Reaction mechanism of the glycerol hydrogenolysis to 1,3-propanediol over Ir–ReOx/SiO2 catalyst

Amada, Yasushi; Shinmi, Yasunori; Koso, Shuichi; Kubota, Takeshi; Nakagawa, Yoshinao; Tomishige, Keiichi

doi:10.1016/j.apcatb.2011.04.001

Cited by 303 publications

(356 citation statements)

References 58 publications

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“…This may be through coordination of tungsten to glycerol, as described for ReO x and MoO x , which have a similar 13PD favoring coordination as that envisaged for tungsten compounds. [17,18,27,28] However, the subsequent hydrogenation plays a major role for the yield of 13PD as well. A swift hydrogenation of 3-hydroxypropanal to 13PD prevents the further dehydration of 3-hydroxypropanal.…”

Section: Discussionmentioning

confidence: 99%

Pt/Al₂O₃ Catalyzed 1,3‐Propanediol Formation from Glycerol using Tungsten Additives

et al. 2012

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Screening of four commercial catalysts (Pt/Al2O3, Pt/SiO2, Pd/Al2O3, and Pd/SiO2) and four acidic additives (hydrochloric, tungstic, phosphotungstic, and silicotungstic acids) shows that the combination of a platinum hydrogenation catalyst with tungsten containing acidic additives yields 1,3‐propanediol from aqueous glycerol. The performance of the best catalytic system Pt/Al2O3 with silicotungstic acid as an additive was optimized by experimental design, capturing the influence of reaction time, glycerol concentration, acid concentration, pressure, and temperature on the formation of 1,3‐propanediol from glycerol. High 1,3‐propanediol yield in an aqueous batch system can be achieved (49 % conversion, 28 % selectivity) with excellent 1,3‐propanediol to 1,2‐propanediol ratios. A mechanistic interpretation is given for this bifunctional system, supported by the relative stability of 1,3‐propanediol in comparison with 1,2‐propanediol under the chosen reaction conditions.

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Section: Discussionmentioning

confidence: 99%

Pt/Al₂O₃ Catalyzed 1,3‐Propanediol Formation from Glycerol using Tungsten Additives

et al. 2012

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“…24 According to these authors, the mechanism of glycerol hydrogenolysis to 1,3-propanediol occurs through attack of hydride species at the interface between Ir metal surface and ReO x to the adsorbed glycerol on the ReO x cluster. 23 In this work, we report cyclohexane conversion and glycerol hydrogenolysis over iridium catalysts supported on γ-Al 2 O 3 , SiO 2 and ZrO 2 , comparing these catalysts in terms of C-C and C-O cleavage. We also address the effect of support on the activity and product selectivity in both reactions.…”

Section: Introductionmentioning

confidence: 99%

“…Ir-ReO x /SiO 2 are active in C-O hydrogenolysis of substrates like glycerol, tetrahydrofurfuryl alcohol, tetrahydrofuran and tetrahydropyran. [22][23][24][25][26] Among these substrates, glycerol is a versatile feedstock that is mainly obtained as a by-product of biodiesel production. Consequently, due to the fast growth of biodiesel production worldwide, catalytic transformation of glycerol into highvalue products has gained importance in the last decade.…”

Section: Introductionmentioning

confidence: 99%

Iridium Catalysts for C-C and C-O Hydrogenolysis: Catalytic Consequences of Iridium Sites

Pamphile-Adrián¹,

Florez-Rodriguez²,

Passos³

2015

Journal of the Brazilian Chemical Society

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The support effect on the properties of iridium catalysts for C-C and C-O hydrogenolysis was investigated. Cyclohexane conversion and glycerol hydrogenolysis were used to compare the behavior of iridium catalysts in terms of C-C and C-O cleavage. The nature of the support influenced the catalyst performance in both cyclohexane conversion and glycerol hydrogenolysis. This effect was more evident on the product selectivity. Ir/SiO 2 catalyst presented the highest cyclohexane hydrogenolysis activity and the highest selectivity to minor hydrocarbons formed from hexane re-adsorption. For glycerol hydrogenolysis, all catalysts displayed a higher selectivity to products formed by C-O cleavage, mainly 1,2-propanediol (1,2-PDO). Ir/ZrO 2 catalyst presented the highest activity in all reaction conditions and the lowest selectivity to minor alcohols produced by C-C cleavage like methanol, ethanol and ethylene glycol. The results were explained in terms of the requirements and the structure of the catalytic sites.

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“…Hydrogenation is sometimes considered as a transfer of hydride that takes place on the metal surface. The protic aqueous environment promotes the transfer of protons (during the dehydration reaction) or hydride (during the hydrogenation reaction) [32,33]. The hydrogen can be supplied externally or be produced in situ by APR: this mechanism has been identified in the case of Pt/NaY [34].…”

Section: Dehydrogenation-dehydration-hydrogenation Of An Alcohol Groupmentioning

confidence: 99%

“…defined as hydrogenation of a covalent bond leading to its cleavage, is a special case that was identified in particular in the case of rhodium-rhenium and iridium-rhenium catalysts in the presence of hydrogen [33]. The active site would thus be located at the edge of a rhenium cluster deposited on a precious metal particle (rhodium or iridium).…”

Section: Dehydrogenation-dehydration-hydrogenation Of An Alcohol Groupmentioning

confidence: 99%

Transformation of Sorbitol to Biofuels by Heterogeneous Catalysis: Chemical and Industrial Considerations

Vilcocq

Cabiac

Especel

et al. 2013

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Résumé -Transformation du sorbitol en biocarburants par catalyse hétérogène : considérations chimiques et industrielles -La raréfaction du pétrole et l'augmentation conjointe de la demande en carburants ont conduit à la recherche de carburants alternatifs. Dans un premier temps, la valorisation de ressources agricoles alimentaires pour la production d'éthanol et de biodiesel a permis de développer les biocarburants de première génération. Aujourd'hui les travaux de recherche s'orientent vers l'utilisation de biomasse lignocellulosique comme source de carbone renouvelable (biocarburants de deuxième génération). Alors que la filière de l'éthanol cellulosique est en plein développement, une nouvelle voie consistant à transformer des sucres et polyols d'origine lignocellulosique en alcanes légers par catalyse hétérogène bifonctionnelle en phase aqueuse a été récemment décrite. Ce procédé s'effectue à basse température et pression modérée (T < 300 °C et P < 50 bar). Il nécessite, d'une part, la formation d'hydrogène par reformage catalytique de carbohydrates en phase aqueuse et, d'autre part, la déshydratation/hydrogénation de polyols conduisant à un alcane par ruptures sélectives des liaisons C-O. Un défi lié à cette thématique réside dans le développement de systèmes catalytiques multifonctionnels stables, actifs et sélectifs dans les conditions de la réaction de transformation. L'objectif de l'article est de présenter les réactions mises en jeu, les systèmes catalytiques décrits dans la littérature pour ce type de transformation ainsi que des exemples d'applications industrielles. Abstract

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Reaction mechanism of the glycerol hydrogenolysis to 1,3-propanediol over Ir–ReOx/SiO2 catalyst

Cited by 303 publications

References 58 publications

Pt/Al₂O₃ Catalyzed 1,3‐Propanediol Formation from Glycerol using Tungsten Additives

Pt/Al₂O₃ Catalyzed 1,3‐Propanediol Formation from Glycerol using Tungsten Additives

Iridium Catalysts for C-C and C-O Hydrogenolysis: Catalytic Consequences of Iridium Sites

Transformation of Sorbitol to Biofuels by Heterogeneous Catalysis: Chemical and Industrial Considerations

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Reaction mechanism of the glycerol hydrogenolysis to 1,3-propanediol over Ir–ReOx/SiO2 catalyst

Cited by 303 publications

References 58 publications

Pt/Al2O3 Catalyzed 1,3‐Propanediol Formation from Glycerol using Tungsten Additives

Pt/Al2O3 Catalyzed 1,3‐Propanediol Formation from Glycerol using Tungsten Additives

Iridium Catalysts for C-C and C-O Hydrogenolysis: Catalytic Consequences of Iridium Sites

Transformation of Sorbitol to Biofuels by Heterogeneous Catalysis: Chemical and Industrial Considerations

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Pt/Al₂O₃ Catalyzed 1,3‐Propanediol Formation from Glycerol using Tungsten Additives

Pt/Al₂O₃ Catalyzed 1,3‐Propanediol Formation from Glycerol using Tungsten Additives