Thermochemical conversion of biomass to create fuels and chemical products may be achieved through the gasification route via syngas. The resulting biomass-derived raw syngas contains the building blocks of carbon monoxide and hydrogen as well as undesired impurities, such as tars, hydrocarbons, hydrogen sulfide, ammonia, hydrogen chloride, and other trace contaminants. These impurities require removal, usually through catalytic conditioning, to produce a quality syngas for end-use synthesis of liquid fuels, such as mixed alcohols and Fischer−Tropsch liquids. In the past decade, significant research attention has been focused on these catalytic processes. This contribution builds on previous reviews and focuses on capturing the work on catalytic conditioning of biomass-derived syngas that have been performed since the Dayton review in 2002, with an emphasis on tar destruction and steam reforming catalysts. This review organizes and discusses the investigations of catalytic conditioning of biomass-derived syngas with various catalyst formulations and also discusses the roles of catalyst additives. Key technical challenges and research areas for the advancement of liquid fuel synthesis via thermochemical conversion of biomass are also discussed.

This review examines state-of-the-art mid-and high-temperature sulfur sorbents that remove hydrogen sulfide (H 2 S) from syngas generated from coal gasification and may be applicable for use with biomassderived syngas. Biomass feedstocks contain low percentages of protein-derived sulfur that is converted primarily to H 2 S, as well as small amounts of carbonyl sulfide (COS) and organosulfur compounds during pyrolysis and gasification. These sulfur species must be removed from the raw syngas before it is used for downstream fuel synthesis or power generation. Several types of sorbents based on zinc, copper, iron, calcium, manganese, and ceria have been developed over the last two decades that are capable of removing H 2 S from dry coal-derived syngas at mid-to high-temperature ranges. Further improvement is necessary to develop materials more suitable for desulfurization of biomass-derived syngas because of its hydrocarbon, tar, and potentially high steam content, which presents different challenges as compared to desulfurization of coal-derived syngas.

Pyrolysis offers a rapid and efficient means to depolymerize lignocellulosic biomass, resulting in gas, liquid, and solid products with varying yields and compositions depending on the process conditions. With respect to manufacture of "drop-in" liquid transportation fuels from biomass, a potential benefit from pyrolysis arises from the production of a liquid or vapor that could possibly be integrated into existing refinery infrastructure, thus offsetting the capital-intensive investment needed for a smaller scale, standalone biofuels production facility. However, pyrolysis typically yields a significant amount of reactive, oxygenated species including organic acids, aldehydes, ketones, and oxygenated aromatics. These oxygenated species present significant challenges that will undoubtedly require pre-processing of a pyrolysisderived stream before the pyrolysis oil can be integrated into the existing refinery infrastructure. Here we present a perspective of how the overall chemistry of pyrolysis products must be modified to ensure optimal integration in standard petroleum refineries, and we explore the various points of integration in the refinery infrastructure. In addition, we identify several research and development needs that will answer critical questions regarding the technical and economic feasibility of refinery integration of pyrolysis-derived products. † Electronic supplementary information (ESI) available. See

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Mitigation of tars produced during biomass gasification continues to be a technical barrier to developing systems. This effort combined the measurement of tar-reforming catalyst deactivation kinetics and the production of syngas in a pilot-scale biomass gasification system at a single steady-state condition with mixed woods, producing a gas with an H 2 -to-CO ratio of 2 and 13% methane. A slipstream from this process was introduced into a bench-scale 5.25 cm diameter fluidized-bed catalyst reactor charged with an alkali-promoted Ni-based/Al 2 O 3 catalyst. Catalyst conversion tests were performed at a constant space time and five temperatures from 775 to 875 °C. The initial catalyst-reforming activity for all measured components (benzene, toluene, naphthalene, and total tars) except light hydrocarbons was 100%. The residual steady-state conversion of tar ranged from 96.6% at 875 °C to 70.5% at 775 °C. Residual steady-state conversions at 875 °C for benzene and methane were 81% and 32%, respectively. Catalytic deactivation models with residual activity were developed and evaluated based on experimentally measured changes in conversion efficiencies as a function of time on stream for the catalytic reforming of tars, benzene, methane, and ethane. Both first-and second-order models were evaluated for the reforming reaction and for catalyst deactivation. Comparison of experimental and modeling results showed that the reforming reactions were adequately modeled by either first-order or second-order global kinetic expressions. However, second-order kinetics resulted in negative activation energies for deactivation. Activation energies were determined for firstorder reforming reactions and catalyst deactivation. For reforming, the representative activation energies were 32 kJ/g‚mol for ethane, 19 kJ/g‚mol for tars, 45 kJ/g‚mol for tars plus benzene, and 8-9 kJ/g‚mol for benzene and toluene. For catalyst deactivation, representative activation energies were 146 kJ/g‚mol for ethane, 121 kJ/g‚mol for tars plus benzene, 74 kJ/g‚mol for benzene, and 19 kJ/g‚mol for total tars. Methane was also modeled by a second-order reaction, with an activation energy of 18.6 kJ/g‚mol and a catalyst deactivation energy of 5.8 kJ/g‚mol.