Hydroprocessing of Phenanthrene Over Sulfided Fe–W Supported on Modified SBA-15
Heavy oil hydroprocessing requires catalysts with enhanced mesoporosity and moderate acidity. Mesostructured aluminum modified SBA-15 have been identified as suitable catalytic supports for sulfided phases employed in this process. In this work, a series of SBA-15 based materials were synthesized using hexane as a micellar swelling agent for pore widening. Particularly, the effect of the hexane to Pluronic P123 mass ratio on key properties was assessed. Among the synthesized materials, the one prepared with a hexane: P123 mass ratio of 3.5 showed the best textural properties: BET surface area = 499 m2 × g−1, total pore volume = 1.8 cm3 × g−1, and average pore diameter = 27 nm. The acidity of this material was further modified by grafting aluminum over it. The resulting materials were employed as supports for sulfided Fe–W tested in the hydroprocessing of phenanthrene at 11 MPa and 623 K. Catalysts activity was found to related to the dispersion of the oxide precursor of the active metals which in turn was dependent on Al/Si molar ratio of the supports. Catalysts promoted the formation of 9,10-dihydrophenanthrene, a reaction intermediary in phenanthrene hydroprocessing. The catalyst with an Al/Si molar ratio of 0.04 showed the highest selectivity to this compound. The latter was correlated to a higher content of tetrahedral aluminum in the support. In general, the modifications performed over the SBA-15 support enhanced their pore size distributions and acidity and promoted the selective partial hydrogenation for the central ring of phenanthrene. The findings are important for the search of new catalysts in heavy oil hydroprocessing.
KeywordsHydroprocessing Phenanthrene SBA-15 Pore widening Acidity Fe–W sulfides
This work was possible due to the financial support given by VIE-UIS in the frame of the project “Diseño de catalizadores para hidrocraqueo de fracciones tipo gasóleo y estudio del efecto de moléculas nitrogenadas, code 1329”. Jonatan R. Restrepo-Garcia acknowledges COLCIENCIAS for the “Joven Investigador 2012” fellowship, Diana P. Garcia, Emerson Barrios and Luis A. Nemojón for conducting some experiments at the laboratory. We especially acknowledge Laboratorio de Rayos-X – UIS under the direction of Prof. J.A. Henao for XRD measurements, Laboratorio de RMN-UIS under the direction of Prof. Daniel Molina for NMR measurements, Laboratorio de Microscopía-UIS under the direction of Prof. C.A Rios for SEM imaging, and Jhonatan Rodriguez-Pereira for XPS analysis.
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Conflict of interest
The authors certify that they have NO affiliations with or involvement in any organization or entity with any financial interest (such as honoraria; educational grants; participation in speakers’ bureaus; membership, employment, consultancies, stock ownership, or other equity interest; and expert testimony or patent-licensing arrangements), or non-financial interest (such as personal or professional relationships, affiliations, knowledge or beliefs) in the subject matter or materials discussed in this manuscript.
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