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Title: Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process

Pyrolysis is a promising method for converting biomass to biofuels. However, some of pyrolysis oil's physiochemical properties still limit its commercial applications. Here, the autohydrolysis pretreatment at 175 ± 3 °C for 40 min was conducted to improve the resulting pine pyrolysis oil’s properties as a fuel. During autohydrolysis, deacetylation and decomposition of hemicellulose was observed by ion-exchange chromatography and Fourier transform infrared spectroscopy (FT-IR). Additionally, the cleavage of lignin ether bonds was clearly determined by 13C cross-polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR). Phosphitylation followed by 31P NMR analysis of the heavy oils gave detailed structural information of the hydroxyl groups; the results revealed that autohydrolysis pretreatment led to a reduction of carboxyl acids in the heavy oils generated at all three pyrolysis temperatures (400, 500, and 600 °C). The 31P NMR analysis also revealed that autohydrolysis pretreatment led to a reduction of condensed phenolic hydroxyl groups in the heavy oils produced at 600 °C. 1H- 13C heteronuclear single-quantum correlation (HSQC) NMR analysis showed that at a pyrolysis temperature of 600 °C, the pretreated pine produced lower methoxy group constituents. In both 31P and HSQC NMR results indicated that autohydrolysis pretreatment increased levoglucosan yields in the bio-oils.
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [3] ; ORCiD logo [4]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Key Lab of Energy Thermal Conversion and Control of Minstry of Education, Nanjing (China); Southeast Univ., Nanjing (China)
  3. Auburn Univ., AL (United States)
  4. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725; NSF-CBET-1333372
Type:
Accepted Manuscript
Journal Name:
Fuel
Additional Journal Information:
Journal Volume: 206; Journal Issue: C; Journal ID: ISSN 0016-2361
Publisher:
Elsevier
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 09 BIOMASS FUELS; Autohydrolysis pretreatment; Pine wood; Pyrolysis oil; NMR
OSTI Identifier:
1376585

Hao, Naijia, Bezerra, Tais Lacerda, Wu, Qiong, Ben, Haoxi, Sun, Qining, Adhikari, Sushil, and Ragauskas, Arthur J. Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process. United States: N. p., Web. doi:10.1016/j.fuel.2017.06.013.
Hao, Naijia, Bezerra, Tais Lacerda, Wu, Qiong, Ben, Haoxi, Sun, Qining, Adhikari, Sushil, & Ragauskas, Arthur J. Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process. United States. doi:10.1016/j.fuel.2017.06.013.
Hao, Naijia, Bezerra, Tais Lacerda, Wu, Qiong, Ben, Haoxi, Sun, Qining, Adhikari, Sushil, and Ragauskas, Arthur J. 2017. "Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process". United States. doi:10.1016/j.fuel.2017.06.013. https://www.osti.gov/servlets/purl/1376585.
@article{osti_1376585,
title = {Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process},
author = {Hao, Naijia and Bezerra, Tais Lacerda and Wu, Qiong and Ben, Haoxi and Sun, Qining and Adhikari, Sushil and Ragauskas, Arthur J.},
abstractNote = {Pyrolysis is a promising method for converting biomass to biofuels. However, some of pyrolysis oil's physiochemical properties still limit its commercial applications. Here, the autohydrolysis pretreatment at 175 ± 3 °C for 40 min was conducted to improve the resulting pine pyrolysis oil’s properties as a fuel. During autohydrolysis, deacetylation and decomposition of hemicellulose was observed by ion-exchange chromatography and Fourier transform infrared spectroscopy (FT-IR). Additionally, the cleavage of lignin ether bonds was clearly determined by 13C cross-polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR). Phosphitylation followed by 31P NMR analysis of the heavy oils gave detailed structural information of the hydroxyl groups; the results revealed that autohydrolysis pretreatment led to a reduction of carboxyl acids in the heavy oils generated at all three pyrolysis temperatures (400, 500, and 600 °C). The 31P NMR analysis also revealed that autohydrolysis pretreatment led to a reduction of condensed phenolic hydroxyl groups in the heavy oils produced at 600 °C. 1H-13C heteronuclear single-quantum correlation (HSQC) NMR analysis showed that at a pyrolysis temperature of 600 °C, the pretreated pine produced lower methoxy group constituents. In both 31P and HSQC NMR results indicated that autohydrolysis pretreatment increased levoglucosan yields in the bio-oils.},
doi = {10.1016/j.fuel.2017.06.013},
journal = {Fuel},
number = C,
volume = 206,
place = {United States},
year = {2017},
month = {6}
}