Basicity of Jordanian Natural Clays Studied by Pyrrole-tpd and Catalytic Conversion of Methylbutynol
The main objective of this study is to investigate basic properties of different natural clays, by two methods. The first method is a gas phase conversion of methylbutynol (MBOH). The second method is the application of Pyrrole-tpd. Based on the product distribution from the first method, the acidic, basic and coordinately unsaturated sites were differentiated. It was shown that both the conversion and the selectivity for basic products did not change with reaction time. Nevertheless, a deviation from the stoichiometric ratio R of formed acetylene to acetone was observed (R=0.8…0.97). The conversion normalized to the surface area was used for establishing the activity sequence: White kaolinite > red kaolinite > bentonite > zeolite > diatomite. In addition, the results were compared with synthetic amorphous alumosilicates and typical basic materials like MgO and ZnO. The basic properties were characterized using the Pyrrole-tpd. The Pyrrole-tpd results showed the same basicity sequence as the MBOH gas phase reaction.
[1] M. Frenke, Surface acidity of montmorillonites, Clay Miner. 22 (1974) 435-441.
[2] K. Dermentzis, A. Christoforidis, E. Valsamidou, Removal of nickel, copper, zinc and chromium from synthetic and industrial wastewater by
electrocoagulation, Int. J. Environ. Sci. 1 (2011) 697- 710.
[3] Q. Mohsen a, A. El-maghraby, Characterization and assessment of Saudi clays raw material at different area, Arabian Journal of Chemistry 3 (2010) 271–277.
[4] C.H. Bruce, Smectite dehydration- It’s relation to structural development and hydrocarbon accumulation in northern Gulf of Mexico Basin, Am. Assoc. Petroleum Geologists Bull. 68 (1984) 673-683.
[5] E. Elsinger, D. Pevear, Clay minerals for petroleum geologist and engineers, Soc. Econ. Paleontol, Mineral short course- Notes 22. 1988.
[6] B. C Deb, A. O. Chowdbury, Failure of the international soda method in estimating clay in a subsoil, as revealed by the base-exchange capacity, Soil Sci. 68 (1949) 251-257.
[7] B. Damodaran, J. Litka, L. Malathy, Modified Clays as Efficient Acid–Base Catalyst Systems for Diazotization and Diazocoupling Reactions, Journal Synthetic communications 33 (2003) 863-869.
[8] P. Cloos, A. Moreale, C. Broers, C. Badot, Adsorption and oxidation of aniline and p-chloroaniline by montmorillonite. Clay Miner. 14 (1979) 307-321.
[9] Y. Soma, M. Soma, Chemical Reactions of Organic Compounds on Clay Surfaces, Environmental Health Perspectives 83 (1989) 205-214.
[10] H. H. Murray, Applied clay mineralogy today and tomorrow, Clay Minerals 34 (1999) 39-49.
[11] H. Lauron-Pernot, F. Luck, J. M. Popa, Methylbutynol: a new and simple diagnostic tool for acidic and basic sites of solids, Appl. Catal. 78 (1991) 213-225.
[12] Y. Ono, T. Baba, Selective reactions over solid base catalysts, Catal. Today 38 (1997) 321-337.
[13] U. Meyer, W. F. Hoelderich, Application of basic zeolites in the decomposition reaction of 2-methyl-3 butyn-2-ol and the isomerization of 3-carene, J. Mol. Catal. A-Chem. 142 (1999) 213-222.
[14] M. Huang, S. Kaliaguine, Reactions of methylbutynol on alkali-exchanged zeolites. A Lewis acid-base selectivity study, Catal. Lett. 18 (1993) 373-389.
[15] P. Kuśtrowski, L. Chmielarz, E. Bozek, M. Sawalha, F. Roessner, Acidity and basicity of hydrotalcite derived mixed Mg-Al oxides studied by test reaction of MBOH conversion and temperature programmed desorption of NH3 and CO2, Mater. Res. Bull. 39 (2004) 263-281.
[16] C. Chizallet, G. Costentin, H. Lauron-Pernot, J.M. Krafft, P. Bazin, J. Saussey, F. Delbecq, P. Sautet, M. Che, Role of Hydroxyl Groups in the Basic Reactivity of MgO: a Theoretical and Experimental Study, Oil Gas Sci. Technol. 61 (2006) 479-488.
[17] P. Yuan, D.Q. Wu, H.P. He, Z.Y. Lin, The hydroxyl species and acid sites on diatomite surface: a combined IR and Raman study, Appl. Surf. Sci. 227 (2004) 30-39.
[18] L.I. Bel’chinskaya, O.Yu. Strel’nikova, L.A. Novikova, F. Roessner, O.V. Voishcheva, Enhancement of the Adsorption Selectivity of Nanoporous Clinoptilolite by Hydrophobization with Organosiloxanes, Protect. Met. 44 (2008) 390–393.
[19] L.T. Zhuravlev, The surface chemistry of amorphous silica Zhuravlev model, Colloids Surfaces A: Physicochem. Eng. Aspects, 173 (2000) 1-38.
[20] N. Supamathanon, J. Wittayakun, S. Prayoonpokarach, W. Supronowicz, F. Roessner, Basic properties of potassium oxide supported on zeolite Y studied by pyrrole-tpd and catalytic conversion of methylbutynol, Quim. Nova, 35 (2012) 1719-1723.
[21] M. AlSawalha, F. Roessner, L. Novikova, L. Bel’chinskaya, Acidity of different Jordanian Clays characterized by TPD-NH3 and MBOH, World Academy of Science, Engineering and Technology 5 (2011) 319-323.
[22] M. Almjadleh, S. Alasheh, I. Raheb, Use of Natural and Modified Jordanian Zeolitic Tuff for Removal of Cadmium (II) from Aqueous Solutions”, Jordan Journal of Civil Engineering 8 (2014) 332 -343.
[23] M. Al-Ghouti, M.A.M. Khraisheh, S.J. Allen, M.N. Ahmad, The removal of dyes from textile wastewater: a study of the physical characteristics and adsorption mechanisms of diatomaceous earth, J. Environ. Manage, 69 (2003) 229-238.
[24] M. Nawasreh, Y. Al. Omari, J. Sahawneh, M. Madanat, Natural resources Authority, Jordan (2006) 101-107.
[25] C. Lahousse, J. Bachelier, J. Lavalley, C. Lauron-Pernot, H.A. Govic, Validity of using isopropanol decomposition as a test-reaction for the characterization of metal oxides basicity comparison with results obtained from methylbutynol decomposition, J. Mol. Catal. 87 (1994) 329-332.
[26] H. Hattori, Heterogeneous Basic catalysts, Chem. Rev. 95 (1995) 537-558.
[27] C. Baddeley, C. Hardacre, R. Ormerod, RM. Lambert, Chemisorption and decomposition of pyrrole on Pd, Surface Science 369 (1996) 1-8.
[1] M. Frenke, Surface acidity of montmorillonites, Clay Miner. 22 (1974) 435-441.
[2] K. Dermentzis, A. Christoforidis, E. Valsamidou, Removal of nickel, copper, zinc and chromium from synthetic and industrial wastewater by
electrocoagulation, Int. J. Environ. Sci. 1 (2011) 697- 710.
[3] Q. Mohsen a, A. El-maghraby, Characterization and assessment of Saudi clays raw material at different area, Arabian Journal of Chemistry 3 (2010) 271–277.
[4] C.H. Bruce, Smectite dehydration- It’s relation to structural development and hydrocarbon accumulation in northern Gulf of Mexico Basin, Am. Assoc. Petroleum Geologists Bull. 68 (1984) 673-683.
[5] E. Elsinger, D. Pevear, Clay minerals for petroleum geologist and engineers, Soc. Econ. Paleontol, Mineral short course- Notes 22. 1988.
[6] B. C Deb, A. O. Chowdbury, Failure of the international soda method in estimating clay in a subsoil, as revealed by the base-exchange capacity, Soil Sci. 68 (1949) 251-257.
[7] B. Damodaran, J. Litka, L. Malathy, Modified Clays as Efficient Acid–Base Catalyst Systems for Diazotization and Diazocoupling Reactions, Journal Synthetic communications 33 (2003) 863-869.
[8] P. Cloos, A. Moreale, C. Broers, C. Badot, Adsorption and oxidation of aniline and p-chloroaniline by montmorillonite. Clay Miner. 14 (1979) 307-321.
[9] Y. Soma, M. Soma, Chemical Reactions of Organic Compounds on Clay Surfaces, Environmental Health Perspectives 83 (1989) 205-214.
[10] H. H. Murray, Applied clay mineralogy today and tomorrow, Clay Minerals 34 (1999) 39-49.
[11] H. Lauron-Pernot, F. Luck, J. M. Popa, Methylbutynol: a new and simple diagnostic tool for acidic and basic sites of solids, Appl. Catal. 78 (1991) 213-225.
[12] Y. Ono, T. Baba, Selective reactions over solid base catalysts, Catal. Today 38 (1997) 321-337.
[13] U. Meyer, W. F. Hoelderich, Application of basic zeolites in the decomposition reaction of 2-methyl-3 butyn-2-ol and the isomerization of 3-carene, J. Mol. Catal. A-Chem. 142 (1999) 213-222.
[14] M. Huang, S. Kaliaguine, Reactions of methylbutynol on alkali-exchanged zeolites. A Lewis acid-base selectivity study, Catal. Lett. 18 (1993) 373-389.
[15] P. Kuśtrowski, L. Chmielarz, E. Bozek, M. Sawalha, F. Roessner, Acidity and basicity of hydrotalcite derived mixed Mg-Al oxides studied by test reaction of MBOH conversion and temperature programmed desorption of NH3 and CO2, Mater. Res. Bull. 39 (2004) 263-281.
[16] C. Chizallet, G. Costentin, H. Lauron-Pernot, J.M. Krafft, P. Bazin, J. Saussey, F. Delbecq, P. Sautet, M. Che, Role of Hydroxyl Groups in the Basic Reactivity of MgO: a Theoretical and Experimental Study, Oil Gas Sci. Technol. 61 (2006) 479-488.
[17] P. Yuan, D.Q. Wu, H.P. He, Z.Y. Lin, The hydroxyl species and acid sites on diatomite surface: a combined IR and Raman study, Appl. Surf. Sci. 227 (2004) 30-39.
[18] L.I. Bel’chinskaya, O.Yu. Strel’nikova, L.A. Novikova, F. Roessner, O.V. Voishcheva, Enhancement of the Adsorption Selectivity of Nanoporous Clinoptilolite by Hydrophobization with Organosiloxanes, Protect. Met. 44 (2008) 390–393.
[19] L.T. Zhuravlev, The surface chemistry of amorphous silica Zhuravlev model, Colloids Surfaces A: Physicochem. Eng. Aspects, 173 (2000) 1-38.
[20] N. Supamathanon, J. Wittayakun, S. Prayoonpokarach, W. Supronowicz, F. Roessner, Basic properties of potassium oxide supported on zeolite Y studied by pyrrole-tpd and catalytic conversion of methylbutynol, Quim. Nova, 35 (2012) 1719-1723.
[21] M. AlSawalha, F. Roessner, L. Novikova, L. Bel’chinskaya, Acidity of different Jordanian Clays characterized by TPD-NH3 and MBOH, World Academy of Science, Engineering and Technology 5 (2011) 319-323.
[22] M. Almjadleh, S. Alasheh, I. Raheb, Use of Natural and Modified Jordanian Zeolitic Tuff for Removal of Cadmium (II) from Aqueous Solutions”, Jordan Journal of Civil Engineering 8 (2014) 332 -343.
[23] M. Al-Ghouti, M.A.M. Khraisheh, S.J. Allen, M.N. Ahmad, The removal of dyes from textile wastewater: a study of the physical characteristics and adsorption mechanisms of diatomaceous earth, J. Environ. Manage, 69 (2003) 229-238.
[24] M. Nawasreh, Y. Al. Omari, J. Sahawneh, M. Madanat, Natural resources Authority, Jordan (2006) 101-107.
[25] C. Lahousse, J. Bachelier, J. Lavalley, C. Lauron-Pernot, H.A. Govic, Validity of using isopropanol decomposition as a test-reaction for the characterization of metal oxides basicity comparison with results obtained from methylbutynol decomposition, J. Mol. Catal. 87 (1994) 329-332.
[26] H. Hattori, Heterogeneous Basic catalysts, Chem. Rev. 95 (1995) 537-558.
[27] C. Baddeley, C. Hardacre, R. Ormerod, RM. Lambert, Chemisorption and decomposition of pyrrole on Pd, Surface Science 369 (1996) 1-8.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:77145", author = "M. Z. Alsawalha", title = "Basicity of Jordanian Natural Clays Studied by Pyrrole-tpd and Catalytic Conversion of Methylbutynol", abstract = "The main objective of this study is to investigate basic properties of different natural clays, by two methods. The first method is a gas phase conversion of methylbutynol (MBOH). The second method is the application of Pyrrole-tpd. Based on the product distribution from the first method, the acidic, basic and coordinately unsaturated sites were differentiated. It was shown that both the conversion and the selectivity for basic products did not change with reaction time. Nevertheless, a deviation from the stoichiometric ratio R of formed acetylene to acetone was observed (R=0.8…0.97). The conversion normalized to the surface area was used for establishing the activity sequence: White kaolinite > red kaolinite > bentonite > zeolite > diatomite. In addition, the results were compared with synthetic amorphous alumosilicates and typical basic materials like MgO and ZnO. The basic properties were characterized using the Pyrrole-tpd. The Pyrrole-tpd results showed the same basicity sequence as the MBOH gas phase reaction.
", keywords = "Alumosilicates, basic surface properties, natural clays, normalized conversions with acetylene and acetone, pyrrole-TPD adsorption.", volume = "12", number = "1", pages = "33-5", }
