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Characterization and comparison of fast pyrolysis bio-oils from pinewood, rapeseed cake, and wheat straw using 13C NMR and comprehensive GC × GC

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Abstract
Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative C-13 nuclear magnetic resonance (C-13 NMR) combined with comprehensive two-dimensional gas chromatography (GC x GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. C-13 NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (approximate to 30%) and carbohydrate (approximate to 27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (approximate to 35%) and aromatic (approximate to 30%) carbons, while rapeseed cake based bio-oil had great portions of alkyl carbons (approximate to 82%). More than 200 compounds were identified and quantified using GC x GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC x GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.
Keywords
LIGNOCELLULOSIC BIOMASS PYROLYSIS, 2-DIMENSIONAL GAS-CHROMATOGRAPHY, FLAME IONIZATION DETECTOR, FLIGHT MASS-SPECTROMETRY, CHEMICAL-CHARACTERIZATION, PHYSICAL-PROPERTIES, LIGNIN, FUEL, PRODUCT, LIQUID, Pyrolysis oil, Softwood, Agricultural residue, Bio-oil stability, Chemical shift, Compositional analysis, Light oxygenates, Aromatics

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Chicago
Negahdar, L, Arturo González Quiroga, Daria Otyuskaya, Hilal Ezgi Toraman, Li Liu, JTBH Jastrzebski, Kevin Van Geem, Guy Marin, Joris Thybaut, and BM Weckhuysen. 2016. “Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC.” Acs Sustainable Chemistry & Engineering 4 (9): 4974–4985.
APA
Negahdar, L., González Quiroga, A., Otyuskaya, D., Toraman, H. E., Liu, L., Jastrzebski, J., Van Geem, K., et al. (2016). Characterization and comparison of fast pyrolysis bio-oils from pinewood, rapeseed cake, and wheat straw using 13C NMR and comprehensive GC × GC. ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 4(9), 4974–4985.
Vancouver
1.
Negahdar L, González Quiroga A, Otyuskaya D, Toraman HE, Liu L, Jastrzebski J, et al. Characterization and comparison of fast pyrolysis bio-oils from pinewood, rapeseed cake, and wheat straw using 13C NMR and comprehensive GC × GC. ACS SUSTAINABLE CHEMISTRY & ENGINEERING. 2016;4(9):4974–85.
MLA
Negahdar, L, Arturo González Quiroga, Daria Otyuskaya, et al. “Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC.” ACS SUSTAINABLE CHEMISTRY & ENGINEERING 4.9 (2016): 4974–4985. Print.
@article{8150563,
  abstract     = {Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative C-13 nuclear magnetic resonance (C-13 NMR) combined with comprehensive two-dimensional gas chromatography (GC x GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. C-13 NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (approximate to 30\%) and carbohydrate (approximate to 27\%) carbons; wheat straw bio-oil showed to have high amount of alkyl (approximate to 35\%) and aromatic (approximate to 30\%) carbons, while rapeseed cake based bio-oil had great portions of alkyl carbons (approximate to 82\%). More than 200 compounds were identified and quantified using GC x GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50\% of the total mass of compounds identified and quantified via GC x GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.},
  author       = {Negahdar, L and Gonz{\'a}lez Quiroga, Arturo and Otyuskaya, Daria and Toraman, Hilal Ezgi and Liu, Li and Jastrzebski, JTBH and Van Geem, Kevin and Marin, Guy and Thybaut, Joris and Weckhuysen, BM},
  issn         = {2168-0485},
  journal      = {ACS SUSTAINABLE CHEMISTRY \& ENGINEERING},
  keyword      = {LIGNOCELLULOSIC BIOMASS PYROLYSIS,2-DIMENSIONAL GAS-CHROMATOGRAPHY,FLAME IONIZATION DETECTOR,FLIGHT MASS-SPECTROMETRY,CHEMICAL-CHARACTERIZATION,PHYSICAL-PROPERTIES,LIGNIN,FUEL,PRODUCT,LIQUID,Pyrolysis oil,Softwood,Agricultural residue,Bio-oil stability,Chemical shift,Compositional analysis,Light oxygenates,Aromatics},
  language     = {eng},
  number       = {9},
  pages        = {4974--4985},
  title        = {Characterization and comparison of fast pyrolysis bio-oils from pinewood, rapeseed cake, and wheat straw using 13C NMR and comprehensive GC {\texttimes} GC},
  url          = {http://dx.doi.org/10.1021/acssuschemeng.6b01329},
  volume       = {4},
  year         = {2016},
}

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