Abstract
In view of the promising applicability of adsorption to the capture of CO2 from post-combustion gases, the use of mesoporous silica functionalized with 3-aminopropyltriethoxysilane (APTES) was studied as adsorbent in a fixed bed for CO2–N2 separation under thermal swings. Characterization of the adsorbent performed before and after functionalization indicated that amine grafting was successful. Additionally, CO2 adsorption on a magnetic suspension balance showed a significant increase in uptake of the APTES-functionalized sample over the support, mainly at low relative pressures. Relatively high values of adsorption enthalpy suggest the occurrence of chemical adsorption attributed to CO2 bonding with the amines. Breakthrough curves were measured for pure CO2, N2 and the CO2/N2 (15/75% v/v) mixture, which showed good agreement with respect to the uptake of the individual gases, as determined from gravimetric tests. Full CO2 desorption from the bed required a temperature rise, which suggests that these materials may be suitable for TSA cyclic processes. A temperature of 90 °C was enough for a complete regeneration of the adsorbent during the desorption phase under dynamic conditions. The material showed very stable behavior after 20 successive cycles.
Similar content being viewed by others
References
Alkhabbaz, M.A., Bollini, P., Foo, G.S., Sievers, C., Jones, C.W.: Important roles of enthalpic and entropic contributions to CO2 capture from simulated flue gas and ambient air using mesoporous silica grafted amines. J. Am. Chem. Soc. 136(38), 13170–13173 (2014). https://doi.org/10.1021/ja507655x
Barret, E.P., Joyner, L.G., Halend, P.P.: The determination of pore volume and area distributions in porous substances. i. computations from nitrogen isotherms. J. Am. Chem. Soc. 73, 8 (1951)
Bastos-Neto, M., Moeller, A., Staudt, R., Böhm, J., Gläser, R.: Dynamic bed measurements of CO adsorption on microporous adsorbents at high pressures for hydrogen purification processes. Sep. Purif. Technol. 77(2), 251–260 (2011). https://doi.org/10.1016/j.seppur.2010.12.015
Bird, R.B., Stewart, W.E., Lightfoot, E.N.: Transport Phenomena. John Wiley & Sons Inc., New York (2002)
Brunauer, S., Emmett, P.H., Teller, E.: Adsorption of gases in multimolecular layers. J. Am. Chem. Soc. 60(2), 309–319 (1938). https://doi.org/10.1021/ja01269a023
Caplow, M.: Kinetics of carbamate formation and breakdown. J. Am. Chem. Soc. 90(24), 6795–6803 (1968). https://doi.org/10.1021/ja01026a041
Chakravartula Srivatsa, S., Bhattacharya, S.: Amine-based CO2 capture sorbents: a potential CO2 hydrogenation catalyst. J. CO2 Util. 26, 397–407 (2018). https://doi.org/10.1016/j.jcou.2018.05.028
Chang, F.-Y., Chao, K.-J., Cheng, H.-H., Tan, C.-S.: Adsorption of CO2 onto amine-grafted mesoporous silicas. Sep. Purif. Technol. 70(1), 87–95 (2009). https://doi.org/10.1016/j.seppur.2009.08.016
Chen, C., Son, W.-J., You, K.-S., Ahn, J.-W., Ahn, W.-S.: Carbon dioxide capture using amine-impregnated HMS having textural mesoporosity. Chem. Eng. J. 161(1–2), 46–52 (2010). https://doi.org/10.1016/j.cej.2010.04.019
da Silva, F.W.M., Maia, D.A.S., Oliveira, R.S., Moreno-Piraján, J.C., Sapag, K., Cavalcante, C.L., Zgrablich, G., Azevedo, D.C.S.: Adsorption microcalorimetry applied to the characterisation of adsorbents for CO2 capture. Can. J. Chem. Eng. 90(6), 1372–1380 (2012). https://doi.org/10.1002/cjce.21692
dos Santos, T.C., Bourrelly, S., Llewellyn, P.L., Carneiro, J.W., Ronconi, C.M.: Adsorption of CO2 on amine-functionalised MCM-41: experimental and theoretical studies. Phys. Chem. Chem. Phys. 17(16), 11095–11102 (2015). https://doi.org/10.1039/c5cp00581g
Dreisbach, F., Staudt, R., Keller, J.U.: High pressure adsorption data of methane, nitrogen, carbon dioxide and their binary and ternary mixtures on activated carbon. Adsorption 5(3), 215–227 (1999). https://doi.org/10.1023/A:1008914703884
Hahn, M.W., Steib, M., Jentys, A., Lercher, J.A.: Mechanism and kinetics of CO2 adsorption on surface bonded amines. J. Phys. Chem. C 119(8), 4126–4135 (2015). https://doi.org/10.1021/jp512001t
Hedin, N., Andersson, L., Bergström, L., Yan, J.: Adsorbents for the post-combustion capture of CO2 using rapid temperature swing or vacuum swing adsorption. Appl. Energy 104, 418–433 (2013). https://doi.org/10.1016/j.apenergy.2012.11.034
Hiyoshi, N., Yogo, K., Yashima, T.: Adsorption of carbon dioxide on modified mesoporous materials in the presence of water vapor. In: Steen, E.v., Callanan, L.H., Claeys, M. (eds.) 14th International Zeolite Conference, Cape Town 2004, vol. Part C, pp. 2995-3002. Studies in Surface Science and Catalysis
Hiyoshi, N., Yogo, K., Yashima, T.: Adsorption characteristics of carbon dioxide on organically functionalized SBA-15. Microporous Mesoporous Mater. 84(1–3), 357–365 (2005). https://doi.org/10.1016/j.micromeso.2005.06.010
Ho, M.T., Allinson, G.W., Wiley, D.E.: Reducing the cost of CO2 capture from flue gases using pressure swing adsorption. Ind. Eng. Chem. Res. 47(14), 4883–4890 (2008). https://doi.org/10.1021/ie070831e
IEA: Global Energy & CO2 Status Report. https://www.iea.org/geco/ (2018)
IPCC: Special Report on Carbon Dioxide Capture and Storage. (2005)
Le Thi, M.U., Lee, S.-Y., Park, S.-J.: Preparation and characterization of PEI-loaded MCM-41 for CO2 capture. Int. J. Hydrogen Energy 39(23), 12340–12346 (2014). https://doi.org/10.1016/j.ijhydene.2014.04.112
Kargari, A., Ravanchi, M.T.: Carbon Dioxide: Capturing and Utilization. In: Liu, D.G. (ed.) Greenhouse gases Capturing, Utilization and Reduction. InTech, Rijeka (2012)
Kim, S., Ida, J., Guliants, V.V., Lin, Y.S.: Tailoring pore properties of MCM-48 silica for selective adsorption of CO2. J Phys. Chem B 109(13), 6287–6293 (2005). https://doi.org/10.1021/jp045634x
Knöfel, C., Martin, C., Hornebecq, V., Llewellyn, P.L.: Study of carbon dioxide adsorption on mesoporous aminopropylsilane-functionalized silica and titania combining microcalorimetry and in situ infrared spectroscopy. J. Phys. Chem. C 113(52), 21726–21734 (2009). https://doi.org/10.1021/jp907054h
Mello, M.R., Phanon, D., Silveira, G.Q., Llewellyn, P.L., Ronconi, C.M.: Amine-modified MCM-41 mesoporous silica for carbon dioxide capture. Microporous Mesoporous Mater. 143(1), 174–179 (2011). https://doi.org/10.1016/j.micromeso.2011.02.022
Olea, A., Sanz-Pérez, E.S., Arencibia, A., Sanz, R., Calleja, G.: Amino-functionalized pore-expanded SBA-15 for CO2 adsorption. Adsorption 19(2–4), 589–600 (2013). https://doi.org/10.1007/s10450-013-9482-y
Parfenov, V.A., Ponomarenko, I.V., Zharkov, S.M., Kirik, S.D.: Controlling the microporosity of SBA-15 silicate material by background salt solution. Glass Phys. Chem. 40(1), 69–78 (2014). https://doi.org/10.1134/s1087659614010179
Rezaei, F., Sakwa-Novak, M.A., Bali, S., Duncanson, D.M., Jones, C.W.: Shaping amine-based solid CO 2 adsorbents: effects of pelletization pressure on the physical and chemical properties. Microporous Mesoporous Mater. 204, 34–42 (2015). https://doi.org/10.1016/j.micromeso.2014.10.047
Rios, R.B., Correia, L.S., Bastos-Neto, M., Torres, A.E.B., Hatimondi, S.A., Ribeiro, A.M., Rodrigues, A.E., Cavalcante, C.L., de Azevedo, D.C.S.: Evaluation of carbon dioxide–nitrogen separation through fixed bed measurements and simulations. Adsorption 20(8), 945–957 (2014). https://doi.org/10.1007/s10450-014-9639-3
Sánchez-Zambrano, K.S., Vilarrasa-García, E., Maia, D.A.S., Bastos-Neto, M., Rodríguez-Castellon, E., Azevedo, D.C.S.: Adsorption microcalorimetry as a tool in the characterization of amine-grafted mesoporous silicas for CO2 capture. Adsorption. (2019). https://doi.org/10.1007/s10450-019-00064-y
Sanz-Pérez, E.S., Dantas, T.C.M., Arencibia, A., Calleja, G., Guedes, A.P.M.A., Araujo, A.S., Sanz, R.: Reuse and recycling of amine-functionalized silica materials for CO2 adsorption. Chem. Eng. J. 308, 1021–1033 (2017). https://doi.org/10.1016/j.cej.2016.09.109
Sanz-Pérez, E.S., Olivares-Marín, M., Arencibia, A., Sanz, R., Calleja, G., Maroto-Valer, M.M.: CO2 adsorption performance of amino-functionalized SBA-15 under post-combustion conditions. Int. J. Greenhouse Gas Control 17, 366–375 (2013). https://doi.org/10.1016/j.ijggc.2013.05.011
Sanz, R., Calleja, G., Arencibia, A., Sanz-Pérez, E.S.: Amino functionalized mesostructured SBA-15 silica for CO2 capture: exploring the relation between the adsorption capacity and the distribution of amino groups by TEM. Microporous Mesoporous Mater. 158, 309–317 (2012). https://doi.org/10.1016/j.micromeso.2012.03.053
Sayari, A., Belmabkhout, Y., Serna-Guerrero, R.: Flue gas treatment via CO2 adsorption. Chem. Eng. J. 171(3), 760–774 (2011). https://doi.org/10.1016/j.cej.2011.02.007
Serna-Guerrero, R., Belmabkhout, Y., Sayari, A.: Influence of regeneration conditions on the cyclic performance of amine-grafted mesoporous silica for CO2 capture: an experimental and statistical study. Chem. Eng. Sci. 65(14), 4166–4172 (2010). https://doi.org/10.1016/j.ces.2010.04.029
Silva, B., Solomon, I., Ribeiro, A.M., Lee, U.H., Hwang, Y.K., Chang, J.-S., Loureiro, J.M., Rodrigues, A.E.: H2 purification by pressure swing adsorption using CuBTC. Sep. Purif. Technol. 118, 744–756 (2013). https://doi.org/10.1016/j.seppur.2013.08.024
Siqueira, R.M., Freitas, G.R., Peixoto, H.R., Nascimento, J.F., Musse, A.P.S., Torres, A.E.B., Azevedo, D.C.S., Bastos-Neto, M.: Carbon Dioxide Capture by Pressure Swing Adsorption. Energy Procedia 114, 2182–2192 (2017). https://doi.org/10.1016/j.egypro.2017.03.1355
Thommes, M., Kaneko, K., Neimark, A.V., Olivier, J.P., Rodriguez-Reinoso, F., Rouquerol, J., Sing, K.S.W.: Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87(9–10), 1051–1069 (2015). https://doi.org/10.1515/pac-2014-1117
Vilarrasa-García, E., Cecilia, J.A., Bastos-Neto, M., Cavalcante, C.L., Azevedo, D.C.S., Rodriguez-Castellón, E.: CO2/CH4 adsorption separation process using pore expanded mesoporous silicas functionalizated by APTES grafting. Adsorption 21(8), 565–575 (2015). https://doi.org/10.1007/s10450-015-9700-x
Vilarrasa-García, E., Cecilia, J.A., Santos, S.M.L., Cavalcante, C.L., Jiménez-Jiménez, J., Azevedo, D.C.S., Rodríguez-Castellón, E.: CO2 adsorption on APTES functionalized mesocellular foams obtained from mesoporous silicas. Microporous Mesoporous Mater. 187, 125–134 (2014). https://doi.org/10.1016/j.micromeso.2013.12.023
Vilarrasa-Garcia, E., Moya, E.M.O., Cecilia, J.A., Cavalcante, C.L., Jiménez-Jiménez, J., Azevedo, D.C.S., Rodríguez-Castellón, E.: CO2 adsorption on amine modified mesoporous silicas: effect of the progressive disorder of the honeycomb arrangement. Microporous Mesoporous Mater. 209, 172–183 (2015). https://doi.org/10.1016/j.micromeso.2014.08.032
Wang, L., Yang, R.T.: Increasing selective CO2 adsorption on amine-grafted SBA-15 by increasing silanol density. J. Phys. Chem. C 115(43), 21264–21272 (2011). https://doi.org/10.1021/jp206976d
Wei, L., Gao, Z., Jing, Y., Wang, Y.: Adsorption of CO2 from simulated flue gas on pentaethylenehexamine-loaded mesoporous silica support adsorbent. Ind. Eng. Chem. Res. 52(42), 14965–14974 (2013). https://doi.org/10.1021/ie402162x
Yan, X., Zhang, L., Zhang, Y., Yang, G., Yan, Z.: Amine-modified SBA-15: effect of pore structure on the performance for CO2 capture. Ind. Eng. Chem. Res. 50(6), 3220–3226 (2011). https://doi.org/10.1021/ie101240d
Yıldız, M.G., Davran-Candan, T., Günay, M.E., Yıldırım, R.: CO2 capture over amine-functionalized MCM-41 and SBA-15: exploratory analysis and decision tree classification of past data. J. CO2 Util. 31, 27–42 (2019). https://doi.org/10.1016/j.jcou.2019.02.010
Zhang, G., Zhao, P., Hao, L., Xu, Y.: Amine-modified SBA-15(P): a promising adsorbent for CO2 capture. J. CO2 Util. 24, 22–33 (2018). https://doi.org/10.1016/j.jcou.2017.12.006
Zhao, A., Samanta, A., Sarkar, P., Gupta, R.: Carbon dioxide adsorption on amine-impregnated mesoporous SBA-15 sorbents: experimental and kinetics study. Ind. Eng. Chem. Res. 52(19), 6480–6491 (2013). https://doi.org/10.1021/ie3030533
Zhao, D., Feng, J., Huo, Q., Melosh, N., Fredrickson, G.H., Chmelka, B.F., Stucky, G.D.: Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279, 548–552 (1998). https://doi.org/10.1126/science.279.5350.548
Acknowledgements
The authors acknowledge financial support from CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) and CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior).
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Santiago, R.G., Siqueira, R.M., Alves, C.A. et al. Evaluation of the thermal regeneration of an amine-grafted mesoporous silica used for CO2/N2 separation. Adsorption 26, 203–215 (2020). https://doi.org/10.1007/s10450-019-00112-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10450-019-00112-7