Fractional catalytic pyrolysis is a selective in situ conversion of biopolymers into desired products. Fractional catalytic pyrolysis was used to convert the lignin fraction of hybrid poplar wood into high yields of cresols and phenols while the carbohydrate fraction was selectively converted into gaseous products. Ground air-dried biomass was fractionally pyrolyzed at 450−500 °C in a 2-in fluidized bed reactor. The total liquid, gas, and char/coke yields were 33%, 53%, and 12.5%, respectively. The low viscosity liquid products consisted of almost pure phenolics with minor carbohydrate decomposition products. The major liquid components were phenol, cresols, methyl substituted phenols, and small fractions of indene and substituted naphthalenes. The carbon and oxygen contents and high heating value (HHV) of the oil were 71%, 21%, and 30.5 MJ/kg, respectively. About 90 wt % of the gaseous products was carbon monoxide and carbon dioxide, and the rest was a mixture of hydrocarbons.

Reactive catalytic fast pyrolysis with atmospheric pressure hydrogen improved yield and quality of the resulting bio-crude.

Biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, here we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg −1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg −1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processesanalyses that are critical for subsequent development of selective valorization strategies for these waste streams.

(51) Int. Cl' Methods for fractional catalytic pyrolysis which allow for C013 3/36 (200601) conversion ofbiomass into a slate ofdesired products without C013 60" (200601) the need for post-pyrolysis separation are described. The C101 1/207 (200601) methods involve use of a fluid catalytic bed which is main-C1013/00 (200601) tained at a suitable pyrolysis temperature. Biomass is added (52) us C1' to the catalytic bed, preferably while entrained in a non-USPC """""""" 48/197 R; 48/2013 48/2093 48/2103 reactive gas such as nitrogen, causing the biomass to become _ _ _ 423/644 pyrolyzed and forming the desired products in vapor and gas (58) Fleld 0f Class1ficatlon Search forms, allowing the desired products to be easily separated.

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Catalytic hydropyrolysis of loblolly pine was studied in a high-pressure fluidized bed reactor using a NiMo hydrotreating catalyst. Hydropyrolysis temperature (375–475 °C) influenced the product distribution, product composition, H2 consumption, and process carbon efficiency. The material balances ranged from 84% to 106% with an average of 91%. The organic liquid yields including C4–C6 gases ranged from 20 wt % to 24 wt %, and the gas yields were between 11 and 27 wt %. The yield of the solids varied from 8 wt % to 26 wt %. Catalyst stability was studied at 450 °C and 20.68 bar (300 psig) total pressure with 40 vol % H2 for 10 days. The organic liquid product yield (22.5 ± 1.35 wt %) and quality (2.8 ± 1 wt % O) were consistent over 10 days of experiments with the same catalyst exposed to daily hydropyrolysis, regeneration, and reduction cycles indicating stable and steady-state catalyst performance over this time period.

Ceria as a selective catalyst for the conversion of biomass pyrolysis vapors into linear and cyclic ketones as hydrocarbon fuel precursors.

RTI International is developing an advanced biofuels technology that integrates a catalytic biomass pyrolysis step and a hydroprocessing step to produce infrastructure-compatible biofuels. At the current stage of development, the catalytic biomass pyrolysis process is being scaled-up in a 1 tonne per day (1 TPD) pilot plant based on a single-loop transport reactor design with continuous catalyst circulation and regeneration. The chemistry of biomass pyrolysis is manipulated by the catalyst and by controlling the pyrolysis temperature, vapor residence time, and biomass-to-catalyst ratio. The pilot unit has been successfully operated with a novel catalyst that produces a bio-crude intermediate with 24 wt% oxygen. Product yields and composition in the pilot plant are consistent with results obtained in a laboratory-scale 2.54 cm diameter bubbling fluidized bed reactor. The overall mass balance was 93%, while the carbon closure was 83%.