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Efficient hydrothermal deoxygenation of tall oil fatty acids into n-paraffinic hydrocarbons and alcohols in the presence of aqueous formic acid
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Department of Industrial Engineering, University of Padova, Padova, Italy.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Department of Industrial Engineering, University of Padova, Padova, Italy.
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2022 (English)In: Biomass Conversion and Biorefinery, ISSN 2190-6815, E-ISSN 2190-6823, Vol. 12, no 1, p. 51-62Article in journal (Refereed) Published
Abstract [en]

Hydrothermal deoxygenation of tall oil fatty acids (TOFA) was investigated in the presence of aqueous formic acid (0.5–7.5 wt%) as a H2 donor in the presence of subcritical H2O pressure (569–599 K). Pd and Ru nanoparticles supported on carbon (5% Pd/CSigma, 5% Ru/CSigma, 10% Pd/CO850_DP, and 5% Ru/COPcomm_DP) were found to be efficient catalysts for deoxygenation of TOFA. The reaction pathway was mainly influenced by the concentration of formic acid and the catalyst. In case of Pd catalysts, in the presence of 0–2.5 wt% formic acid, decarboxylation was the dominant pathway producing n-paraffinic hydrocarbons with one less carbon atom (heptadecane yield up to 94 wt%), while with 5–7.5% formic acid, a hydrodeoxygenation/hydrogenation mechanism was favored producing C18 deoxygenation products octadecanol and octadecane as the main products (yields up to 70 wt%). In contrast, Ru catalysts produced a mixture of C5-C20 (n-and iso-paraffinic) hydrocarbons via decarboxylation, cracking and isomerization (up to 58 wt% C17 yield and total hydrocarbon yield up to 95 wt%) irrespective of formic acid concentration. Kinetic studies showed that the rates of deoxygenation displayed Arrhenius type behavior with apparent activation energies of 134.44 ± 31.36 kJ/mol and 148.92 ± 3.66 kJ/mol, for the 5% Pd/CSigma and 5% Ru/CSigma catalyst, respectively. Furthermore, the experiments with glycerol tristearate, rapeseed oil, sunflower oil, rapeseed biodiesel, and hydrolyzed rapeseed oil produced identical products confirming the versatility of the aforementioned catalytic systems for deoxygenation of C18 feedstocks.

Place, publisher, year, edition, pages
Springer, 2022. Vol. 12, no 1, p. 51-62
Keywords [en]
Hydrothermal deoxygnation, Supported carbon catalysts, Transfer hydrogenation, Green diesel
National Category
Chemical Process Engineering Organic Chemistry Biocatalysis and Enzyme Technology
Identifiers
URN: urn:nbn:se:umu:diva-176571DOI: 10.1007/s13399-020-01103-3ISI: 000587192400001Scopus ID: 2-s2.0-85095438534OAI: oai:DiVA.org:umu-176571DiVA, id: diva2:1499302
Projects
Bio4Energy
Funder
Bio4EnergyWallenberg FoundationsThe Kempe FoundationsAvailable from: 2020-11-09 Created: 2020-11-09 Last updated: 2022-07-12Bibliographically approved

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Konwar, Lakhya JyotiSamikannu, AjaikumarMikkola, Jyri-Pekka

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