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Title: Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor

Abstract

We investigate and quantitate the changes in hydrocarbon product composition while evaluating the performance and operability of the National Renewable Energy Laboratory's Davison Circulating Riser (DCR) reactor system when biomass model compounds are cofed with traditional fluid catalyst cracking (FCC) feeds and catalyst: vacuum gas oil (VGO) and equilibrium zeolite catalyst (E-Cat). Three compounds (acetic acid, guaiacol, and sorbitan monooleate) were selected to represent the major classes of oxygenates present in biomass pyrolysis vapors. These vapors can contain 30-50% oxygen as oxygenates, which create conversion complications (increased reactivity and coking) when integrating biomass vapors and liquids into fuel and chemical processes long dominated by petroleum feedstocks. We used these model compounds to determine the appropriate conditions for coprocessing with petroleum and ultimately pure pyrolysis vapors only as compared with standard baseline conditions obtained with VGO and E-Cat only in the DCR. Model compound addition decreased the DCR catalyst circulation rate, which controls reactor temperature and measures reaction heat demand, while increasing catalyst coking rates. Liquid product analyses included 2-dimensional gas chromatography time-of-flight mass spectroscopy (2D GCxGC TOFS), simulated distillation (SIM DIST), 13C NMR, and carbonyl content. Aggregated results indicated that the model compounds were converted during reaction, and despite functionalmore » group differences, product distributions for each model compound were very similar. In addition, we determined that adding model compounds to the VGO feed did not significantly affect the DCR's operability or performance. Future work will assess catalytic upgrading of biomass pyrolysis vapor to fungible hydrocarbon products using upgrading catalysts currently being developed at NREL and at Johnson Matthey.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), 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:
1424825
Alternate Identifier(s):
OSTI ID: 1422870
Report Number(s):
NREL/JA-5100-64865
Journal ID: ISSN 0887-0624
Grant/Contract Number:
AC36-08GO28308
Resource Type:
Journal Article: Published Article
Journal Name:
Energy and Fuels
Additional Journal Information:
Journal Volume: 32; Journal Issue: 2; Journal ID: ISSN 0887-0624
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; Davison Circulating Riser; reactor system; biomass compounds; fluid catalysts

Citation Formats

Jarvis, Mark W., Olstad, Jessica, Parent, Yves, Deutch, Steve, Iisa, Kristiina, Christensen, Earl, Ben, Haoxi, Black, Stuart, Nimlos, Mark, and Magrini, Kim. Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor. United States: N. p., 2018. Web. doi:10.1021/acs.energyfuels.7b02337.
Jarvis, Mark W., Olstad, Jessica, Parent, Yves, Deutch, Steve, Iisa, Kristiina, Christensen, Earl, Ben, Haoxi, Black, Stuart, Nimlos, Mark, & Magrini, Kim. Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor. United States. doi:10.1021/acs.energyfuels.7b02337.
Jarvis, Mark W., Olstad, Jessica, Parent, Yves, Deutch, Steve, Iisa, Kristiina, Christensen, Earl, Ben, Haoxi, Black, Stuart, Nimlos, Mark, and Magrini, Kim. Tue . "Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor". United States. doi:10.1021/acs.energyfuels.7b02337.
@article{osti_1424825,
title = {Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor},
author = {Jarvis, Mark W. and Olstad, Jessica and Parent, Yves and Deutch, Steve and Iisa, Kristiina and Christensen, Earl and Ben, Haoxi and Black, Stuart and Nimlos, Mark and Magrini, Kim},
abstractNote = {We investigate and quantitate the changes in hydrocarbon product composition while evaluating the performance and operability of the National Renewable Energy Laboratory's Davison Circulating Riser (DCR) reactor system when biomass model compounds are cofed with traditional fluid catalyst cracking (FCC) feeds and catalyst: vacuum gas oil (VGO) and equilibrium zeolite catalyst (E-Cat). Three compounds (acetic acid, guaiacol, and sorbitan monooleate) were selected to represent the major classes of oxygenates present in biomass pyrolysis vapors. These vapors can contain 30-50% oxygen as oxygenates, which create conversion complications (increased reactivity and coking) when integrating biomass vapors and liquids into fuel and chemical processes long dominated by petroleum feedstocks. We used these model compounds to determine the appropriate conditions for coprocessing with petroleum and ultimately pure pyrolysis vapors only as compared with standard baseline conditions obtained with VGO and E-Cat only in the DCR. Model compound addition decreased the DCR catalyst circulation rate, which controls reactor temperature and measures reaction heat demand, while increasing catalyst coking rates. Liquid product analyses included 2-dimensional gas chromatography time-of-flight mass spectroscopy (2D GCxGC TOFS), simulated distillation (SIM DIST), 13C NMR, and carbonyl content. Aggregated results indicated that the model compounds were converted during reaction, and despite functional group differences, product distributions for each model compound were very similar. In addition, we determined that adding model compounds to the VGO feed did not significantly affect the DCR's operability or performance. Future work will assess catalytic upgrading of biomass pyrolysis vapor to fungible hydrocarbon products using upgrading catalysts currently being developed at NREL and at Johnson Matthey.},
doi = {10.1021/acs.energyfuels.7b02337},
journal = {Energy and Fuels},
number = 2,
volume = 32,
place = {United States},
year = {Tue Jan 02 00:00:00 EST 2018},
month = {Tue Jan 02 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.energyfuels.7b02337

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