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Title: Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran

Authors:
 [1];  [2];  [2];  [2];  [1];  [1];  [3];  [4];  [1]; ORCiD logo [1]
  1. Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, United States; Catalysis Center for Energy Innovation, U.S. Department of Energy − Energy Frontier Research Center, 150 Academy Street, Newark, Delaware 19716, United States
  2. Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, United States
  3. Catalysis Center for Energy Innovation, U.S. Department of Energy − Energy Frontier Research Center, 150 Academy Street, Newark, Delaware 19716, United States; Department of Chemical and Biomolecular Engineering, University of Delaware, 150 Academy Street, Newark, Delaware 19716, United States
  4. Catalysis Center for Energy Innovation, U.S. Department of Energy − Energy Frontier Research Center, 150 Academy Street, Newark, Delaware 19716, United States; Department of Chemical Engineering, University of Massachusetts Amherst, 686 North Pleasant Street, Amherst, Massachusetts 01003, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388987
DOE Contract Number:
SC0001004
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Sustainable Chemistry & Engineering; Journal Volume: 5; Journal Issue: 5; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), biofuels (including algae and biomass), bio-inspired, hydrogen and fuel cells, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Abdelrahman, Omar A., Park, Dae Sung, Vinter, Katherine P., Spanjers, Charles S., Ren, Limin, Cho, Hong Je, Vlachos, Dionisios G., Fan, Wei, Tsapatsis, Michael, and Dauenhauer, Paul J. Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran. United States: N. p., 2017. Web. doi:10.1021/acssuschemeng.7b00745.
Abdelrahman, Omar A., Park, Dae Sung, Vinter, Katherine P., Spanjers, Charles S., Ren, Limin, Cho, Hong Je, Vlachos, Dionisios G., Fan, Wei, Tsapatsis, Michael, & Dauenhauer, Paul J. Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran. United States. doi:10.1021/acssuschemeng.7b00745.
Abdelrahman, Omar A., Park, Dae Sung, Vinter, Katherine P., Spanjers, Charles S., Ren, Limin, Cho, Hong Je, Vlachos, Dionisios G., Fan, Wei, Tsapatsis, Michael, and Dauenhauer, Paul J. Thu . "Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran". United States. doi:10.1021/acssuschemeng.7b00745.
@article{osti_1388987,
title = {Biomass-Derived Butadiene by Dehydra-Decyclization of Tetrahydrofuran},
author = {Abdelrahman, Omar A. and Park, Dae Sung and Vinter, Katherine P. and Spanjers, Charles S. and Ren, Limin and Cho, Hong Je and Vlachos, Dionisios G. and Fan, Wei and Tsapatsis, Michael and Dauenhauer, Paul J.},
abstractNote = {},
doi = {10.1021/acssuschemeng.7b00745},
journal = {ACS Sustainable Chemistry & Engineering},
number = 5,
volume = 5,
place = {United States},
year = {Thu Mar 23 00:00:00 EDT 2017},
month = {Thu Mar 23 00:00:00 EDT 2017}
}
  • We recently reported biomass-derived tetrahydrofuran-2,5-dicarboxylic acid (THFDCA) as a potential renewable feedstock for adipic acid (AA) production by combining HI and molecular H 2 in organic acid solvents.
  • Consolidated bioprocessing (CBP) by anaerobes, such as Clostridium thermocellum, which combine enzyme production, hydrolysis, and fermentation are promising alternatives to historical economic challenges of using fungal enzymes for biological conversion of lignocellulosic biomass. However, limited research has integrated CBP with real pretreated biomass, and understanding how pretreatment impacts subsequent deconstruction by CBP vs. fungal enzymes can provide valuable insights into CBP and suggest other novel biomass deconstruction strategies. This study focused on determining the effect of pretreatment by dilute sulfuric acid alone (DA) and with tetrahydrofuran (THF) addition via co-solvent-enhanced lignocellulosic fractionation (CELF) on deconstruction of corn stover and Populusmore » with much different recalcitrance by C. thermocellum vs. fungal enzymes and changes in pretreated biomass related to these differences.« less
  • Consolidated bioprocessing (CBP) by anaerobes, such as Clostridium thermocellum, which combine enzyme production, hydrolysis, and fermentation are promising alternatives to historical economic challenges of using fungal enzymes for biological conversion of lignocellulosic biomass. However, limited research has integrated CBP with real pretreated biomass, and understanding how pretreatment impacts subsequent deconstruction by CBP vs. fungal enzymes can provide valuable insights into CBP and suggest other novel biomass deconstruction strategies. This study focused on determining the effect of pretreatment by dilute sulfuric acid alone (DA) and with tetrahydrofuran (THF) addition via co-solvent-enhanced lignocellulosic fractionation (CELF) on deconstruction of corn stover and Populusmore » with much different recalcitrance by C. thermocellum vs. fungal enzymes and changes in pretreated biomass related to these differences.« less
  • Selective solvation of xylan by water in the THF–Water miscibility gap allows tunable solubilization.
  • Xylose, Xylan, Hemicellulose, CELF, THF, Co-solvent, Pretreatment, Biomass ABSTRACT: Xylan is an important polysaccharide found in the hemicellulose fraction of lignocellulosic biomass that can be hydrolysed to xylose and further dehydrated to the furfural, an important renewable platform fuel precursor. Here, pairing molecular simulation and experimental evidences, we reveal how the unique temperature-dependent phase behaviour of water-tetrahydrofuran (THF) co-solvent can delay xylan solubilization to synergistically improve catalytic co-processing of biomass to furfural and 5-HMF. Our results indicate, based on polymer correlations between polymer conformational behaviour and solvent quality, that both co-solvent and aqueous environments serve as ‘good’ solvents for xylan.more » Interestingly, the simulations also revealed that unlike other cell-wall components (i.e., lignin and cellulose), the make-up of the solvation shell of xylan in THF-water is dependent on the temperature-phase behaviour. At temperatures between 333K and 418K, THF and water become immiscible, and THF is evacuated from the solvation shell of xylan, while above and below this temperature range, THF and water are both present in the polysaccharide’s solvation shell. This suggested that the solubilization of xylan in THF-water may be similar to aqueous-only solutions at temperatures between 333K and 418K and different outside this range. Experimental reactions on beachwood xylan corroborate this hypothesis by demonstrating 2-fold reduction of xylan solubilization in THF-water within a miscible temperature regime (445K) and unchanged solubilization within an immiscible regime (400K). Translating this phase-dependent behaviour to processing of maple wood chips, we demonstrate how the weaker xylan solvation in THF-water under miscible conditions can delay furfural production from xylose, allowing 5-HMF production from cellulose to “catch-up” such that their high yield production from biomass can be synergized in a single pot reaction.« less