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Title: Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

Abstract

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sites and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD,more » and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

Authors:
 [1];  [1];  [2];  [2];  [2];  [3];  [2];  [1]
  1. Univ. of Calgary, Calgary, AB (Canada)
  2. Univ. of Alberta, Edmonton, AB (Canada)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1364051
Report Number(s):
NREL/JA-5100-68691
Journal ID: ISSN 2155-5435
Grant/Contract Number:
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 5; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; acetic acid; aromatization; catalyst; methane; ZSM-5

Citation Formats

Wang, Aiguo, Austin, Danielle, Karmakar, Abhoy, Bernard, Guy M., Michaelis, Vladimir K., Yung, Matthew M., Zeng, Hongbo, and Song, Hua. Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b00296.
Wang, Aiguo, Austin, Danielle, Karmakar, Abhoy, Bernard, Guy M., Michaelis, Vladimir K., Yung, Matthew M., Zeng, Hongbo, & Song, Hua. Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst. United States. doi:10.1021/acscatal.7b00296.
Wang, Aiguo, Austin, Danielle, Karmakar, Abhoy, Bernard, Guy M., Michaelis, Vladimir K., Yung, Matthew M., Zeng, Hongbo, and Song, Hua. Wed . "Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst". United States. doi:10.1021/acscatal.7b00296. https://www.osti.gov/servlets/purl/1364051.
@article{osti_1364051,
title = {Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst},
author = {Wang, Aiguo and Austin, Danielle and Karmakar, Abhoy and Bernard, Guy M. and Michaelis, Vladimir K. and Yung, Matthew M. and Zeng, Hongbo and Song, Hua},
abstractNote = {The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sites and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid (13CH3COOH and CH313COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.},
doi = {10.1021/acscatal.7b00296},
journal = {ACS Catalysis},
number = 5,
volume = 7,
place = {United States},
year = {Wed Apr 19 00:00:00 EDT 2017},
month = {Wed Apr 19 00:00:00 EDT 2017}
}

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