Material acrylonitrile production

The propylene-based process developed by Sohio was able to displace all other commercial production technologies because of its substantial advantage in overall production costs, primarily due to lower raw material costs. Raw material costs less by-product credits account for about 60% of the total acrylonitrile production cost for a world-scale plant. The process has remained economically advantaged over other process technologies since the first commercial plant in 1960 because of the higher acrylonitrile yields resulting from the introduction of improved commercial catalysts. Reported per-pass conversions of propylene to acrylonitrile have increased from about 65% to over 80% (28,68—70). 

Essentially all the ammonium sulfate fertilizer used in the United States is by-product material. By-product from the acid scmbbing of coke oven gas is one source. A larger source is as by-product ammonium sulfate solution from the production of caprolactam (qv) and acrylonitrile, (qv) which are synthetic fiber intermediates. A third but lesser source is from the ammoniation of spent sulfuric acid from other processes. In the recovery of by-product crystals from each of these sources, the crystallization usually is carried out in steam-heated sa turator—crystallizers. Characteristically, crystallizer product is of a particle size about 90% finer than 16 mesh (ca 1 mm dia), which is too small for satisfactory dry blending with granular fertilizer materials. Crystals of this size are suitable, however, as a feed material to mixed fertilizer granulation plants, and this is the main fertilizer outlet for by-product ammonium sulfate. 

Acrylonitrile Is produced from propene, ammonia, and oxygen by the following balanced equation (see Example 14-5) 2 C3 Hg + 2 NH3 + 3 O2 2 CH2 CHCN -1- 6 H2 O Relate the rates of reaction of starting materials and products. 

Residual acrylonitrile monomer may also occur in commercially-made polymeric materials used in rugs and other products. Estimated levels include acrylic and modacrylic fibers (less than 1 mg acrylonitrile/kg polymeric material), acrylonitrile-based resins (15 to 50 mg/kg), and nitrile rubber and latex (0 to 750 mg/kg) (IARC 1979 Miller and Villaume 1978). It is possible that acrylonitrile may evaporate into air or leach into water from these products, but no data on this topic were located. 

Propene is used as a starting material for numerous other compounds. Chief among these are isopropyl alcohol, acrylonitrile, and propylene oxide. Isopropyl alcohol results from the hydration of propylene during cracking and is the primary chemical derived from propylene. Isopropyl alcohol is used as a solvent, antifreeze, and as rubbing alcohol, but its major use is for the production of acetone. Acrylonitrile is used primarily as a monomer in the production of acrylic fibers. Polymerized acrylonitrile fibers are produced under the trade names such as Orion (DuPont) and Acrilan (Monsanto). Acrylonitrile is also a reactant in the synthesis of dyes, pharmaceuticals, synthetic rubber, and resins. Acrylonitrile production occurs primarily through ammoxidation of propylene CH3- CH = CH2 + NH3 + 1.5 02—> CH2 = CH - C = N + 3 H20. 

Recently, products composed of styrene, acrylonitrile, and maleic anhydride have been introduced as improvements over the older ABS materials. These products exhibit superior heat resistance and thermal stability in comparison to conventional ABS materials. In addition, the impact resistance of styrene-acrylonitrile-maleic anhydride terpolymers can be improved by the addition of or by grafting onto appropriate elastomers. The product also exhibits desirable rheological behavior due to polar interaction of anhydride groups during processing and drawing. 

Acrylonitrile is used in the production of acrylic fibers, resins, and surface coating as an intermediate in the production of pharmaceuticals and dyes as a polymer modifier and as a fumigant. It may occur in fire-effluent gases because of pyroly-ses of polyacrylonitrile materials. Acrylonitrile was found to be released from the acrylonitrile-styrene copolymer and acrylonitrile-styrene-butadiene copolymer bottles when these bottles were filled wifh food-simulating solvents such as water, 4% acetic acid, 20% ethanol, and heptane and stored for 10 days to 5 months (Nakazawa et al. 1984). The release was greater with increasing temperature and was attributable to the residual acrylonitrile monomer in the polymeric materials. 

The major process currently operated on the commercial scale is known as the acetone cyanohydrin (23) (ACN) process [14]. This process uses readily available cheap raw materials (Scheme 2.3). Acetone is produced from propylene and hydrogen cyanide or can be obtained as a byproduct from acrylonitrile production. Acrylonitrile is manufactured via propylene ammoxidation or by catalytic ammoxidation of natural gas. Sulphuric acid is readily available but constitutes the major environmental problem of the acetone cyanohydrin process since a large excess is required to effect the hydrolysis of acetone cyanohydrin to form the methacrylamide sulphate intermediate. 

The propylene route does not give particularly high yields of acrylonitrile but it is attractive in that raw material costs are low and hydrogen cyanide is obtained as a valuable by-product. This route therefore now dominates acrylonitrile production. 

Because of its relatively high, price, there have been continuing efforts to replace acetylene in its major appHcations with cheaper raw materials. Such efforts have been successful, particularly in the United States, where ethylene has displaced acetylene as raw material for acetaldehyde, acetic acid, vinyl acetate, and chlorinated solvents. Only a few percent of U.S. vinyl chloride production is still based on acetylene. Propjiene has replaced acetylene as feed for acrylates and acrylonitrile. Even some recent production of traditional Reppe acetylene chemicals, such as butanediol and butyrolactone, is based on new raw materials. 

Ammonia is used in the fibers and plastic industry as the source of nitrogen for the production of caprolactam, the monomer for nylon 6. Oxidation of propylene with ammonia gives acrylonitrile (qv), used for the manufacture of acryHc fibers, resins, and elastomers. Hexamethylenetetramine (HMTA), produced from ammonia and formaldehyde, is used in the manufacture of phenoHc thermosetting resins (see Phenolic resins). Toluene 2,4-cHisocyanate (TDI), employed in the production of polyurethane foam, indirectly consumes ammonia because nitric acid is a raw material in the TDI manufacturing process (see Amines Isocyanates). Urea, which is produced from ammonia, is used in the manufacture of urea—formaldehyde synthetic resins (see Amino resins). Melamine is produced by polymerization of dicyanodiamine and high pressure, high temperature pyrolysis of urea, both in the presence of ammonia (see Cyanamides). 

With each succeeding year in the 1950s and 1960s there was a swing away from coal and vegetable sources of raw materials towards petroleum. Today such products as terephthalic acid, styrene, benzene, formaldehyde, vinyl acetate and acrylonitrile are produced from petroleum sources. Large industrial concerns that had been built on acetylene chemistry became based on petrochemicals whilst coal tar is no longer an indispensable source of aromatics. 

The common feature of these materials was that all contained a high proportion of acrylonitrile or methacrylonitrile. The Vistron product, Barex 210, for example was said to be produced by radical graft copolymerisation of 73-77 parts acrylonitrile and 23-27 parts by weight of methyl acrylate in the presence of a 8-10 parts of a butadiene-acrylonitrile rubber (Nitrile rubber). The Du Pont product NR-16 was prepared by graft polymerisation of styrene and acrylonitrile in the presence of styrene-butadiene copolymer. The Monsanto polymer Lopac was a copolymer of 28-34 parts styrene and 66-72 parts of a second monomer variously reported as acrylonitrile and methacrylonitrile. This polymer contained no rubbery component. 

In addition to polystyrene and high-impact polystyrene there are other important styrene-based plastics. Most important of these is ABS, with a global capacity of about 5 X 10 t.p.a. and production of about 3 X 10 t.p.a. The styrenic PPO materials reviewed in Chapter 21 have capaeity and production figures about one-tenth those for ABS. Data for the more specialised styrene-acrylonitrile copolymers are difficult to obtain but consumption estimates for Western Europe in the early 1990s were a little over 60000 t.p.a. 

The term ABS was originally used as a general term to describe various blends and copolymers containing acrylonitrile, butadiene and styrene. Prominent among the earliest materials were physical blends of acrylonitrile-styrene copolymers (SAN) (which are glassy) and acrylonitrile-butadiene copolymers (which are rubbery). Such materials are now obsolete but are referred to briefly below, as Type 1 materials, since they do illustrate some basic principles. Today the term ABS usually refers to a product consisting of discrete cross-linked polybutadiene rubber particles that are grafted with SAN and embedded in a SAN matrix. 

PROPENE The major use of propene is in the production of polypropylene. Two other propene-derived organic chemicals, acrylonitrile and propylene oxide, are also starting materials for polymer synthesis. Acrylonitrile is used to make acrylic fibers (see Table 6.5), and propylene oxide is one component in the preparation oi polyurethane polymers. Cumene itself has no direct uses but rather serves as the starting material in a process that yields two valuable industrial chemicals acetone and phenol. 

An example of the way in which process competition works in the manufacture of plastics is the story of acrylonitrile. The first process for the production of this plastic was based upon the reaction between hydrogen cyanide and acetylene, both hard to handle, poisonous, and explosive chemicals. The raw material costs were relatively low as compared to materials for other monomers, but the plant investment and manufacturing costs were too high. As a result, originally acrylonitrile monomer (1950s) sold for about 30 cents per pound and the future of the material looked dim as other plastics such as polyethylene became available at much lower prices due to their lower production costs. 

---