Ethanol butadiene from

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). 

An example of a combination of parallel and series reactions is the formation of butadiene from ethanol ... 

Lebedev process. Formation of butadiene from ethanol by catalytic pyrolysis. The catalysts used are mixtures of silicates and aluminum and zinc oxides. 

Typical acid-catalyzed reactions such as cracking of hydrocarbons and dehydration of alcohols are catalyzed by Si02 — MgO. The catalytic activity for hydrogen transfer between ethanol and acetone correlates with the number of base sites. The formation of 1,3-butadiene from ethanol occurs on Si02 — MgO. Silica magnesia of 85 % MgO composition shows the maximum activity. At this composition, both acid and base sites exist on the surface, and the reaction proceeds by acid —base bifunctional action. The formation of 1,3-butadiene from ethanol involves several successive steps. Each step proceeds on acid sites and base sites independently. Silica magnesia containing 85 % MgO possesses well balanced acid and base sites and catalyzes the total reaction effectively. 

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. ... 

In the United States butadiene was prepared initially from ethanol and later by cracking four-carbon hydrocarbon streams (see Butadiene). In Germany butadiene was prepared from acetylene via the following steps acetylene — acetaldehyde — 3-hydroxybutyraldehyde — 1,3-butanediol — ... 

The pattern of commercial production of 1,3-butadiene parallels the overall development of the petrochemical industry. Since its discovery via pyrolysis of various organic materials, butadiene has been manufactured from acetylene as weU as ethanol, both via butanediols (1,3- and 1,4-) as intermediates (see Acetylene-DERIVED chemicals). On a global basis, the importance of these processes has decreased substantially because of the increasing production of butadiene from petroleum sources. China and India stiU convert ethanol to butadiene using the two-step process while Poland and the former USSR use a one-step process (229,230). In the past butadiene also was produced by the dehydrogenation of / -butane and oxydehydrogenation of / -butenes. However, butadiene is now primarily produced as a by-product in the steam cracking of hydrocarbon streams to produce ethylene. Except under market dislocation situations, butadiene is almost exclusively manufactured by this process in the United States, Western Europe, and Japan. 

Ethanol s use as a chemical iatemiediate (Table 8) suffered considerably from its replacement ia the production of acetaldehyde, butyraldehyde, acetic acid, and ethyUiexanol. The switch from the ethanol route to those products has depressed demand for ethanol by more than 300 x 10 L (80 x 10 gal) siace 1970. This decrease reflects newer technologies for the manufacture of acetaldehyde and acetic acid, which is the largest use for acetaldehyde, by direct routes usiag ethylene, butane (173), and methanol. Oxo processes (qv) such as Union Carbide s Low Pressure Oxo process for the production of butanol and ethyUiexanol have totaUy replaced the processes based on acetaldehyde. For example, U.S. consumption of ethanol for acetaldehyde manufacture declined steadily from 50% ia 1962 to 37% ia 1964 and none ia 1990. Butadiene was made from ethanol on a large scale duriag World War II, but this route is no longer competitive with butadiene derived from petroleum operations. 

During World War II, production of butadiene (qv) from ethanol was of great importance. About 60% of the butadiene produced in the United States during that time was obtained by a two-step process utilizing a 3 1 mixture of ethanol and acetaldehyde at atmospheric pressure and a catalyst of tantalum oxide and siHca gel at 325—350°C (393—397). Extensive catalytic studies were reported (398—401) including a fluidized process (402). However, because of later developments in the manufacture of butadiene by the dehydrogenation of butane and butenes, and by naphtha cracking, the use of ethanol as a raw material for this purpose has all but disappeared. 

Ethanol in the past has been used commercially to synthesize dozens of other high-volume chemical commodities. However, at present, it has been substituted in many applications by less costly petrochemical feedstocks, e.g., ethylene. The availability of low-cost ethanol and the rising cost of ethylene, however, may change this scenario. For example, there is interest in producing ethylene from ethanol [71-73], while the opposite reaction is commercially current. Already, in markets with abundant agricultural products, but a less developed petrochemical infrastructure, such as the People s Republic of China, Pakistan, India, and Brazil, ethanol can be used to produce chemicals, including ethylene and butadiene, that would be produced from petroleum in the West. For example, ethanol may substitute alkenes for the alkylation of aromatics [82]. 

Different routes for converting biomass into chemicals are possible. Fermentation of starches or sugars yields ethanol, which can be converted into ethylene. Other chemicals that can be produced from ethanol are acetaldehyde and butadiene. Other fermentation routes yield acetone/butanol (e.g., in South Africa). Submerged aerobic fermentation leads to citric acid, gluconic acid and special polysaccharides, giving access to new biopolymers such as polyester from poly-lactic acid, or polyester with a bio-based polyol and fossil acid, e.g., biopolymers . 

As many as 70 products were at one time produced commercially from ethanol. Some of these downstream products are butanol, 2-ethyl hexanol, crotonaldehyde, butyraldehyde, acetaldehyde, acetic acid, butadiene, sorbic acid, 2-ethylbutanol, ethyl ether, many esters, ethanol-glycol ethers, acetic anhydride, vinyl acetate, ethyl vinyl ether, even ethylene gas. Many of these products are now more economically made from other feedstocks such as ethylene for acetaldehyde and methanol-carbon monoxide for acetic acid. Time will tell when a revival of biologically-oriented processes will offer lower-cost routes to at least the simpler products. 

Achiral butadienes 143 and 144 formed chiral mixed crystals (substitutional solid solutions) of space group P2 l lx by cooling the melts of both components or on crystallization from ethanol solution. A single large-sized mixed crystal 143144 was pulverized and irradiated resulting in [2 + 2] photocycloaddition, thereby giving the optically active heterodimers 145 as well as the achiral homodi-... 

OSTROMISLENSKY Butadiene Synthesis CatalyHc butadiene synthesis from ethanol and acetaldehyde. 

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)... 

EXPLOSION and FIRE CONCERNS not combustible NFPA rating (not rated) mercurous chloride is ineompatible with bromides, iodides, alkali chlorides, sulfates, sulfites, carbonates, hydroxides, ammonia, silver salts, eopper salts, hydrogen peroxide, iodine, and iodoform mercuric oxide reacts explosively with acetyl nitrate, chlorine and hydrocarbons, butadiene and ethanol and iodine (at 35°C), and hydrogen peroxide and traces of nitric acid forms heat or shock-sensitive explosive mixtures with metals and non-metals contact with acetylene, acetylene products, or ammonia gases may from solid products that are sensitive to shock and which can initiate fires of combustible materials decomposition emits highly toxic fumes of Hg use water spray, fog, or foam for firefighting purposes. 

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