At-Line Sampling and Characterization of Pyrolytic Vapors from Biomass Feedstock Blends Using SPME-GC/MS-PCA: Influence of Char on Fast Pyrolysis

Reyes Molina, Eliezer A.; Soneja, Ravi; Herrera Diaz, Maria; Tilotta, David C.; Kelley, Stephen S.

doi:10.1021/acs.jafc.2c06043

At-Line Sampling and Characterization of Pyrolytic Vapors from Biomass Feedstock Blends Using SPME-GC/MS-PCA: Influence of Char on Fast Pyrolysis

Journal Article · Sun Dec 04 23:00:00 EST 2022 · Journal of Agricultural and Food Chemistry

DOI:https://doi.org/10.1021/acs.jafc.2c06043· OSTI ID:1909907

^[1]; Soneja, Ravi ^[2]; ^[1]; Tilotta, David C. ^[3]; Kelley, Stephen S. ^[3]

North Carolina State University, Raleigh, NC (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
North Carolina State University, Raleigh, NC (United States); AYRES Associates Inc., Madison, WI (United States)
North Carolina State University, Raleigh, NC (United States)

Solid-phase microextraction (SPME) coupled with GC-MS analysis was used for at-line sampling of pyrolytic vapors produced during fast pyrolysis of biomass. The pure and binary blends of switchgrass (SWG) and pine harvest residues (PT6) were used as feedstock. Sequential SPME sampling allowed for monitoring of changes in the pyrolysis vapors as char accumulated in the fluid bed. The concentration and composition of the vapors desorbed from the SPME fibers were investigated using GC-MS, and the data sets were then analyzed using principal component analysis (PCA) to compare the composition of the pyrolysis vapors over the course of the pyrolysis run. The chemical composition of both carbohydrate and lignin fragments varied as the char builds up in the reactor bed. Fragments derived from cellulose and xylan included anhydrosugars, furans and light oxygenated compounds. Lignin fragments included methoxyphenols, phenolic ketones and aldehydes, low molecular weight aromatics. The composition of the carbohydrate fragments changed more than the lignin fragments as the char build-up in the fluid bed. This combination of SPME-GC/MS-PCA were a novel, easy and effective method for measuring the composition and changes in the composition of pyrolysis vapors during the fast pyrolysis process. Here, this work also highlighted the effect of char build-up on the composition of the overall pyrolysis vapors.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

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

Grant/Contract Number:: AC07-05ID14517; EE0006639

OSTI ID:: 1909907

Report Number(s):: INL/JOU-22-68972

Journal Information:: Journal of Agricultural and Food Chemistry, Journal Name: Journal of Agricultural and Food Chemistry Journal Issue: 49 Vol. 70; ISSN 0021-8561

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

Optimization of the SPME device design for field applications Müller, L.; Górecki, T.; Pawliszyn, J. Fresenius' Journal of Analytical Chemistry, Vol. 364, Issue 7 https://doi.org/10.1007/s002160051396	journal	August 1999
Use of amino phase adsorbent for biomass tar sampling and separation Brage, Claes; Yu, Qizhuang; Chen, Guanxing Fuel, Vol. 76, Issue 2 https://doi.org/10.1016/S0016-2361(96)00199-8	journal	January 1997
Virgin olive oil odour notes: their relationships with volatile compounds from the lipoxygenase pathway and secoiridoid compounds Angerosa, F. Food Chemistry, Vol. 68, Issue 3 https://doi.org/10.1016/S0308-8146(99)00189-2	journal	February 2000
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
Volatile–char interactions during biomass pyrolysis: Understanding the potential origin of char activity Huang, Yong; Liu, Shasha; Akhtar, Muhammad Asif Bioresource Technology, Vol. 316 https://doi.org/10.1016/j.biortech.2020.123938	journal	November 2020
Use of a multivariate moving window PCA for the untargeted detection of contaminants in agro-food products, as exemplified by the detection of melamine levels in milk using vibrational spectroscopy Fernández Pierna, J. A.; Vincke, D.; Baeten, V. Chemometrics and Intelligent Laboratory Systems, Vol. 152 https://doi.org/10.1016/j.chemolab.2015.10.016	journal	March 2016
Chromatographic approaches for determination of low-molecular mass aldehydes in bio-oil Tessini, Catherine; Müller, Niels; Mardones, Claudia Journal of Chromatography A, Vol. 1219 https://doi.org/10.1016/j.chroma.2011.10.093	journal	January 2012
Analysis of trace contaminants in hot gas streams using time-weighted average solid-phase microextraction: Proof of concept Woolcock, Patrick J.; Koziel, Jacek A.; Cai, Lingshuang Journal of Chromatography A, Vol. 1281 https://doi.org/10.1016/j.chroma.2013.01.036	journal	March 2013
Review of biomass pyrolysis oil properties and upgrading research Zhang, Qi; Chang, Jie; Wang, Tiejun Energy Conversion and Management, Vol. 48, Issue 1, p. 87-92 https://doi.org/10.1016/j.enconman.2006.05.010	journal	January 2007
Application of biomass fast pyrolysis part I: Pyrolysis characteristics and products Yang, S. I.; Wu, M. S.; Wu, C. Y. Energy, Vol. 66 https://doi.org/10.1016/j.energy.2013.12.063	journal	March 2014
Volatile-char interactions during biomass pyrolysis: Effect of char preparation temperature Li, Bin; Zhao, Lijun; Xie, Xing Energy, Vol. 215 https://doi.org/10.1016/j.energy.2020.119189	journal	January 2021
Energy production from biomass pyrolysis: a new coefficient of pyrolytic valorisation Guehenneux, G.; Baussand, P.; Brothier, M. Fuel, Vol. 84, Issue 6 https://doi.org/10.1016/j.fuel.2004.11.005	journal	April 2005
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
Review of analytical strategies in the production and upgrading of bio-oils derived from lignocellulosic biomass Kanaujia, Pankaj K.; Sharma, Y. K.; Garg, M. O. Journal of Analytical and Applied Pyrolysis, Vol. 105 https://doi.org/10.1016/j.jaap.2013.10.004	journal	January 2014
Effects of thermal conditions on char yield and char reactivity of woody biomass in stepwise pyrolysis Jian, Jie; Lu, Zhimin; Yao, Shunchun Journal of Analytical and Applied Pyrolysis, Vol. 138 https://doi.org/10.1016/j.jaap.2018.12.026	journal	March 2019
Characterization of volatile profiles of three colored quinoas based on GC-IMS and PCA Song, Jianxin; Shao, Yong; Yan, Yiming LWT, Vol. 146 https://doi.org/10.1016/j.lwt.2021.111292	journal	July 2021
Application of off-line pyrolysis with dynamic solid-phase microextraction to the GC–MS analysis of biomass pyrolysis products Torri, Cristian; Fabbri, Daniele Microchemical Journal, Vol. 93, Issue 2 https://doi.org/10.1016/j.microc.2009.05.010	journal	November 2009
Py-SPME-GC-MS with on-fiber derivatization as a new solvent-less technique for the study of polar macromolecules: Application to natural gums Torri, Cristian; Soragni, Elena; Prati, Silvia Microchemical Journal, Vol. 110 https://doi.org/10.1016/j.microc.2013.08.006	journal	September 2013
At-line characterisation of compounds evolved during biomass pyrolysis by solid-phase microextraction SPME-GC-MS Conti, Roberto; Fabbri, Daniele; Torri, Cristian Microchemical Journal, Vol. 124 https://doi.org/10.1016/j.microc.2015.07.017	journal	January 2016
Analytical approaches to characterizing pyrolysis oil from biomass Kanaujia, Pankaj K.; Sharma, Y. K.; Agrawal, U. C. TrAC Trends in Analytical Chemistry, Vol. 42 https://doi.org/10.1016/j.trac.2012.09.009	journal	January 2013
Strategies for coupling solid-phase microextraction with mass spectrometry Deng, Jiewei; Yang, Yunyun; Wang, Xiaowei TrAC Trends in Analytical Chemistry, Vol. 55 https://doi.org/10.1016/j.trac.2013.12.004	journal	March 2014
Solid-Phase Microextraction. A Solvent-Free Alternative for Sample Preparation Zhang, Zhouyao; Yang, Min J.; Pawliszyn, Janusz Analytical Chemistry, Vol. 66, Issue 17 https://doi.org/10.1021/ac00089a001	journal	September 1994
Solid phase microextraction with thermal desorption using fused silica optical fibers Arthur, Catherine L.; Pawliszyn, Janusz. Analytical Chemistry, Vol. 62, Issue 19 https://doi.org/10.1021/ac00218a019	journal	October 1990
Nondestructive Sampling of Living Systems Usingin VivoSolid-Phase Microextraction Ouyang, Gangfeng; Vuckovic, Dajana; Pawliszyn, Janusz Chemical Reviews, Vol. 111, Issue 4 https://doi.org/10.1021/cr100203t	journal	January 2011
Fast Pyrolysis of Forestry Residue. 3. Storage Stability of Liquid Fuel Oasmaa, A.; Kuoppala, E. Energy & Fuels, Vol. 17, Issue 4 https://doi.org/10.1021/ef030011o	journal	July 2003
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
Application of Solid-Phase Microextraction (SPME) as a Tar Sampling Method Ahmadi, Mozhgan; Elm Svensson, Erik; Engvall, Klas Energy & Fuels, Vol. 27, Issue 7 https://doi.org/10.1021/ef400694d	journal	July 2013
Overview of Analytical Methods Used for Chemical Characterization of Pyrolysis Bio-oil Staš, Martin; Kubička, David; Chudoba, Josef Energy & Fuels, Vol. 28, Issue 1 https://doi.org/10.1021/ef402047y	journal	November 2013
Solvent Fractionation Method with Brix for Rapid Characterization of Wood Fast Pyrolysis Liquids Oasmaa, Anja; Kuoppala, Eeva Energy & Fuels, Vol. 22, Issue 6 https://doi.org/10.1021/ef800407d	journal	October 2008
Analysis of Aldehydes in Beer Using Solid-Phase Microextraction with On-Fiber Derivatization and Gas Chromatography/Mass Spectrometry Vesely, Petr; Lusk, Lance; Basarova, Gabriela Journal of Agricultural and Food Chemistry, Vol. 51, Issue 24 https://doi.org/10.1021/jf034410t	journal	October 2003
Toward Understanding of Bio-Oil Aging: Accelerated Aging of Bio-Oil Fractions Meng, Jiajia; Moore, Andrew; Tilotta, David ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 8 https://doi.org/10.1021/sc500223e	journal	July 2014
Principal Component Analysis (PCA) Loading and Statistical Tests for Nuclear Magnetic Resonance (NMR) Metabolomics Involving Multiple Study Groups Jiang, Lin; Sullivan, Hunter; Wang, Bo Analytical Letters, Vol. 55, Issue 10 https://doi.org/10.1080/00032719.2021.2019758	journal	January 2022
Blended Feedstocks for Thermochemical Conversion: Biomass Characterization and Bio-Oil Production From Switchgrass-Pine Residues Blends Edmunds, Charles W.; Reyes Molina, Eliezer A.; André, Nicolas Frontiers in Energy Research, Vol. 6 https://doi.org/10.3389/fenrg.2018.00079	journal	August 2018
HPTLC-PCA Complementary to HRMS-PCA in the Case Study of Arbutus unedo Antioxidant Phenolic Profiling Maldini, Mariateresa; D’Urso, Gilda; Pagliuca, Giordana Foods, Vol. 8, Issue 8 https://doi.org/10.3390/foods8080294	journal	July 2019
Raman Spectroscopy Study of Phosphorites Combined with PCA-HCA and OPLS-DA Models Yao, Xiyu; Hou, Huayi; Liang, Huan Minerals, Vol. 9, Issue 10 https://doi.org/10.3390/min9100578	journal	September 2019

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At-Line Sampling and Characterization of Pyrolytic Vapors from Biomass Feedstock Blends Using SPME-GC/MS-PCA: Influence of Char on Fast Pyrolysis

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