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

Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar; Shetty, Manish; Nimlos, Mark R.; Román-Leshkov, Yuriy

doi:10.1039/C6GC01189F

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

Journal Article · Tue Jul 12 00:00:00 EDT 2016 · Green Chemistry

DOI:https://doi.org/10.1039/C6GC01189F· OSTI ID:1331478

Murugappan, Karthick ^[1]; Mukarakate, Calvin ^[2]; Budhi, Sridhar ^[2]; Shetty, Manish ^[1];

^[2]; Román-Leshkov, Yuriy ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
National Renewable Energy Lab. (NREL), Golden, CO (United States)

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.

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office; National Science Foundation (NSF)

Grant/Contract Number:: AC36-08GO28308; 1454299

OSTI ID:: 1331478

Report Number(s):: NREL/JA-5100-66785; GRCHFJ

Journal Information:: Green Chemistry, Vol. 18, Issue 20; ISSN 1463-9262

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 63 works

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

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