Carbon sulfur compounds

Some carbon-sulfur compounds, such as CS (carbon disulfide), the thiocyanides, and thiocyanates -CNS, such as HCNS (thiocyanic acid), Pb(CNS) (lead thiocyanate), elc. 

This handbook gives data for 680 hydrocarbons, 95 carbon-sulfur compounds, and water from 0 to 150 C. It is indexed by compound name, and by boiling point. 

Fig. 22. Poly( ulfur nitride) (SN)j(, (b) replacing the nitrogens by carbons, and (c) stabilizing radicals in an analog carbon-sulfur compound.

Considerable design and operating data for the Scavinox process are given by Schaack and Chan, and these data form the principal basis for the following discussion. The chemistry of the hydrogen sulfide-formaldehyde reaction is quite complex, producing cyclic carbon-sulfur compounds and, to a lesser extent, mercaptans. The main reaction path can be represented by... 

A major difference between alcohols and thiols concerns their oxidation We have seen earlier m this chapter that oxidation of alcohols gives compounds having carbonyl groups Analogous oxidation of thiols to compounds with C=S functions does not occur Only sulfur is oxidized not carbon and compounds containing sulfur m various oxida tion states are possible These include a series of acids classified as sulfemc sulfimc and sulfonic according to the number of oxygens attached to sulfur... 

Prior to methanation, the gas product from the gasifier must be thoroughly purified, especially from sulfur compounds the precursors of which are widespread throughout coal (23) (see Sulfurremoval and recovery). Moreover, the composition of the gas must be adjusted, if required, to contain three parts hydrogen to one part carbon monoxide to fit the stoichiometry of methane production. This is accompHshed by appHcation of a catalytic water gas shift reaction. 

The ratio of hydrogen to carbon monoxide is controlled by shifting only part of the gas stream. After the shift, the carbon dioxide, which is formed in the gasifier and in the water gas reaction, and the sulfur compounds formed during gasification, are removed from the gas. 

Iron Sulfur Compounds. Many molecular compounds (18—20) are known in which iron is tetrahedraHy coordinated by a combination of thiolate and sulfide donors. Of the 10 or more stmcturaHy characterized classes of Fe—S compounds, the four shown in Figure 1 are known to occur in proteins. The mononuclear iron site REPLACE occurs in the one-iron bacterial electron-transfer protein mbredoxin. The [2Fe—2S] (10) and [4Fe—4S] (12) cubane stmctures are found in the 2-, 4-, and 8-iron ferredoxins, which are also electron-transfer proteins. The [3Fe—4S] voided cubane stmcture (11) has been found in some ferredoxins and in the inactive form of aconitase, the enzyme which catalyzes the stereospecific hydration—rehydration of citrate to isocitrate in the Krebs cycle. In addition, enzymes are known that contain either other types of iron sulfur clusters or iron sulfur clusters that include other metals. Examples include nitrogenase, which reduces N2 to NH at a MoFe Sg homocitrate cluster carbon monoxide dehydrogenase, which assembles acetyl-coenzyme A (acetyl-CoA) at a FeNiS site and hydrogenases, which catalyze the reversible reduction of protons to hydrogen gas. 

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. 

Sulfur Compounds. Various gas streams are treated by molecular sieves to remove sulfur contaminants. In the desulfurization of wellhead natural gas, the unit is designed to remove sulfur compounds selectively, but not carbon dioxide, which would occur in Hquid scmbbing processes. Molecular sieve treatment offers advantages over Hquid scmbbing processes in reduced equipment size because the acid gas load is smaller in production economics because there is no gas shrinkage (leaving CO2 in the residue gas) and in the fact that the gas is also fliUy dehydrated, alleviating the need for downstream dehydration. 

Steam Reforming Processes. In the steam reforming process, light hydrocarbon feedstocks (qv), such as natural gas, Hquefied petroleum gas, and naphtha, or in some cases heavier distillate oils are purified of sulfur compounds (see Sulfurremoval and recovery). These then react with steam in the presence of a nickel-containing catalyst to produce a mixture of hydrogen, methane, and carbon oxides. Essentially total decomposition of compounds containing more than one carbon atom per molecule is obtained (see Ammonia Hydrogen Petroleum). 

Other miscellaneous compounds that have been used as inhibitors are sulfur and certain sulfur compounds (qv), picryUiydrazyl derivatives, carbon black, and a number of soluble transition-metal salts (151). Both inhibition and acceleration have been reported for styrene polymerized in the presence of oxygen. The complexity of this system has been clearly demonstrated (152). The key reaction is the alternating copolymerization of styrene with oxygen to produce a polyperoxide, which at above 100°C decomposes to initiating alkoxy radicals. Therefore, depending on the temperature, oxygen can inhibit or accelerate the rate of polymerization. 

Sulfonic acids are prone to reduction with iodine [7553-56-2] in the presence of triphenylphosphine [603-35-0] to produce the corresponding iodides. This type of reduction is also facile with alkyl sulfonates (16). Aromatic sulfonic acids may also be reduced electrochemicaHy to give the parent arene. However, sulfonic acids, when reduced with iodine and phosphoms [7723-14-0] produce thiols (qv). Amination of sulfonates has also been reported, in which the carbon—sulfur bond is cleaved (17). Ortho-Hthiation of sulfonic acid lithium salts has proven to be a useful technique for organic syntheses, but has Httie commercial importance. Optically active sulfonates have been used in asymmetric syntheses to selectively O-alkylate alcohols and phenols, typically on a laboratory scale. Aromatic sulfonates are cleaved, ie, desulfonated, by uv radiation to give the parent aromatic compound and a coupling product of the aromatic compound, as shown, where Ar represents an aryl group (18). 

Incompletely Characterized Carbon Sulfides. A poorly characterized black soHd, known as carsul, occurs as a residue ia sulfur distillation or as a precipitate ia molten Frasch sulfur (12,13). Although this material may approach the composition of a carbon sulfide, it is more likely also to contain some chemically bound hydrogen and possibly other elements. Carbon—sulfur surface compounds of the formula C S, where xis greater than 4,... 

Alternative means for removal of carbonyl sulfide for gas streams iavolve hydrogenation. For example, the Beavon process for removal of sulfur compounds remaining ia Claus unit tail gases iavolves hydrolysis and hydrogenation over cobalt molybdate catalyst resulting ia the conversion of carbonyl sulfide, carbon disulfide, and other sulfur compounds to hydrogen sulfide (25). 

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. 

Organic acids, including carbon dioxide, lower the wort pH during fermentation. The principal acids formed are lactic, pymvic citric, malic, and acetic acids, at concentrations ranging from 100—200 ppm. The main sulfur compounds formed during fermentation and thek perception thresholds are as follows H2S (5—10 ppb) ethanethiol (5—10 ppb) dimethyl sulfoxide (35—60 ppb) and diethyl sulfide (3—30 ppb). At low levels, these may have a deskable flavor effect at higher levels they are extremely undeskable. Sulfur dioxide also forms during fermentation, at concentrations of 5—50 ppm its presence can be tasted at levels above 50 ppm. 

Barium sulfide solutions undergo slow oxidation in air, forming elemental sulfur and a family of oxidized sulfur species including the sulfite, thiosulfate, polythionates, and sulfate. The elemental sulfur is retained in the dissolved bquor in the form of polysulfide ions, which are responsible for the yellow color of most BaS solutions. Some of the mote highly oxidized sulfur species also enter the solution. Sulfur compound formation should be minimized to prevent the compounds made from BaS, such as barium carbonate, from becoming contaminated with sulfur. 

Carbon disulfide [75-15-0] (carbon bisulfide, dithiocarbonic anhydride), CS2, is a toxic, dense liquid of high volatiUty and fiammabiUty. It is an important industrial chemical and its properties are well estabUshed. Low concentrations of carbon disulfide naturally discharge into the atmosphere from certain soils, and carbon disulfide has been detected in mustard oil, volcanic gases, and cmde petroleum. Carbon disulfide is an unintentional by-product of many combustion and high temperature industrial processes where sulfur compounds are present. 

As seen in Figure 1, the organo sulfur compounds are methylated at the boiling point (90°C) of dimethyl carbonate, whereas methylation (or alkylation with other alkyl groups) of other functional groups requites higher temperatures. This has resulted in the selective methylation of sulfhydryl groups of compounds that contain other substituents that can be alkylated. The other substituents can then be alkylated at elevated temperatures (63). 

A flow diagram for the system is shown in Figure 5. Feed gas is dried, and ammonia and sulfur compounds are removed to prevent the irreversible buildup of insoluble salts in the system. Water and soHds formed by trace ammonia and sulfur compounds are removed in the solvent maintenance section (96). The pretreated carbon monoxide feed gas enters the absorber where it is selectively absorbed by a countercurrent flow of solvent to form a carbon monoxide complex with the active copper salt. The carbon monoxide-rich solution flows from the bottom of the absorber to a flash vessel where physically absorbed gas species such as hydrogen, nitrogen, and methane are removed. The solution is then sent to the stripper where the carbon monoxide is released from the complex by heating and pressure reduction to about 0.15 MPa (1.5 atm). The solvent is stripped of residual carbon monoxide, heat-exchanged with the stripper feed, and pumped to the top of the absorber to complete the cycle. 

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