Compounds of sulfur

The major part of the sulfur contained in crude petroleum is distributed between the heavy cuts and residues (Table 8.10) in the form of sulfur compounds of the naphthenophenanthrene or naphthenoanthracene type, or in the form of benzothiophenes, that is, molecules having one or several naphthenic and aromatic rings that usually contain a single sulfur atom. 

Interpreting the mass spectra of sulfur compounds is aided by the observation of an M+2 peak because of the presence of the mass 34 isotope of sulfur The major cleav age pathway of thiols is analogous to that of alcohols... 

TABLE 7.36 Raman Frequencies of Sulfur Compounds Continued)... 

Iron Sponge. An old method for removal of sulfur compounds involves contacting gases containing H2S and H2O with CC- or y-ferric oxide... 

Total 1991 world production of sulfur in all forms was 55.6 x 10 t. The largest proportion of this production (41.7%) was obtained by removal of sulfur compounds from petroleum and natural gas (see Sulfurremoval and recovery). Deep mining of elemental sulfur deposits by the Frasch hot water process accounted for 16.9% of world production mining of elemental deposits by other methods accounted for 5.0%. Sulfur was also produced by roasting iron pyrites (17.6%) and as a by-product of the smelting of nonferrous ores (14.0%). The remaining 4.8% was produced from unspecified sources. 

Sweet gas gas found in its natural state containing such small amounts of sulfur compounds that it can be used without purification with no deleterious effect on piping or equipment, and without the potential for health ha2ards. 

The largest use of NMP is in extraction of aromatics from lube oils. In this appHcation, it has been replacing phenol and, to some extent, furfural. Other petrochemical uses involve separation and recovery of aromatics from mixed feedstocks recovery and purification of acetylenes, olefins, and diolefins removal of sulfur compounds from natural and refinery gases and dehydration of natural gas. 

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). 

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). 

The catalyst commonly used in this method is 5 wt % palladium supported on barium sulfate inhibited with quinoline—sulfur, thiourea, or thiophene to prevent reduction of the product aldehyde. A procedure is found in the Hterature (57). Suitable solvents are toluene, benzene, and xylene used under reflux conditions. Interestingly, it is now thought that Rosenmund s method (59) originally was successful because of the presence of sulfur compounds in the xylene used, since the need for an inhibitor to reduce catalyst activity was not described until three years later (60). 

Fuel sulfur is also responsible for a phenomena known as storage and release of sulfur compounds. Sulfur oxides (S02,S02) easily react with ceria, an oxygen storage compound incorporated into most TWC catalysts, and also with alumina. When the air/fuel mixture temporarily goes rich and the catalyst temperature is in a certain range, the stored sulfur is released as H2S yielding a rotten egg odor to the exhaust. A small amount of nickel oxide incorporated into the TWC removes the H2S and releases it later as SO2 (75—79). 

Most natural gas is substantially free of sulfur compounds the terms. sweet and. sour are used to denote the absence or presence of HgS. Some wells, however, dehver gas containing levels of hydrogen sulfide and other sulfur compounds (e.g., thio enes, mercaptans, and organic sulfides) that must be removed before transfer to commercial pipehnes. Pipehne-company contracts typically specify maximum allowable Emits of impurities HgS and tot sulfur compounds seldom exceed 0.023 and 0.46 g/m (1.0 and 20.0 gr/100 std fF),... 

A duplex heat exchanger tube containing a single small perforation was examined. Perforation occurred due to internal surface wastage beneath a deposit layer containing large concentrations of sulfur compounds (Fig. 4.28). 

Temperatures required for corrosion by naphthenic acids range from 450 to 750°F, with maximum rates often occurring between 520 and 535°F. Whenever rates again show an increase with a rise in temperature above 650°F, sueh increase is believed to be caused by the influence of sulfur compounds which become corrosive to carbon and low alloy steels at that temperature. 

Natural gas - Determination of sulfur compounds. Determination of hydrogen sulfide, mercaptan sulfur, and carbonyl sulfide sulfur by potentiometry. Also BS 3156 Subsection 11.4.3 1994 Natural gas - Determination of sulfur compounds. Lmgener combustion method. Also BS 3156 Subsection 11.4.5 1994... 

The presence (and concentration, if known) of corrosive materials, other than the typical concentrations of sulfur compounds in petroleum hydrocarbon streams. 

Aj Hydrodesulfurization Removal of sulfur compounds from crude oil by reaction with hydrogen on CO - Mo on alumina. 

The physical solvent sulfolane provides the system with bulk removal capacity. Sulfolane is an excellent solvent of sulfur compounds such as H2S, COS, and CS2. Aromatic and heavy hydrocarbons and CO2 are soluble in sulfolane to a lesser degree. The relative amounts of DIPA and sulfolane are adjusted for each gas stream to custom fit each application. Sulfinol is usually used for streams with an H2S to CO2 ratio greater than 1 1 or where it is not necessary to remove the CO2 to the same levels as is required for H2S removal. The physical solvent allows much greater solution loadings of acid gas than for pure amine-based systems. Typically, a Sulfinol solution of 40% sulfolane, 40% DIPA and 20% water can remove 1.5 moles of acid gas per mole of Sulfinol solution. 

Thiophene and methylthiophenes have been found in virgin petroleum. 3,4,5-Trimethyl-2-methylthiothiophene has been isolated from a concentrate of sulfur compounds obtained in the refining of Middle East kerosene. ... 

Figure 14.2 Schematic diagram of the cliromatographic system used for the analysis of low concenti ations of sulfur compounds in ethene and propene VI, injection valve V2, column switcliing valve SL, sample loop R, restriction to replace the column SCD, sulfur chemiluminescence detector.

Figure 14.3 Clnomatographic separation of sulfur compounds in propene, obtained by using the system illusti ated in Figure 14.2 1, hydrogen sulfide 2, carbonyl sulfide.

It is for this reason that not only the various Sulfur-containing groups present, but also the mono- and dimethyl-substituted species of benzothiophenes and dibenzoth-iophenes have to be separated and quantified individually. As the number of sulfur compounds present in (heavy) middle distillate fractions may easily exceed 10 000 species, a single high resolution GC capillary column is unable to perform such a separation. 

The System described in the previous section has been extended with a sulfur chemiluminescence detector (SCO) for the detection of Sulfur compounds (32). The separated fractions were thiols + sulfides + thiophenes (as one group), benzothio-phenes, dibenzothiophenes and benzonaphtho-thiophenes. These four groups have been subsequently injected on-line into and separated by the GC unit. Again, no overlap between these groups has been detected, as can be seen from Figure 14.20, in which the total sulfur compounds are shown and from Figure 14.21 in which the separated dibenzothiophenes fraction is presented. The lower limit of detection of this method proved to be 1 ppm (mg kg ) sulfur per compound. 

The use of high-sulfur-content fuels could enhance undesirable carbon-forming tendencies in the engine combustion chamber as well as result in higher amounts of corrosive sulfur oxides in the combustion gases. Mercaptans (a type of sulfur compound) cause odor problems and can attack some fuel system elastomers. Both the concentration of total sulfur compounds as well as the concentration of mercaptan sulfur compounds arc controlled in... 

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