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Catalytic Glycerol Hydrodeoxygenation under Inert Atmosphere: Ethanol as a Hydrogen Donor

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Department of Chemical Engineering, Aristotle University of Thessaloniki, University Campus, GR-54124 Thessaloniki, Greece
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Chemical Process and Energy Resources Institute (CERTH/CPERI), P.O. Box 60361 Thermi, Thessaloniki 57001, Greece
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Author to whom correspondence should be addressed.
Catalysts 2014, 4(4), 397-413; https://doi.org/10.3390/catal4040397
Received: 14 October 2014 / Revised: 24 November 2014 / Accepted: 27 November 2014 / Published: 15 December 2014
(This article belongs to the Special Issue Feature Papers to Celebrate the Landmarks of Catalysts)
Glycerol hydrodeoxygenation to 1,2-propanediol (1,2-PDO) is a reaction of high interest. However, the need for hydrogen supply is a main drawback of the process. According to the concept investigated here, 1,2-propanediol is efficiently formed using bio-glycerol feedstock with H2 formed in situ via ethanol aqueous phase reforming. Ethanol is thought to be a promising H2 source, as it is alcohol that can be used instead of methanol for transesterification of oils and fats. The H2 generated is consumed in the tandem reaction of glycerol hydrodeoxygenation. The reaction cycle proceeds in liquid phase at 220–250 °C and 1.5–3.5 MPa initial N2 pressure for a 2 and 4-h reaction time. Pt-, Ni- and Cu-based catalysts have been synthesized, characterized and evaluated in the reaction. Among the materials tested, Pt/Fe2O3-Al2O3 exhibited the most promising performance in terms of 1,2-propanediol productivity, while reusability tests showed a stable behavior. Structural integrity and no formation of carbonaceous deposits were verified via Temperature Programmed Desorption of hydrogen (TPD-H2) and thermogravimetric analysis of the fresh and used Pt/FeAl catalyst. A study on the effect of various operating conditions (reaction time, temperature and pressure) indicated that in order to maximize 1,2-propanediol productivity and yield, milder reaction conditions should be applied. The highest 1,2-propanediol yield, 53% (1.1 g1,2-PDO gcat−1·h−1), was achieved at a lower reaction temperature of 220 °C. View Full-Text
Keywords: platinum catalyst; nickel catalyst; copper catalyst; glycerol hydrodeoxygenation; ethanol reforming; 1,2-propanediol; aqueous phase platinum catalyst; nickel catalyst; copper catalyst; glycerol hydrodeoxygenation; ethanol reforming; 1,2-propanediol; aqueous phase
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Vasiliadou, E.S.; Lemonidou, A.A. Catalytic Glycerol Hydrodeoxygenation under Inert Atmosphere: Ethanol as a Hydrogen Donor. Catalysts 2014, 4, 397-413.

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