Conversion of Phenolic Oil from Biomass Pyrolysis into Phenyl Esters

Bakshi, Santanu; Rover, Marjorie R.; Smith, Ryan G.; Brown, Robert C.

doi:10.1021/acs.energyfuels.2c00769

Conversion of Phenolic Oil from Biomass Pyrolysis into Phenyl Esters

Journal Article · Wed Jun 01 00:00:00 EDT 2022 · Energy and Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.2c00769· OSTI ID:2228314

^[1]; Rover, Marjorie R. ^[2]; Smith, Ryan G. ^[2]; ^[2]

Iowa State University, Ames, IA (United States); Iowa State University
Iowa State University, Ames, IA (United States)

Bio-oil is among the most economical approaches for advanced biofuel production. However, bio-oil faces several challenges including high acidity and viscosity, poor storage, and thermal stability. This study focuses on the upgradation of lignocellulosic (corn stover and yellow pine) bio-oil derived phenolic oil (PO), produced by the autothermal fast pyrolysis, through acid-catalyzed esterification reaction. Our strategy exploits a little recognized chemistry: the Fischer esterification of PO and carboxylic acids into carboxylic acid phenyl esters (CAPE) using Dean Stark distillation. Analyses by the Folin–Ciocalteu method, Karl Fischer titration, gas chromatography flame ionization detector, and the molecular weight determination by gel permeation chromatography suggest the conversion of 50 wt% added phenolics to their corresponding CAPE. The Fourier transform infrared spectroscopy analysis confirmed the formation of new C=O and two C–O stretching bands and decrease in the intensity of phenolic-OH bands in the CAPE. The ¹³C NMR analysis supports the formation of CAPE together with some unreacted precursors. A base-catalyzed ester hydrolysis experiment and mass balance calculation show an excellent agreement (within 5% range) of the equivalent weight between the produced ester and the phenyl hexanoate. Brookfield analysis indicates that CAPE has 330-fold lower viscosity than starting PO. Heating values of CAPE were higher than PO, from which they were derived (42.2 and 43.6%, respectively, for PO from pyrolysis of corn stover and yellow pine), while moisture content decreased by 98.3 and 98.7%, respectively. The CAPE, which is a phenolic analogue of methyl esters used in biodiesel, has improved stability compared to PO from which it was derived.

View Accepted Manuscript (DOE)

Research Organization:: RAPID Manufacturing Institute, New York, NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0007888

OSTI ID:: 2228314

Alternate ID(s):: OSTI ID: 1977825

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 12 Vol. 36; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (36)

Production of Clean Pyrolytic Sugars for Fermentation Rover, Marjorie R.; Johnston, Patrick A.; Jin, Tao ChemSusChem, Vol. 7, Issue 6, p. 1662-1668 https://doi.org/10.1002/cssc.201301259	journal	April 2014
The Effect of Functional Groups in Bio-Derived Fuel Candidates Jenkins, Rhodri W.; Moore, Cameron M.; Semelsberger, Troy A. ChemSusChem, Vol. 9, Issue 9 https://doi.org/10.1002/cssc.201600159	journal	April 2016
Direct esterification of phenols with higher fatty acids Aelony, David Journal of the American Oil Chemists' Society, Vol. 32, Issue 3 https://doi.org/10.1007/BF02640332	journal	March 1955
Promoting microbial utilization of phenolic substrates from bio-oil Davis, Kirsten; Rover, Marjorie R.; Salvachúa, Davinia Journal of Industrial Microbiology & Biotechnology, Vol. 46, Issue 11 https://doi.org/10.1007/s10295-019-02208-z	journal	July 2019
Stability mechanism investigation of emulsion fuels from biomass pyrolysis oil and diesel Guo, Zuogang; Wang, Shurong; Wang, Xiangyu Energy, Vol. 66 https://doi.org/10.1016/J.ENERGY.2014.01.010	journal	March 2014
Fast pyrolysis of rape seed in a well-swept fixed-bed reactor Onay, Ö; Beis, S. H.; Koçkar, Ö. M. Journal of Analytical and Applied Pyrolysis, Vol. 58-59 https://doi.org/10.1016/S0165-2370(00)00133-9	journal	April 2001
A review of catalytic upgrading of bio-oil to engine fuels Mortensen, P. M.; Grunwaldt, J.-D.; Jensen, P. A. Applied Catalysis A: General, Vol. 407, Issue 1-2, p. 1-19 https://doi.org/10.1016/j.apcata.2011.08.046	journal	November 2011
Process intensification of biomass fast pyrolysis through autothermal operation of a fluidized bed reactor Polin, Joseph P.; Peterson, Chad A.; Whitmer, Lysle E. Applied Energy, Vol. 249 https://doi.org/10.1016/j.apenergy.2019.04.154	journal	September 2019
Review of fast pyrolysis of biomass and product upgrading Bridgwater, A. V. Biomass and Bioenergy, Vol. 38, p. 68-94 https://doi.org/10.1016/j.biombioe.2011.01.048	journal	March 2012
Production of Fuels and Chemicals from Biomass: Condensation Reactions and Beyond Wu, Lipeng; Moteki, Takahiko; Gokhale, Amit A. Chem, Vol. 1, Issue 1 https://doi.org/10.1016/j.chempr.2016.05.002	journal	July 2016
Application of the Shvo catalyst in homogeneous hydrogenation of bio-oil obtained from pyrolysis of white poplar: New mild upgrading conditions Busetto, Luigi; Fabbri, Daniele; Mazzoni, Rita Fuel, Vol. 90, Issue 3 https://doi.org/10.1016/j.fuel.2010.10.036	journal	March 2011
Stabilization of bio-oils using low temperature, low pressure hydrogenation Rover, Marjorie R.; Hall, Patrick H.; Johnston, Patrick A. Fuel, Vol. 153 https://doi.org/10.1016/j.fuel.2015.02.054	journal	August 2015
Enabling biomass combustion and co-firing through the use of Lignocol Rover, Marjorie; Smith, Ryan; Brown, Robert C. Fuel, Vol. 211 https://doi.org/10.1016/j.fuel.2017.09.076	journal	January 2018
Fast pyrolysis of sesame stalk: yields and structural analysis of bio-oil Ateş, F.; Pütün, E.; Pütün, A. E. Journal of Analytical and Applied Pyrolysis, Vol. 71, Issue 2 https://doi.org/10.1016/j.jaap.2003.11.001	journal	June 2004
Characterization of water insoluble solids isolated from various biomass fast pyrolysis oils Mullen, Charles A.; Boateng, Akwasi A. Journal of Analytical and Applied Pyrolysis, Vol. 90, Issue 2 https://doi.org/10.1016/j.jaap.2010.12.004	journal	March 2011
Characterization of bio-oil recovered as stage fractions with unique chemical and physical properties Pollard, A. S.; Rover, M. R.; Brown, R. C. Journal of Analytical and Applied Pyrolysis, Vol. 93 https://doi.org/10.1016/j.jaap.2011.10.007	journal	January 2012
Quantification of total phenols in bio-oil using the Folin–Ciocalteu method Rover, Marjorie R.; Brown, Robert C. Journal of Analytical and Applied Pyrolysis, Vol. 104 https://doi.org/10.1016/j.jaap.2013.06.011	journal	November 2013
The effect of pyrolysis temperature on recovery of bio-oil as distinctive stage fractions Rover, Marjorie R.; Johnston, Patrick A.; Whitmer, Lysle E. Journal of Analytical and Applied Pyrolysis, Vol. 105 https://doi.org/10.1016/j.jaap.2013.11.012	journal	January 2014
Detailed characterization of red oak-derived pyrolysis oil: Integrated use of GC, HPLC, IC, GPC and Karl-Fischer Choi, Yong S.; Johnston, Patrick A.; Brown, Robert C. Journal of Analytical and Applied Pyrolysis, Vol. 110 https://doi.org/10.1016/j.jaap.2014.08.016	journal	November 2014
Esterification of guaiacol with octanoic acid over functionalized mesoporous silica Xu, Xiwei; Jiang, Enchen; Lei, Zhiwei Renewable Energy, Vol. 119 https://doi.org/10.1016/j.renene.2017.11.052	journal	April 2018
Evaluation methods and research progresses in bio-oil storage stability Chen, Dengyu; Zhou, Jianbin; Zhang, Qisheng Renewable and Sustainable Energy Reviews, Vol. 40 https://doi.org/10.1016/j.rser.2014.07.159	journal	December 2014
Separation of sugars and phenolics from the heavy fraction of bio-oil using polymeric resin adsorbents Stanford, John P.; Hall, Patrick H.; Rover, Marjorie R. Separation and Purification Technology, Vol. 194 https://doi.org/10.1016/j.seppur.2017.11.040	journal	April 2018
Catalytically Upgrading Bio-oil via Esterification Liu, Yichen; Li, Zhonglai; Leahy, James J. Energy & Fuels, Vol. 29, Issue 6 https://doi.org/10.1021/acs.energyfuels.5b00163	journal	May 2015
The direct esterification of phenols Offenhauer, Robert D. Journal of Chemical Education, Vol. 41, Issue 1 https://doi.org/10.1021/ed041p39	journal	January 1964
Recyclization apparatus for esterification Naff, M. Benton; Naff, Anna S. Journal of Chemical Education, Vol. 44, Issue 11 https://doi.org/10.1021/ed044p680	journal	November 1967
Identification of an unknown ester: An analytical-organic experiment Grob, Robert L.; Husk, G. Ronald Journal of Chemical Education, Vol. 46, Issue 11 https://doi.org/10.1021/ed046p769	journal	November 1969
Overview of Applications of Biomass Fast Pyrolysis Oil Czernik, S.; Bridgwater, A. V. Energy & Fuels, Vol. 18, Issue 2, p. 590-598 https://doi.org/10.1021/ef034067u	journal	March 2004
Pyrolysis of Wood/Biomass for Bio-oil: A Critical Review Mohan, Dinesh; Pittman,, Charles U.; Steele, Philip H. Energy & Fuels, Vol. 20, Issue 3, p. 848-889 https://doi.org/10.1021/ef0502397	journal	May 2006
Production and Fuel Properties of Pine Chip Bio-oil/Biodiesel Blends Garcia-Perez, Manuel; Adams, Thomas T.; Goodrum, John W. Energy & Fuels, Vol. 21, Issue 4 https://doi.org/10.1021/ef060533e	journal	May 2007
Maximizing the Stability of Pyrolysis Oil/Diesel Fuel Emulsions Martin, Jonathan A.; Mullen, Charles A.; Boateng, Akwasi A. Energy & Fuels, Vol. 28, Issue 9 https://doi.org/10.1021/ef5015583	journal	September 2014
Thorough Study of Reactivity of Various Compound Classes toward the Folin−Ciocalteu Reagent Everette, Jace D.; Bryant, Quinton M.; Green, Ashlee M. Journal of Agricultural and Food Chemistry, Vol. 58, Issue 14 https://doi.org/10.1021/jf1005935	journal	July 2010
Production and purification of crystallized levoglucosan from pyrolysis of lignocellulosic biomass Rover, Marjorie R.; Aui, Alvina; Wright, Mark Mba Green Chemistry, Vol. 21, Issue 21 https://doi.org/10.1039/c9gc02461a	journal	January 2019
Challenges and Opportunities in Fast Pyrolysis of Biomass: Part II Bridgwater, Tony Johnson Matthey Technology Review, Vol. 62, Issue 2 https://doi.org/10.1595/205651318X696738	journal	April 2018
Synthesis of Dimerate Esters by Solvent-Free Method Abu Hassan, Noor Armylisa'S Journal of Oil Palm Research, Vol. 29, Issue 1 https://doi.org/10.21894/jopr.2017.2901.12	journal	March 2017
Combustion Performance and Emission Characteristics of a Diesel Engine Using a Water-Emulsified Heavy Fuel Oil and Light Diesel Blend Feng, Liyan; Du, Baoguo; Tian, Jiangping Energies, Vol. 8, Issue 12 https://doi.org/10.3390/en81212387	journal	December 2015
Total Phenol Analysis: Automation and Comparison with Manual Methods Slinkard, Karen; Singleton, Vernon L. American Journal of Enology and Viticulture, Vol. 28, Issue 1 https://doi.org/10.5344/ajev.1977.28.1.49	journal	January 1977

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