Olefin methylation over iron zeolites and the methanol to hydrocarbons reaction

LaFollette, Mark R.; Lobo, Raul F.

doi:10.1016/j.apcata.2022.118645

Olefin methylation over iron zeolites and the methanol to hydrocarbons reaction

Journal Article · Mon May 02 04:00:00 EDT 2022 · Applied Catalysis. A, General

DOI:https://doi.org/10.1016/j.apcata.2022.118645· OSTI ID:1976832

LaFollette, Mark R. ^[1]; Lobo, Raul F. ^[2]

University of Delaware, Newark, DE (United States); OSTI
University of Delaware, Newark, DE (United States)

The effect of olefin addition to a stream of dimethyl ether on the methanol homologation reaction is investigated using iron-substituted zeolites Fe-beta and Fe-ZSM-5. The reaction was investigated using plug-flow microreactors in the temperature range of 240–400 °C, at a total pressure of 0.239 MPa and a WHSV of 6.12 (g DME/_gcat-hr). For Fe-beta (Si/Fe= 9.2) catalysts, isobutene co-feeding almost doubles dimethyl ether (DME) consumption rate and shifts selectivity towards larger olefins with carbon numbers from 5 to 7. Addition of isobutene above 6.3%, however, resulted in a reduction of DME consumption rates, an effect assigned to the replacement of surface methoxy groups for adsorbed olefins in the zeolite pores. Below a temperature of 340 °C hydride-transfer rates are negligible; reaction rates are stable for over 5.5 h and the products consist almost exclusively of olefins and a small amount of methane. Above 360 °C the onset of catalytic hydride transfer processes is observed leading to fast catalyst deactivation rates and an increase in the concentration of aromatic species. Iron ZSM-5 (Si/Fe = 21.4) catalysts under similar reaction conditions consumes methanol faster than Fe-beta at approximately three times the TOF (on a per iron basis). The Fe-ZSM-5 catalyst was selective to a distribution of products (C5 to C8) as compared to Fe-beta which was selective to primarily C5 and C7. Co-feeding larger olefins (2-methyl-2-butene, 2,3-dimethyl-2-butene, 2,3,3-trimethyl-1-butene, and 2,4,4-trimethyl-2-pentene) at a 3.9% olefin concentration over Fe-beta changed selectivity towards cracking products (C4 compounds such as isobutene). As the size of the olefin increases, a reduction of DME consumption rate is also observed. Here these results show that co-feeding olefins with DME over Fe-zeolites is a promising route to increase methylation rates at relatively low temperatures producing larger branched olefins and that the product distribution is highly dependent on the zeolite pore size and structure of the olefin.

View Accepted Manuscript (DOE)

Research Organization:: University of Delaware, Newark, DE (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001004

OSTI ID:: 1976832

Journal Information:: Applied Catalysis. A, General, Journal Name: Applied Catalysis. A, General Journal Issue: C Vol. 641; ISSN 0926-860X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
iron zeolite
methanol homologation
methanol to hydrocarbon
methanol to olefin
methylation reaction

Olefin methylation over iron zeolites and the methanol to hydrocarbons reaction

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References (54)

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