Molybdenum supported

In the second step, methacrolein is oxidized to methacrylic acid at a relatively lower temperature range of 250-350°C. A molybdenum-supported compound with specific promoters catalyzes the oxidation. 

Oxidative Dehydrogenation of Ethane. The dehydrogenation of alkanes also occurs, but in a catalytic manner, over molybdenum supported on silica (22,23). In addition to the stoichiometric reactions, the role of the 0 ion in this catalytic reaction is further suggested by the observation that N2O is an effective oxidant at temperatures as low as 280°C, but no reaction is observed at these temperatures with O2 as the oxidant (22). It should be noted that at moderate temperatues N2O gives rise to 0 , whereas O2 yields O2 over Mo/Si02. Under steady-state conditions the rates of formation of C2Hi were in the ratio of 7 1 at 375°C and 3.7 1 at 450°C when N2O and O2 were used as the oxidants, respectively (23). ... 

Recent experimental results are summarized in Table III. The catalyst used here was molybdenum supported on Cab-O-Sil. We have experienced difficulty in repeating the previous results, which indicated that up to 50% selectivity to methanol could be achieved even at conversions of -15% (18). In the more recent study it has been possible to obtain this selectivity only at conversions of 1%. Nevertheless, at sufficiently low conversions methanol is the principal product, provided steam is present in the system. 

Finally, the MCR-2X catalyst manufactured by Haldor Tops0e, whose behaviour in the Adam I reactor was described above (see Figure 3 and Table 1), should be mentioned. This is almost certainly composed of nickel and molybdenum supported on Zr02-Al203 and fired at high temperatures.111 The other catalyst, MCR-4, used in the test discussed above for the second and third reactors, may be a more conventional Ni-Mg0-Al203 formulation.91... 

The catalyst used in the experiments was a commercial cobalt molybdenum supported on y-alumina (Procatalyse HR306). It contains 14 wt% of molybdenum oxide and 3 wt% of cobalt oxide and has a surface area of 210 m2/g. It was sulfided according to a standard laboratory procedure at 400 °C under a mixture of 15 vol.% of H2S in H2. In one experiment, the activity of... 

In the first series of tests the germanium crystal was separated from a molybdenum supporting block by a thin slab of pile graphite and was held in place by molybdenum wires passing through quartz tubes, to prevent contact between ger-... 

S. Chavan, W. Maes, J. Wahlen, P. Jacobs, D. De Vos, W. Dehaen, Benzimidazole-functionalized dendrons as molybdenum supports for selective epoxidation catalysis, Catal. Commun. 6 (2005) 241. 

A similar procedure was developed to grow ZSM-5 crystals in situ on a molybdenum support [245]. The high thermal conductivity (138 W mK 1) and the high mechanical stability at elevated temperatures of the molybdenum support allow the application of ZSM-5 coatings in microreactors for high temperature processes involving large heat effects. The effect of the composition of the synthesis mixture on... 

Although tantalum is by far the most widely used of the refractory metals to impart corrosion resistance to chemical-process vessels and components, there are some applications where molybdenum has been used with great success. Molybdenum support structures have replaced graphite in the processing of high-purity alcohols. Molybdenum-rhenium alloys, first developed because of their vastly improved ductility at low temperatures and in the recrystallized condition, have been used as vessel lining and piping components for the manufacture of Freon replacements. ... 

The feed used for all experiments was straight-run gas oil obtained from a heavy crude oil, whose properties are presented in Table 7.3. The commercial catalyst used for the experiments was a presulfided cobalt-molybdenum supported on y-alumina. The reactor was loaded with 99.43 g (100 mL) of powdered catalyst previously crushed and sieved, the properties of which are also given in Table 7.3. The bench-scale reactor is operated in downflow and isothermal mode provided with independent temperature control of a three-zone electric furnace. The internal diameter of the reactor is 2.54cm, and at the center, a thermowell of external diameter of 0.635 cm was placed. Catalytic length was of 25.2 cm (Figure 7.14). 

The alkyl derivatives of thiazoles can be catalytically oxidized in the vapor phase at 250 to 400°C to afford the corresponding formyl derivatives (21). Molybdenum oxide, V2O5, and tin vanadate are used as catalysts either alone or with a support. The resulting carbonyl compounds can be selectively oxidized to the acids. 

Early catalysts for acrolein synthesis were based on cuprous oxide and other heavy metal oxides deposited on inert siHca or alumina supports (39). Later, catalysts more selective for the oxidation of propylene to acrolein and acrolein to acryHc acid were prepared from bismuth, cobalt, kon, nickel, tin salts, and molybdic, molybdic phosphoric, and molybdic siHcic acids. Preferred second-stage catalysts generally are complex oxides containing molybdenum and vanadium. Other components, such as tungsten, copper, tellurium, and arsenic oxides, have been incorporated to increase low temperature activity and productivity (39,45,46). 

Oxidation of methanol to formaldehyde with vanadium pentoxide catalyst was first patented in 1921 (90), followed in 1933 by a patent for an iron oxide—molybdenum oxide catalyst (91), which is stiU the choice in the 1990s. Catalysts are improved by modification with small amounts of other metal oxides (92), support on inert carriers (93), and methods of preparation (94,95) and activation (96). In 1952, the first commercial plant using an iron—molybdenum oxide catalyst was put into operation (97). It is estimated that 70% of the new formaldehyde installed capacity is the metal oxide process (98). 

Benzene-Based Catalyst Technology. The catalyst used for the conversion of ben2ene to maleic anhydride consists of supported vanadium oxide [11099-11-9]. The support is an inert oxide such as kieselguhr, alumina [1344-28-17, or sUica, and is of low surface area (142). Supports with higher surface area adversely affect conversion of benzene to maleic anhydride. The conversion of benzene to maleic anhydride is a less complex oxidation than the conversion of butane, so higher catalyst selectivities are obtained. The vanadium oxide on the surface of the support is often modified with molybdenum oxides. There is approximately 70% vanadium oxide and 30% molybdenum oxide [11098-99-0] in the active phase for these fixed-bed catalysts (143). The molybdenum oxide is thought to form either a soUd solution or compound oxide with the vanadium oxide and result in a more active catalyst (142). 

The same properties that make molybdenum metal effective in high temperature furnace appHcations make it useful as support wires for tungsten filaments in incandescent light bulbs and as targets in x-ray tubes. 

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. 

The catalyst for the second stage is also a bifimctional catalyst containing hydrogenating and acidic components. Metals such as nickel, molybdenum, tungsten, or palladium are used in various combinations and dispersed on sofid acidic supports such as synthetic amorphous or crystalline sihca—alumina, eg, zeofites. These supports contain strongly acidic sites and sometimes are enhanced by the incorporation of a small amount of fluorine. 

The predominant process for manufacture of aniline is the catalytic reduction of nitroben2ene [98-95-3] ixh. hydrogen. The reduction is carried out in the vapor phase (50—55) or Hquid phase (56—60). A fixed-bed reactor is commonly used for the vapor-phase process and the reactor is operated under pressure. A number of catalysts have been cited and include copper, copper on siHca, copper oxide, sulfides of nickel, molybdenum, tungsten, and palladium—vanadium on alumina or Htbium—aluminum spinels. Catalysts cited for the Hquid-phase processes include nickel, copper or cobalt supported on a suitable inert carrier, and palladium or platinum or their mixtures supported on carbon. 

In past years, metals in dilute sulfuric acid were used to produce the nascent hydrogen reductant (42). Today, the reducing agent is hydrogen in the presence of a catalyst. Nickel, preferably Raney nickel (34), chromium or molybdenum promoted nickel (43), or supported precious metals such as platinum or palladium (35,44) on activated carbon, or the oxides of these metals (36,45), are used as catalysts. Other catalysts have been suggested such as molybdenum and platinum sulfide (46,47), or a platinum—nithenium mixture (48). 

The tert-huty hydroperoxide is then mixed with a catalyst solution to react with propylene. Some TBHP decomposes to TBA during this process step. The catalyst is typically an organometaHic that is soluble in the reaction mixture. The metal can be tungsten, vanadium, or molybdenum. Molybdenum complexes with naphthenates or carboxylates provide the best combination of selectivity and reactivity. Catalyst concentrations of 200—500 ppm in a solution of 55% TBHP and 45% TBA are typically used when water content is less than 0.5 wt %. The homogeneous metal catalyst must be removed from solution for disposal or recycle (137,157). Although heterogeneous catalysts can be employed, elution of some of the metal, particularly molybdenum, from the support surface occurs (158). References 159 and 160 discuss possible mechanisms for the catalytic epoxidation of olefins by hydroperoxides. 

EBHP is mixed with a catalyst solution and fed to a horizontal compartmentalized reactor where propylene is introduced into each compartment. The reactor operates at 95—130°C and 2500—4000 kPa (360—580 psi) for 1—2 h, and 5—7 mol propylene/1 mol EBHP are used for a 95—99% conversion of EBHP and a 92—96% selectivity to propylene oxide. The homogeneous catalyst is made from molybdenum, tungsten, or titanium and an organic acid, such as acetate, naphthenate, stearate, etc (170,173). Heterogeneous catalysts consist of titanium oxides on a siUca support (174—176). 

It is carried out in the Hquid phase at 100—130°C and catalyzed by a soluble molybdenum naphthenate catalyst, also in a series of reactors with interreactor coolers. The dehydration of a-phenylethanol to styrene takes place over an acidic catalyst at about 225°C. A commercial plant (50,51) was commissioned in Spain in 1973 by Halcon International in a joint venture with Enpetrol based on these reactions, in a process that became known as the Oxirane process, owned by Oxirane Corporation, a joint venture of ARCO and Halcon International. Oxirane Corporation merged into ARCO in 1980 and this process is now generally known as the ARCO process. It is used by ARCO at its Channelview, Texas, plant and in Japan and Korea in joint ventures with local companies. A similar process was developed by Shell (52—55) and commercialized in 1979 at its Moerdijk plant in the Netherlands. The Shell process uses a heterogeneous catalyst of titanium oxide on siHca support in the epoxidation step. Another plant by Shell is under constmction in Singapore (ca 1996). 

Nicotinonitrile is produced by ammoxidation of alkylpyridines (11—24). A wide variety of different catalysts have been developed for this appHcation. For example, a recent patent describes a process ia which 3-methylpyridine is reacted over a molybdenum catalyst supported on siHca gel. The catalyst (PV Mo 20 ) was prepared from NH VO, H PO, and (NH Moy024. Reaction at 380°C at a residence time of 2.5 seconds gave 95% of nicotinonitrile at a 99% conversion (16). 

In catalytic toluene hydrodealkylation, toluene is mixed with a hydrogen stream and passed through a vessel packed with a catalyst, usually supported chromium or molybdenum oxides, platinum or platinum oxides, on siHca or alumina (50). The operating temperatures range from 500—595°C... 

Although supported Pd catalysts have been the most extensively studied for butadiene hydrogenation, a number of other catalysts have also been the object of research studies. Some examples are Pd film catalysts, molybdenum sulfide, metal catalysts containing Fe, Co, Ni, Ru, Rh, Os, Ir, Pt, Cu, MgO, HCo(CN) on supports, and LaCoC Perovskite. There are many others (79—85). Studies on the weU-characteri2ed Mo(II) monomer and Mo(II) dimer on siUca carrier catalysts have shown wide variations not only in catalyst performance, but also of activation energies (86). 

The catalysts are prepared by impregnating the support with aqueous salts of molybdenum and the promoter. In acidic solutions, molybdate ions are present largely in the form of heptamers, [Mo2024] , and the resulting surface species are beHeved to be present in islands, perhaps containing only seven Mo ions (100). Before use, the catalyst is treated with H2 and some sulfur-containing compounds, and the surface oxides are converted into the sulfides that are the catalyticaHy active species. 

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