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Title: Tailoring diesel bioblendstock from integrated catalytic upgrading of carboxylic acids: a “fuel property first” approach

Abstract

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 C 2/C 4 acids. This screening step allowed for down-selection to a non-cyclic branched C 14 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 thenmore » converted through an integrated catalytic process scheme to achieve >80% overall carbon yield to a hydrocarbon mixture product containing >60% of the target C 14 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 C 14 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 C 14 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.« less

Authors:
 [1]; ORCiD logo [2];  [2]; ORCiD logo [2];  [2];  [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [2];  [3];  [4];  [4];  [4];  [5]; ORCiD logo [2]; ORCiD logo [2] more »; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2] « less
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Univ. of Massachusetts, Lowell, MA (United States)
  4. Yale Univ., New Haven, CT (United States)
  5. Colorado School of Mines, Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
OSTI Identifier:
1567033
Alternate Identifier(s):
OSTI ID: 1560696
Report Number(s):
NREL/JA-5100-74727
Journal ID: ISSN 1463-9262; GRCHFJ
Grant/Contract Number:  
AC36-08GO28308; EE0007983; DE347AC36-99GO10337
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Name: Green Chemistry; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; carboxylic acids; catalytic upgrading; diesel bioblendstock; low sooting potential; fuel property first

Citation Formats

Huo, Xiangchen, Huq, Nabila A., Stunkel, James J., Cleveland, Nicholas S., Starace, Anne K., Settle, Amy E., York, Allyson, Nelson, Robert S., Brandner, David, Fouts, Lisa A., St. John, Peter C., Christensen, Earl D., Luecke, Jon H., Mack, J. Hunter, McEnally, Charles S., Cherry, Patrick A., Pfefferle, Lisa D., Strathmann, Timothy J., Salvachua Rodriguez, Davinia, Kim, Seon Ah, McCormick, Robert L., Beckham, Gregg T., and Vardon, Derek R. Tailoring diesel bioblendstock from integrated catalytic upgrading of carboxylic acids: a “fuel property first” approach. United States: N. p., 2019. Web. doi:10.1039/C9GC01820D.
Huo, Xiangchen, Huq, Nabila A., Stunkel, James J., Cleveland, Nicholas S., Starace, Anne K., Settle, Amy E., York, Allyson, Nelson, Robert S., Brandner, David, Fouts, Lisa A., St. John, Peter C., Christensen, Earl D., Luecke, Jon H., Mack, J. Hunter, McEnally, Charles S., Cherry, Patrick A., Pfefferle, Lisa D., Strathmann, Timothy J., Salvachua Rodriguez, Davinia, Kim, Seon Ah, McCormick, Robert L., Beckham, Gregg T., & Vardon, Derek R. Tailoring diesel bioblendstock from integrated catalytic upgrading of carboxylic acids: a “fuel property first” approach. United States. doi:10.1039/C9GC01820D.
Huo, Xiangchen, Huq, Nabila A., Stunkel, James J., Cleveland, Nicholas S., Starace, Anne K., Settle, Amy E., York, Allyson, Nelson, Robert S., Brandner, David, Fouts, Lisa A., St. John, Peter C., Christensen, Earl D., Luecke, Jon H., Mack, J. Hunter, McEnally, Charles S., Cherry, Patrick A., Pfefferle, Lisa D., Strathmann, Timothy J., Salvachua Rodriguez, Davinia, Kim, Seon Ah, McCormick, Robert L., Beckham, Gregg T., and Vardon, Derek R. Tue . "Tailoring diesel bioblendstock from integrated catalytic upgrading of carboxylic acids: a “fuel property first” approach". United States. doi:10.1039/C9GC01820D.
@article{osti_1567033,
title = {Tailoring diesel bioblendstock from integrated catalytic upgrading of carboxylic acids: a “fuel property first” approach},
author = {Huo, Xiangchen and Huq, Nabila A. and Stunkel, James J. and Cleveland, Nicholas S. and Starace, Anne K. and Settle, Amy E. and York, Allyson and Nelson, Robert S. and Brandner, David and Fouts, Lisa A. and St. John, Peter C. and Christensen, Earl D. and Luecke, Jon H. and Mack, J. Hunter and McEnally, Charles S. and Cherry, Patrick A. and Pfefferle, Lisa D. and Strathmann, Timothy J. and Salvachua Rodriguez, Davinia and Kim, Seon Ah and McCormick, Robert L. and Beckham, Gregg T. and Vardon, Derek R.},
abstractNote = {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.},
doi = {10.1039/C9GC01820D},
journal = {Green Chemistry},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {8}
}

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