Sulfide from sulfur

In metallurgy, hydrogen sulfide is used to precipitate copper sulfide from nickel—copper-containing ore leach solutions in Alberta, Canada, or to precipitate nickel and cobalt sulfides from sulfuric acid leaching oflaterite ores in Moa Bay, Cuba (120) (see Metallurgy, extractive metallurgy). 

Sulfate. As for the production of hydrogen sulfide from sulfur dioxide/sulfite at least three possible pathways for the light-dependent synthesis of hydrogen sulfide in response to sulfate can be assumed, i.e. first the light-dependent reduction of sulfate to carrier-bound sulfide followed by a release of the sulfide moiety from its carrier second the light-dependent reduction of sulfate to carrier-bound sulfide followed by an incorporation of the sulfide moiety into cysteine and subsequent degradation of cysteine third the release of sulfite from carrier-bound sulfite followed by reduction of free sulfite to sulfide (see Figure 1). 

Lovering, T.S., 1963. Deposition of sulfides from sulfur-deficient solutions. Econ. Geol., 56 68—97. 

Kletzin A (1989) Coupled enzymatic production of sulfite, thiosulfite, and hydrogen sulfide from sulfur purification and properties of a sulfur oxygenase reductase from the facultative anaerobic archaebacterium Desulfurolobus ambivalens. J Bacteriol 171 1638-1643 Kobayashi K, Takahashi E, Ishimoto M (1972) Biochemical studies on sulfate reducing bacteria IX. Purification and some properties of sulfite reductase, desulfoviridin. J Biochem 72 879-887... 

Two efficient syntheses of strained cyclophanes indicate the synthetic potential of allyl or benzyl sulfide intermediates, in which the combined nucleophilicity and redox activity of the sulfur atom can be used. The dibenzylic sulfides from xylylene dihalides and -dithiols can be methylated with dimethoxycarbenium tetrafiuoroborate (H. Meerwein, 1960 R.F. Borch, 1968, 1969 from trimethyl orthoformate and BFj, 3 4). The sulfonium salts are deprotonated and rearrange to methyl sulfides (Stevens rearrangement). Repeated methylation and Hofmann elimination yields double bonds (R.H. Mitchell, 1974). 

Carbonate is measured by evolution of carbon dioxide on treating the sample with sulfuric acid. The gas train should iaclude a silver acetate absorber to remove hydrogen sulfide, a magnesium perchlorate drying unit, and a CO2-absorption bulb. Sulfide is determined by distilling hydrogen sulfide from an acidified slurry of the sample iato an ammoniacal cadmium chloride solution, and titrating the precipitated cadmium sulfide iodimetrically. 

Eig. 1. The key steps for the Phillips PPS process are (/) production of aqueous sodium sulfide from aqueous sodium hydrogen sulfide (or hydrogen sulfide) and aqueous sodium hydroxide 2) dehydration of the aqueous sodium sulfide and NMP feedstocks 5) polymerization of the dehydrated sulfur source with -dichlorobenzene to yield a slurry of PPS and by-product sodium chloride in the solvent (4) polymer recovery (5) polymer washing for the removal of by-product salt and residual solvent (6) polymer drying (7) optional curing, depending on the appHcation and (< ) packaging. 

Commercial-scale processes have been developed for the production of hydrogen sulfide from heavy fuel oils and sulfur as well as from methane, water vapor, and sulfur. The latter process can be carried out in two steps reaction of methane with sulfur to form carbon disulfide and hydrogen sulfide followed by hydrolysis of carbon disulfide (116). 

The practical importance of the higher sulfanes relates to their formation in sour-gas wells from sulfur and hydrogen sulfide under pressure and their subsequent decomposition which causes well plugging (134). The formation of high sulfanes in the recovery of sulfur by the Claus process also may lead to persistance of traces of hydrogen sulfide in the sulfur thus produced (100). Quantitative deteanination of H2S and H2S in Claus process sulfur requires the use of a catalyst, eg, PbS, to accelerate the breakdown of H2S (135). 

Conversion Processes. Most of the adsorption and absorption processes remove hydrogen sulfide from sour gas streams thus producing both a sweetened product stream and an enriched hydrogen sulfide stream. In addition to the hydrogen sulfide, this latter stream can contain other co-absorbed species, potentially including carbon dioxide, hydrocarbons, and other sulfur compounds. Conversion processes treat the hydrogen sulfide stream to recover the sulfur as a salable product. 

NKK s Bio-SR process is another iron-based redox process which instead of chelates, uses Thiobacillusferroidans )2iQ. - 2i to regenerate the solution (9). This process absorbs hydrogen sulfide from a gas stream into a ferric sulfate solution. The solution reacts with the hydrogen sulfide to produce elemental sulfur and ferrous sulfate. The sulfur is separated via mechanical means, such as filtering. The solution is regenerated to the active ferric form by the bacteria. 

As worldwide attention has been focused on the dangers of acid rain, the demand to reduce sulfur dioxide [7446-09-5] emissions has risen. Several processes have been developed to remove and recover sulfur dioxide. Sulfur can be recovered from sulfur dioxide as Hquid sulfur dioxide, sulfuric acid, or elemental sulfur. As for the case of hydrogen sulfide, sulfur dioxide removal processes are categorized as adsorption, absorption, or conversion processes. 

Black Liquor Soap Acidulation. Only two-thirds of a typical black Hquor soap consists of the sodium salts of fatty acids and resin acids (rosin). These acids are layered in a Hquid crystal fashion. In between these layers is black Hquor at the concentration of the soap skimmer, with various impurities, such as sodium carbonate, sodium sulfide, sodium sulfate, sodium hydroxide, sodium Hgnate, and calcium salts. This makes up the remaining one-third of the soap. Cmde tall oil is generated by acidifying the black Hquor soap with 30% sulfuric acid to a pH of 3. This is usually done in a vessel at 95°C with 20—30 minutes of vigorous agitation. Caution should be taken to scmb the hydrogen sulfide from the exhaust gas. 

The sulfur chlorides give higher xanthate sulfides. For example, the following product is obtained from sulfur monochloride and an ether suspension at room temperature ... 

Arsenic pentasulfide (arsenic(V) sulfide), As S q, is stable in air up to 95°C, but at higher temperatures begins to dissociate into arsenous sulfide and sulfur. It is prepared by the fusion of arsenic with sulfur foUowed by extraction with ammonia and reprecipitation at low temperatures by addition of hydrochloric acid. Arsenic pentasulfide is precipitated at low temperatures from strongly acidic arsenate solutions by a rapid stream of hydrogen sulfide. It is hydrolyzed by boiling with water, yielding arsenous acid and sulfur. Salts derived from a number of thioarsenic acids are formed from arsenic pentasulfide and alkaH metal sulfides. 

Citric acid is used to chelate vanadium catalyst in a process for removing hydrogen sulfide from natural and refinery gas and forming elemental sulfur, a valuable product (133). 

The KF-S reaction presumably involves attack of a fluonnated caibanion on sulfur, whereas the S-Sbp5 reaction may involve electrophilic attack by a cationic sulfur species on the olefin under the strong Lewis acid conditions Electrophilic attack on a fluonnated olefin may also account for formation of a perfluorinated sulfide from reaction of bis(pentafluorophenyl)disulfide with hexafluoropropylene under superacid conditions [IS5] (equation 28)... 

An interesting addition reaction of sulfur dichloride has been discovered that allows the preparation in good yield of bridged cyclic sulfides from cyclic dienes. Two examples of the reaction have been described (cyclo-octadiene and in the other 1,5-cyclooctadiene. The former sequence is shown in the scheme. The experimental details of the latter sequence are given below. 

Sulfur dioxide can be removed from the smokestack emissions of power plants by reacting it with hydrogen sulfide, producing sulfur and water. What volume of hydrogen sulfide at 27°C and 755 mm Hg is required to remove the sulfur dioxide produced by a power plant that bums one metric ton of coal containing 5.0% sulfur by mass How many grams of sulfur are produced by the reaction of H2S with S02 ... 

Ammonia, hydrogen sulfide, and sulfur dioxide may result from the decomposition of chemical treatments (although in large boiler plants, ammonia is often deliberately added to raise the boiler, steam, or condensate system pH). 

The solubility of a solid can be increased by removing one of its ions from solution acid can be used to dissolve a hydroxide, sulfide, sulfite, or carbonate precipitate and nitric acid can be used to oxidize metal sulfides to sulfur and a soluble salt. 

The only continuous major natural source of the sulfur in these aerosol particles is dimethyl sulfide from marine phytoplankton (algae). 

The reaction at Eq. (12) allows the preparation of Na2S4 and K2S5 from the alkali metals, hydrogen sulfide and sulfur in anhydrous ethanol (ROH). First the metal is dissolved in the alcohol with formation of ethanolate (MOR) and hydrogen. Bubbling of H2S into this solution produces the hydrogen sulfide (MHS). To obtain the polysulfide the solution is refluxed with the calculated amount of elemental sulfur. After partial evaporation of the solvent and subsequent cooling the product precipitates. 

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