Catalytic Hydrotreatment of Humins to Bio‐Oil in Methanol over Supported Metal Catalysts

Cheng, Ziwei; Saha, Basudeb; Vlachos, Dionisios G.

doi:10.1002/cssc.201801535

Title: Catalytic Hydrotreatment of Humins to Bio‐Oil in Methanol over Supported Metal Catalysts

Journal Article · 24 September 2018 · ChemSusChem

DOI: https://doi.org/10.1002/cssc.201801535 · OSTI ID:1473986

Cheng, Ziwei ^[1];

^[2];

^[1]

Department of Chemical and Biomolecular Engineering University of Delaware Newark DE 19716 USA, Catalysis Center for Energy Innovation University of Delaware Newark DE 19716 USA
Catalysis Center for Energy Innovation University of Delaware Newark DE 19716 USA

Abstract Valorization of humins, the polymeric byproducts formed during the acid‐catalyzed production of HMF (5‐hydroxymethylfurfural) or furfural, is necessary to improve process economics and make biorefineries viable. We report the one‐step catalytic hydrotreatment of humins in methanol to humin oil containing fully or partially deoxygenated compounds. First, we compare four commercial noble‐metal catalysts (Ru/C, Rh/C, Pt/C, and Pd/C). Aromatic hydrocarbons, phenols, and esters are the main products detected by GC. Rh/C achieves the best GC‐detectable oil yield and 75 % humins conversion in 3 h at 400 °C, 30 bar H ₂ , and a catalyst‐to‐humins mass ratio of 1:10. High H ₂ pressures and intermediate temperatures, reaction times, and catalyst loadings enhance GC‐detectable oil yields. In contrast, high temperatures and long reaction times enhance gasification. Aromatics and phenols are found at high temperatures and long reaction times, whereas esters are the major species at short reaction times and high catalyst loading. ¹³ C‐isotopic labeling studies confirm, for the first time, that methanol participates in the alkylation and esterification reactions to form aromatic, phenolic and ester products. The reactivity in isopropanol is also discussed.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001004

OSTI ID:: 1473986

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 20 Vol. 11; ISSN 1864-5631

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (37)

Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin Wang, Xingyu; Rinaldi, Roberto ChemSusChem, Vol. 5, Issue 8, p. 1455-1466 https://doi.org/10.1002/cssc.201200040	journal	April 2012
Production of Dimethylfuran from Hydroxymethylfurfural through Catalytic Transfer Hydrogenation with Ruthenium Supported on Carbon Jae, Jungho; Zheng, Weiqing; Lobo, Raul F. ChemSusChem, Vol. 6, Issue 7, p. 1158-1162 https://doi.org/10.1002/cssc.201300288	journal	June 2013
Formation, Molecular Structure, and Morphology of Humins in Biomass Conversion: Influence of Feedstock and Processing Conditions van Zandvoort, Ilona; Wang, Yuehu; Rasrendra, Carolus B. ChemSusChem, Vol. 6, Issue 9 https://doi.org/10.1002/cssc.201300332	journal	July 2013
Dehydration of Different Ketoses and Aldoses to 5-Hydroxymethylfurfural van Putten, Robert-Jan; Soetedjo, Jenny N. M.; Pidko, Evgeny A. ChemSusChem, Vol. 6, Issue 9 https://doi.org/10.1002/cssc.201300345	journal	August 2013
Valorization of Humin-Based Byproducts from Biomass Processing-A Route to Sustainable Hydrogen Hoang, Thi Minh Chau; Lefferts, Leon; Seshan, K. ChemSusChem, Vol. 6, Issue 9 https://doi.org/10.1002/cssc.201300446	journal	August 2013
Catalytic Depolymerization of Lignin in Supercritical Ethanol Huang, Xiaoming; Korányi, Tamás I.; Boot, Michael D. ChemSusChem, Vol. 7, Issue 8 https://doi.org/10.1002/cssc.201402094	journal	May 2014
Catalytic Hydrotreatment of Humins in Mixtures of Formic Acid/2-Propanol with Supported Ruthenium Catalysts Wang, Yuehu; Agarwal, Shilpa; Kloekhorst, Arjan ChemSusChem, Vol. 9, Issue 9 https://doi.org/10.1002/cssc.201501371	journal	February 2016
Hydrodeoxygenation of Furfural Over Supported Metal Catalysts: A Comparative Study of Cu, Pd and Ni Sitthisa, Surapas; Resasco, Daniel E. Catalysis Letters, Vol. 141, Issue 6 https://doi.org/10.1007/s10562-011-0581-7	journal	March 2011
A model that distinguishes the pyrolysis of d-glucose, d-fructose, and sucrose from that of cellulose. Application to the understanding of cigarette smoke formation Sanders, Edward B.; Goldsmith, Alan I.; Seeman, Jeffrey I. Journal of Analytical and Applied Pyrolysis, Vol. 66, Issue 1-2 https://doi.org/10.1016/S0165-2370(02)00104-3	journal	January 2003
The production of gasoline range hydrocarbons from Alcell® lignin using HZSM-5 catalyst Thring, Ronald W.; Katikaneni, Sai P. R.; Bakhshi, Narendra N. Fuel Processing Technology, Vol. 62, Issue 1 https://doi.org/10.1016/S0378-3820(99)00061-2	journal	January 2000
Liquid phase catalytic transfer hydrogenation of furfural over a Ru/C catalyst Panagiotopoulou, Paraskevi; Vlachos, Dionisios G. Applied Catalysis A: General, Vol. 480 https://doi.org/10.1016/j.apcata.2014.04.018	journal	June 2014
Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts Güvenatam, Burcu; Kurşun, Osman; Heeres, Erik H. J. Catalysis Today, Vol. 233 https://doi.org/10.1016/j.cattod.2013.12.011	journal	September 2014
Experimental studies on the pyrolysis of humins from the acid-catalysed dehydration of C6-sugars Rasrendra, C. B.; Windt, M.; Wang, Y. Journal of Analytical and Applied Pyrolysis, Vol. 104 https://doi.org/10.1016/j.jaap.2013.07.003	journal	November 2013
Catalytic pyrolysis of recalcitrant, insoluble humin byproducts from C6 sugar biorefineries Agarwal, Shilpa; van Es, Daan; Heeres, Hero Jan Journal of Analytical and Applied Pyrolysis, Vol. 123 https://doi.org/10.1016/j.jaap.2016.12.014	journal	January 2017
Effect of hydrogen donor on liquid phase catalytic transfer hydrogenation of furfural over a Ru/RuO2/C catalyst Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G. Journal of Molecular Catalysis A: Chemical, Vol. 392 https://doi.org/10.1016/j.molcata.2014.05.016	journal	October 2014
A Quantitative Scale of Oxophilicity and Thiophilicity Kepp, Kasper P. Inorganic Chemistry, Vol. 55, Issue 18 https://doi.org/10.1021/acs.inorgchem.6b01702	journal	August 2016
Group Additivity and Modified Linear Scaling Relations for Estimating Surface Thermochemistry on Transition Metal Surfaces: Application to Furanics Vorotnikov, Vassili; Vlachos, Dionisios G. The Journal of Physical Chemistry C, Vol. 119, Issue 19 https://doi.org/10.1021/acs.jpcc.5b01696	journal	April 2015
Common Pathways in Ethanolysis of Kraft Lignin to Platform Chemicals over Molybdenum-Based Catalysts Ma, Xiaolei; Ma, Rui; Hao, Wenyue ACS Catalysis, Vol. 5, Issue 8 https://doi.org/10.1021/acscatal.5b01159	journal	July 2015
Catalytic Liquefaction of Humin Substances from Sugar Biorefineries with Pt/C in 2-Propanol Wang, Y.; Agarwal, S.; Heeres, H. J. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 1 https://doi.org/10.1021/acssuschemeng.6b01834	journal	December 2016
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L. Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599 https://doi.org/10.1021/cr900354u	journal	June 2010
DFT Study of Furfural Conversion to Furan, Furfuryl Alcohol, and 2-Methylfuran on Pd(111) Vorotnikov, Vassili; Mpourmpakis, Giannis; Vlachos, Dionisios G. ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300395a	journal	October 2012
Brønsted–Evans–Polanyi and Transition State Scaling Relations of Furan Derivatives on Pd(111) and Their Relation to Those of Small Molecules Wang, Shengguang; Vorotnikov, Vassili; Sutton, Jonathan E. ACS Catalysis, Vol. 4, Issue 2 https://doi.org/10.1021/cs400942u	journal	December 2013
Formation and Growth of Humins via Aldol Addition and Condensation during Acid-Catalyzed Conversion of 5-Hydroxymethylfurfural Patil, Sushil K. R.; Lund, Carl R. F. Energy & Fuels, Vol. 25, Issue 10 https://doi.org/10.1021/ef2010157	journal	October 2011
Composition Analysis of Organosolv Lignin and Its Catalytic Solvolysis in Supercritical Alcohol Hu, Jun; Shen, Dekui; Wu, Shiliang Energy & Fuels, Vol. 28, Issue 7 https://doi.org/10.1021/ef500068h	journal	February 2014
Heterogeneous Catalysis in Continuous Stirred Tank Reactor Tajbl, D. G.; Simons, J. B.; Carberry, J. J. Industrial & Engineering Chemistry Fundamentals, Vol. 5, Issue 2 https://doi.org/10.1021/i160018a003	journal	May 1966
Conjugation-Driven “Reverse Mars–van Krevelen”-Type Radical Mechanism for Low-Temperature C–O Bond Activation Mironenko, Alexander V.; Vlachos, Dionisios G. Journal of the American Chemical Society, Vol. 138, Issue 26 https://doi.org/10.1021/jacs.6b02871	journal	June 2016
Valorization of Biorefinery Side-Stream Products: Combination of Humins with Polyfurfuryl Alcohol for Composite Elaboration Pin, Jean-Mathieu; Guigo, Nathanael; Mija, Alice ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 9 https://doi.org/10.1021/sc5003769	journal	July 2014
Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides Chheda, Juben N.; Román-Leshkov, Yuriy; Dumesic, James A. Green Chem., Vol. 9, Issue 4, p. 342-350 https://doi.org/10.1039/B611568C	journal	January 2007
Clean liquid fuels from direct coal liquefaction: chemistry, catalysis, technological status and challenges Vasireddy, Sivakumar; Morreale, Bryan; Cugini, Anthony Energy Environ. Sci., Vol. 4, Issue 2 https://doi.org/10.1039/C0EE00097C	journal	January 2011
Humin based by-products from biomass processing as a potential carbonaceous source for synthesis gas production Hoang, T. M. C.; van Eck, E. R. H.; Bula, W. P. Green Chemistry, Vol. 17, Issue 2 https://doi.org/10.1039/C4GC01324G	journal	January 2015
A synergistic biorefinery based on catalytic conversion of lignin prior to cellulose starting from lignocellulosic biomass Parsell, Trenton; Yohe, Sara; Degenstein, John Green Chemistry, Vol. 17, Issue 3 https://doi.org/10.1039/C4GC01911C	journal	January 2015
Structural characterization of ¹³ C-enriched humins and alkali-treated ¹³ C humins by 2D solid-state NMR van Zandvoort, Ilona; Koers, Eline J.; Weingarth, Markus Green Chemistry, Vol. 17, Issue 8 https://doi.org/10.1039/C5GC00327J	journal	January 2015
Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium( iii ) chloride and hydrochloric acid solution Dallas Swift, T.; Nguyen, Hannah; Anderko, Andrzej Green Chemistry, Vol. 17, Issue 10 https://doi.org/10.1039/C5GC01257K	journal	January 2015
Molecular structure, morphology and growth mechanisms and rates of 5-hydroxymethyl furfural (HMF) derived humins Tsilomelekis, George; Orella, Michael J.; Lin, Zhexi Green Chemistry, Vol. 18, Issue 7 https://doi.org/10.1039/C5GC01938A	journal	January 2016
Exploratory catalyst screening studies on the liquefaction of model humins from C6 sugars Wang, Y.; Agarwal, S.; Tang, Z. RSC Advances, Vol. 7, Issue 9 https://doi.org/10.1039/C6RA24218A	journal	January 2017
Structural analysis of humins formed in the Brønsted acid catalyzed dehydration of fructose Cheng, Ziwei; Everhart, Jeffrey L.; Tsilomelekis, George Green Chemistry, Vol. 20, Issue 5 https://doi.org/10.1039/C7GC03054A	journal	January 2018
Humin-like substances formed under the conditions of industrial hydrolysis of wood Sumerskii, I. V.; Krutov, S. M.; Zarubin, M. Ya. Russian Journal of Applied Chemistry, Vol. 83, Issue 2 https://doi.org/10.1134/S1070427210020266	journal	February 2010

Similar Records

Strategy for Extending the Stability of Bio‐oil‐Derived Phenolic Oligomers by Mild Hydrotreatment with Ionic‐Liquid‐Stabilized Nanoparticles

Journal Article · 2017 · ChemSusChem · OSTI ID:1401035

Kim, Kwang Ho; Brown, Robert C.; Daugaard, Tannon; +4 more

Simultaneous upgrading of biomass-derived sugars to HMF/furfural via enzymatically isomerized ketose intermediates

Journal Article · 2019 · Biotechnology for Biofuels · OSTI ID:1618769

Wang, Wei; Mittal, Ashutosh; Pilath, Heidi; +3 more

SnCl₄-catalyzed isomerization/dehydration of xylose and glucose to furanics in water

Journal Article · 2015 · Catalysis Science and Technology · OSTI ID:1571043

Enslow, Kristopher R.; Bell, Alexis T.

Title: Catalytic Hydrotreatment of Humins to Bio‐Oil in Methanol over Supported Metal Catalysts

Citation Formats

References (37)

Similar Records

Related Subjects