11.4 ACRYLONITRILE Discovered in 1893 by the Frenchman Charles Moreu, acrylonitrile (d?° = 0.806, mp = —83.5°C, bp, o13 = 77.3°C) remained a laboratory curiosity until the end of the First World War. Its industrial importance emerged around 1930, when it was used in Germany and the United States to manufacture nitrile rubber, Buna N, a copolymer of butadiene and acrylonitrile, displaying high resistance to hydrocarbons. Since then, its applications have expanded considerably, including textile fibers, synthetic resins, elas- tomers, and intermediates of organic syntheses. Nearly all the acrylonitrile produced worldwide is obtained by the ammoxidation of propylene. Furthermore, nearly 90 per cent of installed production capacities employ the Sohio process. This company has developed a whole series of increasingly better- performing catalysts, with the first commercial achievement dating from 1960. The other technologies of this type offering an industrial character are those of Chemie Linz OSW (Osterreichische Stickstoff Werke), Montedison/UOP (Universal Oil Products), SNAM (Societa Nazionale Metanodotti), Ugine/ Distillers (PCUK/Distillers). (6) Specific gravity, 68.0/39.2. The earlier methods were the following: (a) Addition of hydrogen cyanide to ethylene oxide to form cyanohydrin, which is then dehydrated to acrylonitrile. Developed by 1G Farben, this process was adopted by American Cyanamid and Union Carbide, and then abandoned in 1965. (b) Reaction of hydrogen cyanide with acetylene, developed by Bayer, used by Amer- ican Cyanamid, Du Pont, Monsanto until 1970. (c) Production of lactonitrile from acetaldehyde and hydrogen cyanide, and its dehy- dration to acrylonitrile. Developed and industrialized by Hoechst in Greisheim (Knapsack-Greisheim) until 1959, it is still partly used by the Japanese company Nusashino to manufacture lactic acid by lactonitrile hydrolysis. (d) Ammoxidation of propylene by nitrogen oxides, commercialized by Du Pont in Beaumont, Texas, until 1966 Many developments are currently under way to employ ethylene, propane and butane directly. 11.4.1. Acrylonitrile manufacture by ammoxidation of propylene Although a large number of its basic patents already lie in the public domain, the process commercialized by Sohio, concerning the ammoxidation of propylene, has acquired a virtual monopoly in view of the technological know-how accumulated in the past decade. 1.4.1.1 Transformation principle ‘The formation of acrylonitrile by ammoxidation occurs according to the following highly exothermic reaction: CH,=CH—CH, + NH, + 3/20, + CH,=CH—CN + 3H,0 AHS og = $15 kJ/molIt now appears clear that this overall result can be explained by the production of acrolein as the main intermediate. In these conditions, the reaction scheme is as follows: CH,=CH-—CH, + 0, > CH) =CH—CHO + H,0 (CH, =CH—CHO + NH, + CH,=CH—CH=NH +H,0 CH, =CH—CH=NH + 1/20, + CH,=CH-CN + H,0 This transformation is also characterized by the importance assumed by degradation side reactions of propylene and of its oxygen and nitrogen derivatives, which lead simultaneously to the formation of hydrogen cyanide, acetonitrile, nitrogen, carbon monoxide and carbon dioxide: 2CH, =CH—CHy + 3NH; + 30, + 3CH,CN + 6H,0 CH, =CH—CH, + 3NH, + 30, + 3HCN + 6H,0 CH, =CH—CH, + 30, > 3CO + 3H,0 2CH, =CH—CH, +90, + 6CO, + 6H,0 Since these reactions are themselves highly exothermic, it is found in practice that the total exothermicity of acrylonitrile manufacture is higher than indicated by theory, and is as high as 650 to 670 kJ/mol. A. Catalysts To offset the lower yield resulting from the development of side reactions, many catalyst formulations have been suggested, and their performance has steadily improved with time. They are all using mixed oxides based on antimony, arsenic, bismuth, cobalt, tin, iron, molybdenum, nickel, phosphorus, rare earths, tellurium, uranium, vanadium, etc., with or without a support. The most significant development was achieved by Sohio, who initially employed bismuth phosphomolybdate. This system was replaced in 1967 by a mixture based on oxides of antimony and uranium (catalyst 21). In 1972, Sohio then returned to an iron and bismuth phosphomolybdate (catalyst 41‘) doped by additions of cobalt, nickel and potassium, and achieving acrylonitrile productivity gains of 10 to 35 per cent. A fourth generation of catalysts (type 49) finally emerged in 1978, achieving a slight improvement in yield, but offering better mechanical properties. Cooperation between Distillers and PCUK, followed by Border Chemicals, was ori- ginally based on the development of a two-step process. In the first step, propylene was converted to acrolein on a catalyst based on selenium and copper oxides, and, in the second step, ammonia reacted in the presence of a system including MoO, and various other compounds. A single-step technology was subsequently developed, involving the use of molybdenum oxide promoted by caustic soda, or cobalt molybdate and tellurium oxide, followed by the use of systems of antimony and tin oxides. The best results are now obtained with formulations based on cobalt, iron and molybdenum. While SNAM developed mixtures based on the use of bismuth and vanadium com- pounds, Montedison, whose exclusive operating license was acquired in 1975 by UOP, preferred a supported catalyst based on oxides of cerium, molybdenum and tellurium on silica. OSW employs a mixture of metallic bismuth and molybdenum deposited on a support. The latest developments in catalysts for manufacturing acrylonitrile are those of the Japanese firm Nitto Chemical, which commercialized a system in 1974 based on doped antimony and iron, called NS 733A or catalyst 13, offering higher productivity in com- parison with Sohio catalyst 41, as well as lower production of acetonitrile and hydrogen cyanide by-products.These formulations, which operate in the vapor phase, are preferably used in a fluidized bed, to facilitate the removal of the heat generated by the reaction, the homogenization of the thermal level within the reaction medium, better temperature control and hence superior catalyst performance (Sohio, Montedison|UOP, Nitto, etc.). However, this arrangement implies improved mechanical properties. Fixed beds have also been used (PCUK/Distillers/Border, SNAM, Chemie-Linz, etc.), the main problem being the need to withstand a thermal gradient, and possibly the existence of hot points causing the accelerated destruction of the catalyst due to the migration of active phases and to attrition. Apparent residence times range from 2 to 15 s, and catalyst life is generally between one and three years, and possibly more with the latest formulations. B. Operating conditions As a rule, the ammoxidation of propylene takes place in the presence of a slight excess of ammonia and oxygen in comparison with stoichiometry. The purity of the reactants employed is generally high (over 90 per cent weight for propylene, and 99.5 per cent weight for ammonia). With certain catalyst systems, especially the first-generation systems, the addition of steam raises selectivity and limits the conversion of ammonia to nitrogen. However, the current trend, due to the improvement in catalyst performance and the advances in metallurgy, is to eliminate this water hold-up to achieve better optimization of the energy balance of the operation. Table 11.12 lists a number of typical molar feed compositions depending on catalyst type. Experience shows that the acrylonitrile yield increases with the NH ,/propylene ratio. In practice, however, stoichiometry is approached as closely as possible (ratio of 1), and, in certain cases, operations are even conducted at sub-stoichiometric values (0.8). This is because the reaction is normally incomplete, and the ammonia remaining in the reactor exit gases, independent of the initial excess, gives rise to side reactions. These can be avoided by rapidly neutralizing it by sulfuric acid. Thus increasing the NH,/pro- pylene ratio results in needless losses of raw materials, with repercussions at the economic level. From this standpoint, research projects under way are directed both for the develop- ment of better-performing catalysts and the development of ammonia recovery techniques, which allow for its recycling while maintaining high acrylonitrile selectivity. The reaction temperature usually ranges between 400 and 500°C and pressure remains below 0.3 . 10° Pa absolute. The acrylonitrile/acetonitrile molar ratio rises rapidly above 400°C, and reaches a peak around 470 to 480°C. C. Performance Once-through conversion of propylene is virtually complete, that of ammonia is higher in a fluidized bed (over 95 per cent) than in a fixed bed (=85 per cent). Selectivity, and consequently the acrylonitrile transformation yield, is very sensitive to the type of catalyst and to the operating conditions, especially the residence time, which must remain above 1 s. The yield may be as high as 72 to 75 molar per cent with the latest catalyst systems operating in a fluidized bed, and nearly 78 molar per cent with those operating in a fixed bed. Table 11.13 offers some indications about the typical effluent compositions leaving the propylene ammoxidation reactor according to the technology implemented. It also reveals the high proportion of by-products, whose utilization after separation and puri fication can influence the economics of the operation considerably. Thus the acetonitrile, which could be used as a butadiene extraction solvent, is usually burned. Another possibility is to convert it to acrylonitrile by the following reaction: CH,CN + CH, + 0, + H,O + CH, =CH—CN + CO, + CO +H: (7) Sohio’s catalyst 41 formulation is as follows: Cog. Fe Nip. Bi Po.s Koor M SOyeevsessscacsvecaeets 82.5 per cent weight «175 per cent weight