Acetaldehyde, manufacture

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. 

FIGURE 1 Acetaldehyde manufacture by the single-stage process. 

FIGURE 2 Acetaldehyde manufacture by carbonylation of methyl alcohol (methanol). 

Fig. 10.14. Two-stage acetaldehyde process. (Encyclopedia of Chemical Technology, Kirk and Othmer, Web site ed., acetaldehyde, manufacture, 2002. Copyright by John Wiley Sons, Inc. and reproduced by permission of the copyright owned...

Chemical Safety Data Sheet SD-43, Properties and Essential Information for Safe Handling and Use of Acetaldehyde, Manufacturing Chemists Association, Inc., Washington, D.C., 1952. 

In addition to plants already existing at Farbwerke Hoechst A. G. and Wacker Chemie G.m.b.H. in Germany, other plants have been or are being built by Rhone-Poulenc, France Societa Edison, Italy Pemex, Mexico Celanese Corp. at Bay City, Tex. and Shawinigan Chemicals Ltd., Canada. Plants are also being installed in Japan. Some use the one-stage, others the two-stage process for acetaldehyde manufacture, licensed by the Aldehyd G.m.b.H. 

Acetaldehyde Manufacture, BIOS Final Rept. 1049, U. S. Department of Commerce Office of Technical Services, PB-79186, 1946. 

Up to 600 tons of methylmercury were discharged into Minamata Bay, Japan, between 1932 and 1971 from acetaldehyde manufacturing plants. Human fatalities were documented beginning in 1953 from consumption of methylmercury-contaminated fish and shellfish from the Bay. By 1993, about 2000 victims of Minamata Disease were identified including more than 100 deaths and 59 congenital birth defects from a total regional population of about 200,000 however, at least 10,000... 

Developments in acetaldehyde manufacture allowed acetaldehyde oxidation to remain competitive with, or superior to, Co catalyzed methanol carbonylation and butane oxidation throughout the period 1945-1970 as a means of generating acetic acid. First, as mentioned earlier, ethanol was now available from ethylene via hydration, which lowered the cost of ethanol. Therefore, the oxidative dehydration of ethanol (equation [14]) was now more attractive than when ethanol was derived from fermentation. 

First World War, were based on the oxidation of acetaldehyde derived from either acetylene or fermentation ethanol. The latter could well return to favour in countries such as Brazil (section 12.7.1.). After the Second World War, fermentation ethanol gave way to synthetic ethanol, via the direct hydration of ethylene. (Synthetic ethanol made by the sulphuric acid process had already made some inroads in the U.S.A.). From 1960 onwards, the Wacker oxidation of ethylene added a further option for acetaldehyde manufacture. 

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). 

Acetylation of acetaldehyde to ethyUdene diacetate [542-10-9], a precursor of vinyl acetate, has long been known (7), but the condensation of formaldehyde [50-00-0] and acetic acid vapors to furnish acryflc acid [97-10-7] is more recent (30). These reactions consume relatively more energy than other routes for manufacturing vinyl acetate or acryflc acid, and thus are not likely to be further developed. Vapor-phase methanol—methyl acetate oxidation using simultaneous condensation to yield methyl acrylate is still being developed (28). A vanadium—titania phosphate catalyst is employed in that process. 

Acetaldehyde. Acetaldehyde [75-07-0] C2H4O, (qv) was formerly manufactured principally by hydration of acetylene. 

The reaction is very exothermic. The heat of reaction of propylene oxidation to acrolein is 340.8 kJ /mol (81.5 kcal/mol) the overall reactions generate approximately 837 kJ/mol (200 kcal/mol). The principal side reactions produce acryUc acid, acetaldehyde, acetic acid, carbon monoxide, and carbon dioxide. A variety of other aldehydes and acids are also formed in small amounts. Proprietary processes for acrolein manufacture have been described (25,26). 

Aldehydes fiad the most widespread use as chemical iatermediates. The production of acetaldehyde, propionaldehyde, and butyraldehyde as precursors of the corresponding alcohols and acids are examples. The aldehydes of low molecular weight are also condensed in an aldol reaction to form derivatives which are important intermediates for the plasticizer industry (see Plasticizers). As mentioned earlier, 2-ethylhexanol, produced from butyraldehyde, is used in the manufacture of di(2-ethylhexyl) phthalate [117-87-7]. Aldehydes are also used as intermediates for the manufacture of solvents (alcohols and ethers), resins, and dyes. Isobutyraldehyde is used as an intermediate for production of primary solvents and mbber antioxidants (see Antioxidaisits). Fatty aldehydes Cg—used in nearly all perfume types and aromas (see Perfumes). Polymers and copolymers of aldehydes exist and are of commercial significance. 

Chemical Uses. In Europe, products such as ethylene, acetaldehyde, acetic acid, acetone, butadiene, and isoprene have been manufactured from acetylene at one time. Wartime shortages or raw material restrictions were the basis for the choice of process. Coking coal was readily available in Europe and acetylene was easily accessible via calcium carbide. 

Commercial Manufacture of Pyridine. There are two vapor-phase processes used in the industry for the synthesis of pyridines. The first process (eq. 21) uti1i2es formaldehyde and acetaldehyde as a co-feed with ammonia, and the principal products are pyridine (1) and 3-picoline (3). The second process produces only alkylated pyridines as products. 

Other minor uses of ethyl chloride iaclude blowiag agents for thermoplastic foam (51) and styrene polymer foam (52), the manufacture of polymeric ketones used as lube oil detergents (53), the manufacture of acetaldehyde (qv) (54), as an aerosol propellent (55), as a refrigerant (R-160), ia the preparation of acid dyes (56), and as a local or general anesthetic (57,58). 

Manufacture. Cinnamaldehyde is routinely produced by the base-cataly2ed aldol addition of ben2aldehyde /7(9(9-with acetaldehyde [75-07-0], a procedure which was first estabUshed in the nineteenth century (31). Formation of the (H)-isomer is favored by the transition-state geometry associated with the elimination of water from the intermediate. The commercial process is carried out in the presence of a dilute sodium hydroxide solution (ca 0.5—2.0%) with at least two equivalents of ben2aldehyde and slow addition of the acetaldehyde over the reaction period (32). 

Manufacturing Processing and Uses. In commercial production, aqueous urea solution is mixed with acetaldehyde in 1 1 molar ratios. An acid catalyst is introduced into the reaction mixture which is staged at various process temperatures. After neutralization with a base, the CDU is separated from the mother hquor by filtration or spray drying. 

Health and Safety Factors (Toxicology). Manufacture of cyanamide and calcium cyanamide does not present any serious health hazard. Ingestion of alcohoHc beverages by workmen within several hours of leaving work sometimes results in a vasomotor reaction known as cyanamide flush. Cyanamide interferes with the oxidation of alcohol and accumulation of acetaldehyde probably accounts for this temporary phenomenon. Although extremely unpleasant, it has not been known to result in serious illness or to have any permanent effect. 

Acetaldehyde Cyanohydrin. This cyanohydrin, commonly known as lactonitnle, is soluble in water and alcohol, but insoluble in diethyl ether and carbon disulfide. Lactonitnle is used chiefly to manufacture lactic acid and its derivatives, primarily ethyl lactate. Lactonitnle [78-97-7] is manufactured from equimolar amounts of acetaldehyde and hydrogen cyanide containing 1.5% of 20% NaOH at —10 20 ° C. The product is stabili2ed with sulfuric acid (28). Sulfuric acid hydroly2es the nitrile to give a mixture of lactic acid [598-82-3] and ammonium bisulfate. 

Cyclopentadiene itself has been used as a feedstock for carbon fiber manufacture (76). Cyclopentadiene is also a component of supported metallocene—alumoxane polymerization catalysts in the preparation of syndiotactic polyolefins (77), as a nickel or iron complex in the production of methanol and ethanol from synthesis gas (78), and as Group VIII metal complexes for the production of acetaldehyde from methanol and synthesis gas (79). 

Most of the vinyl acetate produced in the United States is made by the vapor-phase ethylene process. In this process, a vapor-phase mixture of ethylene, acetic acid, and oxygen is passed at elevated temperature and pressures over a fixed-bed catalyst consisting of supported palladium (85). Less than 70% oxygen, acetic acid, and ethylene conversion is realized per pass. Therefore, these components have to be recovered and returned to the reaction zone. The vinyl acetate yield using this process is typically in the 91—95% range (86). Vinyl acetate can be manufactured also from acetylene, acetaldehyde, and the hquid-phase ethylene process (see Vinyl polymers). 

Direct Hydration of Ethylene. Hydration of ethylene to ethanol via a Hquid-phase process cataly2ed by dilute sulfuric acid was first demonstrated more than a hundred years ago (82). In 1923, the passage of an ethylene-steam mixture over alumina at 300°C was found to give a small yield of acetaldehyde, and it was inferred that this was produced via ethanol (83). Since the late 1920s, several industrial concerns have expressed interest in producing ethanol synthetically from ethylene over soHd catalysts. However, not until 1947 was the first commercial plant for the manufacture of ethanol by catalytic hydration started in the United States by Shell the same process was commerciali2ed in the United Kingdom in 1951. 

Other Methods of Preparation. In addition to the direct hydration process, the sulfuric acid process, and fermentation routes to manufacture ethanol, several other processes have been suggested. These include the hydration of ethylene by dilute acids, the hydrolysis of ethyl esters other than sulfates, the hydrogenation of acetaldehyde, and the use of synthesis gas. None of these methods has been successfilUy implemented on a commercial scale, but the route from synthesis gas has received a great deal of attention since the 1974 oil embargo. 

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