Aqueous polyol conversions on ruthenium and on sulfur-modified ruthenium

Montassier, C.; Menezo, J. C.; Hoang, Lê Chiên; Renaud, C.; Barbier, Jean‐Pierre

doi:10.1016/0304-5102(91)85008-p

Cited by 246 publications

(185 citation statements)

References 9 publications

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“…So we deduced that the hydrogenolysis of glycerol in the present catalysis system follows the Langmuir-HinshelwoodHougen-Watson (LHHW) mechanism [33][34][35] in which the adjacent two hydroxyls of glycerol adsorbed on the NiO surface, react with atomic hydrogen on the Ni surface, and the C-O bond cleavage and hydrogen atom addition occur simultaneously to produce 1,2-PDO, as shown in Scheme 1. For the formation of EG, glycerol first of all dehydrogenates to glyceraldehydes, then decarbonylates through retro-aldolization to produce EG [16]. The NiO on the Ni-base catalysts reduced the active sites for dehydrogenation which was the first step in producing EG, so the selectivity to EG decreased.…”

Section: Influence Of Ni Metal State On the Catalytic Performancementioning

confidence: 99%

“…Huang et al, reported that the addition of phosphorus to Ni/SiO2 catalyst could increase the selectivity to 1,2-PDO to 85.9% from 49.9% at 220 °C, they suggested that the formation of a Ni2P alloy phase and its electronic and geometrical properties could affect the hydrogenolysis of C-O and C-C bonds [15]. Montassier et al, found that Ru/C catalyst doped with sulfur could increase the selectivity of 1,2-PDO from 12%-80% because doping of sulfur could prevent the carbonyl hydrogenation and C-C and C-O hydrogenolysis based on electron transfer from Ru to S [16]. Moreover, the effects of promoters like Al, Ba and Zn on the Cu-Cr catalysts in the hydrogenolysis of glycerol was investigated in 2-propanol at 220 °C, in the presence of Ba, the highest selectivity to 1,2-PDO reached 85% at 34% conversion, it was suggested that the increased acid sites and the BaCrO4 phase might be responsible for the improved activity and selectivity [17].…”

Section: Introductionmentioning

confidence: 99%

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Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

Cheng

Liang

et al. 2015

Catalysts

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Ni-based catalysts as replacement for noble metal catalysts are of particular interest in the catalytic conversion of biomass due to their cheap and satisfactory catalytic activity. The Ni/SiO2 catalyst has been studied for the hydrogenolysis of glycerol, and doping with phosphorus (P) found to improve the catalytic performance significantly because of the formation of Ni2P alloys. However, in the present work we disclose a different catalytic phenomenon for the P-doped Ni/Al2O3 catalyst. We found that doping with P has a significant effect on the state of the active Ni species, and thus improves the selectivity to 1,2-propanediol (1,2-PDO) significantly in the hydrogenolysis of glycerol, although Ni-P alloys were not observed in our catalytic system. The structure and selectivity correlations were determined from the experimental data, combining the results of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR) and ammonia temperature-programmed desorption (NH3-TPD). The presence of NiO species, formed from P-doped Ni/Al2O3 catalyst, was shown to benefit the formation of 1,2-PDO. This was supported by the results of the Ni/Al2O3 catalyst containing NiO species with incomplete reduction. Furthermore, the OPEN ACCESSCatalysts 2015, 5 760 role the NiO species played in the reaction and the potential reaction mechanism over the P-doped Ni/Al2O3 catalyst is discussed. The new findings in the present work open a new vision for Ni catalysis and will benefit researchers in designing Ni-based catalysts.

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Section: Influence Of Ni Metal State On the Catalytic Performancementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

Cheng

Liang

et al. 2015

Catalysts

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“…The route of hydroxyacetone [6] involves the glycerol dehydration to form hydroxyacetone which is sequentially hydrogenated to 1,2-propanediol (1,2-PDO). The most plausible mechanism reaction for the glyceraldehyde route was proposed by Montassier et al [7] which involves a dehydrogenation of glycerol to glyceraldehyde followed by hydrogenation to form ethylene glycol (EG) and methanol. Finally, methane (CH 4 ) is formed by deep hydrogenolysis.…”

Section: Introductionmentioning

confidence: 99%

Influence of copper on nickel-based catalysts in the conversion of glycerol

Miranda

Chimentão

Szanyi

et al. 2015

Applied Catalysis B: Environmental

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The catalytic transformation of glycerol to value-added compounds was investigated over bimetallic Ni-Cu/y-Al2 O3 catalysts with Ni/Cu atomic ratios of 8/1, 4/1, 2/1, 1/1, 1/2, 1/4, and 1/8. XPS analysis revealed that the surface composition of the catalyst exhibited progressive enrichment of Cu as its content in the catalyst increased. H2 -chemisorption indicated that the total number of exposed Ni atoms decreased as the Cu content increased. As a result, deep hydrogenolysis to produce CH4 was inhibited by the addition of Cu to the Ni catalyst, yielding higher selectivity toward the dehydration products of glycerol such as hydroxyacetone.FTIR spectra of adsorbed CO reveal that Cu asserts both geometric and electronic effects on the adsorption properties of Ni. The geometrical effect is visualized by the progressive disappearance of the bridge-bound adsorbed CO on metallic Ni by the incorporation of Cu. This suggests that the deep hydrogenolysis of glycerol to CH4 formation requires an ensemble of adjacent active Ni atoms. The electronic effect of Cu on Ni is indicated by the red shift of the IR peak of adsorbed CO as the Cu content increases. The electronic interaction between Cu and Ni species was also substantiated by XANES results. HTREM revealed metal particles very well distributed on the support with particle size of 1.5 to 5 nm. The Ni-Cu samples were not a total intermetallic alloys..

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“…In 1989, Montassier et al [18,25] proposed the first mechanism for the sorbitol transformation in aqueous phase on a Raney Cu catalyst, then applied to a Ru/C catalyst and then Ru/C modified by sulphur, in the presence of hydrogen. This work showed that a first dehydrogenation of glycerol leads to glyceraldehyde, followed by a dehydration catalysed by an electrophilic site (M d+ metal site or acid site) (Fig.…”

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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Aqueous polyol conversions on ruthenium and on sulfur-modified ruthenium

Cited by 246 publications

References 9 publications

Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

Influence of copper on nickel-based catalysts in the conversion of glycerol

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

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