Propylene, ammoxidation to acrylonitrile

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. 

Pig. 1. Propylene ammoxidation to acrylonitrile by the SOHIO process. Reprinted from Ref. (8), Cop3rright (1991), with permission from John Wiley Sons, Inc. 

Antimonate-Based Catalysts. In addition to the bismuth-molybdenum oxide catalyst system, several other mixed metal oxides have been identified as effective catalysts for propylene ammoxidation to acrylonitrile. Several were used commercially at various times. In particular, the iron-antimony oxide catalyst is currently used commercially by Nitto Chemical (now Dia-Nitrix Co. Ltd., Japan) and its licensees around the world, although the catalyst was originally discovered and patented by SOHIO (20,21) and by UCB (22). Nitto Chemical improved the basic iron-antimony oxide catalyst with the addition of several elements that promote activity and selectivity to acrylonitrile. Key among these additives are tellurium, copper, molybdenum, vanadium, and tvmgsten (23-25). 

Fig. 2. Mechanism of selective propylene ammoxidation to acrylonitrile over a bismuth molybdate catalyst. Reprinted from Ref. (56), Copyright (1984), with permission from Academic Press, Inc.

Phase Ml (propane oxidative dehydrogenation to propylene function) Phase M2 (propylene ammoxidation to acrylonitrile function) ... 

Solids blending Propylene ammoxidation to acrylonitrile Reduction of iron oxide Coal gasification... 

A two-step process involving conventional nonoxidative dehydrogenation of propane to propylene in the presence of steam, followed by the catalytic ammoxidation to acrylonitrile of the propylene in the effluent stream without separation, is also disclosed (65). 

Oxidation of the allylic carbon of alkenes may lead to allylic alcohols and derivatives or a, 3-unsaturated carbonyl compounds. Selenium dioxide is the reagent of choice to carry out the former transformation. In the latter process, which is more difficult to accomplish, Cr(VI) compounds are usually applied. In certain cases, mixture of products of both types of oxidation, as well as isomeric compounds resulting from allylic rearrangement, may be formed. Oxidation of 2-alkenes to the corresponding cc,p-unsaturated carboxylic acids, particularly the oxidation of propylene to acrolein and acrylic acid, as well as ammoxidation to acrylonitrile, has commercial importance (see Sections 9.5.2 and 9.5.3). 

Metal oxide catalysts are extensively employed in the chemical, petroleum and pollution control industries as oxidation catalysts (e.g., oxidation of methanol to formaldehyde, oxidation of o-xylene to phthalic anhydride, ammoxidation of propylene/propane to acrylonitrile, selective oxidation of HjS to elemental sulfur (SuperClaus) or SO2/SO3, selective catalytic reduction (SCR) of NO, with NHj, catalytic combustion of VOCs, etc.)- A special class of metal oxide catalysts consists of supported metal oxide catalysts, where an active phase (e.g., vanadium oxide) is deposited on a high surface area oxide support (e.g., alumina, titania, ziiconia, niobia, ceria, etc.). Supported metal oxide catalysts provide several advantages over bulk mixed metal oxide catalysts for fundamental studies since (1) the number of surface active sites can be controlled because the active metal oxide is 100% dispersed on the oxide support below monolayer coverage,... 

This preparation procedure also creates solid-state phases that are key to the performance of the Mo-V-Nb-Te-0 catalyst for propane ammoxidation. High activity and selectivity result when the x-ray powder diffraction pattern shows the presence of specific diffraction lines attributed to two separate phases denoted as Ml and M2 by Mitsubishi Chemical Corp. The diffraction lines assigned to these two phases are given in Table 7 (146). The coexistence of these two phases is viewed as key to the successful functioning of the catalyst. Specifically, the Ml phase is purportedly responsible for the oxidative dehydrogenation of propane to propylene, the key intermediate in the reaction network. This reaction sequence, in which the first step is the formation of a propylene intermediate, is the same as noted previously with other propane ammoxidation catalysts, most notably with the V-Sb-0 catalyst (see above). The M2 phase of the Mo-V-Nb-Te-0 catalyst is reportedly the center for the selective ammoxidation of the propylene intermediate to acrylonitrile. As the first-formed intermediate, propylene is apparently the source of all the observed reaction products. Although a detailed kinetic analysis has not been presented, a cursory report, published in Japan, summarized the kinetic experiments for the conversion of propane and propylene over a... 

An in-depth analysis of the solid-state chemistry of the Mo-V-Te-Nb-0 propane ammoxidation catalyst system reveals the details of the two primary phases designated as Ml and M2 (150,151). Correlations of catalytic activity and phase composition for this catalyst system establish the specific functions of the two catalytically active phases (152,153). Specifically, the Ml phase is the phase primarily responsible for propane activation and conversion to acrylonitrile via intermediate, adsorbed propylene. The M2 phase is essentially inactive for propane activation but is capable for conversion desorbed propylene intermediate to acrylonitrile. 

Since then Centi has also examined catalysts based on vanadiitm antimo-nates." Conversion as high as 60-80%, but only 35 0% yields, were obtained with a VSbsWO catalyst supported on alumina. Bowker confirmed Centi s conclusion that the reaction proceeds in two steps." Propane is first dehydrogenated to propylene, which is then ammoxidized to acrylonitrile by the well-established reaction mechanism. 

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). 

Addition of Hydrogen Cyanide. At one time the predominant commercial route to acrylonitrile was the addition of hydrogen cyanide to acetylene. The reaction can be conducted in the Hquid (CuCl catalyst) or gas phase (basic catalyst at 400 to 600°C). This route has been completely replaced by the ammoxidation of propylene (SOHIO process) (see Acrylonitrile). 

Oxidation Catalysis. The multiple oxidation states available in molybdenum oxide species make these exceUent catalysts in oxidation reactions. The oxidation of methanol (qv) to formaldehyde (qv) is generally carried out commercially on mixed ferric molybdate—molybdenum trioxide catalysts. The oxidation of propylene (qv) to acrolein (77) and the ammoxidation of propylene to acrylonitrile (qv) (78) are each carried out over bismuth—molybdenum oxide catalyst systems. The latter (Sohio) process produces in excess of 3.6 x 10 t/yr of acrylonitrile, which finds use in the production of fibers (qv), elastomers (qv), and water-soluble polymers. 

Catalysts. In industrial practice the composition of catalysts are usuaUy very complex. Tellurium is used in catalysts as a promoter or stmctural component (84). The catalysts are used to promote such diverse reactions as oxidation, ammoxidation, hydrogenation, dehydrogenation, halogenation, dehalogenation, and phenol condensation (85—87). Tellurium is added as a passivation promoter to nickel, iron, and vanadium catalysts. A cerium teUurium molybdate catalyst has successfliUy been used in a commercial operation for the ammoxidation of propylene to acrylonitrile (88). 

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. 

Ammoxidation of propylene is considered under oxidation reactions because it is thought that a common allylic intermediate is formed in both the oxidation and ammoxidation of propylene to acrolein and to acrylonitrile, respectively. 

Both fixed and fluid-bed reactors are used to produce acrylonitrile, but most modern processes use fluid-bed systems. The Montedison-UOP process (Figure 8-2) uses a highly active catalyst that gives 95.6% propylene conversion and a selectivity above 80% for acrylonitrile. The catalysts used in ammoxidation are similar to those used in propylene oxidation to acrolein. Oxidation of propylene occurs readily at... 

Ammoxidation of isobutylene to produce methacrylonitrile is a similar reaction to ammoxidation of propylene to acrylonitrile. However, the yield is low. 

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... 

Telescope the Process by Combining Stages. This has been done successfully in the conversion of propylene to acrylonitrile by direct ammoxidation rather than oxidation to acrolein followed by reaction with ammonia in a separate stage, as was described in the earlier patent literature. The oxychlorination of ethylene and HC1 directly to vinyl chloride monomer is another good example of the telescoping of stages to yield an economic process. 

Another industrially important reaction of propylene, related to the one above, is its partial oxidation in the presence of ammonia, resulting in acrylonitrile, H2C=CHCN. This ammoxidation reaction is also catalyzed by mixed metal oxide catalysts, such as bismuth-molybdate or iron antimonate, to which a large number of promoters is added (Fig. 9.19). Being strongly exothermic, ammoxidation is carried out in a fluidized-bed reactor to enable sufficient heat transfer and temperature control (400-500 °C). 

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). 

SNAM (2) An ammoxidation process for converting propylene to acrylonitrile. The catalyst is based on molybdenum/vanadium or bismuth, operated in a fluidized bed. Operated in Europe in 1968. 

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