Title: Effect of Si/Al Ratio and of Acidity of H-ZSM5 Zeolites on the Primary Products of Methanol to Gasoline Conversion
Abstract: Journal of Chemical Technology & BiotechnologyVolume 66, Issue 2 p. 183-191 Research Article Effect of Si/Al ratio and of acidity of H-ZSM5 zeolites on the primary products of methanol to gasoline conversion Pedro L. Benito, Corresponding Author Pedro L. Benito Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainDepartamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, Spain===Search for more papers by this authorAna G. Gayubo, Ana G. Gayubo Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainSearch for more papers by this authorAndreś T. Aguayo, Andreś T. Aguayo Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainSearch for more papers by this authorMartin Olazar, Martin Olazar Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainSearch for more papers by this authorJarier Bilbao, Jarier Bilbao Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainSearch for more papers by this author Pedro L. Benito, Corresponding Author Pedro L. Benito Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainDepartamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, Spain===Search for more papers by this authorAna G. Gayubo, Ana G. Gayubo Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainSearch for more papers by this authorAndreś T. Aguayo, Andreś T. Aguayo Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainSearch for more papers by this authorMartin Olazar, Martin Olazar Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainSearch for more papers by this authorJarier Bilbao, Jarier Bilbao Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 48080 Bilbao, SpainSearch for more papers by this author First published: June 1996 https://doi.org/10.1002/(SICI)1097-4660(199606)66:2<183::AID-JCTB487>3.0.CO;2-KCitations: 82AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract From experiments in a chromatographic reactor, under conditions of incipient reaction, the effect of the Si/Al ratio of H-ZSM5 zeolites on the nature of the primary products has been proven in the transformation of methanol into gasoline. It has been determined that alkenes (ethene, propene and butenes) are the first reaction products, the proportion of heavier alkenes being greater as the Brönsted/Lewis ratio increases and as total acidity decreases (decrease in acidic site density). By in-situ FTIR analysis of the adsorbed phase, the presence of surface methoxy groups has been determined. By virtue of the results, a mechanism of propagation–decomposition of oxonium ions has been proposed. This mechanism basically occurs in a phase adsorbed on the zeolite and explains the formation of the first CC bond and the presence in the gas phase of the first products according to a reaction–diffusion compromise for each one of the intermediate products of the mechanism. References 1 Hutchings, G. H. & Hunter, R., Hydrocarbon formation from methanol and dimethyl ether: a review of the experimental observations concerning the mechanism of formation of the primary products. Catal. Today, 6 (1990) 279–306. 10.1016/0920-5861(90)85006-A CASGoogle Scholar 2 Chu, C. T. W. & Chang, C. D., Methanol conversion to olefins over ZSM-5. II, Olefin distribution. J. Catal., 86 (1984) 297–300. 10.1016/0021-9517(84)90375-0 CASWeb of Science®Google Scholar 3 Wu, M. M. & Kaeding, W. W., Conversion of methanol to hydrocarbons. II. Reaction paths for olefin formation over HZSM-5 Zeolite Catalyst. J. Catal., 88 (1984) 478–89. 10.1016/0021-9517(84)90025-3 CASWeb of Science®Google Scholar 4 Haag, W. O., Lago, R. M. & Rodewald, P. G., Aromatics, light olefins and gasoline from methanol: mechanistic pathways with ZSM-5 Zeolite Catalyst. J. Mol. Catal., 17 (1982) 161–9. 10.1016/0304-5102(82)85027-X CASWeb of Science®Google Scholar 5 Jansen van Rensburg, L., Hunter, R. & Hutchings, G. J. Methanol conversion of hydrocarbons. Primary versus secondary formation of methane and ethane. Appl. Catal., 42 (1988) 29–34. 10.1016/S0166-9834(00)80073-1 Google Scholar 6 Tau, L.-M., Fort, A. W., Bao, S. & Davis, B. H., Methanol to gasoline. 14C tracer studies of the conversion of methanol/higher alcohol mixtures over ZSM-5. Fuel Processing Technology, 26 (1990) 209–19. 10.1016/0378-3820(90)90006-E CASWeb of Science®Google Scholar 7 Dessau, R. M., On the H-ZSM-5 catalyzed formation of ethylene from ethanol of higher olefins. J. Catal., 99 (1986) 111–16. 10.1016/0021-9517(86)90204-6 CASWeb of Science®Google Scholar 8 Dessau, R. M. & La Pierre, R. B., On the mechanism of methanol conversion to hydrocarbons over HZSM-5. J. Catal., 78 (1982) 136–41. 10.1016/0021-9517(82)90292-5 CASWeb of Science®Google Scholar 9 Mole, T., Comments on the H-ZSM-5 catalyzed formation of ethylene from methanol of higher olefins. J. Catal., 103 (1987) 524–5. 10.1016/0021-9517(87)90146-1 Web of Science®Google Scholar 10 Chang, C. D., Lange, W. H. & Smith, R. L., The conversion of methanol and other O-containing compounds to hydrocarbons over zeolite catalyst. J. Catal., 56 (1979) 169–73. 10.1016/0021-9517(79)90103-9 CASWeb of Science®Google Scholar 11 Cormerais, F. X., Perot, G. & Guisnet, M., Selectivity of the dimethylether to hydrocarbons conversion on various zeolites. Zeolites, 1 (1981) 141–4. 10.1016/S0144-2449(81)80002-4 CASWeb of Science®Google Scholar 12 Perot, G., Cormerais, F. X. & Guisnet, M., The role of ethers in the methanol-hydrocarbon conversion on silica–alumina and ZSM-5 Zeolite. J. Mol. Catal., 17 (1982) 255–60. 10.1016/0304-5102(82)85036-0 Web of Science®Google Scholar 13 Sulikowski, B. & Klinowski, J., Trans-but-2-ene is the first hydrocarbon produced in the conversion of methanol to gasoline over zeolite H-ZSM-5. Appl. Catal., 89 (1992) 69–75. 10.1016/0926-860X(92)80078-Q CASWeb of Science®Google Scholar 14 Derouane, E. G., Conversion of methanol to gasoline over zeolite catalysts. I. Reaction mechanisms. In Zeolites Science and Technology, eds F. R. Ribeiro, A. E. Rodrigues, L. D. Rollmann & C. Naccache, Zeolites Science and Technology, Martinus Nijhoff Publishers, The Hague, 1984, pp. 515–27. 10.1007/978-94-009-6128-9_18 Google Scholar 15 Swabb, E. A. & Gates, B. C., Diffusion, reaction, and fouling in H-mordenite crystallites. The catalytic dehydration of methanol. Ind. Eng. Chem. Fundam., 11 (1972) 540–5. 10.1021/i160044a018 CASWeb of Science®Google Scholar 16 Chang, C. D. & Silvestri, A. J., The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts. J. Catal., 47 (1977) 249–59. 10.1016/0021-9517(77)90172-5 CASWeb of Science®Google Scholar 17 Van den Berg, J. P., Wolthuizen, J. P. & van Hoof, J. H. C., The conversion of dimethylether to hydrocarbons on zeolite H-ZSM-5. The reaction mechanism for formation of primary olefins. In Proceedings of the 5th International Zeolite Conference, ed. L. V. V. Rees. Heydon, London, 1981, pp. 649–60. Google Scholar 18 Clarke, J. K. A., Darcy, R., Hegarty, B. F., O'Donohue, E., Ebrahimi, A. & Rooney, J. J., Free radicals in dimethyl ether on H-ZSM-5 zeolite. A novel dimension of heterogeneous catalysis. J. Chem. Soc., Chem. Commun., (1986) 425–6. Google Scholar 19 Argauer, R. J. & Landolt, G. R., Crystalline zeolite HZSM-5 and method of preparing the same. US Patent 3 702 886, 1972. Google Scholar 20 Chen, N. Y., Miale, J. N. & Reagan, W. J., Preparation of zeolite, example 5. US Patent 4 112 056, 1973. Google Scholar 21 Breck, D. W., Zeolite Molecular Sieves. John Wiley & Sons, New York, 1974, pp. 415–19. Google Scholar 22 Védrine, J. C., Auroux, A., Bolis, V., Dejaifve, P., Naccache, C., Wierzchowski, P., Derouane, E. N., Nagy, J. B., Gibson, J. P., van Hooff, J. H. C., van den Berg, J. P. & Wolthuizen, J., Infrared microcalorimetric, and electron spin resonance investigations of the acidic properties of the H-ZSM-5 zeolite. J. Catal., 59 (1979) 248–62. 10.1016/S0021-9517(79)80029-9 CASWeb of Science®Google Scholar 23 Datka, J. & Tuznik, E., Infrared spectroscopic studies of acid properties of NaHZSM-5 zeolites. J. Catal., 102 (1986) 43–51. 10.1016/0021-9517(86)90139-9 CASWeb of Science®Google Scholar 24 Datka, J. & Piwowarska, Z., Acid properties of NaHZSM-5 zeolites of various Si/Al ratios and of NaHZSM-11 zeolite studied by I. R. spectroscopy. Zeolites, 8 (1988) 30–4. 10.1016/S0144-2449(88)80026-5 Web of Science®Google Scholar 25 Gayubo, A. G., Benito, P. L., Aguayo, A. T., Olazar, M. & Bilbao, J., Relationship between surface acidity and activity of catalysts in transformation of methanol into hydrocarbons. J. Chem. Tech. Biotechnol, 65 (1996) 186–92. 10.1002/(SICI)1097-4660(199602)65:2<186::AID-JCTB401>3.0.CO;2-J CASWeb of Science®Google Scholar 26 Kubelková, L., Nováková, J. & Nedomová, K., Reactivity of surface species on zeolites in methanol conversion. J. Catal., 124 (1990) 441–50. 10.1016/0021-9517(90)90191-L CASWeb of Science®Google Scholar 27 Forester, T. R. & Howe, R. F., In situ FTIR Studies of methanol and dimethyl ether in ZSM-5. J. Am. Chem. Soc., 109 (1986) 5076–82. 10.1021/ja00251a004 Web of Science®Google Scholar 28 Ono, Y. & Mori, T., Mechanism of methanol conversion into hydrocarbons over ZSM-5 zeolite. J. Chem. Soc., Faraday Trans., 77 (1981) 2209–21. 10.1039/f19817702209 CASWeb of Science®Google Scholar 29 Olah, G. A., Higher coordinate (hypercarbon containing) carbocations and their role in electrophilic reactions of hydrocarbons. Pure. Appl. Chem., 53 (1981) 201–7. 10.1351/pac198153010201 CASWeb of Science®Google Scholar 30 Derouane, E. G., Nagy, J. B., Dejaifve, P., Van Hoof, J. H. C., Spekman, B. P., Védrine, J. C. & Naccache, C., Elucidation of the Mechanism of conversion of methanol and ethanol to hydrocarbons on a new type of synthetic zeolite. J. Catal., 53 (1978) 40–55. 10.1016/0021-9517(78)90006-4 CASWeb of Science®Google Scholar 31 Sayed, M. B., Comments on the Mechanism of MTG/HZSM-5 conversion. J. Chem. Soc. Faraday Trans. 1, 83 (1987) 1771–8. 10.1039/f19878301771 Web of Science®Google Scholar Citing Literature Volume66, Issue2June 1996Pages 183-191 ReferencesRelatedInformation
Publication Year: 1996
Publication Date: 1996-06-01
Language: en
Type: article
Indexed In: ['crossref']
Access and Citation
Cited By Count: 3
AI Researcher Chatbot
Get quick answers to your questions about the article from our AI researcher chatbot