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:

Murugappan, Karthick ^[1]; Mukarakate, Calvin ^[2]; Budhi, Sridhar ^[2]; Shetty, Manish ^[1]; Nimlos, Mark R.  ^[2];

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Román-Leshkov, Yuriy ^[1]

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+ Show Author Affiliations

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:

Tue Jul 12 00:00:00 EDT 2016

Research Org.:

National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office; 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