The proposed reaction mechanism of glycerol deoxygenation
over Pt/WO3/ZrO2 is shown in Scheme 1. The mechanisms
involved heterolytic cleavage of hydrogen molecules on catalyst
to form protons and hydride ions, and then sequentially
delivering H+ followed by H- to glycerol and diols.
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4. Conclusions
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This study has demonstrated that the aqueous-phase deoxy-
genation of glycerol to 1,3-PDO is catalyzed by Pt/WO3/ZrO2
catalyst in a fixed-bed continuous flow reactor at relatively
lower temperatures (110–140 ◦C). Aqueous-phase reforming
and degradation of glycerol over Pt/WO3/ZrO2 catalyst can be
avoided at the lower reaction temperature. The predominant
products are 1,3-PDO and n-propanol. The high selectivity,
giving 1,3-PDO and n-propanol rather than 1,2-PDO and i-
propanol, is due to the protonic acid-catalyzed dehydration
preferring dehydration at the secondary over the primary OH
in the glycerol and diol. Both the conversion of glycerol
and the yield of the products significantly varied with the
catalyst composition, catalyst pretreatment, and the reaction
parameters. A 45.6% selectivity of 1,3-PDO, with 1,3-PDO/1,2-
PDO ratio of 17.7 was achieved at 70.2% conversion, 130 ◦C and
4 MPa over 3.0 wt% Pt/WO3/ZrO2 catalyst. The deoxygenation
of glycerol is proposed to occur by an ionic mechanism, involving
proton transfer and hydride transfer steps.
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Acknowledgements
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Financial support by the Research Fund for the Doctoral
Program of Higher Education of China (No. 20070291007) and
the Natural Science Foundation of Jiangsu Province, China (No.
BK2008375) are gratefully acknowledged.
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