Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass
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Supported molybdenum.pdf
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Author(s)
Mukarakate, Calvin
Budhi, Sridhar
Shetty, Manish
Nimlos, Mark R.
Roman-Leshkov, Yuriy
Date Issued
July 2016
Journal
Green Chemistry
Publisher
Royal Society of Chemistry
Citation
Murugappan, Karthick et al. “Supported Molybdenum Oxides as Effective Catalysts for the Catalytic Fast Pyrolysis of Lignocellulosic Biomass.” Green Chem. 18.20 (2016): 5548–5557. © The Royal Society of Chemistry 2016
Version
Final published version
Abstract
The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO[subscript 3]/TiO[subscript 2] and MoO[subscript 3]/ZrO[subscript 2] at 500 °C and H[subscript 2] pressures ≤0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO[subscript 3] catalysts show different levels of deoxygenation based on the cumulative biomass to MoO[subscript 3] mass ratio exposed to the catalytic bed. For biomass to MoO[subscript 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[subscript 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. Post-reaction XPS analysis on supported MoO[subscript 3]/ZrO[subscript 2] and MoO[subscript 3]/TiO[subscript 2] catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo5[superscript +] and Mo3[superscript +]), and that catalyst deactivation is likely associated to coking.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
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DOI of Published Version
https://doi.org/10.1039/C6GC01189F
