernel shell (AC-PKS) adsorbent in pressure swing
adsorption (PSA) using Aspen Adsorption
N.H. Sabri a,⇑, N.H.A. Rani a, N.F. Mohamad a, N.A.S. Mohd Muhsen a, M.S. Md Zaini b
a
School of Engineering Studies (Chemical) UiTM Cawangan Johor Kampus Pasir Gudang, Malaysia
b
School of Engineering Studies (Chemical) UiTM Cawangan Terengganu Kampus Bukit Besi, Malaysia

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

Article history: The creation of energy from fossil fuel burning results in the release of greenhouse gaseous and carbon
Available online xxxx dioxide (CO2) emissions. Carbon capture and storage (CCS) is one of the mature strategies to capture
CO2 through an adsorption process. For the removal of contaminants from contaminated gas and liquid
Keywords: streams, activated carbon (AC) specifically palm kernel shell (PKS) has been acknowledged as one of
Aspen Adsorption the most efficient and helpful adsorbents in the adsorption process since its features include a large
Pressure swing adsorption active surface area, high adsorption capacity, well-developed porous structures, and strong mechanical
Activated carbon
qualities. Modification with imidazoles (IMs) in amine impregnated AC-PKS will improve the initial
Impregnation
and working CO2 adsorption capacities and decrease the heat of adsorption. Recent adsorption technol-
ogy used is pressure swing adsorption (PSA) due to easier operation, lower energy consumption and cost-
effective for CO2 capture. This PSA have been used in industry and laboratory for separation, purification
of gas mixtures. The PSA with modified amine-based adsorbent is rarely highlighted in previous studied.
Hence, this study will focus on the simulation of CO2 adsorption for amine-impregnated AC-PKS adsor-
bent in the PSA system using Aspen Adsorption. The one-bed adsorption column is modelled and ana-
lyzed using extended Langmuir 1 equation. The product purity in terms of bed concentration, product
composition in bed, and bed gas inventory are evaluated. Feed concentration is the main factor contribut-
ing to adsorption performance. Maximum and minimum values need to be set and feed concentration
(20%-80%) of CO2 and H2. The performance of the adsorption process is maintained at a high level, includ-
ing its adsorption capacity, when the higher feed concentration is used. Higher adsorption capacity helps
to reduce the total cost of CO2 capture and secure the sustainability of the environment concurrently.
Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 2nd Regional Congress
on Membrane Technology 2022 in Conjunction with the 16th AUN/SEED-NET Regional Conference on
Environmental Engineering 2022.

1. Introduction
Without rapid action, the Intergovernmental Panel on Climate
Change (IPCC) predicts that global temperatures will rise by
1.5 °C by 2030, 2 °C by 2050, and even more beyond that.
Significant sea level rise, floods, wildfires, harsh weather, famine,
and the destruction of animal habitat are just a few of the negative
effects that will result from such rises. [1] Since the start of
industrialization, the usage of fossil fuels has surged in response
⇑ Corresponding author.
E-mail address: hazwanisabri@uitm.edu.my (N.H. Sabri).
to the increasing global need for energy. These fuels are burned
to produce carbon dioxide (CO2) and other greenhouse gases, both
of which have an impact on global warming [2]. Such an increase in
temperatures could have catastrophic effects on earthly life. The
effective method of capturing and storing carbon dioxide emis-
sions is called carbon capture and storage (CCS). CO2 is present
in the flue gas that power plants generate in amounts between
12 and 15 percent. Therefore, obtaining high-purity CO2 from flue
gas is crucial for reducing the greenhouse effect and supplying CO2
resource. Over the coming generations, there will be a significant
increase in the need for energy supplies, to meet this need, new
and renewable energy sources must be created. It is possible to

https://doi.org/10.1016/j.matpr.2022.12.206
2214-7853/Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 2nd Regional Congress on Membrane Technology 2022 in Conjunction with the 16th AUN/
SEED-NET Regional Conference on Environmental Engineering 2022.

Please cite this article as: N.H. Sabri, N.H.A. Rani, N.F. Mohamad et al., Simulation of CO2 capture for amine impregnated activated carbon - palm kernel
shell (AC-PKS) adsorbent in pressure swing adsorption (PSA) using Aspen Adsorption, Materials Today: Proceedings, https://doi.org/10.1016/j.
matpr.2022.12.206
N.H. Sabri, N.H.A. Rani, N.F. Mohamad et al.
manufacture a variety of high-value chemicals and fuels using cap-
tured CO2, which would address both the problem of energy supply
and pollution control. Different technologies, including adsorption,
membranes, cryogenic distillation, and adsorption, have been pro-
posed to enrich CO2 in flue gas mixtures [3]. The idea that each gas
liquefies at a certain temperature underlies the cryogenic separa-
tion process. This approach introduces the distillation stage at a
relatively low temperature (103 k) and high pressure (80 bars).
The procedure can be carried out at a higher temperature with
the aid of an increase in operating pressure. Cryogenic distillation,
a relatively established technology compared to the other upgrad-
ing techniques, is frequently used because it can handle large
amounts of biogas with high methane purity (up to 99 percent)
and CO2. Due to the huge number of equipment present, it has
the disadvantages of having high energy requirements and being
ineffective at low flow rates and pressure ranges [4]. Based on
selective permeation, the membrane technology for gas separation
functions. The gases dissolve readily in polymeric materials, and
when a pressure difference develops on either side of the mem-
brane, the gas molecules are transported over the membrane. A
higher coefficient of solubility and coefficient of diffusion means
a faster rate of molecular penetration. H2, H2S, and CO2, which have
relatively tiny molecule sizes, will therefore permeate at a higher
and faster rate than CH4. The adoption of membrane technology
for biogas upgrading has several benefits, including low cost, low
energy penalty, high reliability, and low greenhouse gas emissions.
On the other hand, bulk separation with somewhat low selectivity
is not economically feasible using membrane technology [5]. Addi-
tionally, the effectiveness of the membrane materials has a signif-
icant impact on the separation efficiency. Because the solvent from
the top and the catching process take place along the column, raw
biogas is typically fed to the absorption column at the bottom. At
temperatures approximately 90 °C, the rich acid gas exits the col-
umn through a series of heat exchangers and enters the desorption
column. High processing capacity and removal efficiency are two
characteristics of the absorption technique. The disadvantages of
this method, on the other hand, are the high energy cost associated
with the regeneration process, corrosion issues, and purity issues if
other components are included in the biogas mixture [6]. There are
numerous studies that focus specifically on the pressure swing
adsorption (PSA) technique for upgrading biogas and their
acknowledged parametric research, even though the existing eval-
uations provide a wealth of information on the various technolo-
gies [7]. There are few technologies of CO2 capture by adsorption
other than PSA which are Vacuum Pressure Swing Adsorption
Fig. 1. The design for a single bed Pressure Swing Adsorption (PSA).
2
Materials Today: Proceedings xxx (xxxx) xxx
(VPSA), Temperature Swing Adsorption (TSA), and Vacuum Swing
Adsorption (VSA). PSA and VSA technology have been extensively
investigated for post-combustion CO2 capture at bench and pilot-
scale levels in the search for more environmentally friendly and
cost-effective for CO2 capture strategies of both energy and indus-
trial gasses, such as steam reformer off-gas, natural gas, and coal-
fired power plant flue gas [8,9]. Nowadays, PSA is a sort of green
technology that is widely used, especially as a cheap and energy-
efficient air separation system. According to reports, using acti-
vated carbon for equilibrium separation is superior to using carbon
molecular sieve for kinetic separation since it uses less energy [10].
Hence, in gas separation research has largely concentrated on PSA
from solid adsorbents. Besides, PSA is used especially when the
regeneration process is carried out through a pressure reduction
due to its ease of use and reducing environmental impact and cost
of CO2 capture [11]. In a pressure swing approach, CO2 is adsorbed
at high pressures by a solid sorbent before being desorbed at lower
pressures or under slight vacuum (VPSA). Different sorbents
require different pressure profiles but are typically around
10–30 bar in the adsorption cycle [12]. Highly porous solids such
as AC, which are either commercially available or under develop-
ment through research on material science and engineering are
commonly used in adsorption process [13]. There are a variety of
software packages available to simulate the mathematical model
of PSA which are Fluent, Matlab, Aspen Adsorption and gPROMS.
There were few studies cover on Aspen Adsorption, one of the
examples highlight on the adsorption of methane (CH4) and CO2.
The Langmuir isotherm model was used to determine the isotherm
of a mixed gas containing 55 % CH4 and 45 % CO2 to understand the
PSA adsorption characteristics of the CH4 and CO2 gases. Various
key operating parameters, such as feed flowrate, adsorption pres-
sure and adsorption time were simulated and analyzed. The opti-
mal conditions were found to be an adsorption pressure of 6 bar,
an adsorption time of 250 s and a purity of up to 97.92 % with a
flowrate reducing to 2000 m3/h. [14]. Back then, three cycle config-
uration provides a means to internally recycle parts of the product
and CO2-lean gases to improve the separation efficiency as well as
minimizing energy consumption. The dual-site Langmuir model-
DSL (equation (1)) and a non-isothermal model was used. The lin-
ear driving force model and Ergun equation were utilized to repre-
sent the adsorption equilibrium, mass transfer rate and pressure
drop across the bed respectively [9]. Findings from experimental
runs with predicted results from the commercial Aspen adsorption
software were compared and mutual agreements was obtained.
Higher purity of CO2 can be obtained at 8 kPa, and high recovery
N.H. Sabri, N.H.A. Rani, N.F. Mohamad et al.
of CO2 can be obtained at 5 kPa with specific power consumption
of 0.33 MJ/kg CO2 [9]. Based on past research, the performance
of PSA system with different bed numbers are compared. Using
zeolite 13X as the adsorbent, a two-bed, four-step process is inves-
tigated. The simulation results showed that the recovery and pur-
ity of CO2 exceeded 90 %, and that the process consumed 0.536 MJ
per kilogramme of CO2 while producing 1.27 mol CO2 per kilo-
gramme per hour under ideal conditions [15]. A dual-bed, five-
step VPSA mathematical model was proposed to test the model’s
Fig. 2. Configure B1 Block In Aspen Adsorption (PSA).
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Materials Today: Proceedings xxx (xxxx) xxx
accuracy in real-world situations [16]. Silica gel was used as the
adsorbent in their study, and CO2 obtained a purity of 90.8 percent
but only a recovery of 76.6 percent, while energy consumption and
productivity reached 1.51 MJ
(kg CO2)1 and 2.23 mol CO2
h1-

kg1, respectively. A pilot study to verify the actual performance
of zeolite 13X and CO2 was conducted, as a result (94.8 ± 1)% purity
with a recovery of (89.7 ± 5.6)%, while the energy consumption was
(1.22–2.10）±0.132） MJ
(kg CO2)1 and the productivity was
(1.23–1.98）±0.099 ）mol CO2
h1
kg1 was obtained [17]. The
N.H. Sabri, N.H.A. Rani, N.F. Mohamad et al. Materials Today: Proceedings xxx (xxxx) xxx

most effective adsorption can be achieved whenamine- Table 1

impregnated AC materials is used for CO2 adsorption because the The configuration setting for the equipment.
interaction between acidic CO2 molecules and modified basic Equipment Description Specification
active sites on the surface facilitates CO2 adsorption through the Gas Feed Composition of CO2 in forward 0.2kmol/kmol
formation of covalent bonding [18]. The evaluation of oxidative direction
stress performance of amine-impregnated solid sorbents is exten- Composition of H2 in forward 0.8kmol/kmol
sively studied. Tetraethylenepentamine(TEPA) and Polyethylen- direction
Flowrate 0.05kmol/s
imine (PEI) have found to be the best commercialize polymeric
Pressure 5 bar
amines for CO2 capture, although its breakdown quickly in O2- Gas Valve Active specification 2.0 (Cv)
containing conditions. Based on the findings, TEPA has many active Container for specified Cv 2.9 X 10–4 kmol/
sites or amino functional groups and high boiling point which s.bar
demonstrates good CO2 adsorption [19]. However, TEPA has Container for specified flowrate 0.05kmol/s
Gas Tank Void 1 Tank void volume 0.0011 m3
weaker NAH bonds lowering the regeneration process conditions
Composition CO2 within tank void 0.2 kmol/kmol
such as low temperature and pressure. The impregnation was Composition H2 within tank void 0.8 kmol/kmol
modified by loading sterically deprived amine into activated car- Pressure within tank void 4 bar
bon [20]. It has been shown that adding another amine component Gas Tank Void 2 Tank void volume 0.0011 m3
Composition CO2 within tank void 0.2 kmol/kmol
to amine-functionalized solid sorbents can improve the CO2
Composition H2 within tank void 0.8 kmol/kmol
adsorption capacities [19]. TEPA performance can be stabilized if Pressure within tank void 4 bar
the imidazole (IMs) is added to TEPA because IMs will act as proton Gas Bed Film Model Assumption Solid
acceptor and TEPA will act as electron donating group to imidazole. Specification Isotherm Assumed for Layer Extended
IMs contribute to the higher CO2 adsorption capacity in the amine Langmuir 1
Energy Balance Assumption Isothermal
blended system because it promotes proton diffusion [20]. The
Material Balance Assumption Convection only
study on the PSA system is quietly abundant for the amine impreg- Bed Layer Initial CO2 Mole Fraction Within First 0.2 kmol/kmol
nated activated carbon. Hence, in this study will focus on the sim- Element
ulation of PSA system for AC-PKS adsorbent impregnated with H2 Mole Fraction Within First 0.8 kmol/kmol
Element
TEPA and Ims and the characterization of adsorbent based on
Gas Velocity Within First Element 5 ✕ 10–6 m/s
impregnation ratio. Bed Layer Height Of Ad Sorbent Layer, Hb 350 mm
Specification Internal Diameter of Adsorbent 35 mm
Layer, Db
Bulk Solid Density of Adsorbent 1817.4 kg/m3
RHOs
2. Methodology
Adsorbent Particle Radius, Rp 0.05 m

A single bed Pressure Swing Adsorption (PSA) unit is utilized for

the carbon capture process for CO2 and H2 gases. The software
shows the details specifications that will be set up as the model
Aspen Adsorption is used for modeling and simulation due to pro-
inputs.
cess suitability and equipment availability. AC-PKS adsorbent
The feed concentration of the CO2 and H2 is manipulated to
impregnated with TEPA and Ims is used in the gas bed column
study the PSA performances. Different sets of feed concentration
and for the feed gas, carbon dioxide CO2, and hydrogen H2 were
as shown in Table 2 are used to run the simulation and the effects
used as the component list in Aspen Adsorption.
towards the purity and the adsorption capacity is analyzed. For the
Fig. 1 shows a single bed PSA. The bed (B1 block) was filled with
configuration of the gas bed, there are few operating parameters
impregnated activated carbon with TEPA and IMs with the bulk
set and extended Langmuir 1 is employed for the isotherm
density of 1817.4 kg/m3. The feed gas, containing feed concentra-
assumed for the layer. The parameter for the adsorbent layer is
tion of 15 % of CO2 and 85 % of H2 was supplied into a single adsor-
set constant for each different binary gas mixture and constant
bent bed and adjusted by gas tank void (TD1 block) to maintain the
mass transfer coefficient (MTC) and the isotherm parameter (IP)
flow rate. Three (3) pneumatic switch valves were installed in the
is varied for different gas.
feed line, waste line and product line to control the system flow
The performance of PSA is evaluated based on product compo-
during operation. The gas tank void (TD2 block) is located at the
sition in adsorption bed, holdup gas in bed and bed bulk concentra-
product line to easier measure the result of the adsorption process.
tion. The comparison between purity using equation (1) with feed
The cycle organizer is used to control the opening and closing of
concentration is done to interpret the effect of those parameter
the valve present in the system. The opening and closing of the
toward adsorption performance.
valves are program scheduled to allow the system to behave
dynamically. The cyclic time is set until 800 s and the adsorption total mol CO2 in extracted product
CO2 purity ¼  100 ð1Þ
time is determined by the breakthrough simulation. The cycle sim- total mol CO2 and N2 in extracted product
ulations were carried out at a pressure of 5 bar, a temperature of
298 K, a feed flow rate of 0.05kmol/s. Fig. 2 shows the specification
of the column in the PSA model. It has only one vertical adsorbent
layer within the bed with the same packed adsorbent molecular
sieve 5A. B1 block is configure in detail based on its energy balance, Table 2
mass transfer rate, kinetic model, and isotherm method. The The feed concentration of CO2 and H2.
extended Langmuir 1, linear driving force model, and convection Run CO2 (%) H2 (%)
equation were used to represent the adsorption equilibrium, mass
1 15 % 85 %
transfer rate, and pressure drop across the bed, respectively, using 2 20 % 80 %
an isothermal model [14]. Mixed-gas adsorption equilibrium mod- 3 30 % 70 %
els are frequently anticipated based on pure component isotherms 4 40 % 60 %
utilizing the ideal adsorbed solution theory or competitive Lang- 5 50 % 50 %
muir models for more effective process simulations [14]. Table 1
4
N.H. Sabri, N.H.A. Rani, N.F. Mohamad et al.
3. Result and discussion
The graph product composition versus time is taken inside the
bed column after running the simulation for every different feed
concentration. Five different feed concentrations are used to
observe the composition of the gases which are CO2 (represent
by blue line) and H2 (represent by green line) in bed over the time.
In this experiment, CO2 needs to be adsorbed in the bed [21], there-
fore varies feed concentration needs to be observed which one
gives the highest product composition of CO2 in bed over the time.
The breakthrough curve shown in the Fig. 3(a) to (e), the CO2 is ini-
tially started to be adsorbed at 200 s–400 s. From Fig. 3(e), the
breakthrough time is 200 s meanwhile Fig. 3(a) the breakthrough
time is 400 s. The breakthrough curves become steeper and swiftly
reach the breakthrough as feed concentration rises. This is due to
Fig. 3. (a) 15% of CO2 and 85% of H2. (b) 20% of CO2 and 80% of H2. (c) 30% of CO2 and 70% of H2. (d) 40% of CO2 and 60% of H2. (e) 50% of CO2 and 50% of H2.
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Materials Today: Proceedings xxx (xxxx) xxx
the adsorbate’s long enough residence time in the column, which
allows for the achievement of adsorption equilibrium at high feed
concentration. This implies that the amount of time the adsorbate
and adsorbent are in contact is reduced, resulting in early break-
through [22]. Other than that, The H2 composition in bed start to
reduce when the CO2 being absorbed. This is because when a gas
mixture containing CO2 and H2 is introduced into the adsorbent
bed at high pressure, most of the components are pushed to the
surface and bonded to the adsorbent by the adsorption force.
Lighter gas components, including H2, are less strongly coupled
to adsorbent materials and flow through the adsorbent bed with-
out interacting much, whereas the adsorbed gas components con-
centrate on the adsorbent surface [23]. From Fig. 3(a) to (e), the
final CO2 composition is greater than the H2 composition at the
800 s and the increasing trending of the CO2 composition being
N.H. Sabri, N.H.A. Rani, N.F. Mohamad et al.
absorbed in bed can be seen from the beginning of the PSA opera-
tion till the end. The increasing value of the composition of the CO2
in the gas bed column, indicates the adsorbent practically working
[24]. Besides, Fig. 3(e) shows the highest amount of final CO2 com-
position absorbed in gas bed meanwhile Fig. 3(a) show the lowest
amount of final CO2 composition absorbed in gas bed. The final CO2
compositions is dependent on the feed concentration.
Fig. 4 shows the changing trend in bulk concentration for CO2
and H2 as a function of bed distance within the 800 s. As shown
Fig. 4(a), (b), (c), 4(d) and 4(e) for H2, the bulk concentration for
H2 have the same trend in all the runs for the simulation with dif-
ferent feed concentrations. Meanwhile, the bulk concentration of
CO2 change in term of bed distance based on the different feed con-
centration. Bulk concentration of CO2 created maximum peak at
optimal bed distance. At the maximum peak, the adsorption capac-
Fig. 4. (a) 15% of CO2 and 85% of H2. (b) 20% of CO2 and 80% of H2. (c) 30% of CO2 and 70% of H2. (d) 40% of CO2 and 60% of H2. (e) 50% of CO2 and 50% of H2.
6
Materials Today: Proceedings xxx (xxxx) xxx
ity of the adsorbent is highest due to the higher bulk concentration
of the CO2 in the adsorbent. Based on Fig. 4(a), 4(b), 4(c), 4(d) and 4
(e), the maximum peak is increasing with the feed concentration of
CO2. For Fig. 4(a), the bulk concentration of CO2 the distance of
maximum peak formed is higher whereas Fig. 4(e), shows the
shorter distance for the maximum peak to formed. The maximum
peak at bed distance shows that the optimal location of highest
adsorption occurred, after CO2 is fully adsorb the trend of bulk con-
centration goes down shows that the adsorbent is saturated with
CO2 and the adsorption process slowly stop [25].
The purity versus feed concentration of CO2 gas plot is con-
structed from the simulation data obtained for CO2 composition
in the gas bed column and applying the purity formula as shown
in the Fig. 5. The feed concentration is manipulated to evaluate
performance of PSA. The higher the value for the purity of CO2
N.H. Sabri, N.H.A. Rani, N.F. Mohamad et al.
Fig. 5. Purity vs Feed Concentration of CO2.
gas, its proven that the PSA unit can effectively adsorbs high
amount of CO2 [26]. According to Fig. 5, the purity is increase with
the increasing feed concentration and reach constant purity at 40 %
of CO2 feed concentration. Although higher feed concentration can
be fed in, the adsorbent optimally adsorbs up to certain amount of
CO2 and the remaining are remove out from the adsorption bed.
The maximum purity can achieve for this PSA system with AC-
PKS as adsorbent is 98 % which is higher as compared to zeolite
and silica gel adsorbent [3].
4. Conclusion
The modelling and simulation for a single bed PSA unit with
the adsorbent AC-PKS impregnated with TEPA and IMs is suc-
cessfully carried out in the Aspen Adsorption software. The feed
gas used is the mixture of a binary gas which are CO2, and H2.
During simulation, the adsorption capacity of the adsorbent in
gas bed column is measured by evaluating the performance of
PSA in term of product composition in adsorption bed, holdup
gas in bed and bed bulk concentration. The higher the amount
of CO2 is being adsorbed, the higher the efficiency of the PSA
unit performances to separate the binary gas mixture which is
CO2 and H2. According to the findings from the simulation, the
low CO2 feed concentration led to difficulty to achieve higher
purity. Hence, the optimal feed concentration is determined to
increase the purity of CO2. The optimal feed concentration is
40 % CO2 and 60 % H2. The higher feed concentration shortens
the bed distance and accelerate the breakthrough time since
the adsorption mainly occurred at the beginning stage of the
process. The highest purity of CO2 obtained is approximately
98 % with the highest feed concentration which is 40 % of CO2.
The purity of CO2 with a single bed PSA with AC-PKS and
impregnated with TEPA and IMs is higher as compared to other
adsorbent such as zeolite and silica gel. In conclusion, feed con-
centration affects the purity of adsorb material and also increase
the speed of adsorption process with the help of good adsorbent
material AC-PKS and impregnated with TEPA and IMs.
Data availability
Data will be made available on request.
Declaration of Competing Interest
The authors declare the following financial interests/personal
relationships which may be considered as potential competing
7
Materials Today: Proceedings xxx (xxxx) xxx
interests: [Nurul Hazwani Binti Sabri reports financial support
was provided by MARA University of Technology - Pasir Gudang
Campus. Nurul Hazwani Binti Sabri reports a relationship with
MARA University of Technology - Pasir Gudang Campus that
includes: employment and funding grants. there is no other activi-
ties conflicted with this submitted work].
Acknowledgements
The highest appreciation specially addressed to Universiti
Teknologi Mara (UiTM) Cawangan Johor Malaysia for granted the
full financial support for this research with the grant number:
600-TNCPI 5/3/DDN (01) (006/2021).
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