Investigations on heterogeneously catalysed condensations of glycerol to cyclic acetals

Deutsch, J.; Martin, Andreas; Lieske, H.

doi:10.1016/j.jcat.2006.11.006

Cited by 281 publications

(213 citation statements)

References 14 publications

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“…14,15 Glycerol ketals and acetals are formed in the acid-catalyzed reactions with ketones and aldehydes, respectively. 16,17 Solketal, the product formed in the reaction of glycerol with acetone, is a potential additive for gasoline, 18 whereas the acetals formed in the reaction of glycerol with butanal improves the cold flow properties of biodiesel. 19 Metal-supported catalysts are usually employed in the glycerol oxidation, producing many compounds, such as glyceric, mesoxalic and hydropyruvic acid.…”

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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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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“…Agirre et al (Agirre et al, 2010) studied the reaction between ethanol and butanal and the achieved maximum conversion was also around 50% (at 313 K). Other authors like Deutsch et al (Deutsch et al, 2007) and Silva et al (Silva et al, 2010) studied glycerol acetalization reactions with different aldehydes. Deutsch et al (Deutsch et al, 2007) studied the acetalization reaction of glycerol with formaldehyde using different type of solvents and the maximum achieved conversions were between 58-77% (between 313 and 383 K).…”

Section: Kinetics Of Acetals Formation Reactionsmentioning

confidence: 99%

“…Other authors like Deutsch et al (Deutsch et al, 2007) and Silva et al (Silva et al, 2010) studied glycerol acetalization reactions with different aldehydes. Deutsch et al (Deutsch et al, 2007) studied the acetalization reaction of glycerol with formaldehyde using different type of solvents and the maximum achieved conversions were between 58-77% (between 313 and 383 K). On the other hand, Silva et al (Silva et al, 2010) studied the reaction of glycerol with butanal, pentanal, hexanal, octanal and decanal achieving a maximum of 80% (at 343 K) of conversion with butanal.…”

Section: Kinetics Of Acetals Formation Reactionsmentioning

confidence: 99%

Acetals as Possible Diesel Additives

Agirre¹,

Barrio²,

Güemez³

et al. 2011

Economic Effects of Biofuel Production

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“…2,3 One of the uses of glycerol is its chemical transformation into oxygenated fuel additives. [4][5][6][7][8][9][10] Glycerol can be reacted with acetone to produce solketal. 4,11,12 Moreover, glycerol can react with acetic acid to produce monoacetin (MA), diacetin (DA), and triacetin (TA).…”

Section: Introductionmentioning

confidence: 99%

Continuous Synthesis of a Green Fuel Additive Mixture with Highest Quantities of Solketalacetin and Solketal and Lowest Amount of Diacetin from Biodiesel-Derived Glycerol

Gorji¹,

Ghaziaskar²

2017

J. Braz. Chem. Soc.

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This work presents a continuous, easy-to-scale-up system for glycerol conversion to a valuable fuel additive mixture such as solketalacetin ((2,2-dimethyl-1,3-dioxolan-4-yl)methyl acetate), solketal and minimum amount of diacetin with no byproducts. A two-stage reaction was conducted to synthesize the mixture. At first, glycerol was reacted with acetic acid in a continuous system to synthesize monoacetin using a small plug flow reactor and central composite design to optimize the variables related to monoacetin synthesis. Finally, an acetic acid:glycerol mole ratio of 3.7:1, a temperature of 79 °C, a flow rate of 0.9 mL min −1 , and a pressure of 1 bar were determined as the optimum conditions. At the optimum condition, predicted and experimental yields of monoacetin were 63 and 62%, respectively. In the next stage, monoacetin and the residual glycerol were reacted with acetone to obtain a mixture of solketalacetin, solketal, and diacetin with the mole percentage of 62, 30, and 8%, respectively.Keywords: biodiesel additive, monoacetin, solketalacetin, (2,2-dimethyl-1,3-dioxolan-4-yl) methyl acetate, central composite design IntroductionBiodiesel is a renewable energy source that is synthesized via transesterification of the vegetable oil triglycerides.1 In this process, glycerol is produced as a byproduct that accounts for approximately 10 wt.% of the biodiesel produced.2,3 One of the uses of glycerol is its chemical transformation into oxygenated fuel additives. [4][5][6][7][8][9][10] Glycerol can be reacted with acetone to produce solketal. 4,11,12 Moreover, glycerol can react with acetic acid to produce monoacetin (MA), diacetin (DA), and triacetin (TA). 13,18 Although triacetin is one of the best biofuel additives, the process of triacetin synthesis is costly and requires high mole ratio of acetic acid:glycerol, high temperatures, and pressures. 6,13,19,20 Garcia et al. 21 synthesized solketalacetin ((2,2-dimethyl-1,3-dioxolan-4-yl)methyl acetate), whose properties were in some respects superior to those of triacetin as a biodiesel additive, but they used acetic anhydride and triethylamine to synthesize solketalacetin that is not suitable for industrial process due to the cost of these materials, and health and safety problems. They indicated that solketalacetin is a better viscosity improver and does not increase the density as much as triacetin. In our previous work, 22 a novel method was developed for the synthesis of solketalacetin consisting of two stages. In the first stage, a mixture was obtained from the reaction of glycerol and acetic acid in a batch system with the mole percentage of 60, 31, 4 and 5%, for monoacetin, diacetin, triacetin, and the residual glycerol, respectively. In the second stage, solketalacetin was obtained from the reaction of monoacetin with acetone in a continuous system. The final mixture composition changed to solketalacetin, solketal, diacetin, and triacetin with the mole percentage of 60, 5, 31, and 4%, respectively. 22 Among the fuel additives synthesized from glycer...

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Investigations on heterogeneously catalysed condensations of glycerol to cyclic acetals

Cited by 281 publications

References 14 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

Acetals as Possible Diesel Additives

Continuous Synthesis of a Green Fuel Additive Mixture with Highest Quantities of Solketalacetin and Solketal and Lowest Amount of Diacetin from Biodiesel-Derived Glycerol

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