Metal oxide–zeolite composites in transformation of methanol to hydrocarbons: do iron oxide and nickel oxide matter?

Abstract

(2016) Metal oxide-zeolite composites in transformation of methanol to hydrocarbons : do iron oxide and nickel oxide matter? RSC Advances, 6 (79). pp. 75166-75177. Permanent WRAP URL:http://wrap.warwick.ac.uk/81920 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work of researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for-profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher statement:First published by Royal Society of Chemistry 2016 http://dx.doi.org/10.1039/C6RA19471K A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. ABSTRACT: The methanol-to-hydrocarbon (MTH) reaction received considerable attention as utilizing renewable sources of both value-added chemicals and fuels becomes number one priority for the society. Here, for the first time we report the development of hierarchical zeolites (ZSM-5) containing both iron oxide and nickel oxide nanoparticles. Modifying the iron oxide (magnetite, Fe3O4) amounts, we are able to control the catalyst activity and the product distribution in the MTH process. At the medium Fe3O4 loading, the major fraction is composed of the C9-C11 hydrocarbons (gasoline fraction). At the higher Fe3O4 loading, the C1-C4 hydrocarbons prevail in the reaction mixture, while at the lowest magnetite loading the major component is the C5-C8 hydrocarbons. Addition of Ni species to Fe3O4-ZSM-5 leads to the formation of mixed Ni oxides (NiO/Ni2O3) positioned either on top or next to Fe3O4 nanoparticles. This modification allowed us to significantly improve the catalyst stability due to diminishing coke formation and disordering of the coke formed. The incorporation of Ni oxide species also leads to a higher catalyst activity (up to 9.3 g(Methanol)/(g(ZSM-5)×h) and an improved selectivity (11.3% of the C5-C8 hydrocarbons and 23.6% of the C9-C11 hydrocarbons), making these zeolites highly promising for industrial applications.

Effect of nickel loading on the performance of nano- and micro-sized ZSM-5 catalysts for methanol to hydrocarbon conversion

“…The heavy aromatics content, e.g., durene in the liquid products is about 4.8 wt%, which is slightly higher than in the higher liquid products yield. This has been validated by many researchers [11,15,[24][25][26][27]. The TG-DTA results of the spent nickel catalyst are given in Fig 9, and it is clearly seen that for the nano-sized ZSM-5 supported Ni catalyst more weightloss is seen at temperature below 100 o C, which may be due to the physi-sorption compounds such as moisture or methanol reactant.…”

“…Modification of ZSM-5 catalyst with metal oxide has been widely studied, but these metal loading modifications focus on the micro-sized ZSM-5 catalysts, [15][16][17][18][19] and the metal loadings are often very high, which has much more complex distribution in the catalyst [6,19]. Very few studies have been carried out on the effect of low metal loading on nano-sized ZSM-5 catalyst.…”

Molecular behaviour of methanol and dimethyl ether in H-ZSM-5 catalysts as a function of Si/Al ratio: a quasielastic neutron scattering study

“…The higher diffusion coefficients obtained in this study for DME compared to methanol (derived from the differing location of DME allowing more space to be mobile in) suggests that even if a DME-mediated pathway to olefin formation were to occur, its mobility may not limit the establishment of significant surface coverages throughout the pore architecture of H-ZSM-5 catalysts. Previous work 24,74,75 as well as the industrial DICP MTO process 3 in the archived literature support the use of DME, or a mixture of methanol/ DME as feedstock for primary olefin formation over zeolite and zeotype catalysts. Our qualitative and quantitative insights from these QENS measurements may provide a more fundamental understanding of the consequences of using this varied feedstock.…”

Magnetically Recoverable Catalysts: Beyond Magnetic Separation

“…The other example of the reaction pathway change was observed for magnetic zeolites (Mann et al, 2016 ). Zeolite ZSM-5 is a well-known catalyst of methanol-to-hydrocarbon (MTH) and methanol-to-gasoline (MTG) transformations (Olsbye et al, 2012 ).…”

“…While the methanol conversion rate increased by only 15% for magnetic zeolite vs. regular zeolite, the yield of hydrocarbons increased by a factor of 2.7 for Fe 3 O 4 -ZSM-5. Moreover, the yields of important hydrocarbons such C 5 -C 8 (for synthesis of value-added chemicals) and C 9 -C 11 (gasoline fraction) increased by more than 300 and 130%, respectively (Mann et al, 2016 ). Such an increase in the product yield could not be attributed to merely increased catalyst activity (15% increase).…”