Acrolein, production from glycerol

Acrolein Zirconium and niobium mixed oxides have been shown to catalyze the dehydration of glycerol to acrolein, at 300°C in the presence of water with high selectivity (72%) at nearly total glycerol conversion [50]. Silica-supported niobia catalysts can also be used with similar catalytic performance [51]. Catalytic results for small-sized H-ZSM 5 zeolites showed that the high density of Bronsted acid sites favors acrolein production [52]. Acrolein production from glycerol has also been carried out in subcritical water at 360°C and 34 MPa with catalytic quantities of ZnS04 (791 ppm [g/g]) [52],... 

From their study of the pyrogenesis of acrolein (propenal) from glycerol, Doihara et al. (1023) and others deduced that a tobacco smoking product that contains glycerol as a humectant has an enhanced potential for the formation and release of acrolein (propenal) during smoking [see Wynder and Hoffmann (4337)]. 

Quinoline was discovered in coal tar by Friedlieb Ferdinand Runge in 1834 it is present in concentrations of approximately 0.3%. Quinoline is recovered by extraction with sulfuric acid from the methylnaphthalene fraction of coal tar, followed by springing with ammonia and rectification of the crude base mixture. Quinoline can be synthesized by the Skraup method, by the reaction of aniline with glycerol (or acrolein produced from glycerol) and catalytic gas-phase reaction of aniline with acetaldehyde. Since the supply of the tar-derived material has been adequate for a long time, synthetic production is not warrented. 

Some homogeneous metal catalysts have been examined in the production of acrolein from glycerol [20], However, considering all reaction components present, it is more likely that soluble acids, such as HC1 and CF3SO3H, are responsible for glycerol dehydration instead of Pt and Pd phosphine complexes. 

A palladium phosphine complex [e.g., BCPE = l,2-bis(l,5-cyclooctylenephos-phino)ethane] was also reported to produce propanediols and n-propanol from glycerol at 443 K under 6 MPa CO/H2 atmosphere in acidic conditions, n-Propanol is the dominant product, while a slight preference for the formation of propane-1,3-diol is seen in the diol fraction. Reactions were performed at different temperatures in the range 413-448 K. Since acrolein was monitored at high temperature, a reaction network was proposed following a sequential dehydration/hydrogenation pathway [20]. 

Another important bulk chemical that could be derived from glycerol is acrylic acid (Craciun et al., 2005 Shima and Takahashi, 2006 Dubois et al., 2006). Shima and Takahashi (2006) reported a complete process for acrylic acid production involving the steps of glycerol dehydration in a gas phase followed by the application of a gas phase oxidation reaction to a gaseous reaction product formed by the dehydration reaction. Dehydration of glycerol could lead to commercially viable production of acrolein, which is an important and versatile intermediate for the production of acrylic acid esters, superabsorber polymers or detergents (Ott et al., 2006). Sub- and supercritical water have been applied by Ott et al. (2006) as the reaction media for glycerol dehydration, but the conversion and acrolein selectivities that have been achieved so far are not satisfactory for an economical process. 

In the case of the oxidation of glycerol, D,L-glyceric acid has also been isolated. Hlasiwetz and Habermann treated glycerol with chlorine water and obtained the acid as the main product. From the action of bromine water on glycerol, Barth obtained glyceric acid, bromoform and carbon dioxide. In the absence of water, bromine converted glycerol to dibromohydrin and bromoacetic acid. The former decomposed to hydrogen bromide and acrolein. 

Groll H, Heame G. Process of converting a polyhydric alcohol to a carbonyl compound. US2042224 1936. Hoyt HE, Manninen TH. Production of acrolein from glycerol. US2558520 1951. 

Benzanthrone has been prepared by three general methods, the first of which is generally regarded as the best (i) by heating a reduction product of anthraquinone with sulfuric acid and glycerol,1 or with a derivative of glycerol, or with acrolein. The anthraquinone is usually reduced in sulfuric acid solution, just prior to the reaction, by means of aniline sulfate, iron, , or copper. It has also been prepared (2) by the action of aluminum or ferric chloride on phenyl-a-naphthyl ketone, and (3) from i-phenylnaphthalene-2-carboxylic acid. ... 

Biomass is a renewable resource from which various useful chemicals and fuels can be produced. Glycerol, obtained as a co-product of the transesterification of vegetable oils to produce biodiesel, is a potential building block to be processed in biorefineries (1,2). Attention has been recently paid to the conversion of glycerol to chemicals, such as propanediols (3, 4), acrolein (5, 6), or glyceric acid (7, 8). 

The microbiological breakdown of glycerol forms acrolein, a product which causes bitterness in wine by binding with phenolic components (Singleton 1995). Ethanol increases the intensity of the bitter taste, as well as the duration of the bitter sensation (Noble 1994). An increased alcohol concentration resulted in an increase in the bitter sensation (Eischer and Noble 1994). Lactobacillus brevis and L. buchneri, isolated from spoiled wine, can metabolize glycerol in the presence of... 

Derivation (1) By-product of soap manufacture (2) from propylene and chlorine to form allyl chloride, which is converted to the dichlorohydrin with hypo-chlorous acid this is then saponified to glycerol with caustic solution (3) isomerization of propylene oxide to allyl alcohol, which is reacted with peracetic acid, (the resulting glycidol is hydrolyzed to glycerol) (4) hydrogenation of carbohydrates with nickel catalyst (5) from acrolein and hydrogen peroxide. 

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