The reaction pathway and products of cellulose supercritical methanol depolymerization and hydrodeoxygenation (SCM-DHDO) were investigated. Monoalcohols, diols, alcohol ethers, and methyl esters were produced from cellulose at 300 °C with a CuMgAl mixed metal-oxide catalyst. Timecourse experiments show that cellulose is rapidly solubilized and depolymerized within 1 h with C 2 −C 4 diols being intermediates. Experiments with glucose-13 C 6 show that methanol is incorporated in all liquid products accounting for approximately 30−40% of the carbon in these products. Experiments with model compounds (dihydroxyacetone, isosorbide, and 5-hydroxymethylfurfural) indicate that the reaction pathway for cellulose occurs primarily through retroaldol condensation of solubilized cellulose followed by recondensation with methanol. Methanol produces H 2 , CO, and CO 2 through reformation with 30% of the generated H 2 being incorporated into the liquid products. Analysis of the liquid products with Fourier transform ion cyclotron resonance MS (FT-ICR MS) measured C 7 −C 12 partially oxygenated species with 2−6 double bond equivalence which could not be detected via gas chromatography (GC). We conclude that the reaction pathway occurs through rapid solubilization and depolymerization of cellulose followed by retro-aldol condensation to C 2 −C 4 oxygenates. Retro-aldol condensation products undergo hydrodeoxygenation and extensive carbon−carbon coupling to produce C 2 −C 7 alcohols or other oxygenates.
Supercritical methanol depolymerization and hydrodeoxygenation (SCM-DHDO) is a process to produce fuel from biomass with supercritical methanol and CuMgAlOx catalyst. Previous research has shown SCM-DHDO can convert cellulose, lignin and...
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