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Title: Simultaneous Upgrading of Furanics and Phenolics through Hydroxyalkylation/Aldol Condensation Reactions

Abstract

The simultaneous conversion of cyclopentanone and m-cresol has been investigated on a series of solid-acid catalysts. Both compounds are representative of biomass-derived streams. Cyclopentanone can be readily obtained from sugar-derived furfurals through Piancatelli rearrangement under reducing conditions. Cresol represents a family of phenolic compounds, typically obtained from the depolymerization of lignin. In the first biomass conversion strategy proposed here, furfural is converted in high yields and selectivity to cyclopentanone (CPO) over metal catalysts such as Pd-Fe/SiO2 at 600 psi (~4.14 MPa) H2 and 150 °C. Subsequently, CPO and cresol are further converted through acid-catalyzed hydroxyalkylation. This C-C coupling reaction may be used to generate products in the molecular weight range that is appropriate for transportation fuels. As molecules beyond this range may be undesirable for fuel production, a catalyst with a suitable porous structure may be advantageous for controlling the product distribution in the desirable range. If Amberlyst resins were used as a catalyst, C12–C24 products were obtained whereas when zeolites with smaller pore sizes were used, they selectively produced C10 products. Alternatively, CPO can undergo the acid-catalyzed self-aldol condensation to form C10 bicyclic adducts. As an illustration of the potential for practical implementation of this strategy for biofuel production,more » the long-chain oxygenates obtained from hydroxyalkylation/aldol condensation were successfully upgraded through hydrodeoxygenation to a mixture of linear alkanes and saturated cyclic hydrocarbons, which in practice would be direct drop-in components for transportation fuels. Aqueous acidic environments, which are typically encountered during the liquid-phase upgrading of bio-oils, would inhibit the efficiency of base-catalyzed processes. Therefore, the proposed acid-catalyzed upgrading strategy is advantageous for biomass conversion in terms of process simplicity.« less

Authors:
ORCiD logo [1];  [1];  [1]
  1. Univ. of Oklahoma, Norman, OK (United States)
Publication Date:
Research Org.:
Univ. of Oklahoma, Norman, OK (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1533151
Alternate Identifier(s):
OSTI ID: 1401724
Grant/Contract Number:  
EE0006287; SC0004600
Resource Type:
Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 7; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; science & technology; biofuels; C–C coupling; cyclopentanone; hydroxyalkylation; phenolics

Citation Formats

Bui, Tuong V., Sooknoi, Tawan, and Resasco, Daniel E. Simultaneous Upgrading of Furanics and Phenolics through Hydroxyalkylation/Aldol Condensation Reactions. United States: N. p., 2017. Web. https://doi.org/10.1002/cssc.201601251.
Bui, Tuong V., Sooknoi, Tawan, & Resasco, Daniel E. Simultaneous Upgrading of Furanics and Phenolics through Hydroxyalkylation/Aldol Condensation Reactions. United States. https://doi.org/10.1002/cssc.201601251
Bui, Tuong V., Sooknoi, Tawan, and Resasco, Daniel E. Wed . "Simultaneous Upgrading of Furanics and Phenolics through Hydroxyalkylation/Aldol Condensation Reactions". United States. https://doi.org/10.1002/cssc.201601251. https://www.osti.gov/servlets/purl/1533151.
@article{osti_1533151,
title = {Simultaneous Upgrading of Furanics and Phenolics through Hydroxyalkylation/Aldol Condensation Reactions},
author = {Bui, Tuong V. and Sooknoi, Tawan and Resasco, Daniel E.},
abstractNote = {The simultaneous conversion of cyclopentanone and m-cresol has been investigated on a series of solid-acid catalysts. Both compounds are representative of biomass-derived streams. Cyclopentanone can be readily obtained from sugar-derived furfurals through Piancatelli rearrangement under reducing conditions. Cresol represents a family of phenolic compounds, typically obtained from the depolymerization of lignin. In the first biomass conversion strategy proposed here, furfural is converted in high yields and selectivity to cyclopentanone (CPO) over metal catalysts such as Pd-Fe/SiO2 at 600 psi (~4.14 MPa) H2 and 150 °C. Subsequently, CPO and cresol are further converted through acid-catalyzed hydroxyalkylation. This C-C coupling reaction may be used to generate products in the molecular weight range that is appropriate for transportation fuels. As molecules beyond this range may be undesirable for fuel production, a catalyst with a suitable porous structure may be advantageous for controlling the product distribution in the desirable range. If Amberlyst resins were used as a catalyst, C12–C24 products were obtained whereas when zeolites with smaller pore sizes were used, they selectively produced C10 products. Alternatively, CPO can undergo the acid-catalyzed self-aldol condensation to form C10 bicyclic adducts. As an illustration of the potential for practical implementation of this strategy for biofuel production, the long-chain oxygenates obtained from hydroxyalkylation/aldol condensation were successfully upgraded through hydrodeoxygenation to a mixture of linear alkanes and saturated cyclic hydrocarbons, which in practice would be direct drop-in components for transportation fuels. Aqueous acidic environments, which are typically encountered during the liquid-phase upgrading of bio-oils, would inhibit the efficiency of base-catalyzed processes. Therefore, the proposed acid-catalyzed upgrading strategy is advantageous for biomass conversion in terms of process simplicity.},
doi = {10.1002/cssc.201601251},
journal = {ChemSusChem},
number = 7,
volume = 10,
place = {United States},
year = {2017},
month = {3}
}

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