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 · Tue Sep 25 00:00:00 EDT 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.

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Sponsoring Organization:: USDOE

OSTI ID:: 1473986

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

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

Country of Publication:: Germany

Language:: English

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Cited by: 11 works

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