Catalyst studies on the ring opening of tetrahydrofuran-dimethanol to 1,2,6-hexanetriol

被引：68
作者：
Buntara, Teddy [1 ]
Melian-Cabrera, Ignacio [1 ]
Tan, Qiaohua [2 ]
Fierro, Jose L. G. [3 ]
Neurock, Matthew [2 ]
de Vries, Johannes G. [4 ,5 ]
Heeres, Hero J. [1 ]
机构：
[1] Univ Groningen, Dept Chem Engn, NL-9747 AG Groningen, Netherlands
[2] Univ Virginia, Dept Chem Engn, Charlottesville, VA 22904 USA
[3] CSIC, Inst Catalisis & Petr Quim, Madrid 28049, Spain
[4] Univ Groningen, Stratingh Inst Chem, NL-9747 AG Groningen, Netherlands
[5] DSM Innovat Synth BV, NL-6160 MD Geleen, Netherlands
来源：
CATALYSIS TODAY | 2013年 / 210卷
关键词：
Hydrogenolysis; Ring opening; THF-dimethanol; 1,2,6-Hexanetriol; Rh-ReOx/SiO2; catalysts; DFT calculations; TOTAL-ENERGY CALCULATIONS; BIMETALLIC CATALYSTS; SELECTIVE OXIDATION; CYCLIC ETHERS; HYDROGENOLYSIS; GLYCEROL; METAL; 1,3-PROPANEDIOL; SURFACTANT; MECHANISM;
D O I：
10.1016/j.cattod.2013.04.012
中图分类号：
O69 [应用化学];
学科分类号：
081704 ;
摘要：
The metal catalyzed hydrogenolysis of the biomass-derived THF-dimethanol to 1,2,6-hexanetriol using heterogeneous catalysts was investigated. Bimetallic Rh-Re catalysts (4 wt% Rh and a Re/Rh (mol. ratio of 0.5) on a silica support gave the best performance and 1,2,6-hexanetriol was obtained in 84% selectivity at 31% conversion (120 degrees C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 degrees C. The product distribution at prolonged reaction times or higher temperatures or both shows the formation of diols and mono-alcohols, indicating that the 1,2,6-hexanetriol is prone to subsequent hydrodeoxygenation reactions. Different silica supports were investigated and optimal results were obtained with an amorphous silica featuring an intermediate surface area and an average mesopore size of about 6 nm. TPR and XPS surface analysis support the presence of mixed Rh and Re particles. The redox Re delta+/Re-Total surface ratio correlates with the conversion in a volcano type dependency. Both gas phase as well as Rh200Re1OH cluster DFT calculations support an acid-metal bifunctional mechanism and explain the products distribution. (C) 2013 Elsevier B. V. All rights reserved.
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页码：106 / 116
页数：11
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