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Title: Accelerated aging of fast pyrolysis bio-oil: a new method based on carbonyl titration

Abstract

Fast pyrolysis bio-oils are known to age upon storage at room temperature, resulting in changes to both physical properties (increase in viscosity) and chemical composition (decrease in carbonyl content). A widely used accelerated aging test consists of holding samples at 80 degrees C for 24 hours, with viscosity measurement before and after heat treatment. Unfortunately, the viscosity measurement has high variability, and cannot be applied to samples that have phase separated. Here, we show that carbonyl content is a much better metric for tracking bio-oil aging. Furthermore, results from different accelerated aging protocols (for varying times at both 40 degrees C and 80 degrees C) are compared to actual room temperature storage for over 3 years. Based on this, we show that the accepted accelerated aging test (80 degrees C for 24 hours) is too severe a treatment, and results in more extensive aging than would occur with over 3 years of storage at room temperature. A new aging protocol is proposed: heat treatment at 80 degrees C for 2 hours, with carbonyl quantification before and after. This protocol correlates to room temperature storage for 1-3 months. Finally, samples were also kept in cold storage (at both 9 degrees Cmore » and -17 degrees C) for over 3 years. Unexpectedly, these samples also showed a substantial reduction in carbonyl content (by up to 25%), indicating that bio-oil aging still progresses at low temperatures. Both physical and chemical changes will occur in samples in cold storage, which has implications for the archiving of bio-oil samples.« less

Authors:
 [1]; ORCiD logo [2]
  1. Biosciences Center, National Renewable Energy Laboratory, Golden, USA
  2. National Bioenergy Center, National Renewable Energy Laboratory, Golden, USA
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:
1603721
Alternate Identifier(s):
OSTI ID: 1606122
Report Number(s):
[NREL/JA-5100-76080]
[Journal ID: ISSN 2046-2069; RSCACL]
Grant/Contract Number:  
[AC36-08GO28308]
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
[Journal Name: RSC Advances Journal Volume: 10 Journal Issue: 17]; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
09 BIOMASS FUELS; bio-oils; carbonyl; CCTPL

Citation Formats

Black, Stuart, and Ferrell, Jack R. Accelerated aging of fast pyrolysis bio-oil: a new method based on carbonyl titration. United Kingdom: N. p., 2020. Web. doi:10.1039/D0RA00046A.
Black, Stuart, & Ferrell, Jack R. Accelerated aging of fast pyrolysis bio-oil: a new method based on carbonyl titration. United Kingdom. doi:10.1039/D0RA00046A.
Black, Stuart, and Ferrell, Jack R. Mon . "Accelerated aging of fast pyrolysis bio-oil: a new method based on carbonyl titration". United Kingdom. doi:10.1039/D0RA00046A.
@article{osti_1603721,
title = {Accelerated aging of fast pyrolysis bio-oil: a new method based on carbonyl titration},
author = {Black, Stuart and Ferrell, Jack R.},
abstractNote = {Fast pyrolysis bio-oils are known to age upon storage at room temperature, resulting in changes to both physical properties (increase in viscosity) and chemical composition (decrease in carbonyl content). A widely used accelerated aging test consists of holding samples at 80 degrees C for 24 hours, with viscosity measurement before and after heat treatment. Unfortunately, the viscosity measurement has high variability, and cannot be applied to samples that have phase separated. Here, we show that carbonyl content is a much better metric for tracking bio-oil aging. Furthermore, results from different accelerated aging protocols (for varying times at both 40 degrees C and 80 degrees C) are compared to actual room temperature storage for over 3 years. Based on this, we show that the accepted accelerated aging test (80 degrees C for 24 hours) is too severe a treatment, and results in more extensive aging than would occur with over 3 years of storage at room temperature. A new aging protocol is proposed: heat treatment at 80 degrees C for 2 hours, with carbonyl quantification before and after. This protocol correlates to room temperature storage for 1-3 months. Finally, samples were also kept in cold storage (at both 9 degrees C and -17 degrees C) for over 3 years. Unexpectedly, these samples also showed a substantial reduction in carbonyl content (by up to 25%), indicating that bio-oil aging still progresses at low temperatures. Both physical and chemical changes will occur in samples in cold storage, which has implications for the archiving of bio-oil samples.},
doi = {10.1039/D0RA00046A},
journal = {RSC Advances},
number = [17],
volume = [10],
place = {United Kingdom},
year = {2020},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/D0RA00046A

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Works referenced in this record:

Stability of wood fast pyrolysis oil
journal, January 1994


A review and perspective of recent bio-oil hydrotreating research
journal, January 2014

  • Zacher, Alan H.; Olarte, Mariefel V.; Santosa, Daniel M.
  • Green Chem., Vol. 16, Issue 2
  • DOI: 10.1039/C3GC41382A

Characterizations of Phenol-Formaldehyde Resol Resins
journal, March 1994

  • Haupt, Robert A.; Sellers, Terry Jr.
  • Industrial & Engineering Chemistry Research, Vol. 33, Issue 3
  • DOI: 10.1021/ie00027a030

Study of bio-oil properties and ageing through fractionation and ternary mixtures with the heavy fraction as the main component
journal, February 2019


Toward Understanding of Bio-Oil Aging: Accelerated Aging of Bio-Oil Fractions
journal, July 2014

  • Meng, Jiajia; Moore, Andrew; Tilotta, David
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 8
  • DOI: 10.1021/sc500223e

Physical and chemical characteristics of aging pyrolysis oils produced from hardwood and softwood feedstocks
journal, May 2011

  • Ortega, John V.; Renehan, Andrew M.; Liberatore, Matthew W.
  • Journal of Analytical and Applied Pyrolysis, Vol. 91, Issue 1
  • DOI: 10.1016/j.jaap.2011.02.007

Compositional Changes to Low Water Content Bio-oils during Aging: An NMR, GC/MS, and LC/MS Study
journal, May 2016


Heat Generation during the Aging of Wood-Derived Fast-Pyrolysis Bio-oils
journal, December 2015


The irreversible momentum of clean energy
journal, January 2017


Results of the International Energy Agency Round Robin on Fast Pyrolysis Bio-oil Production
journal, April 2017


Controlling the Phase Stability of Biomass Fast Pyrolysis Bio-oils
journal, June 2015


Upgrading the Storage Properties of Bio-oil by Adding a Compound Additive
journal, May 2017


Stability of crude bio-oil and its water-extracted fractions
journal, June 2018


Thermal and Storage Stability of Bio-Oil from Pyrolysis of Torrefied Wood
journal, July 2015


SANS Analysis of the Microstructural Evolution during the Aging of Pyrolysis Oils from Biomass
journal, January 2006

  • Fratini, Emiliano; Bonini, Massimo; Oasmaa, Anja
  • Langmuir, Vol. 22, Issue 1
  • DOI: 10.1021/la051990a

Norms and standards for fast pyrolysis liquids
journal, June 2005


A perspective on oxygenated species in the refinery integration of pyrolysis oil
journal, January 2014

  • Talmadge, Michael S.; Baldwin, Robert M.; Biddy, Mary J.
  • Green Chem., Vol. 16, Issue 2
  • DOI: 10.1039/C3GC41951G

Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method
journal, January 2017

  • Black, Stuart; Ferrell, Jack R.
  • Journal of Visualized Experiments, Issue 120
  • DOI: 10.3791/55165

Accelerated Aging of Bio-oil from Fast Pyrolysis of Hardwood
journal, April 2014


Pyrolysis Oil Multiphase Behavior and Phase Stability: A Review
journal, August 2016


An Approach for Stability Measurement of Wood-Based Fast Pyrolysis Bio-Oils
journal, July 2011

  • Oasmaa, Anja; Korhonen, Jaana; Kuoppala, Eeva
  • Energy & Fuels, Vol. 25, Issue 7
  • DOI: 10.1021/ef2006673

Results of the IEA Round Robin on Viscosity and Stability of Fast Pyrolysis Bio-oils
journal, May 2012

  • Elliott, Douglas C.; Oasmaa, Anja; Preto, Fernando
  • Energy & Fuels, Vol. 26, Issue 6
  • DOI: 10.1021/ef300384t

Results of the IEA Round Robin on Viscosity and Aging of Fast Pyrolysis Bio-oils: Long-Term Tests and Repeatability
journal, November 2012

  • Elliott, Douglas C.; Oasmaa, Anja; Meier, Dietrich
  • Energy & Fuels, Vol. 26, Issue 12
  • DOI: 10.1021/ef301607v

Standardization of chemical analytical techniques for pyrolysis bio-oil: history, challenges, and current status of methods: Bio-oil Analytical Standardization
journal, July 2016

  • Ferrell, Jack R.; Olarte, Mariefel V.; Christensen, Earl D.
  • Biofuels, Bioproducts and Biorefining, Vol. 10, Issue 5
  • DOI: 10.1002/bbb.1661