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Microporous and Mesoporous Materials 121 (2009) 8489

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Microporous and Mesoporous Materials

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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

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.

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

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

is an increasing need to capture the CO2 emitted from coal-red power plants, operating at temperatures around 120 C150 C. A wide range of adsorbent materials have been investigated like zeolites, activated carbons, pillared clays and metal oxides [315]. However, in these conventional adsorbents, physical adsorption plays an important role in the adsorption of CO2. It has been reported by Siriwardene et al. that CO2 adsorption capacity of zeolites 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 increasing temperature. Thus, these adsorbents need to be modied 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 adsorbents 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 . This pore size can accommodate both the immobilized amines in the zeolite pore and the adsorbed CO2. 2. Experimental The amines used in the synthesis of the adsorbents were analytical grade monoethanolamine, ethylene diamine and isopropanol

* Corresponding author. Tel./fax: +91 712 2247828. E-mail address: s_rayalu@neeri.res.in (S.S. Rayalu). 1387-1811/$ - see front matter 2009 Published by Elsevier Inc. doi:10.1016/j.micromeso.2009.01.007

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amine, respectively. These amines were procured from E-Merck, India and were used as such without any further purication. The solvent used was HPLC grade methanol and was procured from Qualigens, India. Zeolite 13X in the form of pellets of approximately 1.5 mm was procured from E-Merck, India. GC grade nitrogen (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 undertaken during the experiments. Details of the synthesis of the different 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 solidliquid 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 initial concentration as 25, 50 and 80 wt%. Amine solution was separated 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 reux method The synthesis of amine loaded zeolite 13X was also carried out by reuxing 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 reuxed with 30 ml of alcoholic amine solution in a round bottom ask equipped with a water condenser. After 2 h reux, 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 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-

Different routes for immobilization of amines in the zeolite matrix

Immobilization in aqueous media. Different intervals of stirring maintained. Study was conducted using three different amine concentrations.

Immobilization in organic solvent, methanol. Wetting of zeolite was done prior to immobilization. Pre-treatment improved amine immobilization. Study was conducted using three different amine concentrations.

Immobilization was done by the reflux method.

Refluxed at a temperature of 700C. Method does not yield higher amine loading as compared to the solvent immobilization method.

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

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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. 1. 2. Adsorbents 13X zeolite matrix 50% MEA/13X zeolite BET surface area (m2/g) 386.4 14.9 Pore volume (cm3/g) 0.2335 0.0441

Fig. 1. XRD pattern of 50% MEA/13X.

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25
13X, dTG

by the interaction of the amine molecule with carbon dioxide. The FT-IR spectrum is presented in Fig. 3. 3.2. Effect of solvent in immobilization of amine To understand the signicance of solvent used in the synthesis, the synthesis was carried out using water and methanol as solvents 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 considering the solubility of amines in water and its use as a universal solvent and its non-hazardous nature. Methanol was chosen specically as the solvent because of lower boiling point (64.7 C) as 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 immobilized sorbents can be dried in a lesser time period as compared to their aqueous counterparts which can be attributed to the high volatility of methanol. Thus, from these observations, we can infer
30 25 20 15 10 5 0 1 5 m in 2 4 0 m in

20

13X-MEA-50, dTG 13X-MEA-50, TG

-0.0005

Weight (mg)

15
13X, TG

-0.001

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.

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-adsorbed 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 wetted 13X zeolite beads. In the case of MEA modied 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 unmodied adsorbent. The presence of a peak at a frequency of about 3400 cm1 is observed in the FTIR spectra of the MEA modied zeolite 13X sample, which was evaluated for CO2 adsorption. This may be attributed to the NH 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

dTG

MEA loading (wt%)

Water Methanol

Agitation Period
Fig. 4. Effect of solvent on MEA loading.

Fig. 3. FTIR spectra of 50% MEA modied 13X zeolite evaluated for CO2 adsorption.

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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 signicant effect on amine loadings (Fig. 4). As evident from the results that the highest loading achieved in case of aqueous medium with contact 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 syntheses 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 rst 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 initial wetting procedure of the zeolite beads with the solvent in a solid 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 conducted at room temperature. It was observed that without pretreatment, there was not any signicant loading. Whereas, for the prewetted zeolite, the loading was observed to be 18.69%. A uniform dispersion of the amine molecules in the zeolite matrix 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 SiOCH3 and water.

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. Targeted loading of MEA on Zeolite - 13X (wt%) Techniques to estimate achieved loading Titrimetry (wt%) 13.53 0.2 18.69 0.2 28.75 0.2 GC-FID (wt%) 14.66 0.2 24.03 0.2 36.92 0.2 TOC (liquid) (wt%) 8.6 0.2 21.3 0.2 29.1 0.2

SiOH CH3 OH ! SiOCH3 H2 O

The SiOCH3 group formed reacts with amine molecule to form a highly reactive species as per the reaction (2).

SiOCH3 HOCH2 CH2 NH2 ! SiOCH2 CH2 CH2 NH2 2

Thus it can be inferred that the pretreatment of the zeolite 13X beads has a profound inuence on the amine immobilization. 3.5. Effect of temperature in amine immobilization The effect of temperature was studied for the immobilization process. Two experiments were planned for this study. In both the experiments the pre-treatment was given to the 13X beads by wetting the beads with solvent and the solid to liquid ratio was kept at 1:2. The rst experiment was conducted by immobilizing MEA on zeolite 13X beads at room temperature by using methanol as the solvent. The second experiment was carried out in a round bottom ask and the reaction mixture was reuxed at 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%. Thus it can be inferred that reux method does not yield higher amine loading than the simple mixing method. 3.6. Comparison of estimation of amine loadings through various techniques After optimizing the different parameters involved in the immobilization techniques, the amine content estimated by the

1. 2. 3.

25 50 80

Table 3 Estimation of ED on the zeolite matrix. S. no. Targeted loading of ED on Zeolite - 13X (wt%) Techniques to estimate achieved loading Titrimetry (wt%) 15.89 0.2 24.53 0.2 18.09 0.2 GC-FID (wt%) 9.50 0.2 19.41 0.2 15.68 0.2 TOC (liquid) (wt%) 7.3 0.2 18.4 0.2 14.9 0.2

1. 2. 3.

25 50 80

Table 4 Estimation of IPA on the zeolite matrix. S. no. Targeted loading of IPA on Zeolite - 13X (wt%) Techniques to estimate achieved loading Titrimetry (wt%) 4.48 0.2 11.10 0.2 16.88 0.2 GC-FID (wt%) 2.28 0.2 11.11 0.2 17.01 0.2 TOC (liquid) (wt%) 4.8 0.2 13.4 0.2 11.9 0.2

1. 2. 3.

25 50 80

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R. Chatti et al. / Microporous and Mesoporous Materials 121 (2009) 8489 Table 5 Breakthrough adsorption capacities of zeolite 13X and amine modied zeolites (50 w%) at 75 C. S. no. 1. 2. 3. Adsorbent material 13X matrix 13X/MEA 13X/IPA Breakthrough adsorption capacity (mg/g) 16.01 19.98 22.78

89

2RNH2 CO2 ! RNHCOO RNH 3 RNHCOO H2 O ! RNH2 HCO : 3

3 4

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0

The enhancement in the adsorption capacity of the amine loaded zeolite materials can be attributed to this chemisorptive interaction of CO2 with amine in the pores of the zeolite 13X. Thus, we observe a hybrid mechanism of absorption and adsorption taking place in these amine modied zeolite 13X sorbents. We may also describe this process as a dry CO2 scrubbing system. IR peak corresponding to carbamate species, which is possibly formed by reaction of CO2 with amine functional groups was observed. Further studies are in progress to elucidate this mechanism. 4. Conclusions Novel amine immobilized adsorbents have been synthesized using 13X zeolite beads as the matrix. They have been analyzed for estimation of the amine content on the zeolite using different analytical approaches. The gas liquid chromatography method has been identied as the method of choice owing to its accuracy. The amine immobilized adsorbents have also been evaluated for their respective CO2 adsorption capacities and it has been observed 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 absorptionadsorption mechanism. Acknowledgements This work has been carried out under the National Thermal Power Corporation (NTPC) sponsored project S-3-1392 and CSIR Network Project No. CORE-08 (1.1). The authors sincerely acknowledge the valuable assistance provided by JNARDDC, Nagpur and M/s. Blue Star India Ltd., Mumbai in various evaluation and characterization studies conducted during the course of this work. One of the authors Ravikrishna Chatti would also take the opportunity to sincerely acknowledge the Council of Scientic and Industrial Research (CSIR) India for granting the Senior Research Fellowship. References
[1] IPCC J.T. Houghton, Y. Ding, D.J. Griggs, M. Noguer, P.J. van der Linden, X. Dai, K. Maskell, C.A. Johnson, Climate Change 2001: The Scientic Basis, Intergovernmental Panel on Climate Change, Cambridge University Press, Cambridge, UK, 2001. [2] M. Gupta, I. Coyle, K. Thambimuthu, in Strawman document for CO2 Capture and storage (CC&S) technology roadmap 1st CC&S Technology Roadmap Workshop, September, 2003, Canada. [3] Y.H. Ma, C. Mancel, AIChE J. 18 (1972) 1148. [4] Y.H. Ma, A.J. Roux, AIChE J. 19 (1973) 105. [5] D. Valenzuela, A.L. Myers, in: Adsorption Equilibrium Data Handbook, Prentice-Hall, Engelwood,Cliffs,Nj, 1989, pp. 3959. [6] R.J. Wilson, R.P. Danner, J. Chem. Eng. Data 28 (1983) 14. [7] D.T. Hayhurst, Chem. Eng. Commun. 4 (1980) 729. [8] C. Han, D.P. Harrison, Chem. Eng. Sci. 49 (1994) 5875. [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. [12] Y. Ding, E. Alpay, Chem. Eng. Sci. 55 (2000) 3461. [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. [15] M. Anand, J. Hufton, S. Mayorga, S. Nataraja, S. Sircar, T. Gaffney, APCI report for DOE, 1995. [16] N.D. Hutson, S.A. Speakman, E.A. Payzant, Chem. Mater. 16 (2004) 4135. [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. [19] P.D. Jadhav, R.V. Chatti, R.B. Biniwale, N.K. Labhsetwar, S. Devotta, S.S. Rayalu, Energy Fuels 21 (2007) 35553559. [20] X. Xu, C. Song, B.G. Miller, A.W. Scaroni, Fuel Process. Technol. 86 (2005) 1457 1472. [21] R.V. Siriwardane, M-S. Shen, E.P. Fisher, Energy Fuels 19 (2005) 11531159. [22] R.S. Franchi, P.J.E. Harlick, A. Sayari, Ind. Eng. Chem. Res. 44 (2005) 8007. [23] T. Filburn, J.J. Helble, R.A. Weiss, Ind. Eng. Chem. Res. 44 (2005) 1542.

C/C 0

13X-MEA-50 13X-IPA-50

10

20

30

40

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. 1. 2. Adsorbent material 13X matrix 13X/MEA Equilibrium adsorption capacity (mg/g) using volumetric adsorption principle 37.33 48.64

present study), chemisorption is the dominant process due to incorporation of the amine group in the zeolite. Thus, we observe an increase in the adsorption capacity at higher temperature, due to increase in the chemisorption process. A representative breakthrough curve of zeolite 13X/MEA and 13X/IPA is shown in Fig. 5. Thus, it is observed that the modication of zeolite 13X using amines has enhanced the adsorption capacity as compared to that of the zeolite 13X matrix. To substantiate the values of adsorption capacities obtained by the breakthrough method, we have also carried out CO2 adsorption studies for the different adsorbents using the volumetric adsorption principle. The experiments have been carried out at 1 bar gauge pressure at 75 C in the presence of pure CO2 stream in comparison to 15 vol% CO2 gas in He balance, as performed in case of the breakthrough method (Table 6). Further studies using the volumetric method, will be the scope of future experimental work. 3.8. Possible reaction mechanism It is envisaged that the amine exists as a solvent in the conned pores of the zeolite. The pores are functioning like micro-reactors for the capture of carbon dioxide. The loading of the amine in the zeolite 13X matrix overcomes the disadvantages or limitations associated with the liquid-amine-based scrubbing systems. The limitations identied are the corrosive nature of the amines being used, higher energy costs in regenerating the scrubbing units and problems associated with the viscous nature of the amine solutions [22]. The reactions taking place between the solid-amine based adsorbents are essentially the same, as that between the liquid amine and the gaseous CO2 [23], wherein there is formation of the carbamate species as shown in reaction (3):