Mixed metal oxide catalyst

The vapor-phase reduction of acrolein with isopropyl alcohol in the presence of a mixed metal oxide catalyst yields aHyl alcohol in a one-pass yield of 90.4%, with a selectivity (60) to the alcohol of 96.4%. Acrolein may also be selectively reduced to yield propionaldehyde by treatment with a variety of reducing reagents. 

Numerous patents have been issued disclosing catalysts and process schemes for manufacture of acrylonitrile from propane. These include the direct heterogeneously cataly2ed ammoxidation of propane to acrylonitrile using mixed metal oxide catalysts (61—64). 

In the vapor phase, acetone vapor is passed over a catalyst bed of magnesium aluminate (206), 2iac oxide—bismuth oxide (207), calcium oxide (208), lithium or 2iac-doped mixed magnesia—alumina (209), calcium on alumina (210), or basic mixed-metal oxide catalysts (211—214). Temperatures ranging... 

MAA and MMA may also be prepared via the ammoxidation of isobutylene to give meth acrylonitrile as the key intermediate. A mixture of isobutjiene, ammonia, and air are passed over a complex mixed metal oxide catalyst at elevated temperatures to give a 70—80% yield of methacrylonitrile. Suitable catalysts often include mixtures of molybdenum, bismuth, iron, and antimony, in addition to a noble metal (131—133). The meth acrylonitrile formed may then be hydrolyzed to methacrjiamide by treatment with one equivalent of sulfuric acid. The methacrjiamide can be esterified to MMA or hydrolyzed to MAA under conditions similar to those employed in the ACH process. The relatively modest yields obtainable in the ammoxidation reaction and the generation of a considerable acid waste stream combine to make this process economically less desirable than the ACH or C-4 oxidation to methacrolein processes. 

Catalytic alkylation of aniline with diethyl ether, in the presence of mixed metal oxide catalysts, preferably titanium dioxide in combination with molybdenum oxide and/or ferric oxide, gives 63% V/-alkylation and 12% ring alkylation (14). 

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). 

As catalysis proceeds at the surface, a catalyst should preferably consist of small particles with a high fraction of surface atoms. This is often achieved by dispersing particles on porous supports such as silica, alumina, titania or carbon (see Fig. 1.2). Unsupported catalysts are also in use. The iron catalysts for ammonia synthesis and CO hydrogenation (the Fischer-Tropsch synthesis) or the mixed metal oxide catalysts for production of acrylonitrile from propylene and ammonia form examples. 

Seiyama, T., Yamazoe, N., Eguchi, K., Charaeterization and aetivity of some mixed metal oxide catalysts. Ind. Eng. Chem., Product Research and Development, 1985, Volume 24, 19-27. 

An important attribute of these materials comes from the two distinct cationic sites (Oh and Td), and the feasibility of cations migration among them due to the redox nature of metalions, while keeping the spinel structure intact. This particular aspect helps to avoid possible segregation/sintering of metal-ions and remain stable for longer period, compared to a mixed metal oxide catalyst. This unique property of spinels makes them an attractive candidate for number of catalytic reactions. 

Light hydrocarbons consisting of oxygen or other heteroatoms are important intermediates in the chemical industry. Selective hydrocarbon oxidation of alkenes progressed dramatically with the discovery of bismuth molybdate mixed-metal-oxide catalysts because of their high selectivity and activity (>90%). These now form the basis of very important commercial multicomponent catalysts (which may contain mixed metal oxides) for the oxidation of propylene to acrolein and ammoxidation with ammonia to acrylonitrile and to propylene oxide. 

A systematic study to identify solid oxide catalysts for the oxidation of methane to methanol resulted in the development of a Ga203—M0O3 mixed metal oxide catalyst showing an increased methanol yield compared with the homogeneous gas-phase reaction.1080,1081 Fe-ZSM-5 after proper activation (pretreatment under vacuum at 800-900°C and activation with N20 at 250°C) shows high activity in the formation of methanol at 20°C.1082 Density functional theory studies were conducted for the reaction pathway of the methane to methanol conversion by first-row transition-metal monoxide cations (MO+).1083 These are key to the mechanistic aspects in methane hydroxylation, and CuO+ was found to be a likely excellent mediator for the reaction. A mixture of vanadate ions and pyrazine-2-carboxylic acid efficiently catalyzes the oxidation of methane with 02 and H202 to give methyl hydroperoxide and, as consecutive products, methanol and formaldehyde.1084 1085... 

Oxo-metal complexes also intervene as active species in the heterogeneous gas-phase oxidation of hydrocarbons over metal oxide or mixed metal oxide catalysts at high temperatures. Characteristic examples are the bismuth molybdate-catalyzed oxidation of propene to acrolein and the V205-catalyzed oxidation of benzene to maleic anhydride (equations 17 and 18).SJ... 

Each bead represents one catalyst as a member of a library of solid catalysts. It may consist of an unporous material like a-Al2C>3 or Steatit or of typical porous support materials - such as A1203, Si02, Ti02, or the like. These beads can be subjected to different synthesis procedures and sequences like impregnation, coating etc. In addition, full mixed metal oxide catalysts can also be formed as spherical particles. 

Sato, H., Hirose, K., Nagai, K., Yoshioka, H. and Nagaoka, Y. Vapour phase nitration of benzene over solid acid catalysts II. Nitration with nitric acid (1) montmorillonite and mixed metal oxide catalysts, Appl. Catal., A, 1998, 175, 201-207. 

Reaction-induced dispersion may be used as a substitute for conventional preparation methods for supported metal oxides (Wachs and Cai, 2001) it constitutes a particular case of solid—solid wetting, which is proposed to play an important role in catalyst preparation (Leyrer et al., 1990). Industrially relevant mixed metal oxide catalysts can be prepared by reaction-induced dispersion at temperatures that are significantly... 

Bulk Mixed-Metal Oxide Catalysts for Alkane Ammoxidation Reactions... 

Fig. 1. High-resolution transmission electron micrograph of a mixed-metal oxide catalyst (a) and metal-support interaction (b) illustrating the complexity of technological catalysts adapted from (77,72) with permission from Elsevier.

Mo-V-Te and Mo-V-Te-Nb mixed-metal oxide catalysts have been characterized by means of C3H8-TPR and NH3 adsorption calorimetry. All samples were strongly heterogeneous, with initial adsorption heats of = 100-80 kJ moT for the Mo-V-Te samples. Introducing an Nb component into the catalysts slightly decreased the initial adsorption heats to = 60 kJ moT but drastically increased the surface density of weak acid sites (<30kJ moT ) [83]. 

More commonly, uranium has been used as a catalyst component for mixed-metal oxide catalysts for selective oxidation. Probably the most well known of these mixed oxide catalysts are those based on uranium and antimony. The uranium-antimony catalysts are exceptionally active and selective and they have been applied industrially. An interpretation of the catalyst structure and reaction mechanism has been reported by GrasselU and coworkers [42, 43] who discovered the catalyst The USb30io mixed oxide has been extensively used for the oxidation/ammoxida-tion reaction of propylene to acrolein and acrylonitrile. The selective ammoxida-tion of propylene was investigated by GrasseUi and coworkers [44], and it has been demonstrated that at 460 °G a 62.0% selectivity to acrolein with a conversion of 65.2% can be achieved. Furthermore, Delobel and coworkers [45] studied the selective oxidation of propylene over USb30io, which at 340 °C gave a selectivity to acrolein of 96.7%. 

Although hydrotalcites are relahvely stable (up to circa 500 °C), they are also of potential applicahon as precursors of mixed metal oxide catalysts, for example Reference [66]. Dehydrahon-rehydration equilibria account for the switching between hydrotalcites and mixed/supported metal oxides, which is somehmes termed the memory effect [67-69]. Recent advances have seen attempts to prepare highly dispersed LDH systems, such as those dispersed within mesoporous carbon [70]. Owing to widespread interest in their application, hydrotalcite catalysts have been the subject of a number of reviews, for example References [71-75]. Other layered-based systems have also attracted attention for application in catalysis, for example Reference [76]. 

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