Catalytic conversion of nonfood woody biomass solids to organic liquids.

This Account outlines recent efforts in our laboratories addressing a fundamental challenge of sustainability chemistry, the effective utilization of biomass for production of chemicals and fuels. Efficient methods for converting renewable biomass solids to chemicals and liquid fuels would reduce society's dependence on nonrenewable petroleum resources while easing the atmospheric carbon dioxide burden. The major nonfood component of biomass is lignocellulose, a matrix of the biopolymers cellulose, hemicellulose, and lignin. New approaches are needed to effect facile conversion of lignocellulose solids to liquid fuels and to other chemical precursors without the formation of intractable side products and with sufficient specificity to give economically sustainable product streams. We have devised a novel catalytic system whereby the renewable feedstocks cellulose, organosolv lignin, and even lignocellulose composites such as sawdust are transformed into organic liquids. The reaction medium is supercritical methanol (sc-MeOH), while the catalyst is a copper-doped porous metal oxide (PMO) prepared from inexpensive, Earth-abundant starting materials. This transformation occurs in a single stage reactor operating at 300-320 °C and 160-220 bar. The reducing equivalents for these transformations are derived by the reforming of MeOH (to H2 and CO), which thereby serves as a "liquid syngas" in the present case. Water generated by deoxygenation processes is quickly removed by the water-gas shift reaction. The Cu-doped PMO serves multiple purposes, catalyzing substrate hydrogenolysis and hydrogenation as well as the methanol reforming and shift reactions. This one-pot "UCSB process" is quantitative, giving little or no biochar residual. Provided is an overview of these catalysis studies beginning with reactions of the model compound dihydrobenzofuran that help define the key processes occurring. The initial step is phenyl-ether bond hydrogenolysis, and this is followed by aromatic ring hydrogenation. The complete catalytic disassembly of the more complex organosolv lignin to monomeric units, largely propyl-cyclohexanol derivatives is then described. Operational indices based on (1)H NMR analysis are also presented that facilitate holistic evaluation of these product streams that within several hours consist largely of propyl-cyclohexanol derivatives. Lastly, we describe the application of this methodology with several types of wood (pine sawdust, etc.) and with cellulose fibers. The product distribution, albeit still complex, displays unprecedented selectivity toward the production of aliphatic alcohols and methylated derivatives thereof. These observations clearly indicate that the Cu-doped solid metal oxide catalyst combined with sc-MeOH is capable of breaking down the complex biomass derived substrates to markedly deoxygenated monomeric units with increased hydrogen content. Possible implementations of this promising system on a larger scale are discussed.