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Title: Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover

Abstract

Phenolic oils were produced from fast pyrolysis of two different biomass feedstocks, red oak and corn stover and evaluated in hydroprocessing tests for production of liquid hydrocarbon products. The phenolic oils were produced with a bio-oil fractionating process in combination with a simple water wash of the heavy ends from the fractionating process. Phenolic oils derived from the pyrolysis of red oak and corn stover were recovered with yields (wet biomass basis) of 28.7 wt% and 14.9 wt%, respectively, and 54.3% and 58.6% on a carbon basis. Both precious metal catalysts and sulfided base metal catalyst were evaluated for hydrotreating the phenolic oils, as an extrapolation from whole bio-oil hydrotreatment. They were effective in removing heteroatoms with carbon yields as high as 81% (unadjusted for the 90% carbon balance). There was nearly complete heteroatom removal with residual O of only 0.4% to 5%, while N and S were reduced to less than 0.05%. Use of the precious metal catalysts resulted in more saturated products less completely hydrotreated compared to the sulfided base metal catalyst, which was operated at higher temperature. The liquid product was 42-52% gasoline range molecules and about 43% diesel range molecules. Particulate matter in the phenolic oilsmore » complicated operation of the reactors, causing plugging in the fixed-beds especially for the corn stover phenolic oil. This difficulty contrasts with the catalyst bed fouling and plugging, which is typically seen with hydrotreatment of whole bio-oil. This problem was substantially alleviated by filtering the phenolic oils before hydrotreating. More thorough washing of the phenolic oils during their preparation from the heavy ends of bio-oil or on-line filtration of pyrolysis vapors to remove particulate matter before condensation of the bio-oil fractions is recommended.« less

Authors:
 [1];  [1];  [2];  [2];  [2];  [2]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  2. Iowa State University, Ames, IA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1179502
Report Number(s):
PNNL-SA-107518
Journal ID: ISSN 2168-0485; BM0101010
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 3; Journal Issue: 5; Journal ID: ISSN 2168-0485
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; bio-oil; fractionation; fast pyrolysis; phenolic; hydrotreating; catalysis

Citation Formats

Elliott, Douglas C., Wang, Huamin, Rover, Majorie, Whitmer, Lysle, Smith, Ryan, and Brown, Robert C. Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover. United States: N. p., 2015. Web. doi:10.1021/acssuschemeng.5b00015.
Elliott, Douglas C., Wang, Huamin, Rover, Majorie, Whitmer, Lysle, Smith, Ryan, & Brown, Robert C. Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover. United States. https://doi.org/10.1021/acssuschemeng.5b00015
Elliott, Douglas C., Wang, Huamin, Rover, Majorie, Whitmer, Lysle, Smith, Ryan, and Brown, Robert C. 2015. "Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover". United States. https://doi.org/10.1021/acssuschemeng.5b00015. https://www.osti.gov/servlets/purl/1179502.
@article{osti_1179502,
title = {Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover},
author = {Elliott, Douglas C. and Wang, Huamin and Rover, Majorie and Whitmer, Lysle and Smith, Ryan and Brown, Robert C.},
abstractNote = {Phenolic oils were produced from fast pyrolysis of two different biomass feedstocks, red oak and corn stover and evaluated in hydroprocessing tests for production of liquid hydrocarbon products. The phenolic oils were produced with a bio-oil fractionating process in combination with a simple water wash of the heavy ends from the fractionating process. Phenolic oils derived from the pyrolysis of red oak and corn stover were recovered with yields (wet biomass basis) of 28.7 wt% and 14.9 wt%, respectively, and 54.3% and 58.6% on a carbon basis. Both precious metal catalysts and sulfided base metal catalyst were evaluated for hydrotreating the phenolic oils, as an extrapolation from whole bio-oil hydrotreatment. They were effective in removing heteroatoms with carbon yields as high as 81% (unadjusted for the 90% carbon balance). There was nearly complete heteroatom removal with residual O of only 0.4% to 5%, while N and S were reduced to less than 0.05%. Use of the precious metal catalysts resulted in more saturated products less completely hydrotreated compared to the sulfided base metal catalyst, which was operated at higher temperature. The liquid product was 42-52% gasoline range molecules and about 43% diesel range molecules. Particulate matter in the phenolic oils complicated operation of the reactors, causing plugging in the fixed-beds especially for the corn stover phenolic oil. This difficulty contrasts with the catalyst bed fouling and plugging, which is typically seen with hydrotreatment of whole bio-oil. This problem was substantially alleviated by filtering the phenolic oils before hydrotreating. More thorough washing of the phenolic oils during their preparation from the heavy ends of bio-oil or on-line filtration of pyrolysis vapors to remove particulate matter before condensation of the bio-oil fractions is recommended.},
doi = {10.1021/acssuschemeng.5b00015},
url = {https://www.osti.gov/biblio/1179502}, journal = {ACS Sustainable Chemistry & Engineering},
issn = {2168-0485},
number = 5,
volume = 3,
place = {United States},
year = {Mon Apr 13 00:00:00 EDT 2015},
month = {Mon Apr 13 00:00:00 EDT 2015}
}

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Cited by: 69 works
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Catalytic Hydroprocessing of Fast Pyrolysis Bio-oil from Pine Sawdust
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journal, April 2014


Hydrocarbon Liquid Production from Biomass via Hot-Vapor-Filtered Fast Pyrolysis and Catalytic Hydroprocessing of the Bio-oil
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Works referencing / citing this record:

Valorization of aqueous waste streams from thermochemical biorefineries
journal, January 2019


Biofuels and Chemicals from Lignin Based on Pyrolysis
book, September 2016


Recent research progress on bio-oil conversion into bio-fuels and raw chemicals: a review: Research progress on bio-oil conversion
journal, July 2018


A Perspective on Catalytic Strategies for Deoxygenation in Biomass Pyrolysis
journal, August 2016


Promoting microbial utilization of phenolic substrates from bio-oil
journal, July 2019


Infrared spectroscopy for carboxylic acid and phenol determination in biocrude and its derived products
journal, January 2020


Functionality and molecular weight distribution of red oak lignin before and after pyrolysis and hydrogenation
journal, January 2017