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Title: One-pot process for hydrodeoxygenation of lignin to alkanes using Ru-based bimetallic and bifunctional catalysts supported on zeolite Y

Abstract

Here, the synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al 2O 3 and HY zeolite.

Authors:
 [1];  [1];  [2];  [1];  [3];  [4];  [4];  [4];  [5];  [5];  [5]; ORCiD logo [1]
  1. Washington State Univ., Richland, WA (United States)
  2. Southwest Research Institute, San Antonio, TX (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Environmental Molecular Sciences Lab., Richland, WA (United States)
  5. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1353424
Alternate Identifier(s):
OSTI ID: 1400822
Report Number(s):
NREL/JA-5100-68188
Journal ID: ISSN 1864-5631
Grant/Contract Number:  
AC36-08GO28308; AC36-08G028308
Resource Type:
Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 8; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bifunctional catalysts; bimetallic catalysts; biofuel; hydrodeoxygenation; lignin

Citation Formats

Wang, Hongliang, Ruan, Hao, Feng, Maoqi, Qin, Yuling, Job, Heather, Luo, Langli, Wang, Chongmin, Engelhard, Mark H., Kuhn, Erik, Chen, Xiaowen, Tucker, Melvin P., and Yang, Bin. One-pot process for hydrodeoxygenation of lignin to alkanes using Ru-based bimetallic and bifunctional catalysts supported on zeolite Y. United States: N. p., 2017. Web. doi:10.1002/cssc.201700160.
Wang, Hongliang, Ruan, Hao, Feng, Maoqi, Qin, Yuling, Job, Heather, Luo, Langli, Wang, Chongmin, Engelhard, Mark H., Kuhn, Erik, Chen, Xiaowen, Tucker, Melvin P., & Yang, Bin. One-pot process for hydrodeoxygenation of lignin to alkanes using Ru-based bimetallic and bifunctional catalysts supported on zeolite Y. United States. doi:10.1002/cssc.201700160.
Wang, Hongliang, Ruan, Hao, Feng, Maoqi, Qin, Yuling, Job, Heather, Luo, Langli, Wang, Chongmin, Engelhard, Mark H., Kuhn, Erik, Chen, Xiaowen, Tucker, Melvin P., and Yang, Bin. Wed . "One-pot process for hydrodeoxygenation of lignin to alkanes using Ru-based bimetallic and bifunctional catalysts supported on zeolite Y". United States. doi:10.1002/cssc.201700160. https://www.osti.gov/servlets/purl/1353424.
@article{osti_1353424,
title = {One-pot process for hydrodeoxygenation of lignin to alkanes using Ru-based bimetallic and bifunctional catalysts supported on zeolite Y},
author = {Wang, Hongliang and Ruan, Hao and Feng, Maoqi and Qin, Yuling and Job, Heather and Luo, Langli and Wang, Chongmin and Engelhard, Mark H. and Kuhn, Erik and Chen, Xiaowen and Tucker, Melvin P. and Yang, Bin},
abstractNote = {Here, the synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite.},
doi = {10.1002/cssc.201700160},
journal = {ChemSusChem},
number = 8,
volume = 10,
place = {United States},
year = {2017},
month = {2}
}

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Works referenced in this record:

Following Solid-Acid-Catalyzed Reactions by MAS NMR Spectroscopy in Liquid Phase-Zeolite-Catalyzed Conversion of Cyclohexanol in Water
journal, November 2013


Hydropyrolysis of Lignin Using Pd/HZSM-5
journal, February 2015

  • Jan, Oliver; Marchand, Ryan; Anjos, Luiz C. A.
  • Energy & Fuels, Vol. 29, Issue 3
  • DOI: 10.1021/ef502779s

Pathways for biomass-derived lignin to hydrocarbon fuels
journal, July 2013

  • Laskar, Dhrubojyoti D.; Yang, Bin; Wang, Huamin
  • Biofuels, Bioproducts and Biorefining, Vol. 7, Issue 5
  • DOI: 10.1002/bbb.1422

Catalytic roles of metals and supports on hydrodeoxygenation of lignin monomer guaiacol
journal, January 2012


Lignin Depolymerization into Aromatic Monomers over Solid Acid Catalysts
journal, November 2014

  • Deepa, Ayillath K.; Dhepe, Paresh L.
  • ACS Catalysis, Vol. 5, Issue 1
  • DOI: 10.1021/cs501371q

Selective Degradation of Wood Lignin over Noble‐Metal Catalysts in a Two‐Step Process
journal, July 2008


Effect of metal–acid site balance on hydroconversion of decalin over Pt/Beta zeolite bifunctional catalysts
journal, November 2015


The role of shape selectivity in catalytic fast pyrolysis of lignin with zeolite catalysts
journal, December 2012


A study of ruthenium in zeolite-Y by X-ray photoelectron spectroscopy
journal, January 1980


Biomass-derived lignin to jet fuel range hydrocarbons via aqueous phase hydrodeoxygenation
journal, January 2015

  • Wang, Hongliang; Ruan, Hao; Pei, Haisheng
  • Green Chemistry, Vol. 17, Issue 12
  • DOI: 10.1039/C5GC01534K

Reductive lignocellulose fractionation into soluble lignin-derived phenolic monomers and dimers and processable carbohydrate pulps
journal, January 2015

  • Van den Bosch, S.; Schutyser, W.; Vanholme, R.
  • Energy & Environmental Science, Vol. 8, Issue 6
  • DOI: 10.1039/C5EE00204D

Selective production of 1,2-propanediol by hydrogenolysis of glycerol over bimetallic Ru–Cu nanoparticles supported on TiO2
journal, July 2014


Conversion of Kraft Lignin Over Hierarchical MFI Zeolite
journal, March 2014

  • Kim, Seong-Soo; Lee, Hyung Won; Ryoo, Ryong
  • Journal of Nanoscience and Nanotechnology, Vol. 14, Issue 3
  • DOI: 10.1166/jnn.2014.8545

Mechanisms of selective cleavage of C–O bonds in di-aryl ethers in aqueous phase
journal, January 2014


Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
journal, October 2015


Noble-metal catalyzed hydrodeoxygenation of biomass-derived lignin to aromatic hydrocarbons
journal, January 2014

  • Laskar, Dhrubojyoti D.; Tucker, Melvin P.; Chen, Xiaowen
  • Green Chemistry, Vol. 16, Issue 2
  • DOI: 10.1039/c3gc42041h

Size-dependent catalytic activity of supported metal clusters
journal, November 1994

  • Xu, Z.; Xiao, F. -S.; Purnell, S. K.
  • Nature, Vol. 372, Issue 6504
  • DOI: 10.1038/372346a0

Ruthenium Nanoparticles Supported on Carbon: An Active Catalyst for the Hydrogenation of Lactic Acid to 1,2-Propanediol
journal, July 2015


In situ trapping of enol intermediates with alcohol during acid-catalysed de-polymerisation of lignin in a nonpolar solvent
journal, January 2015

  • Kaiho, Atsushi; Kogo, Makiko; Sakai, Ryo
  • Green Chemistry, Vol. 17, Issue 5
  • DOI: 10.1039/C5GC00130G

Monolayer bimetallic surfaces: Experimental and theoretical studies of trends in electronic and chemical properties
journal, May 2008


Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons
journal, December 2015

  • Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.
  • Nature, Vol. 528, Issue 7581
  • DOI: 10.1038/nature16173

Hydrogen adsorption, absorption and diffusion on and in transition metal surfaces: A DFT study
journal, April 2012


Why Is Ruthenium an Efficient Catalyst for the Aqueous-Phase Hydrogenation of Biosourced Carbonyl Compounds?
journal, June 2015


Zeolite Catalysis: Water Can Dramatically Increase or Suppress Alkane C–H Bond Activation
journal, August 2014

  • Chen, Kuizhi; Damron, Joshua; Pearson, Carlie
  • ACS Catalysis, Vol. 4, Issue 9
  • DOI: 10.1021/cs500858d

Methylation of phenol over high-silica beta zeolite: Effect of zeolite acidity and crystal size on catalyst behaviour
journal, January 2007


Polyol conversions into furanic derivatives on bimetallic catalysts: CuRu, CuPt and RuCu
journal, November 1991


Conversion of Guaiacol over Supported Ru Catalysts
journal, June 2013


One-Pot Catalytic Conversion of Raw Lignocellulosic Biomass into Gasoline Alkanes and Chemicals over LiTaMoO 6 and Ru/C in Aqueous Phosphoric Acid
journal, July 2015


Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol
journal, October 2013


A Series of NiM (M = Ru, Rh, and Pd) Bimetallic Catalysts for Effective Lignin Hydrogenolysis in Water
journal, April 2014

  • Zhang, Jiaguang; Teo, Jason; Chen, Xi
  • ACS Catalysis, Vol. 4, Issue 5
  • DOI: 10.1021/cs401199f

Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014

  • Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
  • Science, Vol. 344, Issue 6185, p. 1246843-1246843
  • DOI: 10.1126/science.1246843

Catalytic hydrodeoxygenation
journal, June 2000


Effect of Acidic Properties of Mesoporous Zeolites Supporting Pt Nanoparticles on Hydrogenative Conversion of Methylcyclopentane
journal, November 2014

  • Na, Kyungsu; Alayoglu, Selim; Ye, Rong
  • Journal of the American Chemical Society, Vol. 136, Issue 49
  • DOI: 10.1021/ja509273h

Zeolite supported mono- and bimetallic systems: structure and performance as CO hydrogenation catalysts
journal, October 1999


Influence of water in the deactivation of a sulfided NiMo/γ-Al2O3 catalyst during hydrodeoxygenation
journal, March 1994


Historical Developments in Hydroprocessing Bio-oils
journal, May 2007

  • Elliott, Douglas C.
  • Energy & Fuels, Vol. 21, Issue 3, p. 1792-1815
  • DOI: 10.1021/ef070044u

Novel MoP/HY catalyst for the selective conversion of naphthalene to tetralin
journal, March 2015


XPS and reactivity study of bimetallic nanoparticles containing Ru and Pt supported on a gold disk
journal, May 2006


Precise oxygen scission of lignin derived aryl ethers to quantitatively produce aromatic hydrocarbons in water
journal, January 2016

  • Luo, Zhicheng; Wang, Yimeng; He, Mingyuan
  • Green Chemistry, Vol. 18, Issue 2
  • DOI: 10.1039/C5GC01790D

Hydrodeoxygenation of Lignin-Derived Phenolic Monomers and Dimers to Alkane Fuels over Bifunctional Zeolite-Supported Metal Catalysts
journal, January 2014

  • Zhang, Wei; Chen, Jinzhu; Liu, Ruliang
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 4
  • DOI: 10.1021/sc400401n

One step thermal conversion of lignin to the gasoline range liquid products by using zeolites as additives
journal, January 2012


Catalytic Hydrodeoxygenation of Guaiacol on Rh-Based and Sulfided CoMo and NiMo Catalysts
journal, March 2011

  • Lin, Yu-Chuan; Li, Chia-Liang; Wan, Hou-Peng
  • Energy & Fuels, Vol. 25, Issue 3
  • DOI: 10.1021/ef101521z

Catalytic Hydrogenolysis of Aryl Ethers: A Key Step in Lignin Valorization to Valuable Chemicals
journal, February 2015

  • Zaheer, Muhammad; Kempe, Rhett
  • ACS Catalysis, Vol. 5, Issue 3
  • DOI: 10.1021/cs501498f

Catalytic depolymerisation of isolated lignins to fine chemicals using a Pt/alumina catalyst: part 1—impact of the lignin structure
journal, January 2015

  • Bouxin, Florent P.; McVeigh, Ashley; Tran, Fanny
  • Green Chemistry, Vol. 17, Issue 2
  • DOI: 10.1039/C4GC01678E

Catalytic Hydrotreatment of Alcell Lignin Using Supported Ru, Pd, and Cu Catalysts
journal, August 2015


Fe/HY zeolite as an effective catalyst for levulinic acid production from glucose: Characterization and catalytic performance
journal, February 2015


The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010

  • Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
  • Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
  • DOI: 10.1021/cr900354u

Relevance of sulfiding pretreatment on the performance of Re/ZrO2 and Re/ZrO2-sulfated catalysts for the hydrodeoxygenation of guayacol
journal, August 2010


Unlocking the potential of a sleeping giant: lignins as sustainable raw materials for renewable fuels, chemicals and materials
journal, January 2015

  • Bruijnincx, Pieter C. A.; Rinaldi, Roberto; Weckhuysen, Bert M.
  • Green Chemistry, Vol. 17, Issue 11
  • DOI: 10.1039/C5GC90055G

Aromatic Monomers by in Situ Conversion of Reactive Intermediates in the Acid-Catalyzed Depolymerization of Lignin
journal, June 2015

  • Deuss, Peter J.; Scott, Martin; Tran, Fanny
  • Journal of the American Chemical Society, Vol. 137, Issue 23
  • DOI: 10.1021/jacs.5b03693

Following Solid-Acid-Catalyzed Reactions by MAS NMR Spectroscopy in Liquid Phase-Zeolite-Catalyzed Conversion of Cyclohexanol in Water
journal, November 2013

  • Vjunov, Aleksei; Hu, Mary Y.; Feng, Ju
  • Angewandte Chemie International Edition, Vol. 53, Issue 2
  • DOI: 10.1002/anie.201306673

Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin
journal, April 2012


Role of Strain and Ligand Effects in the Modification of the Electronic and Chemical Properties of Bimetallic Surfaces
journal, October 2004


Supported Metal Clusters: Synthesis, Structure, and Catalysis
journal, May 1995


Effect of post-synthesis hydrogen-treatment on the nature of iron species in Fe-BEA as NH 3 -SCR catalyst
journal, January 2014

  • Shwan, Soran; Jansson, Jonas; Olsson, Louise
  • Catal. Sci. Technol., Vol. 4, Issue 9
  • DOI: 10.1039/C4CY00236A

n-Heptane hydroisomerization over Pt/MFI zeolite nanosheets: Effects of zeolite crystal thickness and platinum location
journal, May 2013


Acidolysis of α-O-4 Aryl-Ether Bonds in Lignin Model Compounds: A Modeling and Experimental Study
journal, June 2015

  • Pelzer, Adam W.; Sturgeon, Matthew R.; Yanez, Abraham J.
  • ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 7
  • DOI: 10.1021/acssuschemeng.5b00070

Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts
journal, August 2012

  • Yu, Weiting; Porosoff, Marc D.; Chen, Jingguang G.
  • Chemical Reviews, Vol. 112, Issue 11, p. 5780-5817
  • DOI: 10.1021/cr300096b

Upgrading of lignin-derived bio-oils by catalytic hydrodeoxygenation
journal, January 2014

  • Saidi, Majid; Samimi, Fereshteh; Karimipourfard, Dornaz
  • Energy Environ. Sci., Vol. 7, Issue 1
  • DOI: 10.1039/C3EE43081B

Calculation of Flame Ionization Detector Relative Response Factors Using the Effective Carbon Number Concept
journal, August 1985


ZnCl 2 induced catalytic conversion of softwood lignin to aromatics and hydrocarbons
journal, January 2016

  • Wang, Hongliang; Zhang, Libing; Deng, Tiansheng
  • Green Chemistry, Vol. 18, Issue 9
  • DOI: 10.1039/C5GC02967H

Preparation of Pd-Co-Based Nanocatalysts and Their Superior Applications in Formic Acid Decomposition and Methanol Oxidation
journal, December 2014


    Works referencing / citing this record:

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    Lignin Valorizations with Ni Catalysts for Renewable Chemicals and Fuels Productions
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    Economic feasibility of gasoline production from lignocellulosic wastes in Hong Kong
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    Lignin Valorizations with Ni Catalysts for Renewable Chemicals and Fuels Productions
    journal, May 2019