Butadiene synthesis from ethanol

OSTROMISLENSKY Butadiene Synthesis CatalyHc butadiene synthesis from ethanol and acetaldehyde. 

The first use of butadiene to make synthetic rubber was demonstrated in Russia in 1910 by S.V. Lebchev, who also developed a synthesis of butadiene from ethanol obtained by fermentation. 

The most important contribution in the field of simultaneous dehydrogenation, condensation, and dehydration made by Russian chemists is the synthesis of butadiene from ethanol over a double oxide catalyst by the method of Lebedev. Much has been published on this process. Lebedev s interest in rubber synthesis began with his researches on conversions of dienes in 1908 and his method of synthesis of butadiene was reported in 1927. An experimental synthetic rubber plant was founded for research in the field and the studies on the mechanism of formation of butadiene and of polymerization were continued after Lebedev s death by his students (103,104,105,188,190,378). A survey of the properties and methods of preparation of butadiene was published by Petrov (289). 

Kitayama reported that Mn -exchanged sepiolite can be a selective catalyst for the synthesis of butadiene from ethanol.Butadiene can be produced also from alkali cation containig hectrite. ... 

Ethanol is the key reactant in Eq. (1), and also in Eq. (2) because it is readily converted to acetaldehyde. The process based on Eq. 1 was developed in Russia and the process based on Eq. 2 was developed in the United States. The yield of butadiene for the Russian process is about 30-35%. It is about 70% if mixtures of ethanol and acetaldehyde are employed as in the U.S. process. Equation (3) represents a process that involves 2,3-butylene glycol, a product from the microbial conversion of biomass. The process is carried out in two sequential steps via the glycol diacetate in overall yields to butadiene of about 80%. The process of Eq. (4) starts with a biomass derivative, the cyclic ether tetrahydrofuran, and can be carried out at high yields. When this process was first operated on a large scale in Germany, acetylene and formaldehyde were the raw materials for the synthesis of intermediate tetrahydrofuran. It is manufactured today from biomass feedstocks by thermochemical conversion, as will be discussed later. 

The growth of synthetic fibers has led to the devising of syntheses from petroleum of the chemical intermediates required for this new industry. Leaving aside acetic anhydride from ethylene via synthetic ethanol and from propylene via acetone, already established and used for cellulose acetate in the 193O s, nylon has called for the isolation of petroleum cyclohexane and for the discovery of a route from butadiene to nylon salt Dacron for the isolation of p-xylene from petroleum xylene, and the nitrile fibers for the synthesis of acrylonitrile from ethylene or acetylene. 

Desulfurization of petroleum feedstock (FBR), catalytic cracking (MBR or FI BR), hydrodewaxing (FBR), steam reforming of methane or naphtha (FBR), water-gas shift (CO conversion) reaction (FBR-A), ammonia synthesis (FBR-A), methanol from synthesis gas (FBR), oxidation of sulfur dioxide (FBR-A), isomerization of xylenes (FBR-A), catalytic reforming of naphtha (FBR-A), reduction of nitrobenzene to aniline (FBR), butadiene from n-butanes (FBR-A), ethylbenzene by alkylation of benzene (FBR), dehydrogenation of ethylbenzene to styrene (FBR), methyl ethyl ketone from sec-butyl alcohol (by dehydrogenation) (FBR), formaldehyde from methanol (FBR), disproportionation of toluene (FBR-A), dehydration of ethanol (FBR-A), dimethylaniline from aniline and methanol (FBR), vinyl chloride from acetone (FBR), vinyl acetate from acetylene and acetic acid (FBR), phosgene from carbon monoxide (FBR), dichloroethane by oxichlorination of ethylene (FBR), oxidation of ethylene to ethylene oxide (FBR), oxidation of benzene to maleic anhydride (FBR), oxidation of toluene to benzaldehyde (FBR), phthalic anhydride from o-xylene (FBR), furane from butadiene (FBR), acrylonitrile by ammoxidation of propylene (FI BR)... 

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