Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural

Brentzel, Zachary J.; Barnett, Kevin J.; Huang, Kefeng; Maravelias, Christos T.; Dumesic, James A.; Huber, George W.

doi:10.1002/cssc.201700178

Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural

Journal Article · Thu Mar 09 00:00:00 EST 2017 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.201700178· OSTI ID:1533152

Brentzel, Zachary J. ^[1]; Barnett, Kevin J. ^[2]; Huang, Kefeng ^[2]; Maravelias, Christos T. ^[2]; Dumesic, James A. ^[2]; Huber, George W. ^[2]

Univ. of Wisconsin, Madison, WI (United States); DOE/OSTI
Univ. of Wisconsin, Madison, WI (United States)

A process for the synthesis of 1,5-pentanediol (1,5-PD) with 84 % yield from furfural is developed, utilizing dehydration/hydration, ring-opening tautomerization, and hydrogenation reactions. Although this process has more reaction steps than the traditional direct hydrogenolysis of tetrahydrofurfuryl alcohol (THFA), techno-economic analyses demonstrate that this process is the economically preferred route for the synthesis of biorenewable 1,5-PD. 2-Hydroxytetrahydropyran (2-HY-THP) is the key reaction pathway intermediate that allows for a decrease in the minimum selling price of 1,5-PD. The reactivity of 2-HY-THP is 80 times greater than that of THFA over a bimetallic hydrogenolysis catalyst. This enhanced reactivity is a result of the ring-opening tautomerization to 5-hydoxyvaleraldehyde and subsequent hydrogenation to 1,5-PD.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0006878

OSTI ID:: 1533152

Alternate ID(s):: OSTI ID: 1401522

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 7 Vol. 10; ISSN 1864-5631

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (27)

Total Hydrogenation of Furfural over a Silica‐Supported Nickel Catalyst Prepared by the Reduction of a Nickel Nitrate Precursor Nakagawa, Yoshinao; Nakazawa, Hiroya; Watanabe, Hideo ChemCatChem, Vol. 4, Issue 11 https://doi.org/10.1002/cctc.201200218	journal	July 2012
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino ChemInform, Vol. 37, Issue 52 https://doi.org/10.1002/chin.200652240	journal	December 2006
Glucose Hydrogenation on Ruthenium Catalysts in a Trickle-Bed Reactor Gallezot, Pierre; Nicolaus, Nathalie; Flèche, Guy Journal of Catalysis, Vol. 180, Issue 1 https://doi.org/10.1006/jcat.1998.2261	journal	November 1998
Catalytic Conversions of Furfural to Pentanediols Nakagawa, Yoshinao; Tamura, Masazumi; Tomishige, Keiichi Catalysis Surveys from Asia, Vol. 19, Issue 4 https://doi.org/10.1007/s10563-015-9194-2	journal	August 2015
Deactivation of ruthenium catalysts in continuous glucose hydrogenation Arena, Blaise J. Applied Catalysis A: General, Vol. 87, Issue 2 https://doi.org/10.1016/0926-860X(92)80057-J	journal	August 1992
Chemoselective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over Ir-MoOx/SiO2 catalyst Wang, Zhiqiang; Pholjaroen, Boonrat; Li, Mengxia Journal of Energy Chemistry, Vol. 23, Issue 4 https://doi.org/10.1016/S2095-4956(14)60168-6	journal	July 2014
Stable vapor-phase conversion of tetrahydrofurfuryl alcohol into 3,4-2H-dihydropyran Sato, Satoshi; Igarashi, Jun; Yamada, Yasuhiro Applied Catalysis A: General, Vol. 453 https://doi.org/10.1016/j.apcata.2012.12.017	journal	February 2013
Vapor phase hydrogenation of furfural over nickel mixed metal oxide catalysts derived from layered double hydroxides Sulmonetti, Taylor P.; Pang, Simon H.; Claure, Micaela Taborga Applied Catalysis A: General, Vol. 517 https://doi.org/10.1016/j.apcata.2016.03.005	journal	May 2016
Production of 1,5-pentanediol from biomass via furfural and tetrahydrofurfuryl alcohol Nakagawa, Yoshinao; Tomishige, Keiichi Catalysis Today, Vol. 195, Issue 1 https://doi.org/10.1016/j.cattod.2012.04.048	journal	November 2012
Promoting effect of Mo on the hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over Rh/SiO2 Koso, Shuichi; Ueda, Naoyuki; Shinmi, Yasunori Journal of Catalysis, Vol. 267, Issue 1 https://doi.org/10.1016/j.jcat.2009.07.010	journal	October 2009
Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2 catalysts Sitthisa, Surapas; Sooknoi, Tawan; Ma, Yuguang Journal of Catalysis, Vol. 277, Issue 1 https://doi.org/10.1016/j.jcat.2010.10.005	journal	January 2011
Mechanism of the hydrogenolysis of ethers over silica-supported rhodium catalyst modified with rhenium oxide Koso, Shuichi; Nakagawa, Yoshinao; Tomishige, Keiichi Journal of Catalysis, Vol. 280, Issue 2 https://doi.org/10.1016/j.jcat.2011.03.018	journal	June 2011
Biofuels in the U.S. – Challenges and Opportunities Hoekman, S. Kent Renewable Energy, Vol. 34, Issue 1 https://doi.org/10.1016/j.renene.2008.04.030	journal	January 2009
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098 https://doi.org/10.1021/cr068360d	journal	September 2006
Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts Ide, Matthew S.; Hao, Bing; Neurock, Matthew ACS Catalysis, Vol. 2, Issue 4 https://doi.org/10.1021/cs200567z	journal	March 2012
Ring-Chain Tautomerism of Hydroxy Aldehydes Hurd, Charles D.; Saunders, William H. Journal of the American Chemical Society, Vol. 74, Issue 21 https://doi.org/10.1021/ja01141a030	journal	November 1952
Preparation of Dihydropyran, δ-Hydroxyvaleraldehyde and 1,5-Pentanediol from Tetrahydrofurfuryl Alcohol Schniepp, L. E.; Geller, H. H. Journal of the American Chemical Society, Vol. 68, Issue 8 https://doi.org/10.1021/ja01212a085	journal	August 1946
Selective Hydrogenolysis of Polyols and Cyclic Ethers over Bifunctional Surface Sites on Rhodium–Rhenium Catalysts Chia, Mei; Pagán-Torres, Yomaira J.; Hibbitts, David Journal of the American Chemical Society, Vol. 133, Issue 32 https://doi.org/10.1021/ja2038358	journal	August 2011
Acetal Formation for Ketones and Aromatic Aldehydes with Methanol ¹ Bell, James M.; Kubler, D. G.; Sartwell, P. The Journal of Organic Chemistry, Vol. 30, Issue 12 https://doi.org/10.1021/jo01023a067	journal	December 1965
Fate of the Carbinol Carbon in the Conversion of Tetrahydrofurfuryl Alcohol to Dihydropyran Gensler, Walter J.; McLeod, Gerald L. The Journal of Organic Chemistry, Vol. 28, Issue 11 https://doi.org/10.1021/jo01046a058	journal	November 1963
Production of 1,6-hexanediol from tetrahydropyran-2-methanol by dehydration–hydration and hydrogenation Burt, Samuel P.; Barnett, Kevin J.; McClelland, Daniel J. Green Chemistry, Vol. 19, Issue 5 https://doi.org/10.1039/C6GC03606F	journal	January 2017
Chemoselective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol Koso, Shuichi; Furikado, Ippei; Shimao, Akira Chemical Communications, Issue 15 https://doi.org/10.1039/b822942b	journal	January 2009
Biomass as renewable feedstock in standard refinery units. Feasibility, opportunities and challenges Melero, Juan Antonio; Iglesias, Jose; Garcia, Alicia Energy & Environmental Science, Vol. 5, Issue 6 https://doi.org/10.1039/c2ee21231e	journal	January 2012
Intermediates and products in the catalytic vapour-phase dehydration and ammonolysis of 2-hydroxymethyltetrahydrofuran over alumina Butler, J. D.; Laundon, R. D. Journal of the Chemical Society C: Organic, Issue 2 https://doi.org/10.1039/j39690000173	journal	January 1969
Platform biochemicals for a biorenewable chemical industry Nikolau, Basil J.; Perera, M. Ann D. N.; Brachova, Libuse The Plant Journal, Vol. 54, Issue 4 https://doi.org/10.1111/j.1365-313X.2008.03484.x	journal	May 2008
Challenges in Scaling Up Biofuels Infrastructure Richard, T. L. Science, Vol. 329, Issue 5993 https://doi.org/10.1126/science.1189139	journal	August 2010
High resolution NMR studies of ring-chain tautomerism in ω-hydroxy aldehydes [高分解能核磁気共鳴法によるω-ハイドロキシアルデヒドのring-chain互変異性の分析] Shono, Toshiyuki; Godo, Masayuki; Shinra, Koichiro Bunseki kagaku, Vol. 20, Issue 9 https://doi.org/10.2116/bunsekikagaku.20.1183	journal	January 1971

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Kinetics of the Homogeneous and Heterogeneous Coupling of Furfural with Biomass-Derived Alcohols Goulas, Konstantinos A.; Gokhale, Amit A. ChemCatChem, Vol. 10, Issue 11 https://doi.org/10.1002/cctc.201701866	journal	May 2018
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Homogeneous catalysis for the production of low-volume, high-value chemicals from biomass Bender, Trandon A.; Dabrowski, Jennifer A.; Gagné, Michel R. Nature Reviews Chemistry, Vol. 2, Issue 5 https://doi.org/10.1038/s41570-018-0005-y	journal	April 2018
New catalytic strategies for α,ω-diols production from lignocellulosic biomass He, Jiayue; Huang, Kefeng; Barnett, Kevin J. Faraday Discussions, Vol. 202 https://doi.org/10.1039/c7fd00036g	journal	January 2017
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Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural

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