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

The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO 3/TiO 2 and MoO 3/ZrO 2 at 500 °C and H 2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO 3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO 3 mass ratio exposed to the catalytic bed. For biomass to MoO 3 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 MoO 3 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 MoO 3/ZrO 2 and MoO 3/TiO 2 catalysts reveal that ca. 50% ofmore » Mo surface species exist in their partially reduced forms (i.e., Mo 5+ and Mo 3+), 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:
Report Number(s):
NREL/JA-5100-66785
Journal ID: ISSN 1463-9262; GRCHFJ
Grant/Contract Number:
AC36-08GO28308; 1454299
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
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)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biomass; catalytic fast pyrolysis; hydrodeoxygenation; MoO3
OSTI Identifier:
1331478

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., 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. 2016. "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}
}