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Title: Furan production from glycoaldehyde over HZSM-5

Abstract

Catalytic fast pyrolysis of biomass over zeolite catalysts results primarily in aromatic (e.g. benzene, toluene, xylene) and olefin products. However, furans are a higher value intermediate for their ability to be readily transformed into gasoline, diesel, and chemicals. Here we investigate possible mechanisms for the coupling of glycoaldehyde, a common product of cellulose pyrolysis, over HZSM-5 for the formation of furans. Experimental measurements of neat glycoaldehyde over a fixed bed of HZSM-5 confirm furans (e.g. furanone) are products of this reaction at temperatures below 300 degrees C with several aldol condensation products as co-products (e.g. benzoquinone). However, under typical catalytic fast pyrolysis conditions (>400 degrees C), further reactions occur that lead to the usual aromatic product slate. ONIOM calculations were utilized to identify the pathway for glycoaldehyde coupling toward furanone and hydroxyfuranone products with dehydration reactions serving as the rate determining steps with typical intrinsic reaction barriers of 40 kcal mol-1. The reaction mechanisms for glycoaldehyde will likely be similar to that of other small oxygenates such as acetaldehyde, lactaldehyde, and hydroxyacetone and this study provides a generalizable mechanism of oxygenate coupling and furan formation over zeolite catalysts.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [1]
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  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Univ. of Oxford, Oxford (United Kingdom)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1251590
Report Number(s):
NREL/JA-5100-65724
Journal ID: ISSN 2168-0485
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 4; Journal Issue: 5; Related Information: ACS Sustainable Chemistry and Engineering; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANAYLYTICAL CHEMISTRY; biomass; catalytic fast pyrolysis; upgrading; catalyst ZSM5; computational modeling; zeolite

Citation Formats

Kim, Seonah, Evans, Tabitha J., Mukarakate, Calvin, Bu, Lintao, Beckham, Gregg T., Nimlos, Mark R., Paton, Robert S., and Robichaud, David J. Furan production from glycoaldehyde over HZSM-5. United States: N. p., 2016. Web. doi:10.1021/acssuschemeng.6b00101.
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Kim, Seonah, Evans, Tabitha J., Mukarakate, Calvin, Bu, Lintao, Beckham, Gregg T., Nimlos, Mark R., Paton, Robert S., & Robichaud, David J. Furan production from glycoaldehyde over HZSM-5. United States. https://doi.org/10.1021/acssuschemeng.6b00101
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Kim, Seonah, Evans, Tabitha J., Mukarakate, Calvin, Bu, Lintao, Beckham, Gregg T., Nimlos, Mark R., Paton, Robert S., and Robichaud, David J. Sun . "Furan production from glycoaldehyde over HZSM-5". United States. https://doi.org/10.1021/acssuschemeng.6b00101. https://www.osti.gov/servlets/purl/1251590.
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@article{osti_1251590,
title = {Furan production from glycoaldehyde over HZSM-5},
author = {Kim, Seonah and Evans, Tabitha J. and Mukarakate, Calvin and Bu, Lintao and Beckham, Gregg T. and Nimlos, Mark R. and Paton, Robert S. and Robichaud, David J.},
abstractNote = {Catalytic fast pyrolysis of biomass over zeolite catalysts results primarily in aromatic (e.g. benzene, toluene, xylene) and olefin products. However, furans are a higher value intermediate for their ability to be readily transformed into gasoline, diesel, and chemicals. Here we investigate possible mechanisms for the coupling of glycoaldehyde, a common product of cellulose pyrolysis, over HZSM-5 for the formation of furans. Experimental measurements of neat glycoaldehyde over a fixed bed of HZSM-5 confirm furans (e.g. furanone) are products of this reaction at temperatures below 300 degrees C with several aldol condensation products as co-products (e.g. benzoquinone). However, under typical catalytic fast pyrolysis conditions (>400 degrees C), further reactions occur that lead to the usual aromatic product slate. ONIOM calculations were utilized to identify the pathway for glycoaldehyde coupling toward furanone and hydroxyfuranone products with dehydration reactions serving as the rate determining steps with typical intrinsic reaction barriers of 40 kcal mol-1. The reaction mechanisms for glycoaldehyde will likely be similar to that of other small oxygenates such as acetaldehyde, lactaldehyde, and hydroxyacetone and this study provides a generalizable mechanism of oxygenate coupling and furan formation over zeolite catalysts.},
doi = {10.1021/acssuschemeng.6b00101},
journal = {ACS Sustainable Chemistry & Engineering},
number = 5,
volume = 4,
place = {United States},
year = {Sun Apr 03 00:00:00 EDT 2016},
month = {Sun Apr 03 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acssuschemeng.6b00101
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