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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
Article history:
Received 3 June 2007
Received in revised form 17 December 2008
Accepted 8 January 2009
Available online 18 January 2009
Keywords:
Zeolite
CO2 Capture
Amine immobilization
Quantitative estimations
a b s t r a c t
Novel functionalised adsorbents have been synthesized by immobilization of various amines on synthetic
zeolite 13X. Various primary and secondary amines namely monoethanolamine (MEA), ethylenediamine
(ED) and isopropanol amine (IPA) have been immobilized on zeolite 13X. Quantitative estimations of the
amine loadings were undertaken using different analytical techniques namely titrimetric, total organic
carbon and gas chromatography analysis. Fairly good correlation was obtained for amine loadings estimated using the three techniques. Effect of various parameters like effect of solvent, shaking time, synthesis temperature, and wetting of pellets prior to amine loadings was also studied. The results revealed
that maximum loading was achieved for methanol-mediated synthesis conducted using previously wetted pellets at room temperature and with 15 min of shaking time. Preliminary attempts have also been
made to determine the CO2 adsorption capacities of these newly developed materials. The adsorption
capacities obtained were 16.01 mg/g for unmodied zeolite 13X and 19.98, and 22.78 mg/g for zeolite
modied with monoethanol amine, and isopropanol amine.
2009 Published by Elsevier Inc.
1. Introduction
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, chlorouorocarbons (CFCs), N2O methane, etc.
However, the major culprit is carbon dioxide. CO2 acts as a blanket to trap the infrared radiations coming from the earths atmosphere, thus resulting in warming of the earths surface and rise
in surface temperature. The ambient concentration of CO2 has increased from about 280 ppm from the pre-industrial revolution
period (early 1900) to the current levels of 380 ppm [1]. The development 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 combustion CO2 capture has emerged as one of the signicant options towards reducing the anthropogenic CO2 emissions. CO2 capture has
become a key issue to be addressed by the scientic community.
Research in this key area is going on at a global scale and the existing CO2 capture methods are amine based absorption, membrane
based separation, adsorption and cryogenic separation [2]. There
85
The synthesized adsorbents were characterized to obtain a useful comparison with the unmodied 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 ). To assess the structural integrity of the adsorbents after the incorporation of the
different amines, the adsorbents were analyzed in a 2h range of
560.
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 synthesized 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 RigakuTAS-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 PerkinElmer spectrometer using the KBr pellet technique. The
samples were analyzed in the wavelength region 4000400 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-
Immobilization in aqueous
media.
solvent, methanol.
maintained.
Immobilization in organic
Immobilization was
done by the reflux
method.
Refluxed at a
temperature of 700C.
86
centrations before and after treating with zeolite. The concentrations of amines were determined using titrimetric analysis, gas
chromatography (GC) and total organic carbon estimation (TOC).
The amine concentrations in initial and nal amine solutions
were determined by titrimetric analysis using the procedure described 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) (PerkinElmer,
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 calibration plot for each amine was plotted by injecting a known volume (1 ll) of different molar solutions of amine. After plotting the
calibration plot between the peak area and the molarity of the different 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 initial and residual amine solutions were analyzed using a non-dispersive 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, ow system etc. which
can be very useful to study a simulated ue gas stream as described in our previous studies [18,19]. The experimental set up
had mass ow controllers (Aalborg, USA), adsorption column
(diameter = 1 cm; height = 30 cm), sample selector valve (Valco,
USA), 1 ml sample loop and gas chromatograph (Chemito Technologies; Model GC 7610). In a typical evaluation protocol, 10 g dry
adsorbent was pretreated in He gas ow (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 ow rate of 52 ml/
min. The outlet was continuously monitored using GCTCD tted
with Porapak-Q column and the adsorption breakthrough point
was determined. Commercial zeolite 13X (E-Merck, India) and zeolite 13X modied with MEA and IPA at 50 wt% initial amine concentration 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 concentration 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 zeolite 13X after the incorporation of MEA was observed which indicates that the amine molecules have occupied the pore volume
(Table 1). These results provide a correlation with the pore ling
effect of MEA and also conrm that MEA was immobilized in the
zeolite pores. This trend is reported in literature [20].
It can be observed from the TG prole given in Fig. 2, that
unmodied 13X and MEA modied 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
1.
2.
386.4
14.9
0.2335
0.0441
87
0
13X, dTG
13X-MEA-50, dTG
-0.0005
13X-MEA-50, TG
15
-0.001
dTG
Weight (mg)
20
13X, TG
10
-0.0015
-0.002
0
0
100
200
300
400
500
-0.0025
600
Temperature (C)
Fig. 2. Representative TG prole of the adsorbents.
25
25
Water
Methanol
20
15
10
5
0
1 5 m in
2 4 0 m in
Agitation Period
Fig. 4. Effect of solvent on MEA loading.
Fig. 3. FTIR spectra of 50% MEA modied 13X zeolite evaluated for CO2 adsorption.
88
different techniques like GLC and TOC and was compared with
the simple titrimetric technique followed in the laboratory. Adsorbents 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 subsequent tables (Tables 24) representing each individual amine.
Thus it can be observed that the agreement between the analytical 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 liquid TOC method of estimation is also quite reliable and can be
correlated with the estimated values obtained by the GLC technique. 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 different 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 breakthrough method are presented in Table 5. We observe that the
adsorption capacity of the amine loaded zeolite is increased by
approximately 2030% 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 modied
adsorbent may reduce the adsorption capacity of the adsorbent.
However, this can be explained by the classication of the process
of adsorption, as physical adsorption or physisorption, and chemical adsorption or chemisorption. At ambient temperature, physisorption is dominant over chemisorption. Surface area of the
adsorbent thus holds a vital key to the adsorption process at ambient temperature. However, at elevated temperatures, (75 C in the
Table 2
Estimation of MEA on the zeolite matrix.
S.
no.
GC-FID
(wt%)
TOC (liquid)
(wt%)
1.
2.
3.
25
50
80
13.53 0.2
18.69 0.2
28.75 0.2
14.66 0.2
24.03 0.2
36.92 0.2
8.6 0.2
21.3 0.2
29.1 0.2
Table 3
Estimation of ED on the zeolite matrix.
S.
no.
Targeted loading of ED on
Zeolite - 13X (wt%)
GC-FID
(wt%)
TOC (liquid)
(wt%)
1.
2.
3.
25
50
80
15.89 0.2
24.53 0.2
18.09 0.2
9.50 0.2
19.41 0.2
15.68 0.2
7.3 0.2
18.4 0.2
14.9 0.2
Table 4
Estimation of IPA on the zeolite matrix.
S.
no.
GC-FID
(wt%)
TOC (liquid)
(wt%)
1.
2.
3.
25
50
80
4.48 0.2
11.10 0.2
16.88 0.2
2.28 0.2
11.11 0.2
17.01 0.2
4.8 0.2
13.4 0.2
11.9 0.2
1.
2.
3.
13X matrix
13X/MEA
13X/IPA
16.01
19.98
22.78
C/C 0
S. no.
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
89
13X-MEA-50
13X-IPA-50
10
20
30
40
4. Conclusions
50
60
Time (min)
Fig. 5. Breakthrough curves of CO2 on MEA modied zeolite 13X and IPA modied
zeolite 13X at 75 C.
Table 6
Equilibrium adsorption capacities of zeolite 13X and MEA modied zeolite 13X
(50 w%) at 75 C and 1 bar gauge pressure.
S.
no.
Adsorbent
material
1.
2.
13X matrix
13X/MEA
37.33
48.64