Molybdenum-activated carbon

It was found that a nickel-activated carbon catalyst was effective for vapor phase carbonylation of dimethyl ether and methyl acetate under pressurized conditions in the presence of an iodide promoter. Methyl acetate was formed from dimethyl ether with a yield of 34% and a selectivity of 80% at 250 C and 40 atm, while acetic anhydride was synthesized from methyl acetate with a yield of 12% and a selectivity of 64% at 250 C and 51 atm. In both reactions, high pressure and high CO partial pressure favored the formation of the desired product. In spite of the reaction occurring under water-free conditions, a fairly large amount of acetic acid was formed in the carbonylation of methyl acetate. The route of acetic acid formation is discussed. A molybdenum-activated carbon catalyst was found to catalyze the carbonylation of dimethyl ether and methyl acetate. 

Table V shows the results obtained for the carbonylation of dimethyl ether and methyl acetate with molybdenum catalysts supported on various carrier materials. In the case of dimethyl ether carbonylation, molybdenum-activated carbon catalyst gave methyl acetate with an yield of 5.2% which was about one-third of the activity of nickel-activated carbon catalyst. Silica gel- or y-alumina-supported catalyst gave little carbonylated product. Similar results were obtained in the carbonylation of methyl acetate. The carbonylation activity occured only when molybdenum was supported on activated carbon, and it was about half the activity of nickel-activated carbon catalyst.

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). 

In an equilibrium study of the adsorption of molybdenum(VI) from aqueous solution onto activated carbon it has been found that the data are best explained in terms of an absorption model comprising the three species [HMo207] , Mo03(H20)3, and [HMo04] of which the dimer predominates by far (80). Computer treatment of potentiomet-ric (81) and spectrophotometric data (82) also indicated the possible existence of [HMo207] as a minor species in aqueous solution at low molybdenum concentration ( 2 X 104 Af). However, as its assumed stability region overlaps with several other polynuclear ions more direct evidence is needed before its existence can be accepted with certainty. 

A mixed-valent polymolybdate on active carbon was prepared from molybdenum metal and H202, followed by the addition of active carbon to the aqueous solution [114,115], This catalyzed the epoxidation of several alkenes in 2-propanol using H202 as an oxidant, while the efficiency of H202 utilization was very low (< 25%). The epoxidation likely proceeded mainly on the surface of the catalyst because the recovered catalyst showed almost similar catalytic activity. 

Common catalyst compositions include oxides of chromium or molybdenum, or cobalt and nickel metals, supported on silica, alumina, titania, zirconia, or activated carbon. 

Table V. Carbonylation Activities of Supported Molybdenum and Nickel-Activated Carbon Catalysts ...

Carbon monoxide serves as the sole carbon and energy source for the carboxydo bacteria under aerobic conditions. Using water as the oxygen donor, carbon monoxide oxidase catalyzes the hydroxylation of carbon monoxide, giving carbon dioxide or bicarbonate for assimilation. Most work has been carried out on the enzyme from Pseudomonas carboxydovorans.,ftJ7>W38 The activity of carbon monoxide oxidase is considerably stimulated upon anaerobic treatment with sulfide and dithionite, or by aerobic treatment with selenite. The binding of selenite to the oxidase specifically activates the CO — methylene blue reaction.1039 The molybdenum cofactor liberated from selenium-activated carbon monoxide oxidase does not contain selenium. Here, then, the... 

Concurrently with the discovery and development in this country of the catalytic conversion of paraffins to aromatics (131) three different groups in the U.S.S.R. discovered this reaction independently of each other. Moldavskil and co-workers (238,239) showed that paraffins with six or more carbon atoms form aromatics by closure of a six-membered ring. For example, n-octane gives xylene and some ethylbenzene over amorphous chromia at about 470°C. Olefins also undergo this reaction. In subsequent publications, the group headed by Moldavskil demonstrated that molybdenum sulfide, titanium dioxide, and other oxides as well as activated carbon also may be used for dehydrocyclization (237,239). 

The first polymerizations were free radical reactions. In 1933 researchers at ICI discovered that ethene polymerizes into a branched structure that is now known as low density polyethene (LDPE). In the mid- 50s a series of patents were issued for new processes in which solid catalysts were used to produce polyethene at relatively low pressures. The first was granted to scientists at Standard Oil (Indiana) who applied nickel oxide on activated carbon and molybdenum oxide on alumina. Their research did not lead to commercial processes. In the late 40s Hogan and Banks of Phillips were assigned to study the di- and trimerization of lower olefins. The objective was to produce high octane motor fuels. When they tried a chromium salt as promoter of a certain catalyst (Cr was a known reforming... 

Feedstock Purification. In feedstock purification, mainly desulfurization, adsorption on active carbon was replaced by catalytic hydrogenation over cobalt-molybdenum or nickel-molybdenum catalyst, followed by absorption of the H2S on ZnO pellets with formation of ZnS. By itself this measure has no direct influence on the energy consumption but is a prerequisite for other energy saving measures, especially in reforming and shift conversion. 

The interest in adsorption of molybdenum stems primarily from its use as a carbon-supported catalyst [22]. The use of activated carbon for the removal of Mo-99 (used in nuclear medicine) has also been reported ] 158]. Only hexavalent Mo is stable under a wide pH range and in the absence of other complexing agents. At pH > 8, the dominant species is M0O4-, while at very low pH there is precipitation of the hydrated oxide between these two extremes polymeric anions are formed [123,159]. 

Molybdenum Removal by Adsorption on Activated Carbon [5.34]. The principle of the method is the selective adsorption of thiomolybdate by activated carbon while tungstate will not be retained. 

Several other methods have been employed for the preparation of carbon-supported catalysts, although to a lesser extent that impregnation methods. Nakamura et al. [38] prepared molybdenum catalysts for ethene homologation by physical deposition of gaseous [Mo(CO)6]. Their supports were commercial activated carbons that were subjected to different treatments to modify then-surface. The authors compared these supports with oxidic supports and concluded that the interaction between the metal carbonyl and the carbon supports were weaker. Furthermore, they observed that oxidation of the carbon surface was effective in enhancing the catalytic activity of Mo/C, and they ascribed this effect to the contribution of the surface oxygen groups to the partial oxidation of decomposed [Mo(CO)6]. 

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