New efficient and long-life catalyst for gas-phase glycerol dehydration to acrolein

Lauriol-Garbay, P.; Millet, J.M.M.; Loridant, S.; Bellière-Baca, V.; Rey, Patrick

doi:10.1016/j.jcat.2011.03.005

Cited by 78 publications

(44 citation statements)

References 36 publications

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“…[23][24][25][26][27][28][29][30][31] Figure 2 shows the conversion and selectivity of the catalysts in the oxidative dehydration of glycerol in the presence of air, at 548 K. Acrolein was still the main observed organic product, but acrylic and acetic acid could also be identified, as well as acetaldehyde, which may be produced from the catalytic cracking of 3-hydroxy-propanal, formed as intermediate (Scheme 2). There was a significant amount of unidentified products, most of them with higher retention times than glycerol, indicative of high boiling point.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Indeed, catalyst deactivation is a major problem associated with acid-catalyzed glycerol dehydration. Mixed niobium-zirconium oxides are among the most resistant catalysts for glycerol dehydration, 30,31 showing 82% conversion even after 177 h on stream.A less studied approach is the glycerol oxidative dehydration, which is carried out over bifunctional catalysts in the presence of air or oxygen. The idea is to perform two consecutive reactions: glycerol dehydration to acrolein and its subsequent oxidation to acrylic acid.…”

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confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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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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“…16,17 Pyridine thermal desorption was used to assess the concentration and strength of the surface acid sites of the catalysts. 18 Total acidity was calculated from the total area of the Temperature programmed desorption (TPD) trace. Sites were classified into weak acid sites (desorbing between 150-300 °C), mild acid sites (desorbing between 300-500 °C) and strong acid sites (desorbing at temperatures higher than 500 °C).…”

Section: Catalyst Characterizationmentioning

confidence: 99%

“…Lauriol-Garbay and coworkers reported dehydrated glycerol selectively to acrolein at 300 ºC in the gas phase using a mixture of zirconium and niobium oxides as catalyst. 18 Haider and coworkers dehydrated glycerol to acrolein at 270-300 ºC using Ru heteropolyacid catalysts. 21 The dehydration of glycerol at different temperature also reported by Jia and coworkers using a ZSM-5 catalysts at 320 ºC 22 and Dalla Costa and coworkers using beta zeolite catalysts at 275 ºC.…”

Section: Catalytic Activitymentioning

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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Niobium‐Based Catalysts for Biomass Conversion

Xia

Wang

2017

Nanoporous Catalysts for Biomass Conversion

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New efficient and long-life catalyst for gas-phase glycerol dehydration to acrolein

Cited by 78 publications

References 36 publications

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

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

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

Niobium‐Based Catalysts for Biomass Conversion

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