Molybdenum sulfur compounds

The addition of Mo(CO)3 fragments to iron carbonyl anions has also been used to synthesize iron-molybdenum-sulfur compounds. Thus, the reaction between... 

Cyclopentadienyl molybdenum-sulfur compounds are useful synthons for the preparation of Mo—M—S (e.g. M = Fe (see Section 36.6.2), Co, Ni) clusters103-108 144 in reactions with metal carbonyls. However, the principal interest in molecules of this class has arisen because of the reactivity of the Mo—S system, primarily in respect of the making and breaking of S—H... 

A wide variety of other cydopentadienyl molybdenum-sulfur compounds are known including monomeric [Cp2Mo(SR)2],161,162 [Cp2MoS2] and [Cp2MoS4],163 dimeric... 

The older literature on molybdenum-sulfur chemistry describes several compounds6 that have later been shown to be either incorrectly formulated or non-existent. In recent times, the chemistry of molybdenum-sulfur compounds has been elucidated by modern techniques, both in solution and in the solid state. It is therefore the purpose of the present chapter to review and systematize the best information available in this area. Although the primary emphasis has been placed on molybdenum-sulfur species, for completeness and correlation purposes, certain tungsten or selenium analogs have also been included. 

The thiomolybdites are a class of molybdenum-sulfur compounds which contain molybdenum in a low oxidation state, usually +3. Two main types of such materials exist. The first type has the formula MMoS2 where M is a monovalent cation, usually an alkali metal. The second type has the formula MMo2S4 where M is a divalent cation, usually a transition metal. There are other thiomolybdite species, of composition other than that described above, which have been identified in ternary phase studies involving the M-Mo-S system (M = a transition element), but these have not been well characterized. 

The properties of the molybdenum-sulfur compounds described are of direct importance to hydrodesulfurization catalysis. Hydrodesulfurization and the nature of the catalysts used have been adequately described elsewhere and will not be presented here. References in which this system is described in detail include Refs.161) and 214) through221). 

The recommended daily dietary doses of copper are 0.4-0.7 mg for children under 1 year, 0.7-2.0 mg for children aged 1 to 10 years, 1.5-2.5 mg for adolescents and 1.5-3.0 mg for adults. Resorption of copper and its retention in the body depend on the chemical form in which this element is present in the diet. Experiments on laboratory animals have shown a higher utilisation of copper in the form of neutral and anionic complexes contained in plant material than in the form of copper sulfate. Availability of copper increases the presence of proteins and amino acids in the diet. Also, carboxylic and hydroxycarboxylic acids stimulate resorption of copper. In contrast, higher doses of ascorbic acid, fructose, molybdenum, sulfur compounds and zinc significantly reduce the resorption of copper. Ascorbic acid reduces cupric compounds to slightly soluble cuprous compounds. The effect of phytic acid and dietary fibre on copper resorption is, in comparison with the effect of these components in zinc, less pronounced. 

Thiophene [110-02-17, C H S, and dibenzothiophene [132-65-OJ C22HgS, are models for the organic sulfur compounds found in coal, as well as in petroleum and oil shale. Cobalt—molybdenum and nickel—molybdenum catalysts ate used to promote the removal of organic sulfur (see Coal CONVERSION... 

Natural gas contains both organic and inorganic sulfur compounds that must be removed to protect both the reforming and downstream methanol synthesis catalysts. Hydrodesulfurization across a cobalt or nickel molybdenum—zinc oxide fixed-bed sequence is the basis for an effective purification system. For high levels of sulfur, bulk removal in a Hquid absorption—stripping system followed by fixed-bed residual clean-up is more practical (see Sulfur REMOVAL AND RECOVERY). Chlorides and mercury may also be found in natural gas, particularly from offshore reservoirs. These poisons can be removed by activated alumina or carbon beds. 

Tsigdinos, G. A. Sulfur Compounds of Molybdenum and Tungsten. Their Preparation, Structure, and Properties. 76, 65-105 (1978). 

Autofining A fixed-bed catalytic process for removing sulfur compounds from petroleum distillates. This process uses a conventional cobalt/molybdenum hydrodesulfurization catalyst but does not require additional hydrogen. Developed by The Anglo-Iranian Oil Company in 1948. 

Table 3.4 lists values for A Eq and for some important oxidation and spin states found in bioinorganic molecules. Data are taken from reference 24 and from Table 1 of reference 25 for hemoglobin, myoglobin, and the picket-fence porphyrin model compound, FeTpivPP(l-Melm).25 The myoglobin and hemoglobin model compounds are discussed in Section 4.8.2. Reference 26 provides the Table 3.4 data on iron sulfur clusters found in many bioinorganic species.26 The unusual iron-sulfur and iron-molybdenum-sulfur clusters found in the enzyme nitrogenase are discussed more fully below and in Chapter 6. 

Sulfite oxidase is a dimetallic enzyme that mediates the two-electron oxidation of sulfite by the one-electron reduction of cytochrome c. This reaction is physiologically essential as the terminal step in oxidative degradation of sulfur compounds. The enzyme contains a heme cofactor in the 10 kDa N-terminal domain and a molybdenum center in the 42 kDa C-terminal domain. The catalytic cycle is depicted in Fig. 9. 

One of the major challenges in the petroleum industry today is the removal of sulfur compounds, especially refractive ones such as 4,6-dimethyldibenzo-thiophene (DMDBT), from petroleum fractions such as diesel to concentrations <5-10 ppm from the current values of 50-500 ppm. The current technology is hydrodesulfurization catalyzed by cobalt-nickel-molybdenum sulfides at high pressures. Reducing sulfur concentratios in diesel fuels below 5-10 ppm... 

Figure 14.2 shows that the production of 99% pure hydrogen requires many catalytic processes. The desulfurization section is used to reduce the sulfur content of the natural gas to 0.01 ppm to protect the SMR and WGS catalysts downstream. A supported cobalt-molybdenum catalyst (CoMoS) converts the sulfur compounds into H2S, which is removed by a ZnO catalyst [5]. 

In the SCOT process, the sulfur compounds in the Claus tail gas are converted to hydrogen sulfide by heating and passing it through a cobalt-molybdenum catalyst with the addition of a reducing gas. The gas is then cooled and contacted with a solution of diisopropanolamine (DIPA) that removes all but trace amounts of hydrogen sulfide. The sulfide-rich diisopropanolamine is sent to a stripper, where hydrogen sulfide gas is removed and sent to the Claus plant. The diisopropanolamine is returned to the absorption column. 

Natural gas feedstock is very dependent of the source location in some cases it has high levels of H2S, CO2 and hydrocarbons. Organic sulfur compounds must be removed because they will irreversibly deactivate both reforming and WGS catalysts. Hence a preliminary feed desulfurization step is necessary. This process consists in a medium-pressure hydrogenation (usually on a cobalt-molybdenum catalyst at 290-370 °C), which reduces sulfur compounds to H2S, followed by H2S separation through ZnO adsorption (at 340-390 °C) or amine absorption [9]. 

A similar chain-growth mechanism was said to occur with the first molybdenum-sulfur-potassium based catalysts of table I (15). For such a chain-growth mechanism, the heavier the average molecular weight of alcohols, the greater the formation of heavy compounds and, more often than not, the lower the alcohols selectivity. Furthermore, in Fischer-Tropsch type catalysts (24,25) diffusion limitations, mostly due to the presence of liquid products condensed in the micro porosity, increase with the size of diffusing molecules. These molecules are capable of... 

For a review, see Bonner Grimm, in Kharasch Meyers The Chemistry of Organic Sulfur Compounds, vol. 2 Pcrgamon New York, 1966. pp. 35-71, 410-413. For a review of the mechanism of desulfurization on molybdenum surfaces, see Friend Roberts Acc. Chem. Res. 1988,21, 394-400. 

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