Solid acid co-catalyst for the hydrogenolysis of glycerol to 1,3-propanediol over Ir-ReOx/SiO2

Nakagawa, Yoshinao; Ning, Xuanhe; Amada, Yasushi; Tomishige, Keiichi

doi:10.1016/j.apcata.2012.05.009

Cited by 176 publications

(131 citation statements)

References 35 publications

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“…5, 2016 as H 2 SO 4 , silica-alumina, zeolites and ion-exchange resin promoted the activity of the catalyst. 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.…”

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%

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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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Section: Introductionmentioning

confidence: 99%

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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“…This interpretation is also supported by the formation of 1-and 2-propanol from glycerol over IrReO x /SiO 2 . [48] In addition, to confirm the effect of intermediates on the selectivity to 2-BuOH in the hydrogenolysis of erythritol and 1,4-AHERY, the hydrogenolysis of 1,2,4-BuT was evaluated (Table 3, entry 9). The selectivity to 2-BuOH (8 %) was low, and the sum of the selectivities to BuD and BuOH with a secondary OH group (2-BuOH, 1,2-BuD, and 1,3-BuD) was also much lower (23 %) than that in the case of 1,2,3-BuT (71 %; Table 3, entries 2 and 9).…”

Section: Reaction Kinetics and Reactivity Trendsmentioning

confidence: 99%

Synthesis of 2‐Butanol by Selective Hydrogenolysis of 1,4‐Anhydroerythritol over Molybdenum Oxide‐Modified Rhodium‐Supported Silica

et al. 2016

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Rh-MoOx /SiO2 (Mo/Rh=0.13) is an effective catalyst for the hydrogenolysis of 1,4-anhydroerythritol (1,4-AHERY) and provides 2-BuOH in high yield of 51 %. This is the first report of the production of 2-BuOH from 1,4-AHERY by hydrogenolysis. 1,4-AHERY was more suitable as a starting material than erythritol because the 2-BuOH yield from erythritol was low (34 %). Based on the kinetics and comparison of reactivities of the related compounds using Rh-MoOx /SiO2 and Rh/SiO2 catalysts, the modification of Rh/SiO2 with MoOx leads to the high activity and high selectivity to 2-BuOH because of the generation of reactive hydride species and the strong adsorption of 1,4-AHERY on MoOx species. The reaction proceeds by main two routes, (I) the combination of single C-O hydrogenolysis with the desorption of intermediates, a usual route in hydrogenolysis, and (II) multiple C-O hydrogenolysis without the desorption of intermediates from the active site, and the reaction mechanism for Route (II) is proposed.

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“…Nakagawa and coworkers proposed a route in which propylene glycol form 1-propanol, a product of over-hydrogenolysis. 31 …”

Section: Reaction Of Glycerol (25% Aqueous Solution) Catalyzed By mentioning

confidence: 99%

Selective hydrogenolysis of glycerol to propylene glycol in a continuous flow trickle bed reactor using copper chromite and Cu/Al2O3 catalysts

Sepúlveda¹,

Manuale²,

Santiago³

et al. 2017

Quim. Nova

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CATALYSTS. The glycerol hydrogenolysis reaction was performed in a continuous flow trickle bed reactor using a water glycerol feed and both copper chromite and Cu/Al 2 O 3 catalysts. The commercial copper chromite had a higher activity than the laboratory prepared Cu/Al 2 O 3 and was used for most of the tests. Propylene glycol was the main product with both catalysts, acetol being the main by-product. It was found that temperature is the main variable influencing the conversion of glycerol. When the state of the glycerol-water reactant mixture was completely liquid, at temperatures lower than 190 °C, conversion was low and deactivation was observed. At reaction temperatures of 210-230 °C the conversion of glycerol was complete and the selectivity to propylene glycol was stable at about 60-80% all throughout the reaction time span of 10 h, regardless of the hydrogen pressure level (1 to 20 atm). These optimal values could not be improved significantly by using other different reaction conditions or increasing the catalyst acidity. At higher temperatures (245-250 °C) the conversion was also 100%. Under reaction conditions at which copper chromite suffered deactivation, light by-products and surface deposits were formed. The deposits could be completely burned at 250 °C and the catalyst activity fully recovered.

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Solid acid co-catalyst for the hydrogenolysis of glycerol to 1,3-propanediol over Ir-ReOx/SiO2

Cited by 176 publications

References 35 publications

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

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

Synthesis of 2‐Butanol by Selective Hydrogenolysis of 1,4‐Anhydroerythritol over Molybdenum Oxide‐Modified Rhodium‐Supported Silica

Selective hydrogenolysis of glycerol to propylene glycol in a continuous flow trickle bed reactor using copper chromite and Cu/Al2O3 catalysts

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