title: Integration of chemical catalysis with extractive fermentation to produce fuels.
abstract: Nearly one hundred years ago, the fermentative production of acetone by Clostridium acetobutylicum provided a crucial alternative source of this solvent for manufacture of the explosive cordite. Today there is a resurgence of interest in solventogenic Clostridium species to produce n-butanol and ethanol for use as renewable alternative transportation fuels. Acetone, a product of acetone-n-butanol-ethanol (ABE) fermentation, harbours a nucleophilic α-carbon, which is amenable to C-C bond formation with the electrophilic alcohols produced in ABE fermentation. This functionality can be used to form higher-molecular-mass hydrocarbons similar to those found in current jet and diesel fuels. Here we describe the integration of biological and chemocatalytic routes to convert ABE fermentation products efficiently into ketones by a palladium-catalysed alkylation. Tuning of the reaction conditions permits the production of either petrol or jet and diesel precursors. Glyceryl tributyrate was used for the in situ selective extraction of both acetone and alcohols to enable the simple integration of ABE fermentation and chemical catalysis, while reducing the energy demand of the overall process. This process provides a means to selectively produce petrol, jet and diesel blend stocks from lignocellulosic and cane sugars at yields near their theoretical maxima.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720, USA.
authors.forename: Pazhamalai
authors.initials: P
authors.lastname: Anbarasan
authors.forename: Zachary C
authors.initials: ZC
authors.lastname: Baer
authors.forename: Sanil
authors.initials: S
authors.lastname: Sreekumar
authors.forename: Elad
authors.initials: E
authors.lastname: Gross
authors.forename: Joseph B
authors.initials: JB
authors.lastname: Binder
authors.forename: Harvey W
authors.initials: HW
authors.lastname: Blanch
authors.forename: Douglas S
authors.initials: DS
authors.lastname: Clark
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste
mesh_terms: D020001:1-Butanol / Q000378:metabolism; D000096:Acetone / Q000378:metabolism; D000478:Alkylation; D056804:Biofuels; D018533:Biomass; D002384:Catalysis; D046969:Clostridium acetobutylicum / Q000378:metabolism*; D000431:Ethanol / Q000378:metabolism; D005285:Fermentation; D005742:Gasoline; D007659:Ketones / Q000737:chemistry / Q000378:metabolism; D008031:Lignin / Q000737:chemistry / Q000378:metabolism; D008956:Models, Chemical; D010165:Palladium / Q000737:chemistry*; D031786:Saccharum / Q000737:chemistry; D013997:Time Factors; D014280:Triglycerides / Q000737:chemistry
chemical_list: D056804:Biofuels; D005742:Gasoline; D007659:Ketones; D014280:Triglycerides; C036909:lignocellulose; D000096:Acetone; D000431:Ethanol; D010165:Palladium; D020001:1-Butanol; D008031:Lignin; C005830:tributyrin