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Title: Low-Temperature Electrochemical Upgrading of Bio-oils Using Polymer Electrolyte Membranes

Abstract

While bio-oil-derived fuels hold much promise as a replacement for petroleum, transformation of the highly oxygenated mixture has proven challenging. In particular, bio-oils are reactive and difficult to upgrade through catalytic pyrolysis. To reach a stabilized product capable of deep deoxygenation at elevated pressure and temperature, conversion or separation of reactive groups is required. This paper describes an electrochemical process for stabilization and upgrading of bio-oils prior to hydrotreating at high pressure and temperature. This electrolytic process uses a three-compartment cell designed to hydrogenate reactive carbonyl components while separating small acid molecules, such as acetic and formic acids, which act as catalysts for condensation reactions and consume hydrogen gas to produce low-value gases in hydrotreating. To avoid conductivity issues, electrodes are appended to anion- and cation-exchange membranes. The cell was tested using a mixed acetic acid and formic acid surrogate fed to the cathode compartment, where the decrease in the concentration followed the applied charge to the cell. Experiments performed using pine pyrolysis oil demonstrated a significant reduction in the total acid number (TAN), an increase in pH from 2.6 to over 4, and a modest reduction of the carbonyl concentration. Analysis showed the reduction in TAN was primarily duemore » to removal of carboxylic compounds. Experiments observed a decrease in the reactive carbonyl (aldehydes and ketones) concentration that followed applied charge. The results with the newly devised reactor show promise for the electrochemical route for upgrading bio-oils, but significant improvements in TAN removal and carbonyl conversion are needed. Given the distributed nature of biomass, an electrochemical process paired with pyrolysis could be used to densify and stabilize an oil product near the source. The densified liquid could then be shipped to centralized refineries for final upgrading to fuel and/or chemical products.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [2];  [3];  [4]; ORCiD logo [4]
  1. Chemical, Biological Processing Department, Energy, Environment Division, Idaho National Laboratory, Post Office Box 1625, Idaho Falls, Idaho 83425, United States
  2. Chemical &, Biological Process Development Group, Energy &, Efficiency Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Post Office Box 999, MSIN P8-60, Richland, Washington 99352, United States
  3. Chemical and Biological Technologies Group, Energy System Division, Argonne National Laboratory, 9700 South Cass Avenue, Building 362, Argonne, Illinois 60439, United States
  4. Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, Louisiana 70803, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office
OSTI Identifier:
1488455
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Energy and Fuels
Additional Journal Information:
Journal Volume: 32; Journal Issue: 5; Journal ID: ISSN 0887-0624
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Lister, Tedd E., Diaz, Luis A., Lilga, Michael A., Padmaperuma, Asanga B., Lin, YuPo, Palakkal, Varada Menon, and Arges, Christopher G. Low-Temperature Electrochemical Upgrading of Bio-oils Using Polymer Electrolyte Membranes. United States: N. p., 2018. Web. doi:10.1021/acs.energyfuels.8b00134.
Lister, Tedd E., Diaz, Luis A., Lilga, Michael A., Padmaperuma, Asanga B., Lin, YuPo, Palakkal, Varada Menon, & Arges, Christopher G. Low-Temperature Electrochemical Upgrading of Bio-oils Using Polymer Electrolyte Membranes. United States. https://doi.org/10.1021/acs.energyfuels.8b00134
Lister, Tedd E., Diaz, Luis A., Lilga, Michael A., Padmaperuma, Asanga B., Lin, YuPo, Palakkal, Varada Menon, and Arges, Christopher G. 2018. "Low-Temperature Electrochemical Upgrading of Bio-oils Using Polymer Electrolyte Membranes". United States. https://doi.org/10.1021/acs.energyfuels.8b00134.
@article{osti_1488455,
title = {Low-Temperature Electrochemical Upgrading of Bio-oils Using Polymer Electrolyte Membranes},
author = {Lister, Tedd E. and Diaz, Luis A. and Lilga, Michael A. and Padmaperuma, Asanga B. and Lin, YuPo and Palakkal, Varada Menon and Arges, Christopher G.},
abstractNote = {While bio-oil-derived fuels hold much promise as a replacement for petroleum, transformation of the highly oxygenated mixture has proven challenging. In particular, bio-oils are reactive and difficult to upgrade through catalytic pyrolysis. To reach a stabilized product capable of deep deoxygenation at elevated pressure and temperature, conversion or separation of reactive groups is required. This paper describes an electrochemical process for stabilization and upgrading of bio-oils prior to hydrotreating at high pressure and temperature. This electrolytic process uses a three-compartment cell designed to hydrogenate reactive carbonyl components while separating small acid molecules, such as acetic and formic acids, which act as catalysts for condensation reactions and consume hydrogen gas to produce low-value gases in hydrotreating. To avoid conductivity issues, electrodes are appended to anion- and cation-exchange membranes. The cell was tested using a mixed acetic acid and formic acid surrogate fed to the cathode compartment, where the decrease in the concentration followed the applied charge to the cell. Experiments performed using pine pyrolysis oil demonstrated a significant reduction in the total acid number (TAN), an increase in pH from 2.6 to over 4, and a modest reduction of the carbonyl concentration. Analysis showed the reduction in TAN was primarily due to removal of carboxylic compounds. Experiments observed a decrease in the reactive carbonyl (aldehydes and ketones) concentration that followed applied charge. The results with the newly devised reactor show promise for the electrochemical route for upgrading bio-oils, but significant improvements in TAN removal and carbonyl conversion are needed. Given the distributed nature of biomass, an electrochemical process paired with pyrolysis could be used to densify and stabilize an oil product near the source. The densified liquid could then be shipped to centralized refineries for final upgrading to fuel and/or chemical products.},
doi = {10.1021/acs.energyfuels.8b00134},
url = {https://www.osti.gov/biblio/1488455}, journal = {Energy and Fuels},
issn = {0887-0624},
number = 5,
volume = 32,
place = {United States},
year = {2018},
month = {4}
}