Microporous and Mesoporous Materials 121 (2009) 84–89

Contents lists available at ScienceDirect

Microporous and Mesoporous Materials

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

Amine loaded zeolites for carbon dioxide capture: Amine loading and
adsorption studies
Ravikrishna Chatti, Amit K. Bansiwal, Jayashri A. Thote, Vivek Kumar, Pravin Jadhav,
Satish K. Lokhande, Rajesh B. Biniwale, Nitin K. Labhsetwar, Sadhana S. Rayalu *
National Environmental Engineering Research Institute, Nagpur, India

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

Article history: Novel functionalised adsorbents have been synthesized by immobilization of various amines on synthetic
Received 3 June 2007 zeolite 13X. Various primary and secondary amines namely monoethanolamine (MEA), ethylenediamine
Received in revised form 17 December 2008 (ED) and isopropanol amine (IPA) have been immobilized on zeolite 13X. Quantitative estimations of the
Accepted 8 January 2009
amine loadings were undertaken using different analytical techniques namely titrimetric, total organic
Available online 18 January 2009
carbon and gas chromatography analysis. Fairly good correlation was obtained for amine loadings esti-
mated using the three techniques. Effect of various parameters like effect of solvent, shaking time, syn-
Keywords:
thesis temperature, and wetting of pellets prior to amine loadings was also studied. The results revealed
Zeolite
CO2 Capture
that maximum loading was achieved for methanol-mediated synthesis conducted using previously wet-
Amine immobilization ted pellets at room temperature and with 15 min of shaking time. Preliminary attempts have also been
Quantitative estimations made to determine the CO2 adsorption capacities of these newly developed materials. The adsorption
capacities obtained were 16.01 mg/g for unmodified zeolite 13X and 19.98, and 22.78 mg/g for zeolite
modified with monoethanol amine, and isopropanol amine.
Ó 2009 Published by Elsevier Inc.

1. Introduction is an increasing need to capture the CO2 emitted from coal-fired

With the advent of the industrial revolution, man has improved
the utilization of his resources and this has increased industrial
activity to new heights. However, this has also become the starting
point for serious problems in the environment like the greenhouse
effect leading to the global warming. The major greenhouse gases
are carbon dioxide, chlorofluorocarbons (CFCs), N2O methane, etc.
However, the major culprit is carbon dioxide. CO2 acts as a blan-
ket to trap the infrared radiations coming from the earth’s atmo-
sphere, thus resulting in warming of the earth’s surface and rise
in surface temperature. The ambient concentration of CO2 has in-
creased from about 280 ppm from the pre-industrial revolution
period (early 1900) to the current levels of 380 ppm [1]. The devel-
opment of suitable carbon capture and sequestration technologies
is the solution to tackle this global phenomenon. Research is going
on to develop feasible options for CO2 sequestration. Post combus-
tion CO2 capture has emerged as one of the significant options to-
wards reducing the anthropogenic CO2 emissions. CO2 capture has
become a key issue to be addressed by the scientific community.
Research in this key area is going on at a global scale and the exist-
ing CO2 capture methods are amine based absorption, membrane
based separation, adsorption and cryogenic separation [2]. There
power plants, operating at temperatures around 120 °C–150 °C. A
wide range of adsorbent materials have been investigated like zeo-
lites, activated carbons, pillared clays and metal oxides [3–15].
However, in these conventional adsorbents, physical adsorption
plays an important role in the adsorption of CO2. It has been re-
ported by Siriwardene et al. that CO2 adsorption capacity of zeo-
lites 13X, 4A and activated carbon was about 160, 135 and
110 mg/g adsorbent, respectively, at 25 °C and 1 atm CO2 partial
pressure. The adsorption capacity decreases rapidly with increas-
ing temperature. Thus, these adsorbents need to be modified so
as to facilitate chemical adsorption in these adsorbents. Thus, there
is an increasing demand to design highly selective adsorbents,
which can operate at such high temperatures [16].
The objective of the present work was to synthesize novel adsor-
bents by immobilization of different primary and secondary amines
on zeolite 13X matrix. This immobilization is expected to impart
high adsorption capacity for CO2 as compared to the bare zeolite
13X matrix. The adsorbent support chosen was zeolite 13X as it
has a pore size of 10 Å. This pore size can accommodate both the
immobilized amines in the zeolite pore and the adsorbed CO2.
2. Experimental

* Corresponding author. Tel./fax: +91 712 2247828. The amines used in the synthesis of the adsorbents were analyt-
E-mail address: s_rayalu@neeri.res.in (S.S. Rayalu). ical grade monoethanolamine, ethylene diamine and isopropanol

1387-1811/$ - see front matter Ó 2009 Published by Elsevier Inc.

doi:10.1016/j.micromeso.2009.01.007
 R. Chatti et al. / Microporous and Mesoporous Materials 121 (2009) 84–89 85

amine, respectively. These amines were procured from E-Merck,
India and were used as such without any further purification.
The solvent used was HPLC grade methanol and was procured from
Qualigens, India. Zeolite 13X in the form of pellets of approxi-
mately 1.5 mm was procured from E-Merck, India. GC grade nitro-
gen (99.995%) and ultra pure helium (99.999%) were obtained from
Chemito Technologies, Nashik, India for conducting the adsorption
studies. Carbon dioxide (99.99%) was procured from M/s. Sirin
Gases, Nagpur, India.
2.1. Synthesis of the adsorbents
The synthesis of amine-immobilized adsorbents was carried out
using three different routes. These routes differ in the manner the
amine was immobilized on the zeolite. Scheme 1 represents a
schematic description of the different routes of synthesis under-
taken during the experiments. Details of the synthesis of the differ-
ent adsorbents are given below.
2.1.1. Amine immobilization in aqueous media
Aqueous solutions of monoethanolamine, ethylene diamine and
isopropanol amine were added to appropriate amount of zeolite
13X in a solid–liquid ratio of 1:2 and the mixture was agitated
on a rotary shaker for different periods of time (15 min, 2 h and
4 h). Three different amine concentrations were studied with ini-
tial concentration as 25, 50 and 80 wt%. Amine solution was sepa-
rated from the zeolite after shaking by decantation and the
samples were air dried overnight.
2.1.2. Amine immobilization in organic solvent
The immobilization of amines was also carried out through
alcoholic solutions of amine. The amine solutions with different
concentrations corresponding to 25, 50 and 80 wt% loadings were
prepared in methanol. The zeolite was wetted with methanol prior
to agitation with amine solution by agitating zeolite 13X beads and
methanol in solid liquid ratio of 1:2 for a period of 10 min in two
stages. The wetted beads were then air-dried and then agitated
with alcoholic amine solution for a period of 15 min and 4 h on a
rotary shaker at ambient temperature, keeping the solid liquid
ratio at 1:2. The amine solution was decanted and stored for
analysis whereas the zeolite beads were allowed to dry in air
overnight.
2.1.3. Immobilization of amines through reflux method
The synthesis of amine loaded zeolite 13X was also carried out
by refluxing the zeolite beads with respective amine solution at
70 °C to study the effect of temperature on amine loadings. In a
typical synthesis, 15 g of zeolite 13X beads were refluxed with
30 ml of alcoholic amine solution in a round bottom flask equipped
with a water condenser. After 2 h reflux, the amine solution was
decanted and the beads were allowed to dry in air overnight.
2.2. Characterization of the synthesized adsorbents
The synthesized adsorbents were characterized to obtain a use-
ful comparison with the unmodified zeolite 13X, using different
characterization techniques. Powder X-ray diffraction studies were
carried out using a Phillips Analytical Xpert diffractometer with
monochromatic Cu Ka radiation (k = 1.54 Å). To assess the struc-
tural integrity of the adsorbents after the incorporation of the
different amines, the adsorbents were analyzed in a 2h range of
5°–60°.
A Micromeritics BET surface area analyzer (Model No. ASAP
2020) equipped with TriStar 3000 V6.03-A software was utilized
to determine the N2 BET surface area and pore volume of the syn-
thesized adsorbents. To avoid the possibility of degradation of the
incorporated amine, evacuation of the adsorbents was carried out
at 90 °C and then subjected to N2 adsorption at liquid nitrogen
temperature (196 °C). The BET surface area and pore volume
was determined by using the single point adsorption method.
Thermogravimetric analysis was performed using a Rigaku-
TAS-200 apparatus to study the thermal stability and dehydration
characteristics of the synthesized adsorbents. About 20 mg of the
sample was kept in TG pan and was heated at a heating rate
5 °C/min in an atmosphere of air. The samples were heated from
room temperature to 500 °C. The weight loss and the rate of weight
loss (dTG = dW/dT) was recorded.
The IR spectra of the synthesized materials were recorded using
a Perkin–Elmer spectrometer using the KBr pellet technique. The
samples were analyzed in the wavelength region 4000–400 cm1.
2.3. Determination of amine loadings
The weight percent loadings of the different amines on the
13X zeolite beads were calculated from the difference in amine con-

Different routes for immobilization of amines in the zeolite matrix

• Immobilization in aqueous • Immobilization in organic • Immobilization was

media.
• Different intervals of stirring
maintained.
• Study was conducted using
three different amine
concentrations.
solvent, methanol. done by the reflux
• Wetting of zeolite was done method.
prior to immobilization.
• Refluxed at a
• Pre-treatment improved
amine immobilization. temperature of 700C.
• Study was conducted using
• Method does not yield
three different amine
higher amine loading
concentrations.
as compared to the
solvent immobilization
method.

Scheme 1. Different routes for immobilization of amines in the zeolite matrix.

86 R. Chatti et al. / Microporous and Mesoporous Materials 121 (2009) 84–89
centrations before and after treating with zeolite. The concentra-
tions of amines were determined using titrimetric analysis, gas
chromatography (GC) and total organic carbon estimation (TOC).
The amine concentrations in initial and final amine solutions
were determined by titrimetric analysis using the procedure de-
scribed by Seaman and Allen [17]. According to this procedure,
mixture of amine solution and glacial acetic acid was titrated
against a 0.1 N solution of perchloric acid in glacial acetic acid.
From the difference of amine content in the initial amine solution
(i.e., before loading) and residual amine solution (obtained after
loading) the amount of amine loaded on zeolite 13X was calculated
in terms of weight percent of amine incorporated in the zeolite
matrix.
Gas chromatographic determinations of amines were carried
out with GC with Flame Ionization Detector (FID) (Perkin–Elmer,
Model Autosystem). A chromosorb stainless steel column, 80–
100 mesh provided by PCI services was used in the analysis. GC
grade nitrogen was used as the carrier gas for the analysis. A cali-
bration plot for each amine was plotted by injecting a known vol-
ume (1 ll) of different molar solutions of amine. After plotting the
calibration plot between the peak area and the molarity of the dif-
ferent amine solutions, the experimental solutions of each amine
solution were injected and the estimation of the residual amine
content was done.
Since amine is a source of organic carbon, TOC technique can be
used indirectly to estimate the amine content. The TOC of the ini-
tial and residual amine solutions were analyzed using a non-dis-
persive infrared (NDIR) TOC analyzer (Thermo Electron
Corporation, Model 1200).
2.4. CO2 adsorption studies
CO2 adsorption was studied using breakthrough adsorption
curves method. The breakthrough curve (BTC) method was chosen
as the evaluation method due to its usefulness in comparing the
various adsorbents. In addition, this method offers a distinct
advantage to determine the dynamic adsorption capacity and to
evaluate in practical way, i.e., packed bed, flow system etc. which
can be very useful to study a simulated flue gas stream as de-
scribed in our previous studies [18,19]. The experimental set up
had mass flow controllers (Aalborg, USA), adsorption column
(diameter = 1 cm; height = 30 cm), sample selector valve (Valco,
Fig. 1. XRD pattern of 50% MEA/13X.
USA), 1 ml sample loop and gas chromatograph (Chemito Technol-
ogies; Model GC 7610). In a typical evaluation protocol, 10 g dry
adsorbent was pretreated in He gas flow (20 ml/min) at 140 °C
for 6 h, cooled to adsorption temperature (75 °C) and contacted
with 15 vol% CO2 gas in He balance at a total flow rate of 52 ml/
min. The outlet was continuously monitored using GC–TCD fitted
with Porapak-Q column and the adsorption breakthrough point
was determined. Commercial zeolite 13X (E-Merck, India) and zeo-
lite 13X modified with MEA and IPA at 50 wt% initial amine con-
centration were studied for CO2 adsorption.
3. Results and discussion
3.1. Characterization
Characterization of the representative adsorbents namely bare
zeolite 13X and zeolite 13X contacted with MEA solution of con-
centration 50 wt% was studied. The effect of amine loading on
the structural properties of zeolite matrix was investigated by
obtaining XRD patterns before and after amine incorporation. From
the x-ray diffractogram of monoethanolamine (MEA) incorporated
zeolite presented in Fig. 1 it can be observed that the structural
integrity of zeolite 13X is maintained even after the incorporation
of the amine.
Reduction in the BET surface area and pore volume of the zeo-
lite 13X after the incorporation of MEA was observed which indi-
cates that the amine molecules have occupied the pore volume
(Table 1). These results provide a correlation with the pore filing
effect of MEA and also confirm that MEA was immobilized in the
zeolite pores. This trend is reported in literature [20].
It can be observed from the TG profile given in Fig. 2, that
unmodified 13X and MEA modified 13X zeolites show weight loss
till 400 °C. It has been reported that, zeolites exhibit dehydration
till 350 °C [21]. However, this temperature is dependent on the
Table 1
Surface area and pore volume analysis of adsorbents.
S. no. Adsorbents BET surface area (m2/g) Pore volume (cm3/g)
1. 13X zeolite matrix 386.4 0.2335
2. 50% MEA/13X zeolite 14.9 0.0441
 R. Chatti et al. / Microporous and Mesoporous Materials 121 (2009) 84–89
25
13X, dTG
20 13X-MEA-50, dTG
13X-MEA-50, TG
Weight (mg)
15
13X, TG
10
5 -0.002
0 -0.0025
0 100 200 300 400 500
Temperature (ºC)
Fig. 2. Representative TG profile of the adsorbents.
heating rate used in the experiment. As a higher heating rate was
used in the present study, complete dehydration was observed at
comparatively higher temperature. Initial desorption of the pre-ad-
sorbed moisture and other volatiles (including methanol used for
wetting of 13X) was observed in all the adsorbents.
It can be observed that in case of 13X, there is a presence of only
a single continuous weight loss ‘step’ from room temperature to
450 °C. This has stabilized with a total weight loss of about
18.73%. A major weight loss is observed at 130 °C, which may be
attributed to desorption of methanol and the moisture in the wet-
ted 13X zeolite beads. In the case of MEA modified 13X, it has been
observed that there are a total of three distinct weight loss steps at
70, 150 and 240 °C. Since MEA has a boiling point of 170.8 °C, we
may attribute the second weight loss between 120 and 200 °C to
volatilization and degradation of MEA. The weight loss is observed
to be 5.63% in this region. A total weight loss of 22.56% is observed
which is about 4% higher than the unmodified adsorbent.
The presence of a peak at a frequency of about 3400 cm1 is ob-
served in the FT–IR spectra of the MEA modified zeolite 13X sam-
ple, which was evaluated for CO2 adsorption. This may be
attributed to the N–H stretching vibration. A peak at a frequency
of 3300 cm1 is also observed which may be attributed to the N–
H stretch of carbamate species (–NHCOO–), which may be formed
Fig. 3. FTIR spectra of 50% MEA modified 13X zeolite evaluated for CO2 adsorption.
87
0 by the interaction of the amine molecule with carbon dioxide. The
FT-IR spectrum is presented in Fig. 3.
-0.0005
3.2. Effect of solvent in immobilization of amine
-0.001 To understand the significance of solvent used in the synthesis,
dTG
the synthesis was carried out using water and methanol as sol-
-0.0015 vents for the immobilization. For these experiments, the analysis
technique used was the titrimetric method as this method can be
easily set up in the laboratory. Water was selected as a solvent con-
sidering the solubility of amines in water and it’s use as a universal
solvent and it’s non-hazardous nature. Methanol was chosen spe-
cifically as the solvent because of lower boiling point (64.7 °C) as
600 compared to water (100 °C), which may facilitate the proper drying
of the sample after immobilization. This would ultimately lead to a
uniform loading of the amine on the zeolite matrix. Fig. 4 compares
the estimated MEA loading using methanol and water solvents.
From the above observations, we can conclude that comparable
MEA loadings can be achieved by using methanol in lesser time
than water as solvent. It was also observed that the solvent immo-
bilized sorbents can be dried in a lesser time period as compared to
their aqueous counterparts which can be attributed to the high vol-
atility of methanol. Thus, from these observations, we can infer
30
Water
25 Methanol
MEA loading (wt%)
20
15
10
5
0
1 5 m in 2 4 0 m in
Agitation Period
Fig. 4. Effect of solvent on MEA loading.
88 R. Chatti et al. / Microporous and Mesoporous Materials 121 (2009) 84–89

that methanol is solvent of choice for the immobilization of MEA
on the zeolite matrix.
3.3. Effect of contact time on the amine loadings
The contact time of zeolite and amine solution show a significant
effect on amine loadings (Fig. 4). As evident from the results that
the highest loading achieved in case of aqueous medium with con-
tact time of 4 h, whereas comparative loading was achieved with
15 min contact time using methanol as solvent. Thus, we can infer
that when methanol is used as the solvent, lesser time is required to
immobilize a comparative content of amine on the zeolite. Since
higher loadings were obtained using methanol, all further synthe-
ses were carried out using methanol as the solvent of choice.
3.4. Effect of wetting of the zeolite matrix by methanol
Further, the effect of wetting of the zeolite 13X beads by the
choice solvent, prior to the immobilization procedure was also
studied. Two experiments were planned. The first set of experiment
was the immobilization of the amine onto the surface of the zeolite
beads directly without any pretreatment, i.e., without any wetting
procedure. The second set of experiment was performed by the ini-
tial wetting procedure of the zeolite beads with the solvent in a so-
lid to liquid ratio of 1:2 in two stages. In both of the experiments,
the agitation period was optimized at 15 min and they were con-
ducted at room temperature. It was observed that without pretreat-
ment, there was not any significant loading. Whereas, for the pre-
wetted zeolite, the loading was observed to be 18.69%.
A uniform dispersion of the amine molecules in the zeolite ma-
trix may be attributed to this pre-treatment of zeolite beads in the
process of amine immobilization. The silanol and aluminol groups
present in the zeolite react with methanol to form Si–O–CH3 and
water.
Si—OH þ CH3 OH ! Si—O—CH3 þ H2 O
The Si–O–CH3 group formed reacts with amine molecule to form a
highly reactive species as per the reaction (2).
Si—O—CH3 þ HO—CH2 —CH2 —NH2
! Si—O—CH2 —CH2 —CH2 —NH2
Thus it can be inferred that the pretreatment of the zeolite 13X
beads has a profound influence on the amine immobilization.
3.5. Effect of temperature in amine immobilization
different techniques like GLC and TOC and was compared with
the simple titrimetric technique followed in the laboratory. Adsor-
bents were synthesized using three different concentrations of
each amine. The amine content was analyzed by all the techniques
mentioned above. The results have been discussed in the subse-
quent tables (Tables 2–4) representing each individual amine.
Thus it can be observed that the agreement between the analyt-
ical techniques for estimating loadings of the different amines is
fairly good. However, the titrimetric method involves human error
unlike the instrumental methods. Also, the procedure involves the
constant use of glacial acetic acid, which has harmful effects on the
health of the analyst. Thus estimating the amine content by the
titrimetric method is not a good idea. In a similar manner, the li-
quid TOC method of estimation is also quite reliable and can be
correlated with the estimated values obtained by the GLC tech-
nique. However, the GLC technique is the best method to analyze
the amine content in all the amines. This is because, apart from
being an instrumental technique, the calibration plots for the dif-
ferent amines show linearity with a R2 factor of about 0.99 which
is fairly accurate.
3.7. CO2 adsorption capacities of the adsorbents
The results of the CO2 adsorption studies using the break-
through method are presented in Table 5. We observe that the
adsorption capacity of the amine loaded zeolite is increased by
approximately 20–30% in comparison with that of the bare zeolite
matrix at 75 °C. This may appear contrary to the expectation, that a
decrease in surface area and pore volume of the amine modified
adsorbent may reduce the adsorption capacity of the adsorbent.
However, this can be explained by the classification of the process
of adsorption, as physical adsorption or physisorption, and chemi-
cal adsorption or chemisorption. At ambient temperature, physi-
sorption is dominant over chemisorption. Surface area of the
adsorbent thus holds a vital key to the adsorption process at ambi-
ð1Þ
ent temperature. However, at elevated temperatures, (75 °C in the
Table 2
Estimation of MEA on the zeolite matrix.
S. Targeted loading of MEA on Techniques to estimate achieved loading
ð2Þ no. Zeolite - 13X (wt%)
Titrimetry GC-FID TOC (liquid)
(wt%) (wt%) (wt%)
1. 25 13.53 ± 0.2 14.66 ± 0.2 8.6 ± 0.2
2. 50 18.69 ± 0.2 24.03 ± 0.2 21.3 ± 0.2
3. 80 28.75 ± 0.2 36.92 ± 0.2 29.1 ± 0.2

The effect of temperature was studied for the immobilization

Table 3
process. Two experiments were planned for this study. In both Estimation of ED on the zeolite matrix.
the experiments the pre-treatment was given to the 13X beads
S. Targeted loading of ED on Techniques to estimate achieved loading
by wetting the beads with solvent and the solid to liquid ratio
no. Zeolite - 13X (wt%)
was kept at 1:2. The first experiment was conducted by immobiliz- Titrimetry GC-FID TOC (liquid)
(wt%) (wt%) (wt%)
ing MEA on zeolite 13X beads at room temperature by using meth-
anol as the solvent. The second experiment was carried out in a 1. 25 15.89 ± 0.2 9.50 ± 0.2 7.3 ± 0.2
2. 50 24.53 ± 0.2 19.41 ± 0.2 18.4 ± 0.2
round bottom flask and the reaction mixture was refluxed at
3. 80 18.09 ± 0.2 15.68 ± 0.2 14.9 ± 0.2
70 °C. The concentration of the alcoholic amine solutions was
50 wt% in both the cases. The MEA loadings observed in the former
case was 18.69% and that in the latter was 13.88%. Table 4
Thus it can be inferred that reflux method does not yield higher Estimation of IPA on the zeolite matrix.
amine loading than the simple mixing method.
S. Targeted loading of IPA on Techniques to estimate achieved loading
no. Zeolite - 13X (wt%)
3.6. Comparison of estimation of amine loadings through various Titrimetry GC-FID TOC (liquid)
(wt%) (wt%) (wt%)
techniques
1. 25 4.48 ± 0.2 2.28 ± 0.2 4.8 ± 0.2
2. 50 11.10 ± 0.2 11.11 ± 0.2 13.4 ± 0.2
After optimizing the different parameters involved in the
3. 80 16.88 ± 0.2 17.01 ± 0.2 11.9 ± 0.2
immobilization techniques, the amine content estimated by the
 R. Chatti et al. / Microporous and Mesoporous Materials 121 (2009) 84–89 89

Table 5 2RNH2 þ CO2 ! RNHCOO þ RNHþ3 ð3Þ

Breakthrough adsorption capacities of zeolite 13X and amine modified zeolites
(50 w%) at 75 °C.
RNHCOO þ H2 O ! RNH2 þ HCO3 : ð4Þ

S. no. Adsorbent material Breakthrough adsorption capacity (mg/g) The enhancement in the adsorption capacity of the amine loaded
1. 13X matrix 16.01
zeolite materials can be attributed to this chemisorptive interaction
2. 13X/MEA 19.98 of CO2 with amine in the pores of the zeolite 13X. Thus, we observe
3. 13X/IPA 22.78 a hybrid mechanism of absorption and adsorption taking place in
these amine modified zeolite 13X sorbents. We may also describe
this process as a dry CO2 scrubbing system. IR peak corresponding
1
to carbamate species, which is possibly formed by reaction of CO2
0.9 with amine functional groups was observed. Further studies are in
0.8 progress to elucidate this mechanism.
0.7
C/C 0

0.6 13X-MEA-50
13X-IPA-50
0.5 4. Conclusions
0.4
0.3 Novel amine immobilized adsorbents have been synthesized
0.2 using 13X zeolite beads as the matrix. They have been analyzed
0.1
for estimation of the amine content on the zeolite using different
0
0 10 20 30 40 50 60 analytical approaches. The gas liquid chromatography method
Time (min) has been identified as the method of choice owing to its accuracy.
The amine immobilized adsorbents have also been evaluated for
Fig. 5. Breakthrough curves of CO2 on MEA modified zeolite 13X and IPA modified their respective CO2 adsorption capacities and it has been observed
zeolite 13X at 75 °C.
that there is an enhancement in the adsorption capacity of these
materials over that of the conventional zeolite 13X matrix, which
can be attributed to a hybrid absorption–adsorption mechanism.
Table 6
Equilibrium adsorption capacities of zeolite 13X and MEA modified zeolite 13X
(50 w%) at 75 °C and 1 bar gauge pressure. Acknowledgements
S. Adsorbent Equilibrium adsorption capacity (mg/g) using volumetric
no. material adsorption principle This work has been carried out under the National Thermal
Power Corporation (NTPC) sponsored project S-3-1392 and CSIR
1. 13X matrix 37.33
2. 13X/MEA 48.64
Network Project No. CORE-08 (1.1). The authors sincerely acknowl-
edge the valuable assistance provided by JNARDDC, Nagpur and
M/s. Blue Star India Ltd., Mumbai in various evaluation and charac-
terization studies conducted during the course of this work. One
present study), chemisorption is the dominant process due to
of the authors Ravikrishna Chatti would also take the opportunity
incorporation of the amine group in the zeolite. Thus, we observe
to sincerely acknowledge the Council of Scientific and Industrial
an increase in the adsorption capacity at higher temperature, due
Research (CSIR) India for granting the Senior Research Fellowship.
to increase in the chemisorption process. A representative break-
through curve of zeolite 13X/MEA and 13X/IPA is shown in Fig. 5.
References
Thus, it is observed that the modification of zeolite 13X using
amines has enhanced the adsorption capacity as compared to that [1] IPCC J.T. Houghton, Y. Ding, D.J. Griggs, M. Noguer, P.J. van der Linden, X. Dai, K.
of the zeolite 13X matrix. To substantiate the values of adsorption Maskell, C.A. Johnson, Climate Change 2001: The Scientific Basis,
capacities obtained by the breakthrough method, we have also car- Intergovernmental Panel on Climate Change, Cambridge University Press,
Cambridge, UK, 2001.
ried out CO2 adsorption studies for the different adsorbents using [2] M. Gupta, I. Coyle, K. Thambimuthu, in ‘‘Strawman document for CO2 Capture
the volumetric adsorption principle. The experiments have been and storage (CC&S) technology roadmap” – 1st CC&S Technology Roadmap
carried out at 1 bar gauge pressure at 75 °C in the presence of pure Workshop, September, 2003, Canada.
[3] Y.H. Ma, C. Mancel, AIChE J. 18 (1972) 1148.
CO2 stream in comparison to 15 vol% CO2 gas in He balance, as per- [4] Y.H. Ma, A.J. Roux, AIChE J. 19 (1973) 105.
formed in case of the breakthrough method (Table 6). Further stud- [5] D. Valenzuela, A.L. Myers, in: Adsorption Equilibrium Data Handbook,
ies using the volumetric method, will be the scope of future Prentice-Hall, Engelwood,Cliffs,Nj, 1989, pp. 39–59.
[6] R.J. Wilson, R.P. Danner, J. Chem. Eng. Data 28 (1983) 14.
experimental work. [7] D.T. Hayhurst, Chem. Eng. Commun. 4 (1980) 729.
[8] C. Han, D.P. Harrison, Chem. Eng. Sci. 49 (1994) 5875.
3.8. Possible reaction mechanism [9] A. Kapoor, R.T. Yang, Chem. Eng. Sci. 44 (1989) 1723.
[10] Z. Yong, V.G. Mata, A.E. Rodrigues, Adsorption 7 (2001) 41.
[11] R.V. Siriwardane, M.S. Shen, E.P. Fisher, J.A. Poston, Energy Fuels 15 (2001) 279.
It is envisaged that the amine exists as a solvent in the confined [12] Y. Ding, E. Alpay, Chem. Eng. Sci. 55 (2000) 3461.
pores of the zeolite. The pores are functioning like micro-reactors [13] P.R. Pereira, J. Pires, M.B. Carvalho, Langmuir 14 (1998) 4584.
[14] Z. Yong, V. Mata, A.E. Rodrigues, J. Chem. Eng. Data 45 (2000) 1093.
for the capture of carbon dioxide. The loading of the amine in the
[15] M. Anand, J. Hufton, S. Mayorga, S. Nataraja, S. Sircar, T. Gaffney, APCI report
zeolite 13X matrix overcomes the disadvantages or limitations for DOE, 1995.
associated with the liquid-amine-based scrubbing systems. The [16] N.D. Hutson, S.A. Speakman, E.A. Payzant, Chem. Mater. 16 (2004) 4135.
limitations identified are the corrosive nature of the amines being [17] W. Seaman, E. Allen, Anal. Chem. 23 (1951) 592.
[18] P.D. Jadhav, S.S. Rayalu, R.B. Biniwale, S. Devotta, Curr. Sci. 92 (2007) 724.
used, higher energy costs in regenerating the scrubbing units and [19] P.D. Jadhav, R.V. Chatti, R.B. Biniwale, N.K. Labhsetwar, S. Devotta, S.S. Rayalu,
problems associated with the viscous nature of the amine solutions Energy Fuels 21 (2007) 3555–3559.
[22]. The reactions taking place between the solid-amine based [20] X. Xu, C. Song, B.G. Miller, A.W. Scaroni, Fuel Process. Technol. 86 (2005) 1457–
1472.
adsorbents are essentially the same, as that between the liquid [21] R.V. Siriwardane, M-S. Shen, E.P. Fisher, Energy Fuels 19 (2005) 1153–1159.
amine and the gaseous CO2 [23], wherein there is formation of [22] R.S. Franchi, P.J.E. Harlick, A. Sayari, Ind. Eng. Chem. Res. 44 (2005) 8007.
the carbamate species as shown in reaction (3): [23] T. Filburn, J.J. Helble, R.A. Weiss, Ind. Eng. Chem. Res. 44 (2005) 1542.