Butyl alcohol manufacture

Acetone is obtained by fermentation as a by-product of -butyl alcohol manufacture, or by chemical synthesis from isopropyl alcohol from cumene as a by-product in phenol manufacture or from propane as a by-product of oxidation-cracking. 

Normal butyl alcohol, propyl carbinol, n-butanol, 1-buianol, CH3CH2CH2CH2OH. B.p. 117 C. Manufactured by reduction of crotonaldehyde (2-buienal) with H2 and a metallic catalyst. Forms esters with acids and is oxidized first to butanal and then to butanoic acid. U.S. production 1978 300 000 tonnes. 

Secondary butyl alcohol, methylethyl car-binol, 2-butanol, CH3CH2CH(Me)OH. B.p. I00°C. Manufactured from the butane-butene fraction of the gas from the cracking of petroleum. Used to prepare butanone. 

Propylene oxide [75-56-9] is manufactured by either the chlorohydrin process or the peroxidation (coproduct) process. In the chlorohydrin process, chlorine, propylene, and water are combined to make propylene chlorohydrin, which then reacts with inorganic base to yield the oxide. The peroxidation process converts either isobutane or ethylbenzene direcdy to an alkyl hydroperoxide which then reacts with propylene to make propylene oxide, and /-butyl alcohol or methylbenzyl alcohol, respectively. Table 1 Hsts producers of propylene glycols in the United States. 

Propylene oxide [75-56-9] (methyloxirane, 1,2-epoxypropane) is a significant organic chemical used primarily as a reaction intermediate for production of polyether polyols, propylene glycol, alkanolamines (qv), glycol ethers, and many other useful products (see Glycols). Propylene oxide was first prepared in 1861 by Oser and first polymerized by Levene and Walti in 1927 (1). Propylene oxide is manufactured by two basic processes the traditional chlorohydrin process (see Chlorohydrins) and the hydroperoxide process, where either / fZ-butanol (see Butyl alcohols) or styrene (qv) is a co-product. Research continues in an effort to develop a direct oxidation process to be used commercially. 

Used industrially in the manufacture of butyl alcohol, butyraldehyde, quinaldine, resins, rubber antioxidants, insecticides, and other chemicals used as a solvent, warning agent in fuel gases, as a rubber accelerator, in leather tanning, and as a denaturant in alcohol. 

Other minor petrochemical uses of butene-1 continue to be the manufacture of SBA (secondary butyl alcohol), MA (maleic anhydride), and butylene oxide. 

One of the commercial benefits of this route is the value of the coproducts, tertiary butyl alcohol (TBA) when isobucane is used, and styrene when ethylbenzene is used. TBA also can be easily hydro-treated back to isobutane if a recycle stream for PO manufacture is more advantageous. 

Normal butyl alcohol (NBA) was first recovered in the 1920s as a by-product of acetone manufacture via cornstarch fermentation. That route is almost extinct now. A small percent is still made from acetaldehyde. The primary source of NBA, however, is the Oxo process. 

Mixed C4 olefins (primarily iC4) are isolated from a mixed C olefin and paraffin stream. Two different liquid adsorption high-purity C olefin processes exist the C4 Olex process for producing isobutylene (iCf ) and the Sorbutene process for producing butene-1. Isobutylene has been used in alcohol synthesis and the production of methyl tert-butyl ether (MTBE) and isooctane, both of which improve octane of gasoHne. Commercial 1-butene is used in the manufacture of both hnear low-density polyethylene (LLDPE) and high-density polyethylene (HDPE)., polypropylene, polybutene, butylene oxide and the C4 solvents secondary butyl alcohol (SBA) and methyl ethyl ketone (MEK). While the C4 Olex process has been commercially demonstrated, the Sorbutene process has only been demonstrated on a pilot scale. 

Uses Copolymerized with methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, or 1,1-dichloroethylene to produce acrylic and modacrylic fibers and high-strength fibers ABS (acrylonitrile-butadiene-styrene) and acrylonitrile-styrene copolymers nitrile rubber cyano-ethylation of cotton synthetic soil block (acrylonitrile polymerized in wood pulp) manufacture of adhesives organic synthesis grain fumigant pesticide monomer for a semi-conductive polymer that can be used similar to inorganic oxide catalysts in dehydrogenation of tert-butyl alcohol to isobutylene and water pharmaceuticals antioxidants dyes and surfactants. 

Uses. Intermediate for the production of scorbic acid formerly used in the manufacture of -butyl alcohol formed during the combustion of fossil fuels... 

Since approximately 2.2 lb of /-butyl alcohol would be produced per 1 lb of propylene oxide, an alternative reactant in this method is ethylbenzene hydroperoxide. This eventually forms phenylmethylcarbinol along with the propylene oxide. The alcohol is dehydrated to styrene. This chemistry was covered in Chapter 9, Section 6 as one of the syntheses of styrene. Thus the side product can be varied depending on the demand for substances such as /-butyl alcohol or styrene. Research is being done on a direct oxidation of propylene with oxygen, analogous to that used in the manufacture of ethylene oxide from ethylene and oxygen (Chapter 9, Section 7). But the proper catalyst and conditions have not yet been found. The methyl group is very sensitive to oxidation conditions. 

Direct Oxidation. Direct oxidation of petroleum hydrocarbons has been practiced on a small scale since 1926 methanol, formaldehyde, and acetaldehyde are produced. A much larger project (29) began operating in 1945. The main product of the latter operation is acetic acid, used for the manufacture of cellulose acetate rayon. The oxidation process consists of mixing air with a butane-propane mixture and passing the compressed mixture over a catalyst in a tubular reaction furnace. The product mixture includes acetaldehyde, formaldehyde, acetone, propyl and butyl alcohols, methyl ethyl ketone, and propylene oxide and glycols. The acetaldehyde is oxidized to acetic acid in a separate plant. Thus the products of this operation are the same as those (or their derivatives) produced by olefin hydration and other aliphatic syntheses. 

Another oxo plant, now being constructed, will make butyl compounds (88). These may be the source of butyl alcohol, butyl acetate, butyric acid for the manufacture of cellulose acetate butyrate and other products, butyraldehyde for polyvinyl butyral, and the eight-carbon compounds including 2-ethylhexanol. All these will add to the present production of the same compounds made by the older methods from acetaldehyde via aldol condensation. 

Production of Alcohols by Hydration ofAlkenes. Several alcohols (ethyl alcohol, isopropyl alcohol, sec-butyl alcohol, ferf-butyl alcohol) are manufactured commercially by the hydration of the corresponding olefins.2 45 46 Ethanol, an industrial solvent and a component of alcohol-gasoline blends, and isopropyl alcohol—a solvent and antiknock additive—are the most important compounds. Isopropyl alcohol is often considered the first modem synthetic petrochemical since it was produced on a large scale in the United States in the 1920s. 

It competes direcdy with MTBE as an octane enhancer in the gasoline pool. Since MTBE is more desirable than tert-butyl alcohol because of its total miscibility with gasoline, tert-butyl alcohol will be an important source of isobutylene used in the manufacture of MTBE. High purity isobutylene, C4Hg, can be obtained by dehydration of tert-butyl alcohol, C4H1qO. 

RWE-DEA (former Deutsche Texaco AG) is one of the leading companies in the development and conmercial application of processes using ion excnange resins as acidic catalysts. Our expertise comprises production of bulk chemicals, sucn as MTBE (refs. 2-3), isopropyl alcohol (refs. 2, 4-5) and sec-butyl alcohol (refs. 2, 6-7) as well as manufacture of low-volume chemicals sold at higner prices, sucn as methyl isobutyl ketone, methyl isopropenyl Ketone and methyl isopropyl ketone (refs. 8, 9-10) ... 

A dilute solution of ethanol is obtained, which can be concentrated by distillation to a constant-boiling point mixture that contains 95.6% ethanol by weight. Dehydration of the remaining few percent of water to give absolute alcohol is achieved either by chemical means or by distillation with benzene, which results in preferential separation of the water. Ethanol also is made in large quantities by fermentation, but this route is not competitive for industrial uses with the hydration of ethene. Isopropyl alcohol and tert-butyl alcohol also are manufactured by hydration of the corresponding alkenes. 

The following solvents are now manufactured on the large scale for industrial purposes ethylene dichloride, di-, tri-, and tetra-chloroethy-lene, tetrachloroethane, dichloroethyl ether, hexahydrobenzene, cyclo-hexanol, tetra- and deca-hydronaphthalene (tetralin and dekalin), triacetin, ethylene glycol, butyl alcohol, diacetone alcohol, ethyl lactate, isopropyl ether, etc. 

Methyl methacrylate is also manufactured by oxidation of iso-butene or i-butyl alcohol. 

Alcohols are hydrocarbons with one or more hydrogen atoms substituted by hydroxyl (-OH) groups. Compounds with one hydroxyl group are called alcohols, those with two are called glycols, and those with three hydroxyls are called glycerols. Alcohols are used extensively in industries as solvents for the manufacture of a variety of products. Generally, all alcohols cause irritation to the mucous membranes with mild narcotic effect. There are important classes of alcohols, namely, allyl alcohol, amyl alcohol, n-butyl alcohol, methyl alcohol, ethyl alcohol, and propyl alcohol. 

Uses n-Butyl alcohol is used extensively in a number of industries. For instance, it is used as a solvent in industries associated with the manufacture of paints, varnishes, synthetic resins, gums, pharmaceuticals, vegetable oils, dyes, and alkaloids. n-Butyl alcohol also finds use in the manufacture of artificial leather, rubber, and plastic cements, shellac, raincoats, perfumes, and photographic films. 

The economics of any manufacturing process improves if the co-product or side product has a market. 90% of the world production of phenol is through the cumene hydroperoxide route because of the economic advantage of the coproduct acetone. Oxirane technology for the production of propylene oxide from ethyl benzene leads to a co-product styrene and from isobutane leads to a co-product /-butyl alcohol. 

Isobutene is present in refinery streams. Especially C4 fractions from catalytic cracking are used. Such streams consist mainly of n-butenes, isobutene and butadiene, and generally the butadiene is first removed by extraction. For the purpose of MTBE manufacture the amount of C4 (and C3) olefins in catalytic cracking can be enhanced by adding a few percent of the shape-selective, medium-pore zeolite ZSM-5 to the FCC catalyst (see Fig. 2.23), which is based on zeolite Y (large pore). Two routes lead from n-butane to isobutene (see Fig. 2.24) the isomerization/dehydrogenation pathway (upper route) is industrially practised. Finally, isobutene is also industrially obtained by dehydration of f-butyl alcohol, formed in the Halcon process (isobutane/propene to f-butyl alcohol/ propene oxide). The latter process has been mentioned as an alternative for the SMPO process (see Section 2.7). 

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