Vapor-Phase Catalytic Upgrading of Biomass Pyrolysis Products through Aldol Condensation and Hydrodeoxygenation for the Formation of Fuel-Range Hydrocarbons
Creators: name: Caulkins, Richard S.
Publisher: name: Purdue University Graduate School
Year: 2019
Subjects: Reaction engineering (excl. nuclear reactions)

description: Biomass-derived fuels have long been considered as a possible replacement for traditional liquid fuels derived from petroleum. However, biomass as a feedstock requires significant refinement prior to application as a liquid fuel. The H2Bioil process has previously been proposed in which biomass is pyrolyzed and the resulting vapors are passed over a catalyst bed for upgrading to hydrocarbon products in a hydrogen environment [1]. A PtMo catalyst has been developed for the complete hydrodeoxygenation (HDO) of biomass pyrolysis vapors to hydrocarbons [2]. However, the product hydrocarbons contain a large fraction of molecules smaller than C4 which would not be suitable as liquid fuels. In fast hydropyrolysis of poplar followed by hydrodeoxygenation over a PtMo/MWCNT catalyst at 25 bar H2 and 300oC, only 32.1% of carbon is captured in C4 – C8 products; 21.7% of carbon is captured in C1 – C3 hydrocarbons [2]. Here, approaches are examined to increase selectivity of H2Bioil to desired products. Aldol condensation catalysts could be used prior to the HDO catalyst in order to increase the carbon number of products. These products would then be hydrodeoxygenated to hydrocarbons of greater average carbon number than with an HDO catalyst alone. Application of a 2% Cu/TiO2 catalyst to a classic aldehyde model compound, butanal, shows high selectivity towards aldol condensation products at low H2 pressures. In more complex systems which more closely resemble biomass pyrolysis vapors, this catalyst also shows significant yields to aldol condensation products, but substantial carbon losses presumed to be due to coke formation are observed. Both glycolaldehyde, a significant product of biomass pyrolysis, and cellulose, a component polymer of biomass, have been pyrolyzed and passed through aldol condensation followed by hydrodeoxygenation in a pulsed fixed-bed microreactor. Glycolaldehyde aldol condensation resulted in the formation of products in the C2-C¬9 range, while the major aldol condensation products observed from cellulose were C7 and C8 products. Carbon losses in glycolaldehyde aldol condensation were reduced under operation at increased hydrogen partial pressures, supporting the hypothesis that increasing selectivity to hydrogenation products can reduce coke formation from primary aldol condensation products. The use of feeds which have undergone genetic modification and/or pretreatment by other catalytic processes may also lead to improvements in overall product selectivity. The influence of genetic modifications to poplar lignin on the pyrolysis plus HDO process are investigated, and it is found that these materials have no effect on the final product distribution. The product distribution from a poplar sample which has had lignin catalytically removed is also examined, with the conclusion that the product distribution strongly resembles that of cellulose, however the lignin-removed sample shows high selectivity towards char which is not seen from cellulose. <br>