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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% 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:
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:
Journal Article: 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. 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
}

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  • Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy Q3 carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectivelymore » convert lignocellulose into a liquid fuel—bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating values, high corrosiveness, high viscosity, and instability; they also greatly Q4 limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.« less
  • A series of metal and metal phosphide catalysts were investigated for the hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis (CFP) conditions (350 °C, 0.5 MPa, 12 H 2:1 guaiacol, weight hourly space velocity 5 h $-$1). Ligand-capped Ni, Pt, Rh, Ni 2P, and Rh 2P nanoparticles (NPs) were prepared using solution-phase synthesis techniques and dispersed on a silica support. For the metal phosphide NP-catalysts, a synthetic route that relies on the decomposition of a single molecular precursor was employed. The reactivity of the NP-catalysts was compared to a series of reference materials including Ni/SiO 2 and Pt/SiO 2more » prepared using incipient wetness (IW) impregnation and a commercial (com) Pt/SiO 2 catalyst. The NP-Ni/SiO 2 catalyst exhibited the largest reduction in the oxygen mol% of the organic phase and outperformed the IW-Ni/SiO 2 material. Although it was less active for guaiacol conversion than NP-Ni/SiO 2, NP-Rh2P/SiO 2 demonstrated the largest production of completely deoxygenated products and the highest selectivity to anisole, benzene, and cyclohexane, suggesting that it is a promising catalyst for deoxygenation of aryl-OH bonds. Finally, the com-Pt/SiO 2 and IW-Pt/SiO 2 catalyst exhibited the highest normalized rate of guaiacol conversion per m 2 and per gram of active phase, respectively, but did not produce any completely deoxygenated products.« less