Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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 fuels1,2,3. 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.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1
Figure 2: Product distribution in Pd-catalysed alkylation as a function of reaction parameters and time course.
Figure 3
Figure 4: Block flow diagram for integration of ABE fermentation with chemical catalysis.

References

  1. Alsaker, K. V., Paredes, C. & Papoutsakis, E. T. Metabolite stress and tolerance in the production of biofuels and chemicals: gene-expression-based systems analysis of butanol, butyrate, and acetate stresses in the anaerobe Clostridium acetobutylicum. Biotechnol. Bioeng. 105, 1131–1147 (2010)

    CAS  PubMed  Google Scholar 

  2. Tracy, B. P., Jones, S. W., Fast, A. G., Indurthi, D. C. & Papoutsakis, E. T. Clostridia: the importance of their exceptional substrate and metabolite diversity for biofuel and biorefinery applications. Curr. Opin. Biotechnol. 23, 364–381 (2012)

    Article  CAS  Google Scholar 

  3. Green, E. M. Fermentative production of butanol—the industrial perspective. Curr. Opin. Biotechnol. 22, 337–343 (2011)

    Article  CAS  Google Scholar 

  4. Steen, E. J. et al. Microbial production of fatty-acid-derived fuels and chemicals from plant biomass. Nature 463, 559–562 (2010)

    Article  ADS  CAS  Google Scholar 

  5. Wang, C. et al. Metabolic engineering of Escherichia coli for α-farnesene production. Metab. Eng. 13, 648–655 (2011)

    Article  CAS  Google Scholar 

  6. Peralta-Yahya, P. P. et al. Identification and microbial production of a terpene-based advanced biofuel. Nature Commun. 2, 483 (2011)

    Article  ADS  Google Scholar 

  7. Blommel, P. G., Keenan, G. R., Rozmiarek, R. T. & Cortright, R. D. Catalytic conversion of sugar into conventional gasoline, diesel, jet fuel, and other hydrocarbons. Int. Sugar J. 110, 672–679 (2008)

    CAS  Google Scholar 

  8. Corma, A., de la Torre, O., Renz, M. & Villandier, N. Production of high-quality diesel from biomass waste products. Angew. Chem. Int. Ed. 50, 2375–2378 (2011)

    Article  CAS  Google Scholar 

  9. Huber, G. W., Chheda, J. N., Barrett, C. J. & Dumesic, J. A. Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates. Science 308, 1446–1450 (2005)

    Article  ADS  CAS  Google Scholar 

  10. Ren, C. et al. Identification and inactivation of pleiotropic regulator CcpA to eliminate glucose repression of xylose utilization in Clostridium acetobutylicum. Metab. Eng. 12, 446–454 (2010)

    Article  CAS  Google Scholar 

  11. Guillena, G., Ramón, D. J. & Yus, M. Alcohols as electrophiles in C–C bond-forming reactions: the hydrogen autotransfer process. Angew. Chem. Int. Ed. 46, 2358–2364 (2007)

    Article  CAS  Google Scholar 

  12. Hamid, M. H. S. A., Slatford, P. & Williams, J. M. J. Borrowing hydrogen in the cctivation of alcohols. Adv. Synth. Catal. 349, 1555–1575 (2007)

    Article  CAS  Google Scholar 

  13. Carlini, C., Macinai, A., Raspolli Galletti, A. M. & Sbrana, G. Selective synthesis of 2-ethyl-1-hexanol from n-butanol through the Guerbet reaction by using bifunctional catalysts based on copper or palladium precursors and sodium butoxide. J. Mol. Catal. Chem. 212, 65–70 (2004)

    Article  CAS  Google Scholar 

  14. Salvapati, G. S., Ramanamurty, K. V. & Janardanarao, M. Selective catalytic self-condensation of acetone. J. Mol. Catal. 54, 9–30 (1989)

    Article  CAS  Google Scholar 

  15. Kwon, M. S. et al. Recyclable palladium catalyst for highly selective α alkylation of ketones with alcohols. Angew. Chem. Int. Ed. 44, 6913–6915 (2005)

    Article  CAS  Google Scholar 

  16. Guillena, G., Ramón, J. D. & Yus, M. Hydrogen autotransfer in the N-alkylation of amines and related compounds using alcohols and amines as electrophiles. Chem. Rev. 110, 1611–1641 (2010)

    Article  CAS  Google Scholar 

  17. Dobereiner, G. E. & Crabtree, R. H. Dehydrogenation as a substrate-activating strategy in homogeneous transition-metal catalysis. Chem. Rev. 110, 681–703 (2010)

    Article  CAS  Google Scholar 

  18. Wayman, M. & Parekh, R. Production of acetone-butanol by extractive fermentation using dibutylphthalate as extractant. J. Ferment. Technol. 65, 295–300 (1987)

    Article  CAS  Google Scholar 

  19. Roffler, S. R., Blanch, H. W. & Wilke, C. R. In-situ recovery of butanol during fermentation. Part 2: fed-batch extractive fermentation. Bioprocess Engng 2, 181–190 (1987)

    Article  CAS  Google Scholar 

  20. Roffler, S. R., Blanch, H. W. & Wilke, C. R. In-situ recovery of butanol during fermentation. Part 1: batch extractive fermentation. Bioprocess Engng 2, 1–12 (1987)

    Article  CAS  Google Scholar 

  21. Roffler, S. R., Blanch, H. W. & Wilke, C. R. In situ extractive fermentation of acetone and butanol. Biotechnol. Bioeng. 31, 135–143 (1988)

    Article  CAS  Google Scholar 

  22. Jeon, Y. J. & Lee, Y. Y. Membrane-assisted extractive butanol fermentation. Ann. NY Acad. Sci. 506, 536–542 (1987)

    Article  ADS  CAS  Google Scholar 

  23. Vane, L. M. Separation technologies for the recovery and dehydration of alcohols from fermentation broths. Biofuels Bioprod. Biorefining 2, 553–588 (2008)

    Article  CAS  Google Scholar 

  24. Kraemer, K., Harwardt, A., Bronneberg, R. & Marquardt, W. Separation of butanol from acetone–butanol–ethanol fermentation by a hybrid extraction–distillation process. Comput. Chem. Eng. 35, 949–963 (2011)

    Article  CAS  Google Scholar 

  25. Gürbüz, E. I., Kunkes, E. L. & Dumesic, J. A. Dual-bed catalyst system for C–C coupling of biomass-derived oxygenated hydrocarbons to fuel-grade compounds. Green Chem. 12, 223–227 (2010)

    Article  Google Scholar 

  26. Kunkes, E. L. et al. Catalytic conversion of biomass to monofunctional hydrocarbons and targeted liquid-fuel classes. Science 322, 417–421 (2008)

    Article  ADS  CAS  Google Scholar 

  27. Xing, R. et al. Production of jet and diesel fuel range alkanes from waste hemicellulose-derived aqueous solutions. Green Chem. 12, 1933–1946 (2010)

    Article  CAS  Google Scholar 

  28. Dugar, D. & Stephanopoulos, G. Relative potential of biosynthetic pathways for biofuels and bio-based products. Nature Biotechnol. 29, 1074–1078 (2011)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We are grateful to H.-J. Song for performing initial experiments on the catalytic alkylation of acetone, and V. Mitchell for analysing acid pretreatment hydrolysate inhibitors present in Miscanthus giganteus. F.D.T. and E.G. acknowledge funding from the Director, Office of Science of the US Department of Energy, under contract no. DE-AC02-05CH11231. This work was funded by the Energy Biosciences Institute.

Author information

Authors and Affiliations

Authors

Contributions

Z.C.B. and P.A. contributed equally to this work. P.A. and S.S. performed experiments on the chemical catalysts, and E.G. performed experiments in the flow reactor. Z.C.B. optimized the fermentation and extractive processes. All authors contributed to the conception of the experiments, discussion of the results and preparation of manuscript.

Corresponding author

Correspondence to F. Dean Toste.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Text, Supplementary Figures 1-6 and Supplementary Tables 1-6. (PDF 499 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Anbarasan, P., Baer, Z., Sreekumar, S. et al. Integration of chemical catalysis with extractive fermentation to produce fuels. Nature 491, 235–239 (2012). https://doi.org/10.1038/nature11594

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature11594

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Quick links

Nature Briefing: Translational Research

Sign up for the Nature Briefing: Translational Research newsletter — top stories in biotechnology, drug discovery and pharma.

Get what matters in translational research, free to your inbox weekly. Sign up for Nature Briefing: Translational Research