Sulfur reaction with methane

Methane reacts with sulfur (an active nonmetal element of group 6A) at high temperatures to produce carbon disulfide. The reaction is endothermic, and an activation energy of approximately 160 KJ is required. Activated alumina or clay is used as the catalyst at approximately 675°C and 2 atmospheres. The process starts by vaporizing pure sulfur, mixing it with methane, and passing the mixture over the alumina catalyst. The reaction could be represented as ... 

Bis(diphenylphosphino)methane was converted in two steps to a tetra-dentate phosphine-iminophosphorane ligand that gave the disulfide and the dioxide by reaction with sulfur and hydrogen peroxide, respectively (Scheme 15). ... 

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). 

Methane [74-82-8] reacts with sulfur essentially without side reactions ... 

For equation 26, starting with methane and soHd sulfur at 25°C, and ending with gaseous products at 600°C, the reaction is endothermic and requires 2.95 MJ /kg (705 kcal/kg) of CS2. The reaction of methane and sulfur vapor in the diatomic form is actually exothermic (23,78). Superheating of the sulfur is claimed to be preferable (79), and series operation of reactors offers a means of reducing process temperatures at which the sulfur dissociates (80). 

Potential Processes. Sulfur vapor reacts with other hydrocarbon gases, such as acetjiene [74-86-2] (94) or ethylene [74-85-1] (95), to form carbon disulfide. Higher hydrocarbons can produce mercaptan, sulfide, and thiophene intermediates along with carbon disulfide, and the quantity of intermediates increases if insufficient sulfur is added (96). Light gas oil was reported to be successflil on a semiworks scale (97). In the reaction with hydrocarbons or carbon, pyrites can be the sulfur source. With methane and iron pyrite the reaction products are carbon disulfide, hydrogen sulfide, and iron or iron sulfide. Pyrite can be reduced with carbon monoxide to produce carbon disulfide. 

The reaction of sulfur with methane at high temperature with a suitable catalyst (Si02 or A1203) also produces CS2. 

The chemiluminescent reaction with chlorine dioxide provides a highly sensitive and highly selective method for only two sulfur compounds, hydrogen sulfide and methane thiol [81]. As in the flame photometric detector (FPD), discussed below, atomic sulfur emission, S2(B3S -> ) is monitored in the wave-... 

A gas-phase reaction between methane (A) and sulfur (B) is conducted at 600°C and 101 kPa in a PFR, to produce carbon disulfide and hydrogen sulfide. The reaction is first-order with respect to each reactant, with kB = 12 m3 mol 1 h-1 (based upon the disappearance of sulfur). The inlet molar flow rates of methane and sulfur are 23.8 and 47.6 mol h 1, respectively. Determine the volume (V) required to achieve 18% conversion of methane, and the resulting residence or space time. 

The byproduct obtained from the overall reaction is carbon disulfide (CS ). The reaction between CH and H S given with Eq. 5.47 is the well-known methane process for production of CSj. Most commercial CH -snlfur processes employ silica gel/aluminum catalyst for CSj production. The reaction of CH with sulfur is thermodynamically favorable for CSj formation, and conversion is usually in the range of 90 to 95% with respect to methane (Arpe, 1989). The industrial CH -sulfur pro-... 

Most CFCs are manufactured by combining hydrogen fluoride and either carbon tetrachloride or chloroform. The hydrogen fluoride comes from fluorspar, CaF2, reacting with sulfuric acid. The chlorinated methanes are manufactured from methane. Important reactions in the manufacture of CFC-11 and -12 and HCFC-22 are given in Fig. 12.2. 

It also is obtained by the reaction of methane with sulfur vapor to produce carbon disulfide which on hydrolysis yields H2S ... 

Biedermann and Jacobson, who first prepared thieno[2,3-6]-thiophene (1) in 1886, characterized it as a 2,3,4,5-tetrabromo derivative with m.p. 172°. Later Capelle reported the isolation of a dibromo derivative of thienothiophene 1 with m.p. 122.5°, which was shown by Challenger and Harrison to be 2,3,5-tribromothieno[2,3-6]thiophene (m.p. 123°-124°). Capelle also obtained a tetrabromide, m.p. 223°, by bromination of the product of reaction of acetylene with sulfur. The tetrabromide seems to be identical with that prepared from the product of reaction of methane, acetylene, and hydrogen sulfide, m.p. 229°-230°, and is evidently 2,3,5,6-tetrabromothieno[3,2-6j-thiophene. ... 

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

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