December 2010, Volume 1, No.

2
International Journal of Chemical and Environmental Engineering

CO2 Separation using Modified MCM-41 in PSA

System
N.H Alias a; K.S.N. Kamaruddin; I.Bhatti
Department of Gas Engineering,
Faculty of Petroleum & Renewable Energy Engineering,
Universiti Teknologi Malaysia, Johor, Malaysia.
a
Corresponding author:nurhashimahalias@gmail.com

Abstract
Prevention of excessive amounts of CO2 is one of the main serious environmental problems facing humanity, due to its significant
impact on climate change. Today, CO2 from natural gas is normally separated with alkanoamines in aqueous solution. Nevertheless, this
liquid amine based processes pose operating difficulties due to equipments corrosion, solvent leakage, large equipment size and high
regeneration energy. Adsorption is recognized as an economically attractive and proficient separation method toward substituting
conventional CO2 separation processes as it is predicted to offer low requirements of energy for porous adsorbent regeneration while able
to combine high productivity and selectivity. In this study, mesoporous material MCM-41 was synthesized and modified using
monoethanolamine, MEA directly to the surface of the solid sorbents. The MCM-41 structures and physical properties were
characterized using powder X-Ray Diffraction (XRD), BET surface analysis on nitrogen adsorption at 77K and thermogravimetric
analysis. CO2 adsorption and desorption measurement were determined using of Pressure Swing Adsorption (PSA) system. It was found
that incorporation of MEA into MCM-41 showed better result compared to unmodified MCM-41 in term of improvement in physical and
chemical properties, high CO2 adsorption capacity and modified adsorbents were ease of regeneration.

Keywords: Carbon dioxide, Adsorption, Pressure swing adsorption, Aminated MCM-41

1. Introduction
The production and successive release of CO2 into
the atmosphere, no matter the sources, is becoming an
increasingly serious issue with respect to its affect on
global warming [1]. As one of the more familiar
greenhouse gases, carbon dioxide has the ability to
warm the planet by trapping energy radiated from the
surface of the earth that would otherwise be released to
space. One of the major sources of carbon dioxide
release into the atmosphere is through the burning of
fossil fuels for energy, which unfortunately makes it
ubiquitous.
Absorption on liquid amine base processes has
been commercially applied to separate natural gas with
medium to high CO2 concentration, but due to the high
energy requirements and corrosion problems [2],
adsorption technology which is less energy intensive is
more highly desirable to be developed [3]. Even though
the adsorption method attracted many researchers
attention for the capture of CO2, conventional
adsorbents, such as activated carbons, silica gels,
carbon molecular sieve and zeolite were not effective to
adsorb CO2 from its mixtures. In addition, although
these adsorbents can reversibly adsorb a large quantity
of CO2 at ambient temperature, the selectivity over
water is poor besides its adsorption capacity diminishes
quickly at elevated temperature. Hence these materials
should have a porous structure in which the interior has
a basic organic compound which will help in the
retention of CO2 molecules. This should facilitate both
physical and chemical adsorption.
Various porous supports impregnated with liquid
amines have been reported [4-6]. Amine functional
groups are useful for CO2 removal because of their
ability to form ammonium carbamates and carbonates
reversibly at moderate temperature [7]. In addition, the
impregnation of organic amines into porous adsorbents
is a promising approach for CO2 sorbents combining
good capacity and selectivity at ambient temperature.
Pressure swing adsorption (PSA) has earned
widespread acceptance and is being used extensively
for gas purification and separation [3]. Modified and
new cycles in PSA have been proposed to improve a
performance of CO2 separation or to separate a binary
gas mixture simultaneously ever since the first
introduction of a basic 4-step PSA cycle by Skarstrom
in 1960. The basic 4-step cycle has been most
intensively studied theoretically and experimentally for
production of a light component [8]. PSA cycles and
 conditions can be manipulated to meet a variety of
demand requirements, for example to provide high
purity or high recovery, or to minimize power
requirements as the situation demands [9-11]. Like all
adsorption separation processes, PSA involve two basic
steps:
 During adsorption certain components of a
gaseous mixture are selectively adsorbed on a
porous solid. This operation, performed at
relatively high pressure by contacting the
gaseous mixture with the adsorbent bed. This
produces a gas stream enriched in the less
strongly adsorbed component of the feed
mixture. After certain determined operation
time, the adsorbing bed comes near to
saturated and regeneration is needed.
 During regeneration or desorption step the
adsorbed components are released from the
solid by lowering their gas phase partial
pressures inside the column. After this
operation, the adsorbent is ready to be
employed in a further cycle. The product gases
produced from regeneration is enriched in the
more strongly adsorbed components of the
feed.
Aaron and co-workers [12] claimed that, the cycle
used of PSA technology for removal of CO2 from air
are inappropriate for recovery of CO2 from stream
which contain >3 % CO2, although PSA was a well
known technology for this process.
Former research works, have found that amine-
modified silica materials able to improve CO2
adsorption [13-16]. Specifically, the purpose of this
work is to develop adsorbents presenting a tailored
surface functionality for improved CO2 adsorption. The
novel adsorbents were synthesized by impregnating
monoethanolamine (MEA) on MCM-41. This MEA
modified MCM-41 is predicted to impart high
adsorption capacity for CO2 as compared to the parent
MCM-41. MCM-41, known as one of the M41S
mesoporous molecular sieve family, was initially
discovered by Mobil Corp. in 1992 [17]. It consists of
uniform, hexagonal arrays of mesopores with pore
openings between 1.5 and 10 nm. Both the impregnated
amine in the MCM-41 pore and the adsorbed CO2 can
accommodate by this sizes of pore. The greatest
advantage of MCM-41 is their extremely large surface
areas and hence their potential for adsorption processes.
In this present work also, CO2 separation using
modified and unmodified MCM-41 in PSA was
investigated. As the essential parameters in PSA that
affect the separation are the adsorption and desorption
behavior, the experimental and theoretical studies under
these conditions were performed.
86
2. Materials and Methods
2.1Synthesis of MCM-41
Mesoporous MCM-41 adsorbent was synthesized
following the standard methods in literatures [18-22].
Synthesizing of MCM-41 began by dissolving 2.4 g
cetyltrimethylammonium bromide (CTAB) in 120 g
deionised water and the solution is stirred to form
homogeneous and clear solution. Then 8ml ammonium
hydroxide was added into the solution before it was
stirred for 5 min. Subsequently, 10 ml of tetraethyl
orthosilicate (TEOS) was added into the solution. The
solution was stirred overnight. Then, the solution was
transfered into a container and put in oven at 100ºC for
2 days. After that, pH control was done at 10.2 each
day until stable (about 2 to 3 days). The product was
filtered and washed with deionised water. Finally, the
sample was spread onto a plate and dried in oven at
100ºC for 24 hours before calcination was performed at
550°C for 5 hours.
2.2 Preparation of Amined MCM-41
MEA was introduced into MCM-41 by wet
impregnation. In wet impregnation method the amine
solutions was prepared in methanol solution with 25 wt
% concentration loading. The MCM-41 was wetted
with methanol in 10 minutes in solid liquid ratio of 1:4
before it were then air-dried. Subsequently, amine
solution was prepared in methanol by adding 25 wt %
MEA concentration for period of 15 minutes. The
prepared amine solution was agitated with prepared
wetted MCM-41 for a period 4 hours in ambient
temperature, keeping the solid liquid ratio at 1:4.
Finally, the modified MCM-41 beads were allowed to
dry in air overnight.
2.3 Adsorbent Characterization
The prepared adsorbents were characterized to
attain a distinct comparison between modified and
parent MCM-41, using significant techniques of
characterization. Crystalline structures studies were
performed via Siemens D5000 X-Ray Diffractometer at
a wave length 1.5418 Å of CuKα radiations. In order to
evaluate the adsorbents structural integrity before and
after modification, the adsorbents were analyzed in a 2
range of 1.5 - 10.The BET surface area analysis of
adsorbents were characterized using Micromeritics
BET surface area analyzer (Model No. ASAP 2000).
Analysis on thermal stability and dehydration
characteristics of the adsorbents were performed by
Perkin Elmer TGA 7, Thermogravimetric analyzer. The
weighted samples about 20 mg were held in small
platinum pan before it were heated at a heating rate of
10° C/min in an atmosphere of air from room
temperature to 900° C.
 2.4 CO2 Adsorption
The performance of the adsorbents on CO2
separation was further examined in the PSA column.
The CO2 separation from CO2-N2 gas mixtures using
PSA was done by feeding 24.89 % of CO2 and 75.11 %
of N2 into a two-column PSA unit. A schematic
diagram of the two columns PSA unit was assembled to
carry out the conventional 4-steps Skarstrom cycle as
illustrated in Fig 1 and Fig 2. The two stainless steel
closed end columns were packed with a known amount
of adsorbent. The column dimensions were: 1.5 cm (0.6
in) internal diameter and 15 cm (5.9 in) long. The 3 mm
(1/8 in) stainless steel tubing was used to connect both
columns. The flow rates of feed were monitored by gas
flow controllers. The column pressures were monitored
by two pressure gauges (PG) and other PSA operating
conditions were tabulated in table 1. Finally, a gas
chromatograph analyzer (Agilent 3000A Micro GC)
was used to analyze the product stream concentrations.
2.5 CO2 Desorption
Adsorbing gases at a higher level of pressure and
regenerating the saturated adsorbent at a lower level of
pressure is the basic principle of PSA process. Thus, in
order for PSA process to be constantly continued, the
adsorption must be reversible. Same setup as shown in
Fig. 1 was used to perform CO2 desorption. Firstly, the
first column was fed with CO2 and N2 mixture at
pressure 1.5 atm. The feed flow rate of this gas mixture
was kept at 400 cm3/ min. After certain determined
period of time when this column was started to saturate
with CO2, the column pressure was released to the
atmospheric. Both columns were finally purged with a
stream of nitrogen at pressure of 1 atm. The gas flow
rate of the purging stream was maintained at 300 cm3/
min.

5 2 3 4 5 6 7 8 9 10

2-Theta - Scale

Figure.3 XRD patterns of MCM-41 and MCM-41/MEA 25wt%. A

Figure 1. The schematic diagram of two columns PSA experimental unit
Figure 2. Skarstrom cycle in PSA.
Table 1. Psa Dual Columns Operating Conditions
Bed length (mm)
Volume of adsorbent (cm3)
Mass of zeolite in each
column
Feed flow rate (cm3/min)
Pressure (Padsorption atm)
3. Result and Discussion 
3.1, Characterization 
Characterization of the representative adsorbents
namely bare MCM-41 and MCM-41 impregnated with
MEA solution of concentration 25wt% was studied.
The effect of amine loading on the structural properties
of MCM-41 matrix was investigated by obtaining XRD
patterns before and after amine modification. The XRD
measurement of the adsorbents showed that long-range
order of the materials was retained after the
modification (see figure 3.1). The small angle X-ray
diffraction profiles of the MEA grafted mesoporous
MCM-41 occur at same angle in comparison with
parent MCM-41 indicating no change of mesoporous
matrix after amine grafting [23]; yet there is decrease
in intensities of peaks indicating amine grafting.
There was a slight reduction in the BET surface
area of the MCM-41 after the incorporation of MEA
was observed which indicates that the amine molecules
have occupied the pore volume (table 3.1). These
results provide a correlation with the pore filing effect
40 mm
of MEA and also confirm that MEA was impregnated
7.10 cm3 in the MCM-41 pores. This trend is also reported in
7.0445 g literature [24].
400 Table 2. Specific Surface Area Of Adsorbents.
Adsorbent MCM-41 MCM-41/MEA
1.5 atm
BET area (m2/g) 729 720

87
 TGA data for MCM-41 before and after MCM-
41 modification are shown in Fig 3. It can be observed
that in case of MCM-41, there is a presence of only a
single continuous weight loss ‘step’ from room
temperature to 900 °C. This has stabilized with a total
weight loss of about 3.25%. A major weight loss is
observed at 70 °C, which may be attributed to
desorption of physically adsorbed water in MCM-41
can give higher CO2 adsorption capacity. This indicates
that an excellent CO2 separation from N2 and CO2
mixture perhaps can be improved using MEA modified
MCM-41 adsorbent with higher surface area.
ADSORPTION of MCM-41
100.000

N2 Concentration at Exit
90.000
beads. In the case of MEA modified MCM-41, it has 80.000
been observed that there are a total of three distinct

Stream %
70.000
weight loss steps at 70, 220 and 300 °C. Since MEA
60.000
has a boiling point of 170.8 °C, the second weight loss
between 140 and 220 °C may attributed to volatilization 50.000
and degradation of MEA. A total weight loss of 41.16% 0 2 Number
4 of Half
6 Cycle8 10
is observed which is about 37.91% higher than the MCM-41 Pure
unmodified MCM-41. From all the characterization
Figure 5. Comparison of N2 concentration at exit stream in
done on the synthesized adsorbents, it can be observed MCM-41 and MCM-41/MEA 25wt% adsorption at cyclic
that, MEA was well impregnated into MCM-41. state for run 1-10 (half cycle).
Table 3. Adsorption Analysis Of Adsorbents.
Run Adsorption Adsorption
(Half Cycle) MCM-41/MEA MCM-41 Pure
1. 99.910 94.794
2. 99.878 93.605
3. 99.789 89.447
4. 99.649 89.360
5. 99.651 91.448
6. 99.654 91.083
7. 99.660 91.468
8. 99.633 81.619
9. 99.613 81.555
Figure 4 Representative TG profile of the adsorbents. 10. 99.609 81.943
3.2 CO2 Adsorption
Deviation of N2 concentration with different cycle
Deviation of N2 concentration with different cycle
is shown in Fig. 6. It compares N2 concentration at exits
is shown in Fig. 6. It compares N2 concentration at exits
stream between MCM-41 and modified MCM-41/MEA
stream between MCM-41 and modified MCM-41/MEA
during CO2 desorption. The trend shows N2
during CO2 desorption. The trend shows N2
concentration at exit stream for both adsorbents
concentration at exit stream for both adsorbents
decreased as the number of half cycle increased. MCM-
decreased as the number of half cycle increased. MCM-
41/MEA gives higher percentage of N2, 99.601 %
41/MEA gives higher percentage of N2, 99.601 %
compared to unmodified MCM-41 which is 80.440 %
compared to unmodified MCM-41 which is 80.440 %
after run of 5 cycles. It can be concluded that MCM-41
after run of 5 cycles. It can be concluded that MCM-41
modified MEA not only can offer good CO2 adsorption
Results of the adsorption studies on parent MCM-
capacity, but it also can easily be desorbed at ambient
41 and MEA modified MCM-41 conducted using two-
temperature and yet can easily be maintained and
columns PSA unit at 298K are grafted in Fig 5. From
regenerated even after 5 cycle operation. Based on good
the result, it shows that N2 concentration decreased
CO2 adsorption and desorption behaviour that modified
gradually as the number of cycle increased. This trend
MCM-41/MEA (25 wt %) is the best candidate to be
shows that CO2 concentration in the mixture increased
used as adsorbent in reversible PSA in order to obtain
as the prolonged cyclic was employed. Tabulated table
excellent CO2 separation.
3 compares the N2 concentration at exit stream on both Table 4. Desorption analysis of adsorbents.
MCM-41 and MEA modified MCM-41. It shows that Run Desorption Desorption
N2 concentration retain at exit stream after 5 cycles (Half Cycle) MCM-41/MEA MCM-41 Pure
adsorption (10 number of half cycles) using MCM- 1. 99.898 94.869
2. 99.908 93.158
41/MEA 99.609 % which is higher compared to
3. 99.710 89.596
MCM-41, 81.943 %. Hence, it can be concluded 4. 99.643 89.542
that, more CO2 was adsorbed using MCM-41/MEA 5. 99.642 91.143
adsorbent. This confirmed that modification on MCM- 6. 99.645 91.131
41 offered more CO2 affinity sites to be exposed for 7. 99.639 91.113
chemisorptions. Even though MCM-41/MEA adsorbent 8. 99.629 81.116
9. 99.619 82.630
used in this study provided lower surface area 10. 99.601 80.440
compared to unmodified MCM-41, the adsorbent still
88

DESORPTION of MCM-41
100.000
N2 Concentration at Exit
90.000
80.000
Stream %
70.000
60.000
50.000
0 5 10
Number of Half Cycle
"MCM-41 Pure"
MCM-41/MEA 25WT%
Figure 6. Comparison of N2 concentration at exit stream in
MCM-41 and MCM-41/MEA 25wt% desorption at cyclic state
for run 1-10 (half cycle).
4. Conclusion
A dual PSA process for CO2 adsorption and
desorption were successfully studied using both MCM-
41 and modified MCM-41/MEA (25 wt%). Based on
the study, pure MCM-41 and MCM-41/MEA showed
preferential CO2 adsorption at ambient temperature and
pressure up to 1.5 bar. Therefore it can be concluded
that modified MCM-41/MEA (25 wt %) adsorbent with
lower surface area was able to give very high CO2
adsorption capacity compared to unmodified MCM-41
even after 5 cycles operation. Moreover, desorption by
N2 purging at 1 atm using MCM-41/MEA also gave
higher percentage of CO2 desorption compared to
unmodified MCM-41, therefore it is reversible and ease
to be regenerated at ambient temperature. In
conclusion, although modification on MCM-41 will
reduce the surface area of adsorbents, by employed a
good method of modification the adsorbent can offers
more CO2 affinity site to increase the CO2 adsorption
capacity. The synthesized adsorbent in this study,
modified MCM-41 with 25 wt % loading of MEA,
demonstrates a better adsorption and desorption
behavior for CO2 separation and could be one of good
candidates to replace conventional CO2 separator using
liquid amine based absorption.
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