4.6 Article

Supercritical Methanol Depolymerization and Hydrodeoxygenation of Maple Wood and Biomass-Derived Oxygenates into Renewable Alcohols in a Continuous Flow Reactor

Journal

ACS SUSTAINABLE CHEMISTRY & ENGINEERING
Volume 7, Issue 18, Pages 15361-15372

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.9b02704

Keywords

Solvolysis; Copper mixed metal oxide; Biomass; Alcohols; Fuel; Guerbet coupling

Funding

  1. ExxonMobil
  2. NSF through the University of Wisconsin Materials Research Science and Engineering Center [DMR-1121288]

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Supercritical methanol depolymerization and hydrodeoxygenation (SCM-DHDO) of biomass is a technology to produce C-2-C-9 alcohols in a single reaction step. Previous research has shown that this technology is effective in batch reactors but produces large amounts of undesired CO and H-2 gas from the reforming of the methanol that make the process economically infeasible. In this work, we show that methanol reforming can be minimized to provide the stoichiometric amount of H-2 required for hydrodeoxygenation by recycling the product gases. We also show that methanol can be synthesized during the SCM-DHDO process with a sufficient cofeed of CO and H-2. In addition, we demonstrate that the catalyst is stable for more than 100 h time on stream in a continuous packed bed reactor using glycerol as a model feedstock. The alcohol yields from glycerol in the fixed bed exceeded yields from batch reactions. In a single pass system, the conversion of cellulose and maple wood to alcohols was obtained by first solubilizing in methanol and then converting to monoalcohols over a fixed bed of catalyst.

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