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

Abstract

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 Ga 2O 3 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 Ga 2O 3 particles is not active since H-ZSM-5 and physical mixture of β-Ga 2O 3/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 andmore » exchanged Ga sites further confirms that Ga occupying cationic sites are active sites for enhancing BTX formation. Reduction of physical mixtures (β-Ga 2O 3/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.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Energy & Transportation Sciences Division
  2. 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
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioSciences Division
  6. 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)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1394295
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 19; Journal Issue: 18; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS

Citation Formats

Li, Zhenglong, Lepore, Andrew W., Salazar, Mariam F., Foo, Guo Shiou, Davison, Brian H., Wu, Zili, and Narula, Chaitanya Kumar. Selective Conversion of Bio-Derived Ethanol to Renewable BTX over Ga-ZSM-5. United States: N. p., 2017. Web. doi:10.1039/C7GC01188A.
Li, Zhenglong, Lepore, Andrew W., Salazar, Mariam F., Foo, Guo Shiou, Davison, Brian H., Wu, Zili, & Narula, Chaitanya Kumar. Selective Conversion of Bio-Derived Ethanol to Renewable BTX over Ga-ZSM-5. United States. doi:10.1039/C7GC01188A.
Li, Zhenglong, Lepore, Andrew W., Salazar, Mariam F., Foo, Guo Shiou, Davison, Brian H., Wu, Zili, and Narula, Chaitanya Kumar. Thu . "Selective Conversion of Bio-Derived Ethanol to Renewable BTX over Ga-ZSM-5". United States. doi:10.1039/C7GC01188A.
@article{osti_1394295,
title = {Selective Conversion of Bio-Derived Ethanol to Renewable BTX over Ga-ZSM-5},
author = {Li, Zhenglong and Lepore, Andrew W. and Salazar, Mariam F. and Foo, Guo Shiou and Davison, Brian H. and Wu, Zili and Narula, Chaitanya Kumar},
abstractNote = {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.},
doi = {10.1039/C7GC01188A},
journal = {Green Chemistry},
issn = {1463-9262},
number = 18,
volume = 19,
place = {United States},
year = {2017},
month = {6}
}

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