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

Teddy Buntara; Ignacio Melián-Cabrera; Qiaohua Tan; José L.G. Fierro; Matthew Neurock; Johannes G. De Vries; Hero J. Heeres

doi:10.1016/j.cattod.2013.04.012

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

Teddy Buntara, Ignacio Melián-Cabrera, Qiaohua Tan, José L.G. Fierro, Matthew Neurock, Johannes G. De Vries, Hero J. Heeres

Chemical Engineering and Materials Science

Research output: Contribution to journal › Article › peer-review

70 Scopus citations

Abstract

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 C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 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^δ+/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.

Original language	English (US)
Pages (from-to)	106-116
Number of pages	11
Journal	Catalysis Today
Volume	210
DOIs	https://doi.org/10.1016/j.cattod.2013.04.012
State	Published - Jul 1 2013

Bibliographical note

Funding Information:
We would like to thank ACTS-ASPECT for financial support to this research (ASPECT Project 053.62.017 ); Dr. Rudy Parton, Dr. Rob Meier (DSM), Dr. Peter Witte, Dr. Peter Berben (BASF), Dr. Annemarie Beers (Norit), Dr. Jean-Paul Lange (Shell) and Dr. Bart Zwijnenburg (Johnson Matthey) of the industrial steering committee are thanked for helpful discussions as well as Prof. Bob Davis (University of Virginia) for a stimulating discussion during the NCCC-XIII conference in Noordwijkerhout (The Netherlands).

Copyright:
Copyright 2013 Elsevier B.V., All rights reserved.

Keywords

1,2,6-Hexanetriol
DFT calculations
Hydrogenolysis
Rh-ReO /SiO catalysts
Ring opening
THF-dimethanol

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@article{25bb1225220a4e98a706467bc8c9c383,

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

abstract = "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 C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 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 Reδ+/ReTotal 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.",

keywords = "1,2,6-Hexanetriol, DFT calculations, Hydrogenolysis, Rh-ReO /SiO catalysts, Ring opening, THF-dimethanol",

author = "Teddy Buntara and Ignacio Meli{\'a}n-Cabrera and Qiaohua Tan and Fierro, {Jos{\'e} L.G.} and Matthew Neurock and {De Vries}, {Johannes G.} and Heeres, {Hero J.}",

note = "Funding Information: We would like to thank ACTS-ASPECT for financial support to this research (ASPECT Project 053.62.017 ); Dr. Rudy Parton, Dr. Rob Meier (DSM), Dr. Peter Witte, Dr. Peter Berben (BASF), Dr. Annemarie Beers (Norit), Dr. Jean-Paul Lange (Shell) and Dr. Bart Zwijnenburg (Johnson Matthey) of the industrial steering committee are thanked for helpful discussions as well as Prof. Bob Davis (University of Virginia) for a stimulating discussion during the NCCC-XIII conference in Noordwijkerhout (The Netherlands). Copyright: Copyright 2013 Elsevier B.V., All rights reserved.",

year = "2013",

month = jul,

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doi = "10.1016/j.cattod.2013.04.012",

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T1 - Catalyst studies on the ring opening of tetrahydrofuran-dimethanol to 1,2,6-hexanetriol

AU - Buntara, Teddy

AU - Melián-Cabrera, Ignacio

AU - Tan, Qiaohua

AU - Fierro, José L.G.

AU - Neurock, Matthew

AU - De Vries, Johannes G.

AU - Heeres, Hero J.

N1 - Funding Information: We would like to thank ACTS-ASPECT for financial support to this research (ASPECT Project 053.62.017 ); Dr. Rudy Parton, Dr. Rob Meier (DSM), Dr. Peter Witte, Dr. Peter Berben (BASF), Dr. Annemarie Beers (Norit), Dr. Jean-Paul Lange (Shell) and Dr. Bart Zwijnenburg (Johnson Matthey) of the industrial steering committee are thanked for helpful discussions as well as Prof. Bob Davis (University of Virginia) for a stimulating discussion during the NCCC-XIII conference in Noordwijkerhout (The Netherlands). Copyright: Copyright 2013 Elsevier B.V., All rights reserved.

PY - 2013/7/1

Y1 - 2013/7/1

N2 - 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 C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 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 Reδ+/ReTotal 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.

AB - 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 C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 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 Reδ+/ReTotal 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.

KW - 1,2,6-Hexanetriol

KW - DFT calculations

KW - Hydrogenolysis

KW - Rh-ReO /SiO catalysts

KW - Ring opening

KW - THF-dimethanol

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SN - 0920-5861

VL - 210

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JO - Catalysis Today

JF - Catalysis Today

ER -

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

Abstract

Bibliographical note

Keywords

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