Alcohol production

Lithium aluminum hydnde reacts violently with water and alcohols so it must be used m solvents such as anhydrous diethyl ether or tetrahydrofuran Following reduc tion a separate hydrolysis step is required to liberate the alcohol product... 

Give the structures or build molecular models of both alcohol products for each ketone... 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

Alcohol Production. Studies to assess the costs of alcohol fuels and to compare the costs to those of conventional fuels contain significant uncertainties. In general, the low cost estimates iadicate that methanol produced on a large scale from low cost natural gas could compete with gasoline when oil prices are around 140/L ( 27/bbl). This comparison does not give methanol any credits for environmental or energy diversification benefits. Ethanol does not become competitive until petroleum prices are much higher. 

Most manufacturers sell a portion of their alcohol product on the merchant market, retaining a portion for internal use, typically for the manufacture of plasticizers. Sterling Chemicals linear alcohol of 7, 9, and 11 carbons is all used captively. Plasticizer range linear alcohols derived from natural fats and oils, for instance, octanol and decanol derived from coconut oil and 2-octanol derived from castor oil, are of only minor importance in the marketplace. 

Company and location Capacity 10 t/yi Alcohol products Peedstock... 

This second reaction leads to the small amount of branching (usually less than 5%) observed in the alcohol product. The alpha olefins produced by the first reaction represent a loss unless recovered (8). Additionally, ethylene polymerisation during chain growth creates significant fouling problems which must be addressed in the design and operation of commercial production faciUties (9). 

Hydrolysis. Aluminum alkoxides are hydrolysed using either water or sulfuric acid, usually at around 100°C. In addition to the alcohol product, neutral hydrolysis gives high quaUty alumina (see Aluminum compounds) the sulfuric acid hydrolysis yields alum. The cmde alcohols are washed and then fractionated. 

Olefin Sources. The choice of feedstock depends on the alcohol product properties desired, availabiUty of the olefin, and economics. A given producer may either process different olefins for different products or change feedstock for the same appHcation. Feedstocks beheved to be currentiy available are as follows. 

A.luminum Jilkyl Chain Growth. Ethyl, Chevron, and Mitsubishi Chemical manufacture higher, linear alpha olefins from ethylene via chain growth on triethyl aluminum (15). The linear products are then used as oxo feedstock for both plasticizer and detergent range alcohols and because the feedstocks are linear, the linearity of the alcohol product, which has an entirely odd number of carbons, is a function of the oxo process employed. Alcohols are manufactured from this type of olefin by Sterling, Exxon, ICI, BASE, Oxochemie, and Mitsubishi Chemical. 

Catalytic Oligomeri tion. Shell Chemical provides C —C linear internal olefin feedstock for detergent oxo alcohol production from its SHOP... 

Selectivity is primarily a function of temperature. The amount of by-products tends to increase as the operating temperature is raised to compensate for declining catalyst activity. By-product formation is also influenced by catalyst impurities, whether left behind during manufacture or otherwise introduced into the process. Alkaline impurities cataly2e higher alcohol production whereas acidic impurities, as well as trace iron and nickel, promote heavier hydrocarbon formation. 

The process involving aHyl alcohol has not been iadustriaHy adopted because of the high production cost of this alcohol However, if the aHyl alcohol production cost can be markedly reduced, and also if the evaluated cost of hydrogen chloride, which is obtained as a by-product from the substitutive chlorination reaction, is cheap, then this process would have commercial potential. The high temperature propylene—chlorination process was started by SheH Chemical Corporation ia 1945 as an iadustrial process (1). The reaction conditions are a temperature of 500°C, residence time 2—3 s, pressure 1.5 MPa (218 psi), and an excess of propylene to chlorine. The yield of aHyl chloride is 75—80% and the main by-product is dichloropropane, which is obtained as a result of addition of chlorine. Other by-products iaclude monochioropropenes, dichloropropenes, 1,5-hexadiene. At low temperatures, the amount of... 

Either product can be favored over the other by proper selection of catalyst and reaction conditions. However, the principal source of DIPE is as a by-product from isopropyl alcohol production. Typically, excess DIPE is recycled over acidic catalysts ia the alcohol process where it is hydrated to isopropyl alcohol. DIPE is used to a minor extent ia iadustrial extraction and as a solvent. 

Company (Bayway, New Jersey). This was followed in 1921, by the start-up of isopropyl alcohol production in Clendenin, West Virginia, by the Carbide and Carbon Chemicals (Union Carbide) Corporation. The Shell Oil Company began production in the 1930s at Dominguez, California (55). These three companies are the principal domestic manufacturers as of the mid-1990s. 

Price and Demand. In terms of production volume, isopropyl alcohol is about the fourth largest chemical produced from propylene (66). Total 1993 U.S. nameplate capacity for isopropyl alcohol production was 8.48 x 10 metric tons. The total world capacity is about 2.0 x 10 metric tons (Table 4) (126—128). The 1995 U.S. prices were 0.55/L ( 2.10/gal) for refined 91 vol % and 0.62/L ( 2.36/gal) for anhydrous alcohol (129), an increase from the 0.18/L ( 0.70/gal) average price of 1977. The price of isopropyl alcohol is driven by the price of propylene, the primary feedstock, and by the price of ethyl alcohol, a competing solvent. 

Commercial starch is mainly com starch, but smaller amounts of sorghum, wheat, and potato starch are also produced. In 1992, 1303 million bushels (45.8 X 10 m ) of com were ground for starch and other products (120) 1 m com weighs - 721 kg and yields 438 kg starch, 26 kg oil, and 142 kg combined gluten and hulls. In the United States in 1994—1995, 462 million bushels were used to produce high fmctose com symp, 231 million bushels went to produce D-glucose, 533 million bushels were used for alcohol production, and 247 million bushels were converted to starch (121). 

A large volume of sugar is used for alcohol production. 

Suspension Polymerization. At very low levels of stabilizer, eg, 0.1 wt %, the polymer does not form a creamy dispersion that stays indefinitely suspended in the aqueous phase but forms small beads that setde and may be easily separated by filtration (qv) (69). This suspension or pearl polymerization process has been used to prepare polymers for adhesive and coating appHcations and for conversion to poly(vinyl alcohol). Products in bead form are available from several commercial suppHers of PVAc resins. Suspension polymerizations are carried out with monomer-soluble initiators predominantly, with low levels of stabilizers. Suspension copolymerization processes for the production of vinyl acetate—ethylene bead products have been described and the properties of the copolymers determined (70). Continuous tubular polymerization of vinyl acetate in suspension (71,72) yields stable dispersions of beads with narrow particle size distributions at high yields. 

Irish Whiskey. Irish whiskeys are blends of grain and malt spirits three or more years of age that are produced in either the RepubHc of Ireland or Northern Ireland and comply with the respective laws regulating their manufacture. Since no peat is used in the malting process, Irish whiskey lacks the smokey character of Scotch. In the manufacturing process, the malt is soaked in water and milled to produce the wort. The fermentation usually takes about 60 hours. The first distillation in a pot stiU yields a 22—23% alcohol product. A second pot stiU distiUation produces a product that is 45—46% alcohol. This is foUowed by a third distiUation in another pot stiU to yield the Irish whiskey of about 68—70% alcohol. 

Operational temperatures of 4—27°C are maintained. In this process the flavor components are concentrated in the retentate. A reduced alcohol product is obtained by adding back water to give the desired flavor impact. Typical gas chromatographic results, comparing unprocessed 80° proof whiskey with reverse osmosis processed 54° proof whiskey and diluted 54° proof whiskey, indicate good congener retention in the alcohol-reduced (RO) processed whiskey (Table 7). 

Since the acetal exists in equiUbtium with the aldehyde, it is possible for the aldehyde to be released when water is added in a mixed drink, changing the balance and giving a burst of freshness to a mixed drink. Ethyl esters of terpene alcohols in citms oils and other botanicals, plus the ethyl esters of fatty and volatile acids, are formed during prolonged exposure to ethyl alcohol. Certain beverage alcohol products that need to contain milk, eggs, or other protein containing materials must be developed carefully and the added flavors must be considered to prevent the precipitation of the protein and separation of the product. 

Most flavors that are designed for beverage alcohol products use ethanol as the primary solvent for the flavor. Glycerol [56-81-5] propylene glycol [57-55-6] and water are other common solvents in Hquid flavors. Some beverage alcohol concepts require the addition of an emulsified flavor, either as a vehicle to solubilize the oils in the beverage or as a deflberate attempt to cloud the product. This can best be accompHshed at lower proofs with the alcohol breaking the emulsion. 

The principal commercial source of 1-butanol is -butyraldehyde [123-72-8] obtained from the Oxo reaction of propylene. A mixture of n- and isobutyraldehyde [78-84-2] is obtained in this process this mixture is either separated initially and the individual aldehyde isomers hydrogenated, or the mixture of isomeric aldehydes is hydrogenated direcdy and the n- and isobutyl alcohol product mix separated by distillation. Typically, the hydrogenation is carried out in the vapor phase over a heterogeneous catalyst. For example, passing a mixture of n- and isobutyraldehyde with 60 40 H2 N2 over a CuO—ZnO—NiO catalyst at 25—196°C and 0.7 MPa proceeds in 99.95% efficiency to the corresponding alcohols at 98.6% conversion (7,8) (see Butyraldehydes Oxo process). 

In excess of a million metric tons of 0x0 products are produced in the United States annually. They are used in the manufacture of plasticizers, solvents, and detergents. The principal 0x0 alcohol product, 2-ethyl-1-hexanol [104-76-7] is made from propylene [115-07-1] and represents about 75% of the 0x0 market. 

Because enzymes can be intraceUularly associated with cell membranes, whole microbial cells, viable or nonviable, can be used to exploit the activity of one or more types of enzyme and cofactor regeneration, eg, alcohol production from sugar with yeast cells. Viable cells may be further stabilized by entrapment in aqueous gel beads or attached to the surface of spherical particles. Otherwise cells are usually homogenized and cross-linked with glutaraldehyde [111-30-8] to form an insoluble yet penetrable matrix. This is the method upon which the principal industrial appHcations of immobilized enzymes is based. 

Dehydration The growing use of isopropanol as a clean-rinse fluid in microelectronics produces significant quantities of an 8.5-90 percent isopropanol waste. Removing the water and trace contan ii-nants is required before the alcohol can be reused. Pervaporation produces a 99.99 percent alcohol product in one step. It is subsequently polished to remove metals and organics. In Europe, dehydration or ethanol is the largest pei vaporation application. For the very large ethanol plants typical of the United States, pei vaporation is not competitive with thermally integrated distillation. 

Ethanol fermentation is a particularly good example of product accumulation inhibiting the microbial culture. Most strains of yeast have a much slower alcohol production rate when ethanol reaches about ten percent, and the wine or said strains that achieve over 20 percent by volume of ethanol are very, very slow. A system known as the Vacuferm for removal of alcohol by distillation as it is formed is... 

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