Tailoring Diesel Bioblendstock from Integrated Catalytic Upgrading of Carboxylic Acids: A 'Fuel Property First' Approach

Xiangchen Huo, Nabila A. Huq, Jim Stunkel, Nicholas S. Cleveland, Anne K. Starace, Amy E. Settle, Allyson M. York, Robert S. Nelson, David G. Brandner, Lisa Fouts, Peter C. St. John, Earl D. Christensen, Jon Luecke, J. Hunter Mack, Charles S. McEnally, Patrick A. Cherry, Lisa D. Pfefferle, Timothy J. Strathmann, Davinia Salvachúa, Seonah KimRobert L. McCormick, Gregg T. Beckham, Derek R. Vardon

Research output: Contribution to journalArticlepeer-review

32 Scopus Citations

Abstract

Lignocellulosic biomass offers the potential to produce renewable fuels at a scale commensurate with petroleum consumption. Hybrid approaches that combine biological and chemocatalytic processes have garnered increasing attention due to their flexibility for feedstock utilization and diversity of potential products. Of note, lignocellulosic sugars can be converted biologically to short-chain carboxylic acids, while subsequent chemocatalytic upgrading can elongate the carbon backbone and remove oxygen from the structure to produce drop-in hydrocarbon fuels. However, hybrid conversion processes are typically not designed with the fuel properties in mind a priori. In this work, we apply a "fuel property first" design approach to produce a tailored hydrocarbon bioblendstock with lower intrinsic sooting and drop-in diesel fuel potential. Initially, model predictions for six fuel properties critical to diesel applications (physicochemical requirements, energy content, safety considerations, autoignition ability, and sooting tendency) were used to screen an array of hydrocarbons accessible from upgrading individual and mixed C2/C4 acids. This screening step allowed for down-selection to a non-cyclic branched C14 hydrocarbon (5-ethyl-4-propylnonane) that can be synthesized from butyric acid through sequential catalytic reactions of acid ketonization, ketone condensation, and hydrodeoxygenation. Following evaluation of each conversion step with model compounds, butyric acid was then converted through an integrated catalytic process scheme to achieve >80% overall carbon yield to a hydrocarbon mixture product containing >60% of the target C14 hydrocarbon. The potential of this conversion strategy to produce a hydrocarbon diesel bioblendstock from lignocellulosic biomass was then demonstrated using corn stover-derived butyric acid produced from Clostridium butyricum fermentation. Experimental fuel property testing of the purified C14 blendstock validated the majority of the fuel property model predictions, including <50% of the intrinsic sooting tendency when compared to conventional diesel. Meanwhile, the crude conversion product met fuel property target metrics, validating conversion process development. When the C14 bioblendstock was blended into a petroleum diesel at 20 vol%, the blend maintained low cloud point, high energy density, and cetane number. Notably, the blend reduced sooting tendency by more than 10%, highlighting the potential of the tailored bioblendstock to reduce particulate emissions.

Original languageAmerican English
Pages (from-to)5813-5827
Number of pages15
JournalGreen Chemistry
Volume21
Issue number21
DOIs
StatePublished - 2019

Bibliographical note

Publisher Copyright:
© 2019 The Royal Society of Chemistry.

NREL Publication Number

  • NREL/JA-5100-74727

Keywords

  • carboxylic acids
  • catalytic upgrading
  • diesel bioblendstock
  • fuel property first
  • low sooting potential

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