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A computational study of CO2, N2, and CH4 adsorption in zeolites

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Abstract

The adsorption properties of CO2, N2 and CH4 in all-silica zeolites were studied using molecular simulations. Adsorption isotherms for single components in MFI were both measured and computed showing good agreement. In addition simulations in other all silica structures were performed for a wide range of pressures and temperatures and for single components as well as binary and ternary mixtures with varying bulk compositions. The adsorption selectivity was analyzed for mixtures with bulk composition of 50:50 CO2/CH4, 50:50 CO2/N2, 10:90 CO2/N2 and 5:90:5 CO2/N2/CH4 in MFI, MOR, ISV, ITE, CHA and DDR showing high selectivity of adsorption of CO2 over N2 and CH4 that varies with the type of crystal and with the mixture bulk composition.

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Abbreviations

p:

Pressure, Pa

po:

Saturation pressure, Pa

qSi :

Point charge of silicon

qO :

Point charge of oxygen

References

  • Auerbach, S.M., Kärger, J., Vasenkov, S.: Diffusion in zeolites. In: Auerbach, S.M., Carrado, K.A., Dutta, P.K. (eds.) Handbook of Zeolite Science and Technology. Dekker, New York (2003)

    Google Scholar 

  • Babarao, R., Hu, Z.Q., Jiang, J.W., Chempath, S., Sandler, S.I.: Storage and separation of CO2 and CH4 in silicalite, C-168 schwarzite, and IRMOF-1: a comparative study from Monte Carlo simulation. Langmuir 23, 659–666 (2007)

    Article  CAS  Google Scholar 

  • Baerlocher, C., Meier, W.M., Olson, D.H.: Atlas of Zeolite Structure Types, 5th edn. Elsevier, London (2001)

    Google Scholar 

  • Bernal, M.P., Coronas, J., Menendez, M., Santamaria, J.: Separation of CO2/N-2 mixtures using MFI-type zeolite membranes. AIChE J. 50, 127–135 (2004)

    Article  CAS  Google Scholar 

  • Bezus, A.G., Kiselev, A.V., Lopatkin, A.A., Du, P.Q.: Molecular statistical calculation of thermodynamic adsorption characteristics of zeolites using atom-atom approximation. 1. Adsorption of methane by zeolite Nax. J. Chem. Soc. Faraday Trans. II 74, 367–379 (1978)

    Article  CAS  Google Scholar 

  • Bodoardo, S., Borello, L., Fiorilli, S., Garrone, E., Onida, B., Arean, C.O., Penazzi, N., Palomino, G.T.: Methylene blue encapsulated in silica-based mesophases: characterisation and electrochemical activity. Microporous Mesoporous Mater. 79, 275–281 (2005)

    Article  CAS  Google Scholar 

  • Breck, D.W.: Zeolite Molecular Sieves. Wiley, New York (1974)

    Google Scholar 

  • Calero, S., Dubbeldam, D., Krishna, R., Smit, B., Vlugt, T.J.H., Denayer, J.F.M., Martens, J.A., Maesen, T.L.M.: Understanding the role of sodium during adsorption: A force field for alkanes in sodium-exchanged faujasites. J. Am. Chem. Soc. 126, 11377–11386 (2004)

    Article  CAS  Google Scholar 

  • Choudhary, V.R., Mayadevi, S.: Adsorption of methane, ethane, ethylene, and carbon dioxide on silicalite-I. Zeolites 17, 501–507 (1996)

    Article  CAS  Google Scholar 

  • Delgado, J.A., Uguina, M.A., Gomez, J.M., Ortega, L.: Adsorption equilibrium of carbon dioxide, methane and nitrogen onto Na- and H-mordenite at high pressures. Sep. Purif. Technol. 48, 223–228 (2006)

    Article  CAS  Google Scholar 

  • Dubbeldam, D., Calero, S., Maesen, T.L.M., Smit, B.: Incommensurate diffusion in confined systems. Phys. Rev. Lett. 90, 245901 (2003)

    Article  CAS  Google Scholar 

  • Dubbeldam, D., Calero, S., Vlugt, T.J.H., Krishna, R., Maesen, T.L.M., Beerdsen, E., Smit, B.: Force field parametrization through fitting on inflection points in isotherms. Phys. Rev. Lett. 93 (2004a)

  • Dubbeldam, D., Calero, S., Vlugt, T.J.H., Krishna, R., Maesen, T.L.M., Smit, B.: United atom force field for alkanes in nanoporous materials. J. Phys. Chem. B 108, 12301–12313 (2004b)

    Article  CAS  Google Scholar 

  • Dubbeldam, D., Beerdsen, E., Calero, S., Smit, B.: Molecular path control in zeolite membranes. Proc. Nat. Acad. Sci. USA 102, 12317–12320 (2005)

    Article  CAS  Google Scholar 

  • Frenkel, D., Smit, B.: Understanding Molecular Simulations: From Algorithms to Applications, 2nd edn. Academic, San Diego (2002)

    Google Scholar 

  • Garcia-Perez, E., Dubbeldam, D., Liu, B., Smit, B., Calero, S.: A computational method to characterize framework aluminum in aluminosilicates. Angew. Chem. Int. Ed. 46, 276–278 (2007)

    Article  CAS  Google Scholar 

  • Gardner, T.Q., Falconer, J.L., Noble, R.D.: Adsorption and diffusion properties of zeolite membranes by transient permeation. Desalination 149, 435–440 (2002)

    Article  CAS  Google Scholar 

  • Goj, A., Sholl, D.S., Akten, E.D., Kohen, D.: Atomistic simulations of CO2 and N-2 adsorption in silica zeolites: The impact of pore size and shape. J. Phys. Chem. B 106, 8367–8375 (2002)

    Article  CAS  Google Scholar 

  • Grey, T.J., Travis, K.P., Gale, J.D., Nicholson, D.: A comparative simulation study of the adsorption of nitrogen and methane in siliceous heulandite and chabazite. Microporous Mesoporous Mater. 48, 203–209 (2001)

    Article  CAS  Google Scholar 

  • Harlick, P.J.E., Tezel, F.H.: Adsorption of carbon dioxide, methane, and nitrogen. Sep. Sc. Technol. 37, 33–60 (2002)

    Article  CAS  Google Scholar 

  • Harlick, P.J.E., Tezel, F.H.: Adsorption of carbon dioxide, methane and nitrogen: pure and binary mixture adsorption for ZSM-5 with SiO2/Al2O3 ratio of 280. Sep. Purif. Technol. 33, 199–210 (2003)

    Article  CAS  Google Scholar 

  • Harris, J.G., Yung, K.H.: Carbon dioxide’s liquid-vapor coexistence curve and critical properties as predicted by a simple molecular model. J. Phys. Chem. 99(31), 12021–12024 (1995)

    Article  CAS  Google Scholar 

  • Hasegawa, Y., Kusakabe, K., Morooka, S.: Effect of temperature on the gas permeation properties of NaY-type zeolite formed on the inner surface of a porous support tube. Chem. Eng. Sci. 56, 4273–4281 (2001)

    Article  CAS  Google Scholar 

  • Himeno, S., Tomita, T., Suzuki, K., Yoshida, S.: Characterization and selectivity for methane and carbon dioxide adsorption on the all-silica DD3R zeolite. Microporous Mesoporous Mater. 98, 62–69 (2007)

    Article  CAS  Google Scholar 

  • Hirotani, A., Mizukami, K., Miura, R., Takaba, H., Miya, T., Fahmi, A., Stirling, A., Kubo, M., Miyamoto, A.: Grand canonical Monte Carlo simulation of the adsorption of CO2 on silicalite and NaZSM-5. Appl. Surf. Sci. 120, 81–84 (1997)

    Article  CAS  Google Scholar 

  • Jaramillo, E., Auerbach, S.M.: New force field for Na cations in faujasite-type zeolites. J. Phys. Chem. B 103, 9589–9594 (1999)

    Article  CAS  Google Scholar 

  • Jia, W., Murad, S.: Molecular dynamics simulations of gas separations using faujasite-type zeolite membranes. J. Chem. Phys. 120, 4877–4885 (2004)

    Article  CAS  Google Scholar 

  • Kiselev, A.V., Lopatkin, A.A., Shulga, A.A.: Molecular statistical calculation of gas-adsorption by silicalite. Zeolites 5, 261–267 (1985)

    Article  CAS  Google Scholar 

  • Krishna, R., Smit, B., Calero, S.: Entropy effects during sorption of alkanes in zeolites. Chem. Soc. Rev. 31, 185–194 (2002)

    Article  CAS  Google Scholar 

  • Kusakabe, K., Kuroda, T., Uchino, K., Hasegawa, Y., Morooka, S.: Gas permeation properties of ion-exchanged faujasite-type zeolite membranes. AIChE J. 45, 1220–1226 (1999)

    Article  CAS  Google Scholar 

  • Li, S.G., Falconer, J.L., Noble, R.D.: SAPO-34 membranes for CO2/CH4 separation. J. Membr. Sci. 241, 121–135 (2004)

    Article  CAS  Google Scholar 

  • Li, S.G., Alvarado, G., Noble, R.D., Falconer, J.L.: Effects of impurities on CO2/CH4 separations through SAPO-34 membranes. J. Membrane Sci. 251, 59–66 (2005)

    Article  CAS  Google Scholar 

  • Lillerud, H.R.a.K.P.: Verified Synthesis of Zeolitic Materials. Elsevier, Amsterdam (2001)

    Google Scholar 

  • Llewellyn, P.L., Coulomb, J.P., Grillet, Y., Patarin, J., Andre, G., Rouquerol, J.: Adsorption by Mfi-type zeolites examined by isothermal microcalorimetry and neutron-diffraction. 2. Nitrogen and carbon-monoxide. Langmuir 9, 1852–1856 (1993)

    Article  CAS  Google Scholar 

  • Maesen, T.L.M., Beerdsen, E., Calero, S., Dubbeldam, D., Smit, B.: Understanding cage effects in the n-alkane conversion on zeolites. J. Catal. 237, 278–290 (2006)

    Article  CAS  Google Scholar 

  • Makrodimitris, K., Papadopoulos, G.K., Theodorou, D.N.: Prediction of permeation properties of CO2 and N-2 through silicalite via molecular simulations. J. Phys. Chem. B 105, 777–788 (2001)

    Article  CAS  Google Scholar 

  • Murthy, C.S., Singer, K., Klein, M.L., McDonald, I.R.: Pairwise Additive Effective Potentials for Nitrogen. Mol. Phys. 41, 1387–1399 (1980)

    Article  CAS  Google Scholar 

  • Nam, G.M., Jeong, B.M., Kang, S.H., Lee, B.K., Choi, D.K.: Equilibrium isotherms of CH4, C2H6, C2H4, N-2, and N-2 on zeolite 5A using a static volumetric method. J. Chem. Eng. Data 50, 72–76 (2005)

    Article  CAS  Google Scholar 

  • Parra, J.B., Ania, C.O., Arenillas, A., Rubiera, F., Pis, J.J., Palacios, J.M.: Structural changes in polyethylene terephthalate (PET) waste materials caused by pyrolysis and CO2 activation. Adsorpt. Sci. Technol. 24, 439–449 (2006)

    Article  CAS  Google Scholar 

  • Poshusta, J.C., Tuan, V.A., Falconer, J.L., Noble, R.D.: Synthesis and permeation properties of SAPO-34 tubular membranes. Ind. Eng. Chem. Res. 37, 3924–3929 (1998)

    Article  CAS  Google Scholar 

  • Poshusta, J.C., Noble, R.D., Falconer, J.L.: Temperature and pressure effects on CO2 and CH4 permeation through MFI zeolite membranes. J. Membr. Sci. 160, 115–125 (1999)

    Article  CAS  Google Scholar 

  • Ryckaert, J.P., Bellemans, A.: Molecular-Dynamics of Liquid Alkanes. Faraday Discuss. 95–106 (1978)

  • Schenk, M., Calero, S., Maesen, T.L.M., van Benthem, L.L., Verbeek, M.G., Smit, B.: Understanding zeolite catalysis: Inverse shape selectivity revised. Angew. Chem. Int. Ed. 41, 2500 (2002)

    Article  Google Scholar 

  • Sun, M.S., Shah, D.B., Xu, H.H., Talu, O.: Adsorption equilibria of C-1 to C-4 alkanes, CO2, and SF6 on silicalite. J. Phys. Chem. B 102, 1466–1473 (1998)

    Article  CAS  Google Scholar 

  • Tomita, T., Nakayama, K., Sakai, H.: Gas separation characteristics of DDR type zeolite membrane. Microporous Mesoporous Mater. 68, 71–75 (2004)

    Article  CAS  Google Scholar 

  • van den Broeke, L.J.P., Bakker, W.J.W., Kapteijn, F., Moulijn, J.A.: Transport and separation properties of a silicalite-1 membrane. I. Operating conditions. Chem. Eng. Sci. 54, 245–258 (1999)

    Article  Google Scholar 

  • Watanabe, K., Austin, N., Stapleton, M.R.: Investigation of the air separation properties of zeolites type-a, type-X and type-Y by Monte-Carlo simulations. Mol. Simul. 15, 197 (1995)

    Article  CAS  Google Scholar 

  • Webster, C.E., Cottone, A., Drago, R.S.: Multiple equilibrium analysis description of adsorption on Na-mordenite and H-mordenite. J. Am. Chem. Soc. 121, 12127–12139 (1999)

    Article  CAS  Google Scholar 

  • Yu, J.B., Jiang, Z., Zhu, L., Hao, Z.P., Xu, Z.P.: Adsorption/desorption studies of NOx on well-mixed oxides derived from Co-Mg/Al hydrotalcite-like compounds. J. Phys. Chem. B 110, 4291–4300 (2006)

    Article  CAS  Google Scholar 

  • Zhu, W.D., Hrabanek, P., Gora, L., Kapteijn, F., Moulijn, J.A.: Role of adsorption in the permeation of CH4 and CO2 through a silicalite-1 membrane. Ind. Eng. Chem. Res. 45, 767–776 (2006)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Physical, Chemical and Natural Systems, University Pablo de Olavide, Ctra. Utrera km. 1, 41013, Seville, Spain

    E. García-Pérez & S. Calero

  2. Energy and Environment Department, Instituto Nacional del Carbón, CSIC, P.O. 73, 33080, Oviedo, Spain

    J. B. Parra & C. O. Ania

  3. van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV, Amsterdam, The Netherlands

    A. García-Sánchez, J. M. van Baten & R. Krishna

  4. Chemical and Biological Engineering Department, Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208, USA

    D. Dubbeldam

Authors
  1. E. García-Pérez
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  2. J. B. Parra
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  3. C. O. Ania
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  4. A. García-Sánchez
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  5. J. M. van Baten
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  6. R. Krishna
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  7. D. Dubbeldam
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  8. S. Calero
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Correspondence to S. Calero.

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García-Pérez, E., Parra, J.B., Ania, C.O. et al. A computational study of CO2, N2, and CH4 adsorption in zeolites. Adsorption 13, 469–476 (2007). https://doi.org/10.1007/s10450-007-9039-z

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  • DOI: https://doi.org/10.1007/s10450-007-9039-z

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