Integration of heterogeneous and biochemical catalysis for production of fuels and chemicals from biomass.

The past decade has seen significant government and private investment in fundamental research and process development for the production of biofuels and chemicals from lignocellulosic biomass-derived sugars. This investment has helped create new metabolic engineering and synthetic biology approaches, novel homogeneous and heterogeneous catalysts, and chemical and biological routes that convert sugars, lignin, and waste products such as glycerol into hydrocarbon fuels and valuable chemicals. With the exception of ethanol, economical biofuels processes have yet to be realized. A potentially viable way forward is the integration of biological and chemical catalysis into processes that exploit the inherent advantages of each technology while circumventing their disadvantages. Microbial fermentation excels at converting sugars from low-cost raw materials streams into simple alcohols, acids, and other reactive intermediates that can be condensed into highly reduced, long and branched chain hydrocarbons and other industrially useful compounds. Chemical catalysis most often requires clean feed streams to avoid catalyst deactivation, but the chemical and petroleum industries have developed large scale processes for C-C coupling, hydrogenation, and deoxygenation that are driven by low grade heat and low-cost feeds such as hydrogen derived from natural gas. In this context, we suggest that there is a reasonably clear route to the high yield synthesis of biofuels from biomass- or otherwise derived-fermentable sugars: the microbial production of reactive intermediates that can be extracted or separated into clean feed stream for upgrading by chemical catalysis. When coupled with new metabolic engineering strategies that maximize carbon and energy yields during fermentation, biomass-to-fuels processes may yet be realized.

[1]  Charles M. Cai,et al.  THF co-solvent enhances hydrocarbon fuel precursor yields from lignocellulosic biomass , 2013 .

[2]  Yuriy Román‐Leshkov,et al.  Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates , 2007, Nature.

[3]  Jamie H. D. Cate,et al.  Combining microbial production with chemical upgrading. , 2016, Current opinion in biotechnology.

[4]  H. Blanch,et al.  Engineering Clostridium acetobutylicum for production of kerosene and diesel blendstock precursors. , 2014, Metabolic engineering.

[5]  F. Dean Toste,et al.  Production of Fuels and Chemicals from Biomass: Condensation Reactions and Beyond , 2016 .

[6]  Xiao-Xia Xia,et al.  Direct biosynthesis of adipic acid from a synthetic pathway in recombinant Escherichia coli. , 2014, Biotechnology and bioengineering.

[7]  G. Stephanopoulos,et al.  Relative potential of biosynthetic pathways for biofuels and bio-based products , 2011, Nature Biotechnology.

[8]  Brent H Shanks,et al.  Coupling chemical and biological catalysis: a flexible paradigm for producing biobased chemicals. , 2016, Current opinion in biotechnology.

[9]  G. Moon,et al.  Ethanol distillation : the fundamentals 269 Chapter 18 Ethanol distillation : the fundamentals , 1999 .

[10]  Aditya Bhan,et al.  Mechanism of the Catalytic Conversion of Methanol to Hydrocarbons , 2013 .

[11]  Patrik R. Jones,et al.  Carboxylic acid reductase is a versatile enzyme for the conversion of fatty acids into fuels and chemical commodities , 2012, Proceedings of the National Academy of Sciences.

[12]  Stephanie G. Wettstein,et al.  Bimetallic catalysts for upgrading of biomass to fuels and chemicals. , 2012, Chemical Society reviews.

[13]  Daniel Klein-Marcuschamer,et al.  Renewable fuels from biomass: Technical hurdles and economic assessment of biological routes , 2015 .

[14]  Christos T. Maravelias,et al.  Nonenzymatic Sugar Production from Biomass Using Biomass-Derived γ-Valerolactone , 2014, Science.

[15]  Gregg T. Beckham,et al.  Adipic acid production from lignin , 2015 .

[16]  Xiaoqing Pan,et al.  Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts. , 2017, Nature chemistry.

[17]  Charles M. Cai,et al.  Co-solvent pretreatment reduces costly enzyme requirements for high sugar and ethanol yields from lignocellulosic biomass. , 2015, ChemSusChem.

[18]  L. Lynd,et al.  How biotech can transform biofuels , 2008, Nature Biotechnology.

[19]  Robert Carlson Estimating the biotech sector's contribution to the US economy , 2016, Nature Biotechnology.

[20]  J. Liao,et al.  Fuelling the future: microbial engineering for the production of sustainable biofuels , 2016, Nature Reviews Microbiology.

[21]  J. Liao,et al.  A reverse glyoxylate shunt to build a non-native route from C4 to C2 in Escherichia coli. , 2013, Metabolic engineering.

[22]  Peter Jackson,et al.  Rewriting yeast central carbon metabolism for industrial isoprenoid production , 2016, Nature.

[23]  Eleftherios T. Papoutsakis,et al.  CO2 fixation by anaerobic non-photosynthetic mixotrophy for improved carbon conversion , 2016, Nature Communications.

[24]  Tapio Salmi,et al.  Production of lactic acid/lactates from biomass and their catalytic transformations to commodities. , 2014, Chemical reviews.

[25]  John R. Dorgan,et al.  cis,cis-Muconic acid: separation and catalysis to bio-adipic acid for nylon-6,6 polymerization , 2016 .

[26]  Yuriy Román-Leshkov,et al.  Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose , 2006, Science.

[27]  E. Papoutsakis Reassessing the Progress in the Production of Advanced Biofuels in the Current Competitive Environment and Beyond: What Are the Successes and Where Progress Eludes Us and Why , 2015 .

[28]  Takahiko Moteki,et al.  Mechanistic Insight to C–C Bond Formation and Predictive Models for Cascade Reactions among Alcohols on Ca- and Sr-Hydroxyapatites , 2016 .

[29]  J. Keasling,et al.  Microbial production of fatty-acid-derived fuels and chemicals from plant biomass , 2010, Nature.

[30]  J. M. Bremner,et al.  202. The hydrogenation of furfuraldehyde to furfuryl alcohol and sylvan (2-methylfuran) , 1947 .

[31]  E. Papoutsakis,et al.  Synthetic methylotrophy: engineering the production of biofuels and chemicals based on the biology of aerobic methanol utilization. , 2015, Current opinion in biotechnology.

[32]  J. Liao,et al.  Non-fermentative pathways for synthesis of branched-chain higher alcohols as biofuels , 2008, Nature.

[33]  David H. K. Jackson,et al.  Stabilization of copper catalysts for liquid-phase reactions by atomic layer deposition. , 2013, Angewandte Chemie.

[34]  J. Liao,et al.  Synthetic non-oxidative glycolysis enables complete carbon conservation , 2013, Nature.

[35]  Tiefeng Wang,et al.  Furfural: A Promising Platform Compound for Sustainable Production of C4 and C5 Chemicals , 2016 .

[36]  Johnathan E. Holladay,et al.  Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural , 2007, Science.

[37]  James A. Dumesic,et al.  Bridging the Chemical and Biological Catalysis Gap: Challenges and Outlooks for Producing Sustainable Chemicals , 2014 .

[38]  F. Dean Toste,et al.  Integration of chemical catalysis with extractive fermentation to produce fuels , 2012, Nature.

[39]  M. Bott,et al.  Toward biotechnological production of adipic acid and precursors from biorenewables. , 2013, Journal of biotechnology.

[40]  Manuel Moliner,et al.  "One-pot" synthesis of 5-(Hydroxymethyl)furfural from carbohydrates using tin-Beta zeolite , 2011 .

[41]  Ed de Jong,et al.  Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. , 2013, Chemical reviews.

[42]  James C Liao,et al.  Frontiers in microbial 1-butanol and isobutanol production. , 2016, FEMS microbiology letters.

[43]  James M Clomburg,et al.  Engineered reversal of the β-oxidation cycle for the synthesis of fuels and chemicals , 2011, Nature.

[44]  J. Kampf,et al.  Upgrading ethanol to 1-butanol with a homogeneous air-stable ruthenium catalyst. , 2016, Chemical communications.

[45]  G. Huber,et al.  Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates , 2005, Science.

[46]  Kechun Zhang,et al.  Scalable production of mechanically tunable block polymers from sugar , 2014, Proceedings of the National Academy of Sciences.

[47]  B. Simmons,et al.  Lignin fate and characterization during ionic liquid biomass pretreatment for renewable chemicals and fuels production , 2014 .

[48]  S. Pang,et al.  Synergistic Effects of Alloying and Thiolate Modification in Furfural Hydrogenation over Cu-Based Catalysts. , 2014, The journal of physical chemistry letters.