Highly active metal–acid bifunctional catalyst system for hydrogenolysis of glycerol under mild reaction conditions

Kusunoki, Yohei; Miyazawa, Tomohisa; Kunimori, Kimio; Tomishige, Keiichi

doi:10.1016/j.catcom.2005.06.006

Cited by 219 publications

(133 citation statements)

References 7 publications

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“…43,44 Among the three catalysts, Ir/γ-Al 2 O 3 presented the greater ability for C-C cleavage, forming methanol and ethylene glycol with selectivities of 9.0 and 3.2%, respectively. This result can indicate a better carbon adsorption on the catalyst surface to allow the C-C cleavage and the consequent formation of the mentioned products, which can be related to the properties of the supports.…”

Section: Glycerol Hydrogenolysismentioning

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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Section: Glycerol Hydrogenolysismentioning

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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“…[3][4][5] Replacing oil as feedstock in the chemical industry is one of the main challenges for the coming years. Hydrogenolysis of glycerol over metal catalysts can produce 1,2-and 1,3-propanediol, [6][7][8][9] used in the production of polymers and as anti-freezing agents. Carbonation of glycerol produces glycerol carbonate 10,11 , used as solvent.…”

Section: Introductionmentioning

confidence: 99%

Oxidative dehydration of glycerol to acrylic acid over vanadium-impregnated zeolite beta

Pestana¹,

Guerra²,

Ferreira³

et al. 2013

J. Braz. Chem. Soc.

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A desidratação oxidativa do glicerol a ácido acrílico foi estudada com o uso de zeólita Beta impregnada com vanádio. Os catalisadores foram preparados por impregnação úmida do metavanadato de amônio sobre a zeólita Beta na forma amoniacal, seguida de calcinação em ar a 823 K. A impregnação reduziu a área superficial específica, mas não afetou significativamente a acidez (Brønsted e Lewis) da zeólita. A avaliação dos catalisadores foi realizada num reator de leito fixo usando ar como gás de arraste e injetando o glicerol por meio de uma bomba seringa. Acroleína foi o principal produto formado, tendo também sido observados acetaldeído e hidróxi-acetona (acetol). O ácido acrílico foi formado em aproximadamente 25% de seletividade a 548 K sobre as zeólitas impregnadas. O resultado pode ser explicado por análises de XPS (espectroscopia fotoeletrônica de raios X), que mostraram uma boa dispersão de vanádio nos poros da zeólita.The oxidative dehydration of glycerol to acrylic acid was studied over vanadium-impregnated zeolite Beta. Catalysts were prepared by wet impregnation of ammonium metavanadate over ammonium-exchanged zeolite Beta, followed by air calcination at 823 K. Impregnation reduced the specific surface area, but did not significantly affected the acidity (Brønsted and Lewis) of the zeolites. The catalytic evaluation was carried out in a fixed bed flow reactor using air as the carrier and injecting glycerol by means of a syringe pump. Acrolein was the main product, with acetaldehyde and hydroxy-acetone (acetol) being also formed. Acrylic acid was formed with approximately 25% selectivity at 548 K over the impregnated zeolites. The result can be explained by XPS (X-ray photoelectron spectroscopy) measurements, which indicated a good dispersion of the vanadium inside the pores.Keywords: glycerol, acrylic acid, zeolite, dehydration, oxidation IntroductionGlycerol is usually found in combination with fatty acids of natural occurrence forming the triglycerides. Today, the major source of glycerol is the transesterification of oils and fats to produce biodiesel. 1 In this reaction, a molecule of triglyceride reacts with three molecules of methanol, under base catalysis conditions, to afford three molecules of fatty acid methyl esters (the biodiesel) and a molecule of glycerol (Scheme 1). In recent years, the growing concern about global warming has motivated the use of biofuels. Biodiesel, together with bioethanol, is one of the most important biofuels used nowadays.For each 90 m 3 of biodiesel produced by transesterification, about 10 m 3 of glycerol are obtained. The worldwide glycerol production will reached 2 approximately 1.2 million tons in 2012 and most of this production will come from the biodiesel industry. In Brazil, for instance, there is a mandatory blend of 5% of biodiesel in the petrodiesel, which represents an annual glycerol production of approximately 300,000 tons. The traditional markets for glycerol are cosmetics, soaps, pharmaceuticals and personal care products. However, with the increasing ...

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“…[5][6][7][8][9][10][11][12][13][14][15][16] In liquid-phase hydrogenolysis under hydrogen pressure, glycerol is converted into 1,2-PDO and 1,3-PDO in the presence of supported Rh, 5 Ru, [6][7][8] or Pt. 8,9 In the vapor-phase hydrogenolysis of glycerol, Cu catalyzes 1,2-PDO formation in the presence of high hydrogen pressure.…”

mentioning

confidence: 99%

“…8,9 In the vapor-phase hydrogenolysis of glycerol, Cu catalyzes 1,2-PDO formation in the presence of high hydrogen pressure. [10][11][12][13] Since the hydrogenolysis requires elevated hydrogen pressure, [5][6][7][8][9][10][11] side reactions occur to form several by-products, including ethylene glycol (EG), propanol, lactic acid, and propanoic acid. Hydroxyacetone (HA) is an intermediate product in the conversion of glycerol into 1,2-PDO through the dehydration-hydrogenation reactions.…”

mentioning

confidence: 99%

Selective Conversion of Glycerol into 1,2-Propanediol at Ambient Hydrogen Pressure

Sato¹,

Akiyama²,

Inui³

et al. 2009

Chemistry Letters

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The vapor-phase reaction of glycerol was performed over a copper-alumina catalyst at ambient hydrogen pressure. Glycerol was converted into 1,2-propanediol (PDO) through dehydrationhydrogenation via hydroxyacetone (HA). We also found that 1,2-PDO was produced at the selectivity higher than 93 mol % in hydrogen flow at gradient temperatures: the dehydrogenation into HA was catalyzed at around C, while the following hydrogenation into 1,2-PDO was catalyzed by Cu-alumina catalyst at around 145-160 C.The catalytic conversion of carbon-neutral biomass into useful chemicals is expected to be a potential solution to the severe global environmental pollution problem.1,2 Renewable biomass fuels, such as bioethanol and biodiesel fuel (BDF), i.e., fatty acid methyl esters, are attracting much attention worldwide. Glycerol, a by-product of BDF production for ca. 10 mass % of BDF produced, is one of such promising renewable resources. Its quantity increases as the amount of BDF produced is increased.Recently, quite a number of studies on the reaction of glycerol have appeared in reviews 2-4 and research papers. [5][6][7][8][9][10][11][12][13][14][15][16] In liquid-phase hydrogenolysis under hydrogen pressure, glycerol is converted into 1,2-PDO and 1,3-PDO in the presence of supported Rh, 5 Ru, [6][7][8]9 In the vapor-phase hydrogenolysis of glycerol, Cu catalyzes 1,2-PDO formation in the presence of high hydrogen pressure. [10][11][12][13] Since the hydrogenolysis requires elevated hydrogen pressure, 5-11 side reactions occur to form several by-products, including ethylene glycol (EG), propanol, lactic acid, and propanoic acid. Hydroxyacetone (HA) is an intermediate product in the conversion of glycerol into 1,2-PDO through the dehydration-hydrogenation reactions. Over Cu catalysts, however, 1,2-PDO selectivity higher than 90 mol % is attained: 12,13 low temperatures and high hydrogen pressures favor the shift of equilibrium from HA to 1,2-PDO and reduce the formation of by-products resulting from HA side reactions. 13One effective operation is a two-step process composed of dehydration under vacuum and hydrogenation under hydrogen pressure. 13,15 It is known that copper works as a dehydrogenation catalyst for polyols, such as 1,2-17 and 1,3-diols. 18 However, glycerol can be dehydrated into HA over copper metal catalysts.14-16 It should be noted that copper metal catalyzes the dehydration of glycerol to produce HA with selectivity higher than 90 mol % at 250 C, and that no dehydrogenation proceeds to form dihydroxyacetone.14,16 1,2-PDO is dehydrogenated to form HA in the presence of inert carrier gas over copper catalysts, and the dehydrogenation is controlled by equilibrium.17 This reminds us that 1,2-PDO is favored at high hydrogen partial pressure even at ambient pressure. As copper metal works as a catalyst for the dehydrogenation of 1,2-PDO into HA at 210 C, 17 it is expected to be an efficient catalyst for the reverse hydrogenation at temperatures lower than 210 C. In this paper, we report that the transformation of ...

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Highly active metal–acid bifunctional catalyst system for hydrogenolysis of glycerol under mild reaction conditions

Cited by 219 publications

References 7 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

Oxidative dehydration of glycerol to acrylic acid over vanadium-impregnated zeolite beta

Selective Conversion of Glycerol into 1,2-Propanediol at Ambient Hydrogen Pressure

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