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Influence of acid treatment on structure of clinoptilolite tuff and its adsorption of methane

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Abstract

This study presents the results of the methane adsorption properties of clinoptilolite tuff from Bigadic, Turkey and that of acid treated forms at 273 and 293 K up to 100 kPa using volumetric apparatus. In order to assess changes in structural and gas adsorption properties of clinoptilolite, zeolite sample was treated with acid solutions of varying concentrations (0.1, 0.5, 1.0 and 2.0 M) at 70 °C during 3 h. Structural and thermal characterization of natural and acid treated clinoptilolite samples were carried out using a combination of techniques such as X-ray diffraction, X-ray fluorescence, thermogravimetric, differential thermal analysis and nitrogen adsorption methods. At both temperatures, uptake of methane (CH4) increased in the following order: CLN < CLN-H2 < CLN-H1 < CLN-H05 < CLN-H01. CH4 adsorption capacities of the original and acid treated clinoptilolites were found in the range of 0.476–0.910 mmol/g and 0.398–0.691 mmol/g at 273 and 293 K, respectively.

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Abbreviations

CLN:

Original clinoptilolite

CLN-H01:

Clinoptilolite treated with 0.1 M HCl solution

CLN-H05:

Clinoptilolite treated with 0.5 M HCl solution

CLN-H1:

Clinoptilolite treated with 1.0 M HCl solution

CLN-H2:

Clinoptilolite treated with 2.0 M HCl solution

References

  • Ackley, M.W., Yang, R.T.: Adsorption characteristics of high-exchange clinoptilolites. Ind. Eng. Chem. Res. 30, 2523–2530 (1991)

    Article  CAS  Google Scholar 

  • Ackley, M.W., Giese, R.F., Yang, R.T.: Clinoptilolite: untapped potential for kinetic gas separations. Zeolites 12, 780–788 (1992)

    Article  CAS  Google Scholar 

  • Aguilar-Armenta, G., Hernandez-Ramirez, G., Flores-Loyola, E., Ugarte-Castaneda, A., Silva-Gonzalez, R., Tabares-Munoz, C., Jimenez-Lopez, A., Rodriguez-Castellon, E.: Adsorption kinetics of CO2, O2, N2, and CH4 in cation-exchanged clinoptilolite. J. Phys. Chem. B 105, 1313–1319 (2001)

    Article  CAS  Google Scholar 

  • Aguilar-Armenta, G., Patiño-Iglesias, M.E., Leyva-Ramos, R.: Adsorption kinetic behaviour of pure CO2, N2 and CH4 in natural clinoptilolite at different temperatures. Adsorpt. Sci. Technol. 21, 81–91 (2003)

    Article  CAS  Google Scholar 

  • Aguilar-Armenta, G., Romero-Perez, A.: Adsorption of C2H4, C2H6 and CO2 on cation-exchanged clinoptilolite. Adsorpt. Sci. Technol. 27, 523–536 (2009)

    Article  CAS  Google Scholar 

  • Ahmed, M.J., Theydan, S.K.: Equilibrium isotherms and adsorption heats analysis for ternary mixture of methane, ethane, and propane on 4A zeolite. J. Porous Mater. 21, 747–755 (2014)

    Article  CAS  Google Scholar 

  • Antoniou, M.K., Diamanti, E.K., Enotiadis, A., Policicchio, A., Dimos, K., Ciuchi, F., Maccallini, E., Gournis, D., Agostino, R.G.: Methane storage in zeolite-like carbon materials. Microporous Mesoporous Mater 188, 16–22 (2014)

    Article  CAS  Google Scholar 

  • Arcoya, A., Gonzalez, J.A., Travieso, N., Seoane, X.L.: Physicochemical and catalytic properties of a modified natural clinoptilolite. Clay Miner. 29(1), 123–131 (1994)

    Article  CAS  Google Scholar 

  • Arcoya, A., González, J.A., Llabre, G., Seoane, X.L., Travieso, N.: Role of the countercations on the molecular sieve properties of a clinoptilolite. Microporous Mater. 7(1), 1–13 (1996)

    Article  CAS  Google Scholar 

  • Barrer, R.M.: Zeolites and Clay Minerals as Sorbents and Molecular Sieves. Academic Press, New York (1978)

    Google Scholar 

  • Berlier, K., Olivier, M.G., Jadot, R.: Adsorption of methane, ethane, and ethylene on zeolite. J. Chem. Eng. Data 40, 1206–1208 (1995)

    Article  CAS  Google Scholar 

  • Breck, D.W.: Zeolite Molecular Sieves. Wiley, New York (1984)

    Google Scholar 

  • Brunauer, S., Deming, L.S., Deming, W.E., Teller, E.: On a theory of the van der Waals adsorption of gases. J. Am. Chem. Soc. 62, 1723–1732 (1940)

    Article  CAS  Google Scholar 

  • Cardarelli, F.: Materials Handbook: A Concise Desktop Reference, 2nd edn. Springer, New York (2008)

    Google Scholar 

  • Carson, P., Mumford, C.: Hazardous Chemicals Handbook, 2nd edn. Butterworth-Heinemann, Burlington (2002)

    Google Scholar 

  • Cavenati, S., Grande, C.A., Rodrigues, A.E.: Adsorption equilibrium of methane, carbon dioxide, and nitrogen on zeolite 13X at high pressures. J. Chem. Eng. Data 49, 1095–1101 (2004)

    Article  CAS  Google Scholar 

  • Christidis, G.E., Moraetis, D., Keheyan, E., Akhalbedashvili, L., Kekelidze, N., Gevorkyan, R., Yeritsyan, H., Sargsyan, H.: Chemical and thermal modification of natural HEU-type zeolitic materials from Armenia, Georgia and Greece. Appl. Clay Sci. 24(1–2), 79–91 (2003)

    Article  CAS  Google Scholar 

  • Choudhary, V.R., Mayadevi, S., Pal Singh, A.: Sorption isotherms of methane, ethane, ethene and carbon dioxide on NaX, NaY and Na-mordenite zeolites. J. Chem. Soc., Faraday Trans. 91, 2935–2944 (1995)

    Article  CAS  Google Scholar 

  • Çakıcıoğlu-Özkan, F., Ülkü, S.: The effect of HCl treatment on water vapor adsorption characteristics of clinoptilolite rich natural zeolite. Microporous Mesoporous Mater. 77, 47–53 (2005)

    Article  Google Scholar 

  • Ding, T.F., Ozawa, S., Yamazaki, T., Watanuki, I., Ogino, Y.: A generalized treatment of adsorption of methane onto various zeolites. Langmuir 4, 392–396 (1988)

    Article  CAS  Google Scholar 

  • Dyer, A.: An Introduction to Zeolite Molecular Sieves. Wiley, New York (1988)

    Google Scholar 

  • Esenli, F., Sirkecioğlu, A.: The relationship between zeolite (heulandite–clinoptilolite) content and the ammonium-exchange capacity of pyrodastic rocks in Gordes, Turkey. Clay Miner. 40(4), 557–564 (2005)

    Article  CAS  Google Scholar 

  • Galli, E., Gottardi, G., Mayer, H., Preisinger, A., Passaglia, E.: The structure of potassium-exchanged heulandite at 293, 373 and 593 K. Acta Crystallogr. B 39, 189–197 (1983)

    Article  Google Scholar 

  • Garcia-Basabe, Y., Rodriguez-Iznaga, I., de Menorval, L., Llewellyn, P., Maurin, G., Lewisf, D.W., Binionsf, R., Autieg, M.A., Ruiz-Salvadora, R.: Step-wise dealumination of natural clinoptilolite: structural and physicochemical characterization. Microporous Mesoporous Mater. 135(1–3), 187–196 (2010)

    Article  CAS  Google Scholar 

  • Gottardi, G., Galli, E.: Natural Zeolites. Springer, Berlin (1985)

    Book  Google Scholar 

  • Grande, C.A., Blom, R.: Cryogenic adsorption of methane and carbon dioxide on zeolites 4A and 13X. Energy Fuels 28, 6688–6693 (2014)

    Article  CAS  Google Scholar 

  • Gregg, S.J., Sing, K.S.W.: Adsorption, Surface Area and Porosity, 2nd edn. Academic Press, London (1982)

    Google Scholar 

  • Hamzah, S.A., Mahmood, N.Z., Sulaiman, A.H.: Ozone depletion substances (ODS) emission analysis from the life cycle of chemical substances and electricity used in potable water production in Malaysia. Aust. J. Basic & Appl. Sci. 4 (9), 4286–4293 (2010)

    Google Scholar 

  • Hernandez-Beltran, N.A., Olguin, M.T.: Elemental composition variability of clinoptilolite-rich tuff after the treatment with acid phosphate solutions. Hydrometallurgy 89, 374–378 (2007)

    Article  CAS  Google Scholar 

  • Hernández-Huesca, R., Díaz, L., Aguilar-Armenta, G.: Adsorption equilibria and kinetics of CO2, CH4 and N2 in natural zeolites. Sep. Purif. Technol. 15, 163–173 (1999)

    Article  Google Scholar 

  • Jayaraman, A., Yang, R.T., Chinn, D., Munson, C.L.: Tailored clinoptilolites for nitrogen/methane separation. Ind. Eng. Chem. Res. 44, 5184–5192 (2005)

    Article  CAS  Google Scholar 

  • Korkuna, O., Leboda, R., Skubiszewska-Zeiba, J., Vrublevska, T., Gunko, V.M., Ryczkowski, J.: Structural and physicochemical properties of natural zeolites: clinoptilolite and mordenite. Microporous Mesoporous Mater. 87, 243–254 (2006)

    Article  CAS  Google Scholar 

  • Kouvelosa, E., Kesoreb, K., Steriotisa, T., Grigoropoulouc, H., Bouloubasid, D., Theophiloud, N., Tzintzosd, S., Kanelopoulosa, N.: High pressure N2/CH4 adsorption measurements in clinoptilolites. Microporous Mesoporous Mater. 99, 106–111 (2007)

    Article  Google Scholar 

  • Koyama, K., Takeuchi, Y.: Clinoptilolite: the distribution of potassium atoms and its role in thermal analysis. Z. Kristallogr. 145, 216–239 (1977)

    Article  CAS  Google Scholar 

  • Lide, D.R.: CRC Handbook of Chemistry and Physics. CRC Press, Boca Raton (2003)

    Google Scholar 

  • Macedonia, M.D., Moore, D.D., Maginn, E.J., Olken, M.M.: Adsorption studies of methane, ethane, and argon in the zeolite mordenite: molecular simulations and experiments. Langmuir 16, 3823–3834 (2000)

    Article  CAS  Google Scholar 

  • Maple, M.J., Williams, C.D.: Separating nitrogen/methane on zeolite like molecular sieves. Microporous Mesoporous Mater. 111, 627–631 (2008)

    Article  CAS  Google Scholar 

  • Merkle, A.B., Slaughter, M.: Determination and refinement of the structure of heulandite. Am. Mineral. 53, 1120–1138 (1968)

    CAS  Google Scholar 

  • Moore, D.M., Reynolds Jr, R.C.: X-ray Diffraction and the Identification and Analysis of Clay Minerals, 2nd edn. Oxford University Press, New York (1997)

    Google Scholar 

  • Mumpton, F.A.: Clinoptilolite redefined. Am. Mineral. 45, 351–369 (1960)

    CAS  Google Scholar 

  • Patnaik, P.: Handbook of Environmental Analysis, Chemical Pollutants in Air, Water, Soil, and Solid Wastes, 2nd edn. CRC Press, Boca Raton (2010)

    Book  Google Scholar 

  • Petrakakis, Y., Mylona, E., Georgantas, D., Grigoropoulou, H.: Leaching of lead from clinoptilolite at acidic conditions. Global NEST J. 9(3), 207–213 (2007)

    Google Scholar 

  • Predescu, L., Tezel, F.H., Stelmack, P.: Adsorption of Nitrogen and Methane on Natural Clinoptilolite. In: Bonneviot, L., Kaliaguin, S. (eds.) Zeolites: A Refined Tool for Designing Catalytic Sites, pp. 507–512. Elsevier, Amsterdam (1995)

    Chapter  Google Scholar 

  • Radosavljević-Mihajlović, A., Dondur, V., Daković, A., Lemić, J., Tomašević-Čanović, M.: Physicochemical and structural characteristics of HEU-type zeolitic tuff treated by hydrochloric acid. J. Serb. Chem. Soc. 69(4), 273–281 (2004)

    Article  Google Scholar 

  • Rozic, M., Cerjan-Stefanovic, S., Kurajica, S., Rozmari Maeefat, M., Margeta, K., Farkas, A.: Decationization and dealumination of clinoptilolite tuff and ammonium exchange on acid-modified tuff. J. Colloid Interface Sci. 284, 48–56 (2005)

    Article  CAS  Google Scholar 

  • Salvestrini, S., Sagliano, P., Iovino, P., Capasso, S., Colella, C.: Atrazine adsorption by acid activated zeolite-rich tuffs. Appl. Clay Sci. 49, 330–335 (2010)

    Article  CAS  Google Scholar 

  • Shindell, D.T., Faluvegi, G., Koch, D.M., Schmidt, G.A., Unger, N., Bauer, S.E.: Improved attribution of climate forcing to emissions. Science 326(5953), 716–718 (2009)

    Article  CAS  Google Scholar 

  • Triebe, R.W., Tezel, F.H., Khulbe, K.C.: Adsorption of methane, ethane and ethylene on molecular sieve zeolites. Gas Sep. Purif. 10, 81–84 (1996)

    Article  CAS  Google Scholar 

  • Tsitsishvili, G.V.: Physicochemical properties of high silica L and clinoptilolite zeolites. In: Meier, W.M., Uytterhoeven, J.B. (eds.) Molecular Sieves, pp. 291–298. ACS, Washington DC (1973)

    Chapter  Google Scholar 

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Acknowledgments

Special thanks to Dr. Matthias Thommes for his helpful suggestions.

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  1. Department of Physics, Faculty of Science, Anadolu University, 26470, Eskisehir, Turkey

    Burcu Erdoğan Alver & Meryem Sakizci

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  1. Burcu Erdoğan Alver
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  2. Meryem Sakizci
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Correspondence to Burcu Erdoğan Alver.

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Alver, B.E., Sakizci, M. Influence of acid treatment on structure of clinoptilolite tuff and its adsorption of methane. Adsorption 21, 391–399 (2015). https://doi.org/10.1007/s10450-015-9679-3

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  • DOI: https://doi.org/10.1007/s10450-015-9679-3

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