Coproducts

Styrene is manufactured by alkylating benzene with ethene followed by dehydrogenation, or from petroleum reformate coproduction with propylene oxide. Styrene is used almost exclusively for the manufacture of polymers, of which the most important are polystyrene, ABS plastics and styrene-butadiene rubber. U.S. production 1980 3 megatonnes. 

Further steps m glycolysis use the d glyceraldehyde 3 phosphate formed m the aldolase catalyzed cleavage reaction as a substrate Its coproduct dihydroxyacetone phosphate is not wasted however The enzyme triose phosphate isomerase converts dihydroxyacetone phosphate to d glyceraldehyde 3 phosphate which enters the glycol ysis pathway for further transformations... 

Since 1960, the Hquid-phase oxidation of ethylene has been the process of choice for the manufacture of acetaldehyde. There is, however, stiU some commercial production by the partial oxidation of ethyl alcohol and hydration of acetylene. The economics of the various processes are strongly dependent on the prices of the feedstocks. Acetaldehyde is also formed as a coproduct in the high temperature oxidation of butane. A more recently developed rhodium catalyzed process produces acetaldehyde from synthesis gas as a coproduct with ethyl alcohol and acetic acid (83—94). 

This process comprises passing synthesis gas over 5% rhodium on Si02 at 300°C and 2.0 MPa (20 atm). Principal coproducts are acetaldehyde, 24% acetic acid, 20% and ethanol, 16%. Although interest in new routes to acetaldehyde has fallen as a result of the reduced demand for this chemical, one possible new route to both acetaldehyde and ethanol is the reductive carbonylation of methanol (85). 

Most of the world s acetone is now obtained as a coproduct of phenol by the cumene process, which is used by 21 of 31 producing companies in North America, Western Europe, and Japan. Cumene is oxidi2ed to the hydroperoxide and cleaved to acetone and phenol. The yield of acetone is beheved to average about 94%, and about 0.60—0.62 unit weight of acetone is obtained per unit of phenol (13). 

A yield of about 95% of theoretical is achieved using this process (1.09 units of isopropyl alcohol per unit of acetone produced). Depending on the process technology and catalyst system, such coproducts as methyl isobutyl ketone and diisobutyl ketone can be produced with acetone (30). 

The economics of acetone production and its consequent market position are unusual. Traditional laws of supply and demand cannot be appHed because supply depends on the production of phenol and demand is controUed by the uses of acetone. Therefore, coproduct acetone from the cumene to phenol process will continue to dominate market supply. DeHberate production of acetone from isopropyl alcohol accommodates demand in excess of that suppHed by the phenol process. More than 75% of world and 90% of U.S. production comes from the cumene to phenol process. 

ARCO has developed a coproduct process which produces KA along with propylene oxide [75-56-9] (95—97). Cyclohexane is oxidized as in the high peroxide process to maximize the quantity of CHHP. The reactor effluent then is concentrated to about 20% CHHP by distilling off unreacted cyclohexane and cosolvent tert-huty alcohol [75-65-0]. This concentrate then is contacted with propylene [115-07-1] in another reactor in which the propylene is epoxidized with CHHP to form propylene oxide and KA. A molybdenum catalyst is employed. The product ratio is about 2.5 kg of KA pet kilogram of propylene oxide. 

Because chlorine and caustic soda are electrolysis coproducts and chlorine cannot be stored economically, caustic soda production has been very... 

Chlorine and caustic soda are coproducts of electrolysis of aqueous solutions of sodium chloride [7647-14-5] NaCl, (commonly called brine) following the overall chemical reaction... 

Early demand for chlorine centered on textile bleaching, and chlorine generated through the electrolytic decomposition of salt (NaCl) sufficed. Sodium hydroxide was produced by the lime—soda reaction, using sodium carbonate readily available from the Solvay process. Increased demand for chlorine for PVC manufacture led to the production of chlorine and sodium hydroxide as coproducts. Solution mining of salt and the avadabiHty of asbestos resulted in the dominance of the diaphragm process in North America, whereas soHd salt and mercury avadabiHty led to the dominance of the mercury process in Europe. Japan imported its salt in soHd form and, until the development of the membrane process, also favored the mercury ceU for production. 

Chlorine from Potassium Hydroxide Manufacture. One of the coproducts during the electrolytic production of potassium hydroxide employing mercury and membrane ceHs is chlorine. The combined name plate capacity for caustic potash during 1988 totaled 325,000 t/yr and growth of U.S. demand was expected to be steady at 2% through 1990 (68). 

Synthetic Processes. Traditional Solvay plants produce large volumes of aqueous, chloride-containing waste which must be discharged. This fact, in addition to a noncompetitive cost position, is largely responsible for the demise of U.S. synthetic plants. In countries other than the United States, waste is sent to the ocean, rivers, or deep underground wells. The AC and NA coproduct processes produce less aqueous waste than the traditional Solvay and NA mono processes. Related environmental concerns are added whenever a plant complex includes lime quarries and ammonia-producing equipment. 

Separation of a fat or oil from its source material can be accompHshed by several different methods. Selection of an extraction process is based on (/) obtaining oil substantially undamaged and relatively free of undesirable impurities, (2) achieving the highest practical yield, and (J) obtaining the maximum economic return on the oil and coproducts. 

Manufacture of Fatty Acids and Derivatives. Splitting of fats to produce fatty acids and glycerol (a valuable coproduct) has been practiced since before the 1890s. In early processes, concentrated alkaU reacted with fats to produce soaps followed by acidulation to produce the fatty acids. Acid-catalyzed hydrolysis, mostly with sulfuric and sulfonic acids, was also practiced. Pressurized equipment was introduced to accelerate the rate of the process, and finally continuous processes were developed to maximize completeness of the reaction (105). Lipolytic enzymes maybe utilized to spHt... 

The term feedstock in this article refers not only to coal, but also to products and coproducts of coal conversion processes used to meet the raw material needs of the chemical industry. This definition distinguishes between use of coal-derived products for fuels and for chemicals, but this distinction is somewhat arbitrary because the products involved in fuel and chemical appHcations are often identical or related by simple transformations. For example, methanol has been widely promoted and used as a component of motor fuel, but it is also used heavily in the chemical industry. Frequendy, some or all of the chemical products of a coal conversion process are not isolated but used as process fuel. This practice is common in the many coke plants that are now burning coal tar and naphtha in the ovens. 

Most coal-tar chemicals are recovered from coproduct coke ovens. Since the primary product of the ovens is metallurgical coke, production of coal chemicals from this source is highly dependent on the level of activity in the steel industry. In past years most large coke producers operated thein own coproduct recovery processes. Because of the decline in the domestic steel industry, the recent trend is for independent refiners to coUect cmde coal tars and light oils from several producers and then separate the marketable products. 

In 1990, U.S. coke plants consumed 3.61 x 10 t of coal, or 4.4% of the total U.S. consumption of 8.12 x ICf t (6). Worldwide, roughly 400 coke oven batteries were in operation in 1988, consuming about 4.5 x 10 t of coal and producing 3.5 x 10 t metallurgical coke. Coke production is in a period of decline because of reduced demand for steel and increa sing use of technology for direct injection of coal into blast furnaces (7). The decline in coke production and trend away from recovery of coproducts is reflected in a 70—80% decline in volume of coal-tar chemicals since the 1970s. 

As the economic value of coproducts has decreased, it has become more difficult to provide capital for environmental controls on air emissions and wastewater streams such as toxic phenoHc effluents from chemical recovery operations. Some former coke and manufactured gas sites may require remediation to clean up contaminated soil and groundwater. These difficulties will force the shutdown of some operations and discourage recovery of coproducts in future installations. 

Sasol produces synthetic fuels and chemicals from coal-derived synthesis gas. Two significant variations of this technology have been commercialized, and new process variations are continually under development. Sasol One used both the fixed-bed (Arge) process, operated at about 240°C, as weU as a circulating fluidized-bed (Synthol) system operating at 340°C. Each ET reactor type has a characteristic product distribution that includes coproducts isolated for use in the chemical industry. Paraffin wax is one of the principal coproducts of the low temperature Arge process. Alcohols, ketones, and lower paraffins are among the valuable coproducts obtained from the Synthol process. 

Often the aldehyde is hydrogenated to the corresponding alcohol. In general, addition of carbon monoxide to a substrate is referred to as carbonylation, but when the substrate is an olefin it is also known as hydroformylation. The eady work on the 0x0 synthesis was done with cobalt hydrocarbonyl complexes, but in 1976 a low pressure rhodium-cataly2ed process was commerciali2ed that gave greater selectivity to linear aldehydes and fewer coproducts. 

Synthol coproducts include alcohols, ketones, and lower paraffins. They are used mainly as solvents in the paint and printing industries, although some alcohols are blended into fuels. In 1992 Sasol began producing 17,500 t/yr 1-butanol [71-36-3] from 5-07-acetaldehyde [75-07-0] and plaimed to start a plant to produce high purity ethanol [64-17-5] in 1993. Acetone [67-64-1] and methyl ethyl ketone [78-93-3] are two ketone coproducts sold as solvents. 

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