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Title: Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles

Abstract

Mechanistic aspects of deconstruction and hydrodeoxygenation of organosolv lignin using supported Ni catalysts with (Ni/HZSM-5 and Ni/HBEA) and without Brønsted acid sites (Ni/SiO2) are reported. Lignin was deconstructed and converted to saturated cyclic hydrocarbons ranging from C5 to C14. In the one-stage reaction, full conversion with total yield of 70 ± 5 wt.% saturated hydrocarbons was achieved at 593 K and 20 bar H2. The organosolv lignin used consists of seven to eight monolignol subunits and has an average molecular weight of ca. 1200 g mol-1. The monolignols were mainly guaiacyl, syringyl and phenylcoumaran, randomly interconnected through β-O-4, 4-O-5, β-1, 5-5’ and β-β ether bonds. In situ IR spectroscopy was used to follow the changes in lignin constituents during reaction. The proposed reaction pathways for the catalytic transformation of this organosolv lignin to alkanes start with the hydrogenolysis of aryl alkyl ether bonds, followed by hydrogenation of the aromatic compounds on Ni to cyclic alcohols. Oxygen is removed from the alcohols via dehydration on Brønsted acid sites to yield cyclic alkenes that are further hydrogenated to alkanes. Formation of condensation products may occur via intermolecular recombination of aromatic monomers or alkylation of aromatic compounds by alkenes. The financial support frommore » TUM-PNNL cooperation project “Development of new methods for in situ characterization in liquid phase reactions” (CN-177939) is highly appreciated. The work by S.K., H.S., and J.A.L was partially supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1243246
Report Number(s):
PNNL-SA-111607
Journal ID: ISSN 1463-9262; KC0302010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 17; Journal Issue: 11; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Kasakov, Stanislav, Shi, Hui, Camaioni, Donald M., Zhao, Chen, Barath, Eszter, Jentys, Andreas, and Lercher, Johannes A. Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles. United States: N. p., 2015. Web. doi:10.1039/c5gc02160j.
Kasakov, Stanislav, Shi, Hui, Camaioni, Donald M., Zhao, Chen, Barath, Eszter, Jentys, Andreas, & Lercher, Johannes A. Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles. United States. https://doi.org/10.1039/c5gc02160j
Kasakov, Stanislav, Shi, Hui, Camaioni, Donald M., Zhao, Chen, Barath, Eszter, Jentys, Andreas, and Lercher, Johannes A. 2015. "Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles". United States. https://doi.org/10.1039/c5gc02160j.
@article{osti_1243246,
title = {Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles},
author = {Kasakov, Stanislav and Shi, Hui and Camaioni, Donald M. and Zhao, Chen and Barath, Eszter and Jentys, Andreas and Lercher, Johannes A.},
abstractNote = {Mechanistic aspects of deconstruction and hydrodeoxygenation of organosolv lignin using supported Ni catalysts with (Ni/HZSM-5 and Ni/HBEA) and without Brønsted acid sites (Ni/SiO2) are reported. Lignin was deconstructed and converted to saturated cyclic hydrocarbons ranging from C5 to C14. In the one-stage reaction, full conversion with total yield of 70 ± 5 wt.% saturated hydrocarbons was achieved at 593 K and 20 bar H2. The organosolv lignin used consists of seven to eight monolignol subunits and has an average molecular weight of ca. 1200 g mol-1. The monolignols were mainly guaiacyl, syringyl and phenylcoumaran, randomly interconnected through β-O-4, 4-O-5, β-1, 5-5’ and β-β ether bonds. In situ IR spectroscopy was used to follow the changes in lignin constituents during reaction. The proposed reaction pathways for the catalytic transformation of this organosolv lignin to alkanes start with the hydrogenolysis of aryl alkyl ether bonds, followed by hydrogenation of the aromatic compounds on Ni to cyclic alcohols. Oxygen is removed from the alcohols via dehydration on Brønsted acid sites to yield cyclic alkenes that are further hydrogenated to alkanes. Formation of condensation products may occur via intermolecular recombination of aromatic monomers or alkylation of aromatic compounds by alkenes. The financial support from TUM-PNNL cooperation project “Development of new methods for in situ characterization in liquid phase reactions” (CN-177939) is highly appreciated. The work by S.K., H.S., and J.A.L was partially supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.},
doi = {10.1039/c5gc02160j},
url = {https://www.osti.gov/biblio/1243246}, journal = {Green Chemistry},
issn = {1463-9262},
number = 11,
volume = 17,
place = {United States},
year = {2015},
month = {11}
}