Lignocellulosic biomass (grape seeds) was deconstructed in both hydrothermal and supercritical ethanol media with metal chloride catalyst (TiCl4/MgCl2) to produce bio-oils. The use of catalyst in the deconstruction in supercritical ethanol achieved the highest bio-oil yield of 49.2 wt% at 300 °C with a residence time of 30 min, which was 35.8wt% higher than the bio-oil yield obtained from the same condition with no catalyst. Both the hydrothermal and supercritical ethanol deconstruction reactions with the highest catalyst loading (TiCl4/MgCl2=4mmol/4mmol) produced the bio-oils with a higher heating value (HHV) of 35 MJ/Kg which was comparable of the HHV of petroleum based liquid fuels. As for the structral changes of bio-oils, gas chromatography–mass spectrometry (GC-MS) analysis of the bio-oils showed that the major products in bio-oils from the hydrothermal deconstruction were acids while majority products in bio-oils form the supercritical ethanol deconstruction were esters. 31P Nuclear magnetic resonance (NMR) data suggested that both catalytic hydrothermal/supercritical ethanol deconstruction reactions significantly reduced the non-condensed OH in bio-oils while only catalytic supercritical ethanol deconstrction reduced the aliphatic OH in bio-oils. Heteronuclear single quantum coherence (HSQC) NMR revealed that catalytic deconstruction in both supercritical ethanol and hydrothermal medias largely removed oxygenated lignin sub-units while the removal of O-alkylated structures were only found in the catalytic ethanol deconstruction.

One-pot transformation of lignocellulosic biomass into crude bio-oil with metal chloride catalyst via hydrothermal and supercritical ethanol processing

2019 Spring National Meeting

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