Sulfur compounds oxidation levels

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. 

Sulfoxides are compounds that contain a sulfinyl group covalendy bonded at the sulfur atom to two carbon atoms. They have the general formula RS(0)R, ArS(0)Ar, and ArS(0)R, where Ar and Ar = aryl. Sulfoxides represent an intermediate oxidation level between sulfides and sulfones. The naturally occurring sulfoxides often are accompanied by the corresponding sulfides or sulfones. The only commercially important sulfoxide is the simplest member, dimethyl sulfoxide [67-68-5] (DMSO) or sulfinylbismethane. 

Various types of non-hydrocarbon compounds occur in crude oils and refinery streams. The most important are the organic sulfur, nitrogen, and oxygen compounds. Traces of metallic compounds are also found in all crudes. The presence of these impurities is harmful and may cause problems to certain catalytic processes. Fuels having high sulfur and nitrogen levels cause pollution problems in addition to the corrosive nature of their oxidization products. 

Desulfurization using purified enzymes Investigations into enzymatic desulfurization as an alternative to microbial desulfurization has revealed several enzymes capable of the initial oxidation of sulfur. A study reported use of laccase with azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as a mediator for oxidation of DBT [181]. The rate of this reaction was compared to hydrogen peroxide-based phosphotungstic acid-catalyzed oxidation and the latter was found to be about two orders of magnitude higher. The authors also oxidized diesel oil sulfur to no detectable levels via extraction of the oxidized sulfur compounds from diesel. In Table 9, the enzymes used in oxidation of DBT to DBTO are reported. 

The largest investment has been in desulfurization, and in most instances it has been proven that the sulfur compounds have been transformed into oxidized moieties, but the actual cleavage of the last C—S bond in most cases does not take place to the extent desired or to levels needed for implementing BDS. Other processes such as demetallization and upgrading are just starting to be studied. Collateral technologies, for gas treatment and reducing viscosity by emulsification ( in well treatments) are commercially available. 

Sulfur It is now well established that sulfur compounds in low ppm (parts per million) concentrations in fuel gas are detrimental to MCFCs (74,75,76,77,78). The tolerance of MCFCs to sulfur compounds (74) is strongly dependent on temperature, pressure, gas composition, cell components, and system operation (i.e., recycle, venting, gas cleanup). The principal sulfur compound that has an adverse effect on cell performance is H2S. At atmospheric pressure and high gas utilization (-75%), <10 ppm H2S in the fuel can be tolerated at the anode (tolerance level depends on anode gas composition and partial pressure of H2), and <1 ppm SO2 is acceptable in the oxidant (74). These concentration limits increase when the temperature increases, but they decrease at increasing pressures. 

An overall strategy for the synthesis of 1,2,5-thiadiazoles from the acyclic N-C-C-N grouping and sulfur monochloride was proposed in 1967 (1967JOC2823). The N-C function could vary over oxidation levels of amine, imine, cyanide, oxime and nitroso derivatives. Aliphatic and aromatic compounds having these functionalities in many combinations reacted with sulfur monochloride to form appropriately substituted or fused 1,2,5-thiadiazoles. Based on this model, a large... 

While the emphasis has been on oxidation of DMS and other reduced sulfur compounds in the gas phase, there is some indication that oxidation in the aqueous phase in clouds and fogs should also be considered. For example, Lee and Zhou (1994) have shown that DMS reacts with 03 in aqueous solutions quite rapidly, with a rate constant at 288 K of 4 X 108 L mol-1 s-1. They estimate that at 30 ppb 03, a level found globally, the lifetime for in-cloud oxidation of DMS is about 3 days, of the same order of magnitude as that for the gas-phase oxidation by OH (see Table 8.17). Given the moderately high solubility of not only DMS but other sulfur compounds as well (see Henry s law constants in Table 8.1), this is clearly an area that warrants further research. 

Typical ambient levels. Concentrations of S02 in remote areas are quite low, 10-50 ppt (e.g., Bandy et al., 1993), since the only source is oxidation of biogeni-cally produced organic sulfur compounds such as dimethyl sulfide (see Chapter 8.E). In rural-suburban areas, concentrations of l-20 ppb (e.g., Luria et al., 1987 Boatman et al., 1988) are common and in polluted urban areas, levels up to several hundred ppb are observed (e.g., Bennett et al., 1986). 

Thiophthalide (452) is the oxo form of l-hydroxybenzo[c]thiophene. It is a stable compound, being intermediate in oxidation level between o-xylene and phthalic acid. It can be formed from o-xylene by oxidation with a mixture of sulfur and water at high temperatures it can also be formed by reduction of phthalic anhydride with H2S + H2 (72AHC( 14)331). It reacts with vinyllithium to form a complex which on hydrolysis undergoes ring expansion to 4,5,6,7-tetrahydro-2//-benzo[c]thiepin-5-one (453), as shown in Scheme 154. 

The anaerobic metabolism of acrylate and 3-mercaptopropionate (3-MPA) was studied in slurries of coastal marine sediments. The rate of these compounds is important because they are derived from the algal osmolyte dimethylsulfoniopropionate (DMSP), which is a major organic sulfur compound in marine environments. Micromolar levels of acrylate were fermented rapidly in the slurries to a mixture of acetate and propionate (1 2 molar ratio). Sulfate-reducing bacteria subsequently removed the acetate and propionate. 3-MPA has only recently been detected in natural environments. In our experiments 3-MPA was formed by chemical addition of sulfide to aciylate and was then consumed by biological processes. 3-MPA is a known inhibitor of fatty acid oxidation in mammalian systems. In accord with this fact, high concentrations of 3-MPA caused acetate to accumulate in sediment slurries. At lower concentrations, however, 3-MPA was metabolized by anaerobic bacteria. We conclude that the degradation of DMSP may ultimately lead to the production of substrates which are readily metabolized by microbes in the sediments. 

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