Acrylonitrile propylene ammoxidation

Most, if not all, of the acetonitrile that was produced commercially in the United States in 1995 was isolated as a by-product from the manufacture of acrylonitrile by propylene ammoxidation. The amount of acetonitrile produced in an acrylonitrile plant depends on the ammoxidation catalyst that is used, but the ratio of acetonitrile acrylonitrile usually is ca 2—3 100. The acetonitrile is recovered as the water azeotrope, dried, and purified by distillation (28). U.S. capacity (1994) is ca 23,000 t/yr. 

Acrylonitrile is produced in commercial quantities almost exclusively by the vapor-phase catalytic propylene ammoxidation process developed by Sohio... 

Fig. 1. Process flow diagram of the commercial propylene ammoxidation process for acrylonitrile. BFW, boiler feed water.

Because of the large price differential between propane and propylene, which has ranged from 155/t to 355 /1 between 1987 and 1989, a propane-based process may have the economic potential to displace propylene ammoxidation technology eventually. Methane, ethane, and butane, which are also less expensive than propylene, and acetonitrile have been disclosed as starting materials for acrylonitrile synthesis in several catalytic process schemes (66,67). 

Mixed Metal Oxides and Propylene Ammoxidation. The best catalysts for partial oxidation are metal oxides, usually mixed metal oxides. For example, phosphoms—vanadium oxides are used commercially for oxidation of / -butane to give maleic anhydride, and oxides of bismuth and molybdenum with other components are used commercially for oxidation of propylene to give acrolein or acrylonitrile. 

The full cost of acrylonitrile manufacture based on methane was about 22)4/lb in 1960 (allowing 15% return). But the marginal cost—with no capital charges or overheads—was only 7 /lb. The full cost of propylene ammoxidation (with 15% return) was about 13-16ff/lb according to location. Thus, as soon as it was clear that ammoxidation was likely to... 

Acrylonitrile produced industrially via propylene ammoxidation contains trace amounts of benzene. When using Pseudonocardia thermophila JCM3095 or Rhodococcus rhodochrous J-1 as microbial NHase catalyst for conversion of acrylonitrile to acrylamide, concentrations of benzene of <4 ppm produced a significant increase in the reaction rate [16]. Maintaining the concentration of HCN and oxazole at <5 ppm and <10 ppm respectively produced high-quality acrylamide suitable for polymerization. 

Acrylonitrile is produced commercially by the process of propylene ammoxidation, in which propylene, ammonia and air are reacted in a fluidized bed in the presence of a catalyst (EPA 1984, 1985a). Production in the United States has increased gradually over the past 20 years from 304,300 kkgain 1967 (Cogswell 1984) to 1,112,754 kkg in 1987 (USITC 1988). 

Production of acrylonitrile by ammoxidation of propylene (SOHIO process) ... 

Processes based on propane ammoxidation to manufacture acrylonitrile have also been developed,915 966 and BP has announced commercialization.966 Dehydrogenation at high reaction temperature (485-520°C), which is about 100°C higher than for propylene ammoxidation, results in the formation of propylene, which subsequently undergoes normal ammoxidation. Despite higher investments and the markedly lower selectivity (30-40%), the process can be economical because of the price difference between propylene and propane.966 Better selectivites can be achieved at lower (40-60%) conversions. 

Most, if not all, of the acetonitrile produced commercially in the United States recently was isolated as a by-product from the manufacture of acrylonitrile by propylene ammoxidation. The acetonitrile is recovered as the water azeotrope, dried, and purified by distillation. 

Example 2.1 Acrylonitrile by Ammoxidation of Propylene Input/Output Analysis... 

Molybdate based scheelites have been intensively studied in this respect, one reason being that they are found with molybdenum in both the penta- and hexavalent state. Bismuth molybdates in particular are useful catalysts for selective oxidation of propylene to acrolein, propylene ammoxidation to acrylonitrile and the oxidative dehydrogenation of butene to butadiene. 

The Sohio process is considered one of the most successful applications of FCB. Problems in industrial application of the reaction arose from the strong exothermicity of propylene ammoxidation and from the intermediate production of acrylonitrile in the consecutive reactions (V9). It is particularly noticeable that the catalyst gives high selectivity, and the reactor design aims at better fluidization and higher contact efficiency than in the FCC process. 

The most industrially significant and well studied allylic oxidations center around the formation of acrylonitrile from ammoxidation (Eq. 7), and acrolein from oxidation (Eq. 8) of propylene ... 

Specifically, the process makes use of HCN, a very toxic reactant. Difficulties in its acquisition, though, can be met in fact, HCN is a by-product of propylene ammoxidation. Integration of acrylonitrile and MM A products requires the balance... 

Desulfurization of petroleum feedstock (FBR), catalytic cracking (MBR or FI BR), hydrodewaxing (FBR), steam reforming of methane or naphtha (FBR), water-gas shift (CO conversion) reaction (FBR-A), ammonia synthesis (FBR-A), methanol from synthesis gas (FBR), oxidation of sulfur dioxide (FBR-A), isomerization of xylenes (FBR-A), catalytic reforming of naphtha (FBR-A), reduction of nitrobenzene to aniline (FBR), butadiene from n-butanes (FBR-A), ethylbenzene by alkylation of benzene (FBR), dehydrogenation of ethylbenzene to styrene (FBR), methyl ethyl ketone from sec-butyl alcohol (by dehydrogenation) (FBR), formaldehyde from methanol (FBR), disproportionation of toluene (FBR-A), dehydration of ethanol (FBR-A), dimethylaniline from aniline and methanol (FBR), vinyl chloride from acetone (FBR), vinyl acetate from acetylene and acetic acid (FBR), phosgene from carbon monoxide (FBR), dichloroethane by oxichlorination of ethylene (FBR), oxidation of ethylene to ethylene oxide (FBR), oxidation of benzene to maleic anhydride (FBR), oxidation of toluene to benzaldehyde (FBR), phthalic anhydride from o-xylene (FBR), furane from butadiene (FBR), acrylonitrile by ammoxidation of propylene (FI BR)... 

Table 11.15 lists the average commercial specifications of acrylonitrile and of the byproducts formed in propylene ammoxidation (acetonitrile and hydrogen cyanide). 

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