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Maleic metal oxide catalysts

A variety of metal oxides (e.g. V2O5) have been employed for oxidation reactions, besides noble metals (e.g. Pt and Ag). Auto-exhaust catalysts employ metals such as Rh, Pd and Pt besides Ce02 and other oxides. The use of metal oxide catalysts for oxidation reactions has been discussed quite widely in the literature (Grasselli Brazdil, 1985). Perovskite oxides of the type CaMn03 and Laj A jM03 (A = Ca, Sr M = Co, Mn) are excellent candidates as oxidation catalysts. The 14-electron oxidation of butane to maleic anhydride is effectively carried out over phosphorus vanadium oxide catalysts of the type VOPO4 (Centi et al., 1988). [Pg.523]

The present chapter will primarily focus on oxidation reactions over supported vanadia catalysts because of the widespread applications of these interesting catalytic materials.5 6,22 24 Although this article is limited to well-defined supported vanadia catalysts, the supported vanadia catalysts are model catalyst systems that are also representative of other supported metal oxide catalysts employed in oxidation reactions (e.g., Mo, Cr, Re, etc.).25 26 The key chemical probe reaction to be employed in this chapter will be methanol oxidation to formaldehyde, but other oxidation reactions will also be discussed (methane oxidation to formaldehyde, propane oxidation to propylene, butane oxidation to maleic anhydride, CO oxidation to C02, S02 oxidation to S03 and the selective catalytic reduction of NOx with NH3 to N2 and H20). This chapter will combine the molecular structural and reactivity information of well-defined supported vanadia catalysts in order to develop the molecular structure-reactivity relationships for these oxidation catalysts. The molecular structure-reactivity relationships represent the molecular ingredients required for the molecular engineering of supported metal oxide catalysts. [Pg.38]

Catalytic oxidation is the most important technology for the conversion of hydrocarbon feedstocks (olefins, aromatics and alkanes) to a variety of bulk industrial chemicals.1 In general, two types of processes are used heterogeneous, gas phase oxidation and homogeneous liquid phase oxidation. The former tend to involve supported metal or metal oxide catalysts e.g. in tne manufacture of ethylene oxide, acrylonitrile and maleic anhydride whilst the latter generally employ dissolved metal salts, e.g. in the production of terephthalic acid, benzoic acid, acetic acid, phenol and propylene oxide. [Pg.33]

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... [Pg.324]

Bulk mixed metal oxide catalytic materials consist of multiple metal oxide components. Such mixed metal oxide catalysts find wide application as selective oxidation catalysts for the synthesis of chemical intermediates. For example, bulk iron-molybdate catalysts are employed in the selective oxidation of CH3OH to H2CO [122], bulk bismuth-molybdates are the catalysts of choice for selective oxidation of CH2=CHCH3 to acrolein (CH2=CHCHO) and its further oxidation to acrylic acid (CH2=CHCOOH) [123], selective ammoxidation of CH2=CHCH3 to acrylonitrile (CH2=CHCN) [123], and selective oxidation of linear CH3CH2CH2CH3 to cyclic maleic anhydride consisting of a flve-membered ring (four carbons and one O atom) [124]. The characterization of the surface... [Pg.24]

It can be argued that some mixed metal oxides can also be technically considered as supported metal oxide catalysts because the surface is discernibly different from the underlying mixed metal oxide in terms of composition and molecular structure. For example, the vanadium phosphorus oxide (VPO) catalyst is used in the commercial production of maleic anhydride from butane [12]. The most active crystal phase is the vanadium pyrophosphate (VO)2P207, and the surface structure proposed to be the active phase is a nanometer-thick amorphous VPO layer enriched in phosphorus [12,15]. As another example, Wachs and coworkers [16]... [Pg.32]

In addition to these principal commercial uses of molybdenum catalysts, there is great research interest in molybdenum oxides, often supported on siHca, ie, MoO —Si02, as partial oxidation catalysts for such processes as methane-to-methanol or methane-to-formaldehyde (80). Both O2 and N2O have been used as oxidants, and photochemical activation of the MoO catalyst has been reported (81). The research is driven by the increased use of natural gas as a feedstock for Hquid fuels and chemicals (82). Various heteropolymolybdates (83), MoO.-containing ultrastable Y-zeoHtes (84), and certain mixed metal molybdates, eg, MnMoO Ee2(MoO)2, photoactivated CuMoO, and ZnMoO, have also been studied as partial oxidation catalysts for methane conversion to methanol or formaldehyde (80) and for the oxidation of C-4-hydrocarbons to maleic anhydride (85). Heteropolymolybdates have also been shown to effect ethylene (qv) conversion to acetaldehyde (qv) in a possible replacement for the Wacker process. [Pg.477]

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. [Pg.180]

Vanadium phosphates have been established as selective hydrocarbon oxidation catalysts for more than 40 years. Their primary use commercially has been in the production of maleic anhydride (MA) from n-butane. During this period, improvements in the yield of MA have been sought. Strategies to achieve these improvements have included the addition of secondary metal ions to the catalyst, optimization of the catalyst precursor formation, and intensification of the selective oxidation process through improved reactor technology. The mechanism of the reaction continues to be an active subject of research, and the role of the bulk catalyst structure and an amorphous surface layer are considered here with respect to the various V-P-O phases present. The active site of the catalyst is considered to consist of V and V couples, and their respective incidence and roles are examined in detail here. The complex and extensive nature of the oxidation, which for butane oxidation to MA is a 14-electron transfer process, is of broad importance, particularly in view of the applications of vanadium phosphate catalysts to other processes. A perspective on the future use of vanadium phosphate catalysts is included in this review. [Pg.189]

The selective oxidation of toluene has been studied over a number of catalysts based on metal oxides, with the U/Mo oxide system being one of the most achve and selective[50, 51]. The main products in the oxidation of toluene, excluding the non-oxidative coupling products, were benzaldehyde, benzoic acid, maleic anhydride, benzene, benzoquinone, CO and CO2. Under the same reachon condihons toluene may also yield coupling products such as phthalic anhydride, methyldi-phenylmethane, benzophenone, diphenylethanone and anthraquinone, as shown by Zhu and coworkers [51]. A range of different uranium-based oxides were tested [51] and the results obtained are shown in Table 13.4. [Pg.552]

This review analyzes the properties which are necessary for heterogeneous catalysts to promote the oxyfunctionalization of light paraffins to valuable chemicals. Three catalytic systems are discussed i) vanadium/phosphorus mixed oxide, the industrial catalyst for the oxidation of n-butane to maleic anhydride, which is here also examined for reactions aimed at the transformation of other hydrocarbons ii) Keggin-type heteropolycompounds, which are claimed for the oxidation of propane and isobutane, whose composition can be tuned in order to direct the reaction either to the formation of olefins or to the formation of oxygenated compounds iii) rutile-based mixed oxides, where rutile can act as the matrix for hosting transition metal ions or favour the dispersion of other metal oxides, thus promoting the different role of the various elements in the formation of acrylonitrile from propane. [Pg.19]

To promote both the conversion of reactants and the selectivity to partial oxidation products, many kinds of metal compounds are used to create catalytically active sites in different oxidation reaction processes [4]. The most well-known oxidation of lower alkanes is the selective oxidation of n-butane to maleic anhydride, which has been successfully demonstrated using crystalline V-P-O complex oxide catalysts [5] and the process has been commercialized. The selective conversions of methane to methanol, formaldehyde, and higher hydrocarbons (by oxidative coupling of methane [OCM]) are also widely investigated [6-8]. The oxidative dehydrogenation of ethane has also received attention [9,10],... [Pg.433]

Although little experimental data is available, numerous patents have been issued for the vapor phase catalytic oxidation of various other derivatives containing the benzene nucleus, as well as heterocyclic compounds Thus, fluorene (diphenyl methane) is oxidized to fluorenone with air in the presence of a catalyst containing iron vanadate or other suitable metal salt of the fifth or sixth group of the periodic system at a temperature of 360° to 400°.1,2 Maleic acid and anhydride are formed by the catalytic oxidation of compounds of the furan series, such as furan, furfural alcohol, furfural, methyl furfural, hydroxymethylfurfural, pyromucic acid or mixtures, with air over catalysts of molybdenum, vanadium, or other metals.133 Dimethyl benzaldehyde is formed by oxidizing pseudocumene with air at 550° C. in the presence of a tungsten oxide catalyst. Molybdenum, vanadium, or tantalum oxide catalysts may also be used to form aromatic aldehydes from o-, m-, or p-xylenes, mesitylene, p-cymene, or o-chlorotoluene by air oxidation. Times of contact of 0.3 to 0.4 seconds... [Pg.401]

Red-ox type catalysts are mostly used in oxidation or related types of reactions. For instance, vanadium catalysts containing ions of different valence state are used in the oxidation of benzene to maleic anhydride. Bismuth molybdate catalyst can be used both for the oxidation or ammoxidation of propene. Anchored metal-complex catalysts combine the advantage of both homogeneous and heterogeneous catalysts, however in these catalysts the molecular character of the active sites is maintained. In the last generation of this type of catalysts, heteropolyacids are fixed first to the support and in the second step different metal-complexes are anchored to the heteropolyacid. In this way highly active and stable catalyst have been prepared for different reactions. ... [Pg.2]

Mixed metal oxides are used quite often in industrial partial oxidation reactions, examples being Bi Oj-MoOj for the oxidation of propene to acrolein and V O -MoOj for oxidation of benzene to maleic anhydride. Some mixed oxides also are quite active deep oxidation catalysts, a good example being MnOj-CuO. The difficulties in understanding mixed oxides are of course more formidable than they are for single metal oxides. It is a well-established empirical fact that mixed oxides behave quite differently than as individual oxides in most catalytic reactions. This situation is further complicated by the often dramatic effect of promoters, such as alkali metal oxides that are added to the catalyst intentionally. [Pg.167]

Today, the air oxidation of toluene is the source of most of the world s synthetic benzaldehyde. Both vapor- and Hquid-phase air oxidation processes have been used. In the vapor-phase process, a mixture of air and toluene vapor is passed over a catalyst consisting of the oxides of uranium, molybdenum, or related metals. High temperatures and short contact times are essential to maximize yields. Small amounts of copper oxide maybe added to the catalyst mixture to reduce formation of by-product maleic anhydride. [Pg.34]


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See also in sourсe #XX -- [ Pg.643 ]




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