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Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al{sub 2}O{sub 3} catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR

Abstract

Raw residual wood biomass, containing cellulose, hemicellulose and lignin, was liquefied at low temperature by ultrasound-assisted solvolysis and acidolysis by glycerol, diethylene glycol and p-toluenesulfonic acid. Liquefied biomass was consequently upgraded by hydrotreatment utilizing heterogeneous catalysis over NiMo/Al{sub 2}O{sub 3} bifunctional catalyst. Effects of temperature (200−350 °C), heating rate (2.5–10.0 K min{sup −1}), hydrogen/nitrogen pressure (2−8 MPa), mixing (250−1000 min{sup −1}), hydrogen donor solvent (tetralin) and catalyst contents on deoxygenation were established. Reactions of liquefaction products, such as levulinic acid, were quantified based on their functional groups by Fourier transform infrared spectroscopy, whereas catalyst was examined by scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction analysis (XRD). Chemical kinetics of hydrodeoxygenation (HDO), decarbonylation and decarboxylation were determined by originally developed lumped model, based on reaction mechanisms and pathways, while the external mass transfer resistance proved to be negligible under the applied hydrodynamic conditions. The presence of hydrocracking reactions was confirmed by a decrease in product viscosity, and the upgrade for energetic or fuel applications by measurements of calorific value. - Highlights: • Liquefaction of waste lignocellulosic biomass with glycerol at low temperature. • Hydrotreatment, hydrocracking and hydrodeoxygenation of liquefied waste biomass. • Deoxygenation using heterogeneous catalysis over NiMo/Al{sub 2}O{sub 3} bifunctional catalyst. •  More>>
Publication Date:
Apr 15, 2014
Product Type:
Journal Article
Resource Relation:
Journal Name: Biomass and Bioenergy; Journal Volume: 63; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 09 BIOMASS FUELS; ALUMINIUM OXIDES; BIOCHEMICAL REACTION KINETICS; BIOFUELS; BIOMASS; CALORIFIC VALUE; CATALYSTS; CELLULOSE; DECARBOXYLATION; FOURIER TRANSFORMATION; GLYCEROL; GLYCOLS; HEMICELLULOSE; HETEROGENEOUS CATALYSIS; HYDROCRACKING; INFRARED SPECTRA; LIQUEFACTION; SCANNING ELECTRON MICROSCOPY; SOLVOLYSIS; X-RAY DIFFRACTION; X-RAY SPECTROSCOPY
OSTI ID:
22404195
Country of Origin:
United Kingdom
Language:
English
Other Identifying Numbers:
Journal ID: ISSN 0961-9534; CODEN: BMSBEO; Other: PII: S0961-9534(14)00077-4; TRN: GB15R0779109987
Availability:
Available from http://dx.doi.org/10.1016/j.biombioe.2014.02.014
Submitting Site:
INIS
Size:
page(s) 300-312
Announcement Date:
Dec 03, 2015

Citation Formats

Grilc, M., Likozar, B., E-mail: blaz.likozar@ki.si [Laboratory of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana (Slovenia), Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana (Slovenia)], Levec, J., and Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana (Slovenia)]. Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al{sub 2}O{sub 3} catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR. United Kingdom: N. p., 2014. Web. doi:10.1016/J.BIOMBIOE.2014.02.014.
Grilc, M., Likozar, B., E-mail: blaz.likozar@ki.si [Laboratory of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana (Slovenia), Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana (Slovenia)], Levec, J., & Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana (Slovenia)]. Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al{sub 2}O{sub 3} catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR. United Kingdom. https://doi.org/10.1016/J.BIOMBIOE.2014.02.014
Grilc, M., Likozar, B., E-mail: blaz.likozar@ki.si [Laboratory of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana (Slovenia), Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana (Slovenia)], Levec, J., and Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana (Slovenia)]. 2014. "Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al{sub 2}O{sub 3} catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR." United Kingdom. https://doi.org/10.1016/J.BIOMBIOE.2014.02.014.
@misc{etde_22404195,
title = {Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al{sub 2}O{sub 3} catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR}
author = {Grilc, M., Likozar, B., E-mail: blaz.likozar@ki.si [Laboratory of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana (Slovenia), Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana (Slovenia)], Levec, J., and Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000 Ljubljana (Slovenia)]}
abstractNote = {Raw residual wood biomass, containing cellulose, hemicellulose and lignin, was liquefied at low temperature by ultrasound-assisted solvolysis and acidolysis by glycerol, diethylene glycol and p-toluenesulfonic acid. Liquefied biomass was consequently upgraded by hydrotreatment utilizing heterogeneous catalysis over NiMo/Al{sub 2}O{sub 3} bifunctional catalyst. Effects of temperature (200−350 °C), heating rate (2.5–10.0 K min{sup −1}), hydrogen/nitrogen pressure (2−8 MPa), mixing (250−1000 min{sup −1}), hydrogen donor solvent (tetralin) and catalyst contents on deoxygenation were established. Reactions of liquefaction products, such as levulinic acid, were quantified based on their functional groups by Fourier transform infrared spectroscopy, whereas catalyst was examined by scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction analysis (XRD). Chemical kinetics of hydrodeoxygenation (HDO), decarbonylation and decarboxylation were determined by originally developed lumped model, based on reaction mechanisms and pathways, while the external mass transfer resistance proved to be negligible under the applied hydrodynamic conditions. The presence of hydrocracking reactions was confirmed by a decrease in product viscosity, and the upgrade for energetic or fuel applications by measurements of calorific value. - Highlights: • Liquefaction of waste lignocellulosic biomass with glycerol at low temperature. • Hydrotreatment, hydrocracking and hydrodeoxygenation of liquefied waste biomass. • Deoxygenation using heterogeneous catalysis over NiMo/Al{sub 2}O{sub 3} bifunctional catalyst. • Proposal of reaction mechanism; chemical kinetics and mass transfer considerations. • Effect of temperature, heating rate, pressure, mixing, solvent and catalyst content.}
doi = {10.1016/J.BIOMBIOE.2014.02.014}
journal = []
volume = {63}
journal type = {AC}
place = {United Kingdom}
year = {2014}
month = {Apr}
}