Advances in the Catalytic Production of Valuable Levulinic Acid Derivatives

Replacing petroleum feedstocks by biomass requires efficient methods to convert carbohydrates to a variety of chemical compounds. We report the catalytic conversion of sugars giving high yield to 5-hydroxymethylfurfural (HMF), a versatile intermediate. Metal halides in 1-alkyl-3-methylimidazolium chloride are catalysts, among which chromium (II) chloride is found to be uniquely effective, leading to the conversion of glucose to HMF with a yield near 70%. A wide range of metal halides is found to catalyze the conversion of fructose to HMF. Only a negligible amount of levulinic acid is formed in these reactions.

Efficient synthesis of renewable fuels remains a challenging and important line of research. We report a strategy by which aqueous solutions of gamma-valerolactone (GVL), produced from biomass-derived carbohydrates, can be converted to liquid alkenes in the molecular weight range appropriate for transportation fuels by an integrated catalytic system that does not require an external source of hydrogen. The GVL feed undergoes decarboxylation at elevated pressures (e.g., 36 bar) over a silica/alumina catalyst to produce a gas stream composed of equimolar amounts of butene and carbon dioxide. This stream is fed directly to an oligomerization reactor containing an acid catalyst (e.g., H ZSM-5, Amberlyst-70), which couples butene monomers to form condensable alkenes with molecular weights that can be targeted for gasoline and/or jet fuel applications. The effluent gaseous stream of CO2 at elevated pressure can potentially be captured and then treated or sequestered to mitigate greenhouse gas emissions from the process.