Selective Conversion of Bio-Derived Ethanol to Renewable BTX over Ga-ZSM-5

Li, Zhenglong; Lepore, Andrew W.; Salazar, Mariam F.; Foo, Guo Shiou; Davison, Brian H.; Wu, Zili; Narula, Chaitanya Kumar

doi:10.1039/C7GC01188A

Title: Selective Conversion of Bio-Derived Ethanol to Renewable BTX over Ga-ZSM-5

Journal Article · Thu Jun 01 00:00:00 EDT 2017 · Green Chemistry

DOI:https://doi.org/10.1039/C7GC01188A· OSTI ID:1394295

^[1]; Lepore, Andrew W. ^[2]; Salazar, Mariam F. ^[3];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Energy & Transportation Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division; Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioSciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Selective conversion of bio-derived ethanol to benzene, toluene and xylenes (BTX) is desirable for producing renewable BTX. Here in this work, we show that addition of Ga to H-ZSM-5 leads to two-fold increase in the BTX yield as compared with H-ZSM-5 when ethanol is converted over these zeolites at 450 °C and ambient pressure. Besides promoting BTX formation, Ga also plays an important role in enhancing molecular hydrogen production and suppressing hydrogen transfer reactions for light alkane formation. The ion exchange synthesis of Ga-ZSM-5 results in the majority of Ga at the outer surface of zeolite crystals as extra-zeolitic Ga₂O₃ particles and only a small fraction of Ga exchanging with the Brønsted acid sites which appears to be responsible for higher ethanol conversion to BTX. The interface between H-ZSM-5 and Ga₂O₃ particles is not active since H-ZSM-5 and physical mixture of β-Ga₂O₃/H-ZSM-5 furnish almost identical product distribution. Hydrogen reduction of the physical mixtures facilitates movement of Ga to ion exchange locations and dramatically increases BTX yield becoming comparable to those obtained over ion-exchanged Ga-ZSM-5, suggesting that exchanged Ga(III) cations are responsible for the increased BTX production. Linear correlation between BTX site time yield and exchanged Ga sites further confirms that Ga occupying cationic sites are active sites for enhancing BTX formation. Reduction of physical mixtures (β-Ga₂O₃/H-ZSM-5) also provides an economical and environmentally friendly non-aqueous method for large scale catalyst synthesis without sacrificing catalyst performance for ethanol conversion application.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1394295

Journal Information:: Green Chemistry, Vol. 19, Issue 18; ISSN 1463-9262

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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