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Title: Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass

Abstract

The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO3/TiO2 and MoO3/ZrO2 at 500 °C and H2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO3 mass ratio exposed to the catalytic bed. For biomass to MoO3 mass ratios <1.5, predominantly olefinic and aromatic hydrocarbons are produced with no detectable oxygen-containing species. For ratios ≥ 1.5, partially deoxygenated species comprised of furans and phenols are observed, with a concomitant decrease of olefinic and aromatic hydrocarbons. For ratios ≥ 5, primary pyrolysis vapours break through the bed, indicating the onset of catalyst deactivation. Product quantification with a tandem micropyrolyzer-GCMS setup shows that fresh supported MoO3 catalysts convert ca. 27 mol% of the original carbon into hydrocarbons comprised predominantly of aromatics (7 C%), olefins (18 C%) and paraffins (2 C%), comparable to the total hydrocarbon yield obtained with HZSM-5 operated under similar reaction conditions. In conclusion, post-reaction XPS analysis on supported MoO3/ZrO2 and MoO3/TiO2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo5+ and Mo3+),more » and that catalyst deactivation is likely associated to coking.« less

Authors:
 [1];  [2];  [2];  [1]; ORCiD logo [2];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
  2. 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), Bioenergy Technologies Office (EE-3B); National Science Foundation (NSF)
OSTI Identifier:
1331478
Report Number(s):
NREL/JA-5100-66785
Journal ID: ISSN 1463-9262; GRCHFJ
Grant/Contract Number:  
AC36-08GO28308; 1454299
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 18; Journal Issue: 20; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biomass; catalytic fast pyrolysis; hydrodeoxygenation; MoO3

Citation Formats

Murugappan, Karthick, Mukarakate, Calvin, Budhi, Sridhar, Shetty, Manish, Nimlos, Mark R., and Román-Leshkov, Yuriy. Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass. United States: N. p., 2016. Web. doi:10.1039/C6GC01189F.
Murugappan, Karthick, Mukarakate, Calvin, Budhi, Sridhar, Shetty, Manish, Nimlos, Mark R., & Román-Leshkov, Yuriy. Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass. United States. doi:10.1039/C6GC01189F.
Murugappan, Karthick, Mukarakate, Calvin, Budhi, Sridhar, Shetty, Manish, Nimlos, Mark R., and Román-Leshkov, Yuriy. Tue . "Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass". United States. doi:10.1039/C6GC01189F. https://www.osti.gov/servlets/purl/1331478.
@article{osti_1331478,
title = {Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass},
author = {Murugappan, Karthick and Mukarakate, Calvin and Budhi, Sridhar and Shetty, Manish and Nimlos, Mark R. and Román-Leshkov, Yuriy},
abstractNote = {The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO3/TiO2 and MoO3/ZrO2 at 500 °C and H2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO3 mass ratio exposed to the catalytic bed. For biomass to MoO3 mass ratios <1.5, predominantly olefinic and aromatic hydrocarbons are produced with no detectable oxygen-containing species. For ratios ≥ 1.5, partially deoxygenated species comprised of furans and phenols are observed, with a concomitant decrease of olefinic and aromatic hydrocarbons. For ratios ≥ 5, primary pyrolysis vapours break through the bed, indicating the onset of catalyst deactivation. Product quantification with a tandem micropyrolyzer-GCMS setup shows that fresh supported MoO3 catalysts convert ca. 27 mol% of the original carbon into hydrocarbons comprised predominantly of aromatics (7 C%), olefins (18 C%) and paraffins (2 C%), comparable to the total hydrocarbon yield obtained with HZSM-5 operated under similar reaction conditions. In conclusion, post-reaction XPS analysis on supported MoO3/ZrO2 and MoO3/TiO2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo5+ and Mo3+), and that catalyst deactivation is likely associated to coking.},
doi = {10.1039/C6GC01189F},
journal = {Green Chemistry},
number = 20,
volume = 18,
place = {United States},
year = {2016},
month = {7}
}

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Works referenced in this record:

Bio-oil production from fast pyrolysis of waste furniture sawdust in a fluidized bed
journal, January 2010


Jute stick pyrolysis for bio-oil production in fluidized bed reactor
journal, January 2008


Bench-Scale Fluidized-Bed Pyrolysis of Switchgrass for Bio-Oil Production
journal, March 2007

  • Boateng, Akwasi A.; Daugaard, Daren E.; Goldberg, Neil M.
  • Industrial & Engineering Chemistry Research, Vol. 46, Issue 7
  • DOI: 10.1021/ie0614529

Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds
journal, April 2013

  • Wang, Huamin; Male, Jonathan; Wang, Yong
  • ACS Catalysis, Vol. 3, Issue 5
  • DOI: 10.1021/cs400069z

Overview of Applications of Biomass Fast Pyrolysis Oil
journal, March 2004

  • Czernik, S.; Bridgwater, A. V.
  • Energy & Fuels, Vol. 18, Issue 2, p. 590-598
  • DOI: 10.1021/ef034067u

Validation of a new set-up for continuous catalytic fast pyrolysis of biomass coupled with vapour phase upgrading
journal, September 2013

  • Yildiz, Güray; Pronk, Marty; Djokic, Marko
  • Journal of Analytical and Applied Pyrolysis, Vol. 103
  • DOI: 10.1016/j.jaap.2013.02.001

Catalytic fast pyrolysis of lignocellulosic biomass
journal, January 2014

  • Liu, Changjun; Wang, Huamin; Karim, Ayman M.
  • Chem. Soc. Rev., Vol. 43, Issue 22
  • DOI: 10.1039/C3CS60414D

A review on ex situ catalytic fast pyrolysis of biomass
journal, August 2014


Comparison of non-catalytic and catalytic fast pyrolysis of corncob in a fluidized bed reactor
journal, February 2009


Techno-economic and uncertainty analysis of in situ and ex situ fast pyrolysis for biofuel production
journal, November 2015


Real-time monitoring of the deactivation of HZSM-5 during upgrading of pine pyrolysis vapors
journal, January 2014

  • Mukarakate, Calvin; Zhang, Xiaodong; Stanton, Alexander R.
  • Green Chem., Vol. 16, Issue 3
  • DOI: 10.1039/C3GC42065E

Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part I: Conversion over various catalysts
journal, December 1995


Investigation into the shape selectivity of zeolite catalysts for biomass conversion
journal, April 2011

  • Jae, Jungho; Tompsett, Geoffrey A.; Foster, Andrew J.
  • Journal of Catalysis, Vol. 279, Issue 2, p. 257-268
  • DOI: 10.1016/j.jcat.2011.01.019

Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components
journal, September 2011

  • Mihalcik, David J.; Mullen, Charles A.; Boateng, Akwasi A.
  • Journal of Analytical and Applied Pyrolysis, Vol. 92, Issue 1
  • DOI: 10.1016/j.jaap.2011.06.001

Screening heterogeneous catalysts for the pyrolysis of lignin
journal, May 2009

  • Jackson, Michael A.; Compton, David L.; Boateng, Akwasi A.
  • Journal of Analytical and Applied Pyrolysis, Vol. 85, Issue 1-2, p. 226-230
  • DOI: 10.1016/j.jaap.2008.09.016

Upgrading biomass pyrolysis vapors over β-zeolites: role of silica-to-alumina ratio
journal, January 2014

  • Mukarakate, Calvin; Watson, Michael J.; ten Dam, Jeroen
  • Green Chem., Vol. 16, Issue 12
  • DOI: 10.1039/C4GC01425A

Review of fast pyrolysis of biomass and product upgrading
journal, March 2012


Catalytic conversion of biomass-derived feedstocks into olefins and aromatics with ZSM-5: the hydrogen to carbon effective ratio
journal, January 2011

  • Zhang, Huiyan; Cheng, Yu-Ting; Vispute, Tushar P.
  • Energy & Environmental Science, Vol. 4, Issue 6, p. 2297-2307
  • DOI: 10.1039/c1ee01230d

Aromatic Production from Catalytic Fast Pyrolysis of Biomass-Derived Feedstocks
journal, January 2009

  • Carlson, Torren R.; Tompsett, Geoffrey A.; Conner, William C.
  • Topics in Catalysis, Vol. 52, Issue 3
  • DOI: 10.1007/s11244-008-9160-6

Production of Renewable Aromatic Compounds by Catalytic Fast Pyrolysis of Lignocellulosic Biomass with Bifunctional Ga/ZSM-5 Catalysts
journal, December 2011


The effect of zeolite ZSM-5 catalyst deactivation during the upgrading of biomass-derived pyrolysis vapours
journal, June 1995


Effective hydrodeoxygenation of biomass-derived oxygenates into unsaturated hydrocarbons by MoO3 using low H2 pressures
journal, January 2013

  • Prasomsri, Teerawit; Nimmanwudipong, Tarit; Román-Leshkov, Yuriy
  • Energy & Environmental Science, Vol. 6, Issue 6, p. 1732-1738
  • DOI: 10.1039/c3ee24360e

Reactivity and stability investigation of supported molybdenum oxide catalysts for the hydrodeoxygenation (HDO) of m-cresol
journal, November 2015


Selective vapor-phase hydrodeoxygenation of anisole to benzene on molybdenum carbide catalysts
journal, November 2014


Acetone Hydrodeoxygenation over Bifunctional Metallic–Acidic Molybdenum Carbide Catalysts
journal, January 2016


Chemical Titration and Transient Kinetic Studies of Site Requirements in Mo 2 C-Catalyzed Vapor Phase Anisole Hydrodeoxygenation
journal, June 2015


Structure and site evolution of molybdenum carbide catalysts upon exposure to oxygen
journal, June 2015


Molybdenum incorporated mesoporous silica catalyst for production of biofuels and value-added chemicals via catalytic fast pyrolysis
journal, January 2015

  • Budhi, Sridhar; Mukarakate, Calvin; Iisa, Kristiina
  • Green Chemistry, Vol. 17, Issue 5
  • DOI: 10.1039/C4GC02477J

Ex situ hydrodeoxygenation in biomass pyrolysis using molybdenum oxide and low pressure hydrogen
journal, January 2016

  • Nolte, Michael W.; Zhang, Jing; Shanks, Brent H.
  • Green Chemistry, Vol. 18, Issue 1
  • DOI: 10.1039/C5GC01614B

Field-to-Fuel Performance Testing of Lignocellulosic Feedstocks: An Integrated Study of the Fast Pyrolysis–Hydrotreating Pathway
journal, April 2015


Insights into the stability of gold nanoparticles supported on metal oxides for the base-free oxidation of glucose to gluconic acid
journal, January 2014

  • Wang, Yuran; Van de Vyver, Stijn; Sharma, Krishna K.
  • Green Chem., Vol. 16, Issue 2
  • DOI: 10.1039/C3GC41362D

Molecular characterization of the pyrolysis of biomass
journal, March 1987


Elucidation of Biomass Pyrolysis Products Using a Laminar Entrained Flow Reactor and Char Particle Imaging
journal, January 2011

  • Jarvis, Mark W.; Haas, Thomas J.; Donohoe, Bryon S.
  • Energy & Fuels, Vol. 25, Issue 1
  • DOI: 10.1021/ef100832d

Production of hydrocarbon fuels from biomass using catalytic pyrolysis under helium and hydrogen environments
journal, June 2011


Comparison of in-situ and ex-situ catalytic pyrolysis in a micro-reactor system
journal, December 2014


XPS study of as-prepared and reduced molybdenum oxides
journal, February 1996


Use of catalyst coke content in deactivation modeling
journal, April 1984

  • Nam, In Sik; Kittrell, J. R.
  • Industrial & Engineering Chemistry Process Design and Development, Vol. 23, Issue 2
  • DOI: 10.1021/i200025a008

Challenges in the design and operation of processes for catalytic fast pyrolysis of woody biomass
journal, May 2016

  • Yildiz, Güray; Ronsse, Frederik; Duren, Ruben van
  • Renewable and Sustainable Energy Reviews, Vol. 57
  • DOI: 10.1016/j.rser.2015.12.202

A Critical View on Catalytic Pyrolysis of Biomass
journal, April 2015