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Functionalized Fly ash based alumino-silicates for capture of carbon dioxide

Vivek Kumar, Nitin K. Labhsetwar, Siddharth Meshram, and Sadhana Suresh Rayalu
Energy Fuels, Just Accepted Manuscript Publication Date (Web): 08 September 2011 Downloaded from http://pubs.acs.org on September 9, 2011

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Functionalized Fly ash based alumino-silicates for capture of carbon dioxide

Vivek Kumara, Nitin Labhsetwara, Siddharth Meshramb and Sadhana Rayalua*
National Environmental Engineering Research Institute (NEERI),Nehru Marg, Nagpur, Maharashtra440020, India b Laxminarayan Institute of Technology (LIT), Department of Chemistry, RTM Nagpur University, Nagpur-440010, India

Abstract Fly ash contains mainly alumina and silica as its main constituents. A novel method for extraction of highly stable alumino-silicates from fly ash has been developed. The asextracted alumino-silicate has been further functionalized with APTES (3-Aminopropyl triethoxy silane), TRIS buffer (Tris hydroxymethyl aminomethane) and AMP (3-Amino 2methyl 1-Propanol) to impart basicity for carbon dioxide adsorption. A dynamic adsorption capacity to the tune of 6.62 mg/g has been observed for FAS (Fly ash based alumino-silicate) which has improved by a factor of 4.0 with adsorption capacity of 26.5 mg/g for AMPfunctionalized FAS at 55 0C with 15% CO2 in N2. The positive influence of water was observed with an improvement of adsorption capacity to 34.82 mg/g at 55 0C with 15% CO2, 82% N2 and 3% water vapor. The adsorbent is studied for adsorption capacity at varying temperatures and the best performing adsorbent is characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, thermal analysis and elemental analysis to study the morphological properties of the present adsorbent support. The excellent thermal stability of synthesized material suggested the formation of promising alumino-silicate for CO2 adsorption.

*Corresponding author: E-mail: s_rayalu@neeri.res.in; Telefax: +91-712-2247828 1

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1. INTRODUCTION Fossil fuel combustion supplies more than 85% of energy for industrial activities, and is thus the main source of greenhouse gases (GHG) in the form of CO2. This is expected to remain almost unchanged over the next 25 years as world energy consumption doubles. Coal, which has the highest carbon footprint per unit of energy, accounts for approximately 25% of the world energy supply and 40% of the carbon emissions. Over the next one hundred years, it has been projected that the combustion of fossil fuels can add massive amounts of carbon dioxide into the atmosphere that can outsize the uptake capacity of natural sinks1. The concentration of carbon dioxide in the Earth's atmosphere was at a maximum of 391 ppm by volume as of April 20102. Annual mean growth rate for Mauna Loa, Hawaii suggests an increase in the concentration by about 2 ppm in 2009 with latest concentration of 393.69 ppm as of on June 20113. The continuing use of fossil fuels and in turn the emission of carbon dioxide in the atmosphere has raised the precondition for proficient capture, storage and sequestration methodologies4. Post combustion carbon dioxide absorption has been applied on various occasions5-7. The

significance of carbon dioxide absorption methodology suggests a non feasible solution towards efficient carbon dioxide removal from power plants8, 9. Research over the alternative methodology selection such as pre combustion CO2 capture failed to provide expected results10. Adsorptive removal of emitted carbon dioxide from flue gas has provided efficient methodology and amine modified mesoporous adsorbents have an edge over other classes of adsorbents11,
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. The use of microporous adsorbents such as activated carbon13, nitrogen

enriched carbon14, silica gel15, advanced membranes16, 17 and amine incorporated zeolites18 have been reported in the recent time. There is need to develop low cost materials with reasonably good capacity for carbon capture. In this connection, fly ash a waste material of thermal power industry is proposed to be used. Fly ash is estimated to be generated in India to

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the tune of about 175 million tonnes by the year 2012. From about 83 existing thermal power plants and1800 selected industrial units which had captive thermal power plants of >1MW, it is expected to amplify to 200 MTPA in another decade. Fly ash can cause serious environmental hazardous. Additionally, the land requirement envisaged for disposal of fly ash is about 50,000 acre, with an annual expenditure of about Rs 500 million for transportation. These problems undoubtedly make obvious the fact that utilization of fly ash is absolutely essential. Technologies have been developed for gainful utilization of fly ash. The utilization ranges from low to high valueadded applications. Utilization of fly ash in India records a very low percentage of 23% as compared to a corresponding figure of 3080% for developed countries. This requires development of some innovative technologies to promote fly ash utilization. The possibility of synthesizing high value-added products such as zeolites from fly ash was explored19-23. Over 250 species of naturally occurring and synthetic zeolitic compositions are available. In general, crystalline zeolites are alumino-silicates that consist of AlO4 and SiO4 tetrahedra connected by mutual sharing of oxygen atoms and characterized by pore openings of uniform dimension. Zeolites show remarkable ion-exchange capacity; they are capable of reversibly desorbing adsorbed phases that are dispersed throughout the voids of the crystal without displacing any atoms, which make up the permanent crystal structure. The use of such zeolitic alumino-silicate adsorbents for carbon dioxide adsorption is extensively reported in literature24-33. In general, the zeolite-synthesizing process from fly ash involves alkaline treatment, using caustic soda at higher temperatures (80100 0C). Most preceding studies evaluated the conversion of fly ash to zeolite-like materials under ambient pressure conditions. There are reports available for usage of flash based adsorbents for capture of carbon dioxide34- 37.

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Related studies are reported wherein seawater has been used for precipitation of calcite and aragonite from varying salinity samples38. With this background, efforts have been made to develop low cost adsorbents by avoiding a hydrothermal crystallization step, which is one of the most energy intensive steps. This has been achieved by precipitating alumino-silicate using double salt effect. Based on this, it has been attempted to synthesize low cost aluminosilcates as an alternate to zeolites for capture of carbon dioxide. This paper thus addresses the synthesis of alumino-silcates from fly ash by varying conditions within feasible parametric ranges for optimization of conditions along with characterization of fly ash-based alumino-silcates (FAS).

2. MATERIALS AND METHODS 2.1. Materials Fly ash sample was collected from the hopper of an electrostatic precipitator at Koradi Thermal Power Plant, Nagpur. The raw fly ash samples were first screened through a Nonaka Rikaki testing sieve of 100 micron mesh size to eliminate the larger particles. TRIS buffer (Tris hydroxymethyl aminomethane) was procured from M/s.Calbiochem, Germany. 2amino-2-methyl-1-propanol (AMP) and Aminopropyl triethoxysilane (APTES) were procured from E-Merck, India and were used as such without any further purification. Commercially available sea salt was procured from M/S Sigma Life Sciences, India.

2.2. FAS synthesis The elemental content of flyash was as follows: SiO2: 62.27; Al2O3: 30.96; Fe2O3: 1.25; TiO2: 1.67: CaO: 3.02; Na2O: 0.12; K2O: 0.41; and LOI: 0.29. In the present investigation, fly ash based alumino-silicate (FAS) was synthesized by reacting fly ash with caustic soda. The methodology used was the following:

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2.2.1. Fusion method The FAS sample was synthesized by fusing fly ash with sodium hydroxide. A homogenous fusion mixture was primed by proper grinding and mixing of fly ash and caustic soda in 1:1.2 ratio. This mixture was heated at 550 0C for 2 h. The resultant fused mass was cooled, milled and mixed thoroughly in distilled water (200 ml). The decant obtained after filtration of the solid mass was mixed with 200 ml of artificial sea water containing 10 g of sea salt. A white precipitate which was termed FAS was recovered by filtration. This was vacuum-dried at 50 0C overnight to obtain granules of alumino-silicate.

2.3 Functionalization of alumino-silicate In-situ functionalization of FAS was done using APTES (3-Aminopropyl triethoxy silane), TRIS buffer (Tris hydroxymethyl aminomethane) and AMP (3-Amino-2- methyl 1Propanol) by adding the functional molecule to fly ash decant solution during precipitation The as-synthesized adsorbent was named FAS-APTES, FAS-TRIS and FAS-AMP was pelletized and sieved to obtain granules of size 2-6 mm, suitable for breakthrough curve CO2 adsorption analysis.

2.4 Evaluation of materials for CO2 adsorption Among several solutions of post combustion CO2 capture, fluidized bed adsorption processes are considered to have high potential option for capturing CO2 gas from bulk flue gas. The bed was filled with sorbent to adsorb gases. Initial screening for selection of best functionalization molecule has been performed at 55 0C followed by evaluation at 30 and 75
0

C. As flue gas comprises of CO2 mixed mainly with N2, CO, water vapors and particulate

matter; we restricted our evaluations with 15% CO2 balanced with N2 and introduction of 3% water vapour for selected adsorbent-conditions. 5
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2.5 Breakthrough adsorption studies in flow through system In this method, the gas stream to be treated is passed over a fixed bed of adsorbent. An unsteady state condition prevails, in that the adsorbent bed continues to take up increasing amounts of adsorbate gases. The composition of the gas stream at the outlet of the bed is monitored continuously. Then the amount of a particular gas is followed as the fraction of the concentration of that gas in the effluent gas from the adsorption column Ce over that of the gas concentration in the feed gas, C0. This method matches practical (actual end use) conditions like flow conditions, temperatures and multi-component streams and we can calculate the dynamic adsorption capacities of the materials. The gas manifold system consisted of Four lines fitted with mass flow controllers from Aalborg (USA) with flows ranging between 1 and 200 ml/min. The controllers had an accuracy of 1% full scale and a repeatability of 0.1% full scale. One of the lines was used to feed in an inert gas, He, in order to dry the sample before each experiment. The other three lines fed in CO2, N2 and water vapor; so that different gas mixtures akin to the concentrations representative of different post-combustion capture gas streams could be prepared. Water was being introduced using a peristaltic pump capable of releasing the minimum flow to the range of 1-5 ml/min. The gases flowing through the different lines were mixed in a helicoidal dispenser that ensured perfect mixing of the feed gas before it entered the bed. A K-type thermocouple, located at a height of 50 mm above the porous plate (exit end of the column), was used to continuously monitor the column temperature with an accuracy of 1.5 C. The temperature was controlled by coupling the heating element coiled around the reactor inside an insulated fabrication. The bed pressure was observed by means of a backpressure regulator located in the outlet pipe with a repeatability of 0.5% full scale (0-40 bar). The system was also equipped with a continuous gas analyzer, gas chromatograph (GC), Claurus 500 from Perkin Elmer, fitted with a thermal conductive detector (TCD) in which He 6
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was used as the carrier gas. Feed gas and product stream were fed to auto sampler valve on GC by using sample selector valve for selecting the desired stream. GC column used was Porapak-Q with analysis conditions as follows; carrier gas = Nitrogen at 20 ml/min, temperatures: oven = 60 C, injector =110 C, detector = 130 C. The TCD response was calibrated employing CO2/N2 mixtures of known composition. The bed was packed with adsorbent in order to measure the dynamics of the CO2 in the column. The feed gas inlet flow rate was kept constant (20 ml/min). The CO2 composition in the column effluent gas was continuously monitored as a function of time (breakthrough curve) until the composition approached the inlet gas composition value, i.e., until saturation was reached. Each sample was subjected to pretreatment for cleaning of the adsorbent surface. Subsequently the adsorbent was exposed to feed gas flow and adsorption capacities were estimated. About 5 g adsorbent was packed in a glass column having effective working length 300 mm, internal diameter 10 mm, wall thickness 2 mm; and was heated from room temperature to 110 C for a period of 6 h in a flow of 20 ml He /min. The column was then cooled to the predefined adsorption temperature. This was done to clean the adsorbent surface and to remove any pre-adsorbed volatile matter in the adsorbent bed. A flow of CO2 was used with circa 15 mol% balanced with N2 (Flow rates: CO2 = 3, N2 = 17 ml/min) for the adsorption study. The total flow rate for adsorption was maintained at 20 ml/min. Concentration of CO2 in exit gas stream was monitored continuously at an interval of 1 min using TCD-GC and a pneumatically controlled sample injector. Experiments were continued till saturation was reached and then CO2 flow was stopped (Figure 1).

2.6 Characterization

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All the prepared adsorbents were characterized using low and wide angle X-ray diffraction (XRD) analyses to access the structural integrity of the adsorbent samples after incorporation of the amines. The XRD patterns have been recorded using X-ray diffractometer, Model (Phillips: PW-1830). The radiations of Cu-K were generated using Xray generator of model (PW 1729) of same make and the radiation were filtered using monochromators. The Fourier Transform Infrared (FTIR) 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 cm-1. This was done for confirming the formation of the carbamate and bicarbonate groups, which are formed as the adsorption product of CO2. Scanning Electron Microscopy (SEM) analysis was carried out using JEOL, JSM 6380 A, analytical Scanning Electron Microscope. The elemental analysis of the samples was determined by using a Thermo Flash Elemental analyser (EA) 1112 fitted with a MAS 200R autosampler including instrument control. Data analysis was conducted with the help of Eager Xperience software package. The standard method of Brunauer, Emmett and Teller (BET) was used for measuring specific surface area of the adsorbent based on the physical adsorption of a gas on the solid surface. Specific surface area of the catalysts was determined using Micromeritics Gemini 2375 gas adsorption system. The samples were degassed at 105 C. This temperature range was chosen keeping in mind the boiling point of TEPA used in the present study. Isothermal analysis of adsorbents was performed using thermogravimetric analysis (TGA) on a Perkin Elmer TGA. The combustion activities of the different adsorbents were assessed using isothermal TGA from 25 to 700 0C. The adsorbents were heated at a rate of 10 0C min-1 from 25 C to 700 0C under nitrogen with a flow rate of 20 ml/min (STP) to check the thermal stability.

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3 RESULTS AND DISCUSSION 3.1 Selection of functionalization molecule Bare FAS was functionalized and evaluated at 55 0C and 15% CO2 concentration with 10, 25 and 50 wt % of APTES, TRIS buffer and AMP. The dynamic CO2 adsorption capacity of bare FAS was 6.62 mg/g at 55 0C which improved to 7.4 mg/g after 10 wt% APTES loading. The adsorption capacity improved marginally to 10.8 mg/g after further increased loading of 25 wt% and remained constant as the loading was increased to 50 wt%. TRIS buffer provided the maximum adsorption capacity of 11.1 mg/g with 10 wt % loading and failed to provide any further improvement after increased loading of 25 and 50 wt%. Encouraging CO2 adsorption capacity was observed when FAS was loaded with AMP solution. The adsorption capacity increased from 10.8 mg/g to 24.2 mg/g when AMP loading was increased from 10 to 25 wt%. The small increase of 5% in loading provided increased adsorption capacity to 26.5 mg/g suggested further increase in AMP loading. Though, the adsorption capacity followed a decreasing trend when loading was increased from 30 to 40, 50, 80 and 100 wt % AMP signifying the selection of FAS-AMP-30 as the best performing adsorbent (Table 2).

3.2 Effect of temperature on adsorption of CO2 The selected adsorbent FAS-AMP-30 was subjected to adsorption performance studies at 30 and 75 0C with 15% CO2. The Breakthrough Curve (BTC) CO2 adsorption capacity of adsorbent did not show any improvement at the selected temperatures when compared to the performance at 55 0C (Figure 2). The optimal performance of FAS-AMP-30 was achieved at 55 0C with 15% CO2 and 20 ml/min flow rate. The decrease in adsorption capacity at 75 0C also suggests the possibility of coupled physiosorption and chemisorption analogous to the conventional adsorbents like zeolites and activated carbons (Table 3).

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3.3 Effect of moisture on adsorption of CO2 An improved adsorption performance of selected adsorbent FAS-AMP-30 has been observed when water is being introduced at 55 0C with 15% CO2, 82% N2 and 3% water vapor, maintaining 20 ml/min flow rate. The adsorption capacity of FAS-AMP-30 increased to 34.82 mg/g reflecting the positive influence of water vapor towards adsorption performance.

3.4 XRD Wide angle XRD of FAS bare compared with FAS-AMP-30 suggests the amorphous unordered morphology and pure adsorbent formation including the decrease in intensity after AMP incorporation (Figure 3). The JCPDS card description # 46-1045 suggests Potassium Aluminium Silicate (Microline) formation confirmed by 100% intense peak at 2 position

31.800. The use of sea salt as precipitating agent resulted in to the formation of calcium Sodium Aluminate at 2 position 45.560. The formation of charoite (Potassium calcium position 31.7 (JCPDS

Silicate hydroxide hydrate) gets confirmed with the intense peak at 2

card description # 42-1402) with cell parameters: a 19.61, b 32.12 and c 7.20. An intense peak at 2 position 27.4 suggests the formation of tarasovite (Potassium Sodium Aluminium

Silicate hydroxide hydrate) with cell parameters: a 5.13 and c 44.01.

3.5 BET Surface area and pore analysis The pore characteristics and surface area variation of APTES, TRIS buffer and AMP immobilized FAS were compared with bare FAS in Table 4. An unusual increase in surface area of FAS-AMP-30 has been observed compared to bare and APTES/TRIS buffer immobilized FAS (Table 4). The BET surface area has increased from 0.5413 to 91.3743 m2/g after AMP impregnation (Figure 4 and 5). Also substantial increase in pore volume

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from 0.003262 to 0.207041 cm3/g has been observed. These improved characteristics have resulted in improved CO2 adsorption capacity by a factor of 4 (Table 2). The reason behind the increase in surface area could be due to enhanced surface characteristics improvement by AMP over the FAS surface. Also the possibility of leaching of surface metal ions from FAS due to mixing of AMP or the role of AMP as a template for surface modification cannot be ruled out which was not functional in case of APTES or TRIS immobilized FAS. The pore size distribution curves (Figure 6 and 7) also support this possibility.

3.6 Elemental analysis of adsorbents Elemental analysis data significantly provided information regarding the varying amount of nitrogen functionality affecting the overall CO2 adsorption properties. Theoretically, the high N/C ratio shall facilitate enhanced CO2 adsorption capacity. The trend did not follow the said hypothesis and 50% loading of APTES, TRIS buffer and AMP failed to provide the increased adsorption capacity practically (Table 5). The elemental content of FAS was as follows: SiO2: 44.85; Al2O3: 25.71; Fe2O3: 0.41; TiO2: 0.11: CaO: 13.86; Na2O: 0.35; K2O: 10.93, other 2.10; and LOI: 0.32. The increase in calcium and potassium content may be attributed to the addition of sea salt for precipitation of alumino-silicate.

3.7 Thermal stability Bare FAS and FAS-AMP-30 were subjected to thermal treatment under nitrogen from ambient to 700 0C. The excellent stability of bare FAS was observed with almost no weight loss during the entire thermal treatment. An inconsequential weight loss similar to bare FAS was observed for FAS-AMP-30 up to 200 0C which sharply started degradation after further increase in temperature. Almost 20 % weight loss was recorded between 200-700 0C and this could be due to the presence of AMP loading over FAS. The thermogravimetric temperature

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effect is provided in Figure 8. The complete crystallization of FAS-bare below 100 0C is evident from almost no weight loss after increased temperature.

3.8 SEM A distinct variation in surface morphology is observed through SEM images (Figure 9 A and B). The as-synthesized FAS bare has a smooth surface where a change in surface morphology is evident for FAS-AMP-30. AMP has probably provided roughness to the FAS surface thus providing sites for CO2 adsorption, as suggested by the BET results.

3.9 FTIR The presence of a peak at a frequency of about 3400 cm-1 was observed in the FT-IR spectra of the AMP modified FAS sample (Figure 10). This may be attributed to the N-H stretching vibration. Figure 11 represents the FTIR spectrum of the aminated FAS-AMP-30 which was evaluated for adsorption of CO2. Further loading of amine on FAS was confirmed by FTIR studies. In case of CO2 exposed sample, a peak at a frequency of 3300 cm-1 was also observed, which may be attributed to the N-H stretch of carbamate species (-NHCOO-), possibly formed by the interaction of the amine molecule with carbon dioxide (Figure 11) 18. This further substantiates the CO2 adsorption through interaction of CO2 with functional groups of the adsorbent.

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4. CONCLUSION A novel method for extraction of highly stable alumino-silicates from fly ash has been developed. The in-situ incorporation of AMP resulted in an adsorbent with significantly improved characteristics to adsorb carbon dioxide at lower temperature and its performance is

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analyzed using a conventional carbon dioxide capture methodology. The adsorbent is characterized for surface morphology using XRD, SEM, FTIR, Elemental and thermal analyses. XRD of the synthesized FAS revealed the formation of amorphous mesoporous alumino-silicates. It is observed that the presence of nitrogen functionality does not facilitate better adsorption of CO2. The optimized loading of functionalized molecule along with the availability of adsorption pores (sites) facilitates the CO2 adsorption process.

ACKNOWLEDGEMENT The authors acknowledge the support extended by Director, NEERI for his encouragement. They also acknowledge the support extended by Dr. Wadodkar, JNARDDC, Nagpur and Dr. Peshwe and Miss Gauri Deshmukh from VNIT, Nagpur for providing characterization results. They acknowledge the facilities provided by Dr. Trevor Drage, Associate Professor at Department of Chemical and Environmental Engineering and Dr. Lee Stevans, University of Nottingham, UK. One of the authors Mr. Vivek Kumar would also like to kindly acknowledge the Council of Scientific and Industrial Research (CSIR), India for granting Senior Research Fellowship to him.

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10. Garca, S.; Gil, M.V.; Martn, C.F.; Pis, J.J.; Rubiera, F.; Pevida, C.; Breakthrough adsorption study of a commercial activated carbon for pre-combustion CO2 capture, Chem. Eng. J., 2011, 171, 549 556. 11. Sayari, Abdelhamid; Belmabkhout, Youssef; Serna-Guerrero, Rodrigo; Flue gas treatment via CO2 adsorption, Chem. Eng. J., 2011, 171, 760 774. 12. Zhao, Guoying ; Aziz, Baroz; Hedin, Niklas; Carbon dioxide adsorption on mesoporous silica surfaces containing amine-like motifs, Applied Energy, 2010, 87, 29072913. 13. Drage, Trevor C.; Blackman, James M.; Pevida, Cova; and Snape, Colin E.; Evaluation of Activated Carbon Adsorbents for CO2 Capture in Gasification, Energy and Fuels, 2009, 23, 27902796. 14. Thote, Jayshri A.; Iyer, Kartik S.; Chatti, Ravikrishna; Labhsetwar, Nitin K. ; Biniwale, Rajesh B. ; Rayalu, Sadhana S. ; In situ nitrogen enriched carbon for carbon dioxide capture, CARBON, 2010, 48, 369-402. 15. Leal, Orlando; Bolivar, Carmelo; Ovalles, Cesar; Garcia, Juan Jose; Espidel, Youssef; Reversible adsorption of carbon dioxide on amine surface-bonded silica gel, Inorganica chimica Acta, 1995, 240, 183-189. 16. Du, Naiying; Park, Ho Bum; Robertson, Gilles P.; Dal-Cin, Mauro M.; Visser Tymen; Scoles, Ludmila; and Guiver, Michael D.; Polymer nanosieve membranes for CO2 capture applications, Nature Materials, 2011, 10, 372-375. 17. Kumbharkar, S.C.; Liu, Y. ; Li, K.; High performance polybenzimidazole based asymmetric hollow fibre membranes for H2/CO2 separation, Journal of Membrane Science, 2011, 375, 231240.

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376 377 378 379 380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 396 397 398 399

18. Chatti, Ravikrishna; Bansiwal, Amit K.; Thote, Jayashri A.; Kumar, Vivek; Jadhav, Pravin; Lokhande, Satish K.; Biniwale, Rajesh B.; Labhsetwar, Nitin K.; Rayalu, Sadhana S.; Amine loaded zeolites for carbon dioxide capture: Amine loading and adsorption studies, Microporous & Mesoporous Materials, 2009, 121, 84-89. 19. Rayalu, S.S.; Udhoji, J.S.; Munshi, K.N.; Hasan, M.Z.; Highly crystalline zeolite a from flyash of bituminous and lignite coal combustion, Journal of Hazardous Materials, 2001, B88, 107121. 20. Rayalu, S. S.; Bansiwal, A. K.; Meshram, S. U.; Labhsetwar, Nitin; and Devotta, Sukumar; Fly ash based zeolite analogues: versatile materials for energy and environment conservation, Catalysis Surveys from Asia, 2006, Vol. 10, No. 2. 21. Rayalu, S.; Meshram, S.U.; Hasan, M.Z.; Highly crystalline faujasitic zeolites from flyash, Journal of Hazardous Materials, 2000, B77, 123131. 22. Ojha, Keka; Pradhan Narayan C; and Samanta, Amar Nath; Zeolite from fly ash: synthesis and characterization, Bull. Mater. Sci., 2004, Vol. 27, No. 6, pp. 555564. 23. Rungsuk, Doungmanee ; Apiratikul, Ronbanjob; Pavarajarn, Varong and Pavasant, Prasert; The 2nd Joint International Conference on Sustainable Energy and Environment (SEE 2006) , 21-23 November 2006, Bangkok, Thailand. 24. Dunne, J.A.; Rao, M.; Sircar, S.; Gorte, R.J.; Myers, A.L.; A thermogravimetric study of the adsorption of CO2 on zeolites synthesized from fly ash, Langmuir, 1996, 12, 58965904. 25 Wang, Z.M.; Arai, T.; Kumagai, M.; Adsorption Separation of Low Concentrations of CO2 and NO2 by Synthetic Zeolites, Energy and Fuels, 1998, 12, 1055-1060. 26. Hernandez-Huesca, R.; Diaz, L.; Aguilar-Armenta, G.; Adsorption equilibria and kinetics of CO2, CH4 and N2 in natural zeolites, Sep. Purif. Tech., 1999, 15, 163-173.

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400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421

27. Katoh, M.; Yoshikawa, T.; Tomonari, T.; Katayama, K.; Tomida, T.; Adsorption Characteristics of Ion-Exchanged ZSM-5 Zeolites for CO2/N2 Mixtures, J. Coll. Inter. Sci., 2000, 226, 145-150. 28. Rege, S. U.; Yang, R. T.; A novel FTIR method for studying mixed gas adsorption at low concentrations: H2O and CO2 on NaX zeolite and -alumina, Chem. Eng. Sci. 2001, 56, 3781-3796. 29. Lee, J. S.; Kim, J. H.; Kim, J. T.; Suh, J. K.; Lee, J. M.; Lee, C. H.; Adsorption equilibria of CO2 on zeolite 13X and zeolite X/Activated carbon composite, J Chem Eng Data, 2002, 47, 1237-1242. 30. Ko, D.; Siriwardane, R.; Biegler, L.T.; Optimization of a Pressure-Swing Adsorption Process Using Zeolite 13X for CO2 Sequestration, Ind.Eng.Chem.Res., 2003, 42, 339348. 31. Cheng, Y. S.; Huang, Q. L.; Eic, M.; Balcom, B. J.; CO2 dynamic adsorption/desorption on zeolite 5A studied by C-13 magnetic resonance imaging, Langmuir, 2005, 21, 43764381. 32. Siriwardane, R.V.; Shen, M.S.; Fisher, E.P.; Adsorption of CO2 on zeolites at moderate temperatures, Energy and Fuels, 2005, 19, 1153-1159 33. Jadhav, P. D.; Chatti, R. V.; Biniwale, R. B.; Labshetwar, N. K.; Devotta,S.; Rayalu, S.S.; Monoethanol Amine Modified Zeolite 13X for CO2 Adsorption at Different Temperatures, Energy and Fuels, 2007, 21, 3555. 34. Majchrzak-Kuceba, I.; Nowak, W.; A thermogravimetric study of the adsorption of CO2 on zeolites synthesized from fly ash, Thermochimica Acta, 2005, 437, 6774.

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422 423 424 425 426 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446

35. Gray , M.L. ; Soong, Y. ; Champagne, K.J. ; Baltrus, John ; Stevens, R.W. ; Jr Toochinda, P. ; Chuang, S.S.C. ; CO2 capture by amine-enriched fly ash carbon sorbents, Separation and Purification Technology, 2004, 35, 3136. 36. Arenillas, A. ; Smith, K.M. ; Drage, T.C. ; Snape, C.E. ; CO2 capture using some fly ashderived carbon materials, Fuel, 2005, 84, 22042210. 37. Maroto-Valer , M. Mercedes; Lu, Zhe ; Zhang, Yinzhi; Tang, Zhong ; Sorbents for CO2 capture from high carbon fly ashes, Waste Management, 2008, 28, 23202328. 38. Zhong Shaojun and Mucci, Alfonso; Calcite and aragonite precipitation from seawater solutions of various salinities: Precipitation rates and overgrowth compositions, Chemical Geology, 1989, 78, 283-299.

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447 448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466

List of tables: Table 1: CO2 adsorption capacities of different alumino-silicate adsorbents under various experimental conditions Table 2: BTC results for Fly ash based alumino-silicates with 15% CO2 Table 3: BTC results for FAS-AMP-30 with 15% CO2 Table 4: Textural properties of FAS-bare and FAS-AMP-30 adsorbents Table 5: Chemical analysis of FAS adsorbents

List of figures: Figure 1: Experimental setup used for breakthrough adsorption studies Figure 2: Breakthrough curve for FAS-AMP-30 at different temperature Figure 3: XRD comparison of FAS-bare and FAS-AMP-30 Figure 4: N2 adsorption isotherm for FAS-bare Figure 5: N2 adsorption isotherm for FAS-AMP-30 Figure 6: Pore size distribution curve for FAS-bare Figure 7: Pore size distribution curve for FAS-AMP-30 Figure 8: Thermal stability of FAS-bare and FAS-AMP-30 adsorbents Figure 9: SEM image of A) FAS bare and B) FAS-AMP-30 Figure 10: Comparative FTIR of FAS bare and FAS-AMP-30 Figure 11: FTIR of CO2 adsorbed FAS-AMP-30

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Table 1: CO2 adsorption capacities of different alumino-silicate adsorbents under various experimental conditions S.No. Type of aluminosilicate NaX NaX Na-ZSM-5 H-ZSM-5 H-ZSM-5 4A 5A 13X NaY USY Na-Modernite H- Modernite ZAPS(erionite) ZNT(modernite) ZN-19(clinoptilolite) Li-ZSM-5 Na -ZSM-5 K-ZSM-5 Rb-ZSM-5 Cs-ZSM-5 13 X Adsorption temperature and experimental conditions Volumetric method 304.4 K,214.38 Torr 305.8 K,213.87 Torr 297.1 K,235.14 Torr 296.9 K,230.47 Torr 295.5 K, 140.95 Torr 60C TPD procedure Adsorption capacity (mg/g) 205.7 mg/g 203.2 mg/g 63.2 mg/g 48.8 mg/g 38.3 mg/g 42.3 mg/g 22.73 mg/g 32.03 mg/g 3.75 mg/g 0 mg/g 62.86 mg/g 1.779 mg/g 134 mg/g 84.2 mg/g 78.2 mg/g g 35.59 mg/g 35.59 mg/g 29.66 mg/g 29.66 mg/g 7.908 mg/g 13.6 mg/g Reference Dunne et al.(1996) (Ref.24)

Wang et al.(1998) (Ref.25)

17C , Volumetric system

Hernandez-Huesca et al. (1999) (Ref.26) Katoh et al.(2000) (Ref.27)

30C to 150C GC method For 0.5 MPA

FTIR , 22C

Rege & Yang (2001) (Ref.28)

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13 X

Static volumetric method 0C 20C 40C 60C 80C

140.8 mg/g (20.35kPa) 114.9 mg/g (20.43 kPa) 95 mg/g (23.66kPa) 74.4 mg/g (27.00kPa) 58.1 mg/g (23.85 kPa)

Lee et al.(2002) (Ref.29)

13 X

PSA 30C 40C 50C MRI technique at 2 atm and by adsorption of 13 CO2, 25C TPD studies at 120C

184.8 mg/g 202.4mg/g 228.8 mg/g 290 mg/g 30.8 mg/g 16.7 mg/g 22 mg/g 26.4 mg/g 16.7 mg/g 55 mg/g 15 mg/g 6.62 mg/g 10.8 mg/g 26.5 mg/g 22.6 mg/g

Ko et al.(2003) (Ref.30)

5A 4A 5A 13X APG-II WE-G 592 13X 13X FAS-bare FAS-AMP-30 FAS-AMP-30 FAS-AMP-30

Cheng et al.(2005) (Ref.31) Siriwardane et al.(2005) (Ref.32)

10 11

Breakthrough studies 30C 75C Breakthrough studies 55C 30C 55C 75C 21
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Table 2: BTC results for Fly-ash based alumino-silicates with 15% CO2 Material FAS- bare FAS-APTES-10 FAS-APTES-25 FAS-APTES-50 FAS-TRIS-10 FAS-TRIS-25 FAS-TRIS-50 FAS-AMP-10 FAS-AMP-25 FAS-AMP-30 FAS-AMP-40 FAS-AMP-50 FAS-AMP-80 FAS-AMP-100 Feed flow rate (ml/min) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Adsorption temperature (0C) 55 55 55 55 55 55 55 55 55 55 55 55 55 55 Adsorption capacity (mg/g) 6.62 7.4 10.8 10.8 11.1 6.9 6.9 10.8 24.2 26.5 22.6 22.6 19.2 14.7

Table 3: BTC results for FAS-AMP-30 with 15% CO2 Material FAS-AMP-30 FAS-AMP-30 FAS-AMP-30 FAS-AMP-30 * In presence of 3% water vapor Feed flow rate (ml/min) 20 20 20 20 Adsorption temperature (0C) 30 55 75 55 Adsorption capacity (mg/g) 10.8 26.5 22.6 34.82*

Table 4: Textural properties of FAS-bare and FAS-AMP-30 adsorbents Adsorbent FAS- bare FAS-APTES-25 FAS-TRIS-25 FAS -AMP-30
a b

Vtot (cm3/g) b 0.003262 0.007270 0.002883 0.207041

SBET (m2/g) c 0.5413 2.07 1.4237 91.3743

DBJH (nm) d 24.20 14.03 8.09 9.26

Nitrogen, Carbon and Hydrogen content measured by elemental analysis Total pore volumes calculated as the amount of N2 adsorbed at P/Po = 0.99 c Brunauer-Emmet-Teller (BET) surface areas d Pore diameter calculated by Barett-Joyner-Halenda (BJH) method using the adsorption branches

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Table 5: Chemical analysis of FAS adsorbents Adsorbent FAS- bare FAS-APTES-10 FAS -APTES-25 FAS -APTES-50 FAS -TRIS-10 FAS -TRIS-25 FAS -TRIS-50 FAS -AMP-10 FAS -AMP-25 FAS -AMP-30 FAS -AMP-40 FAS -AMP-50 FAS -AMP-80 FAS -AMP-100 N mol % 0.01 0.65 2.05 3.41 4.21 11.65 14.21 0.87 2.78 4.21 5.12 5.89 7.45 11.84 C mol % 0.66 4.22 5.11 6.32 5.11 4.15 7.54 5.11 6.44 8.15 7.15 7.81 7.42 12.45 H mol % 2.08 4.15 4.51 5.14 4.14 7.11 8.14 1.24 4.54 7.45 4.84 5.12 4.18 7.84 N/C 0.01 0.15 0.40 0.53 0.82 2.80 1.88 0.17 0.43 0.51 0.71 0.75 1.00 0.95

CO2 N2

MFC MFC

Mixer

Temperature Controller

Tubular Furnace

To TCD-GC Auto-sampler valve on GC Sample Selector

Stream for feed Analysis

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Fig 1: Experimental setup used for breakthrough adsorption studies

Fig 2: Breakthrough curve for FAS-AMP-30 at different temperature

Charoite Calcium Sodium Aluminate

Tarasovite

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Fig 3: XRD comparison of FAS-bare and FAS-AMP-30

Figure 4: N2 adsorption isotherm for FAS-bare

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Figure 5: N2 adsorption isotherm for FAS-AMP-30

Figure 6: Pore size distribution curve for FAS-bare

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Figure 7: Pore size distribution curve for FAS-AMP-30

Fig 8: Thermal stability of FAS-bare and FAS-AMP-30 adsorbents

Fig 9: SEM image of A) FAS bare and B) FAS-AMP-30

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FAS BARE

FAS AMP

%T

4000.0

3600

3200

2800

2400

2000

1800 cm-1

1600

1400

1200

1000

800

600

450.0

Fig 10: Comparative FTIR of FAS bare and FAS-AMP-30

3960.80 3746.02

651.06 631.11

518.59

616.87 595.17 456.04 588.94 575.33

488.18 482.86 474.81 468.12

1379.48 1407.04 1647.74 812.89

1307.50

%T
1577.00 1558.96 1551.32 1476.83 3283.58

2886.61 2947.54 2825.68

1087.39

4000.0

3600

3200

2800

2400

2000

1800 cm-1

1600

1400

1200

1000

800

600

450.0

Fig 11: FTIR of CO2 adsorbed FAS-AMP-30 28

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