Sulfur compound separation

Raw synthesis gas is a mixture of hydrogen, carbon monoxide, carbon dioxide, water vapor and residual unconverted hydrocarbons. Hydrogen and carbon-monoxide-rich offgas streams from petrochemical and refinery processes contain these and other contaminents such as nitrogen, argon and sulfur compounds. Separation and purification is necessary to produce hydrogen and carbon monoxide suitable for use as feedstock in petrochemical processes and a variety of methods have been developed to achieve these separations. 

Other sulfur compounds such as thiourea, ammonium dithiocarbamate, or hydrogen sulfide also lead to 2-mercaptothiazoles. Thus thiourea has been used in the syntheses of 4,5-dimethyl (369) and 4-aryl-2-mercapto-thiazoles (Table 11-30) (519). The reactions were carried out by condensing the ia -thiocyanatoketones with thiourea in alcohol and water acidified with hydrochloric acid. By this procedure, 4-aryl-2-mercaptothiazoles were obtained in yields of 40 to 80% with bis-(4-aryl-2-thiazolyl) sulfides as by-products (519). These latter products (194) have also been observed as a result of the action of thiourea on 2-chloro-4-arylthiazole under the same experimental conditions. They can be separated from 2-mercaptothiazoles because of their different degrees of solubility in sodium hydroxide solution at 5%. In this medium bis-(4-phenyl-2-thiazolyl)sulfide is... 

Benzene [71-43-2] toluene [108-88-3] xylene [1330-20-7] and solvent naphtha are separated from the light oil. Benzene (qv), toluene (qv), and xylene are useful as solvents and chemical intermediates (see Xylenes and ethylbenzene). The cmde light oil is approximately 60—70% ben2ene, 12—16% toluene, 4—8% xylenes, 9—16% other hydrocarbons, and about 1% sulfur compounds (5) (see BTX processing). 

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. 

Chlorates are strong oxidising agents. Dry materials, such as cloth, leather, or paper, contaminated with chlorate may be ignited easily by heat or friction. Extreme care must be taken to ensure that chlorates do not come in contact with heat, organic materials, phosphoms, ammonium compounds, sulfur compounds, oils, greases or waxes, powdered metals, paint, metal salts (especially copper), and solvents. Chlorates should be stored separately from all flammable materials in a cool, dry, fireproof building. 

Certain refinery wastewater streams are treated separately, prior to the wastewater treatment plant, to remove contaminants that would not easily be treated after mixing with other wastewater. One such waste stream is the sour water drained from distillation reflux drums. Sour water contains dissolved hydrogen sulfide and other organic sulfur compounds and ammonia which are stripped in a tower with gas or steam before being discharged to the wastewater treatment plant. 

Other Techniques Continuous methods for monitoring sulfur dioxide include electrochemical cells and infrared techniques. Sulfur trioxide can be measured by FTIR techniques. The main components of the reduced-sulfur compounds emitted, for example, from the pulp and paper industry, are hydrogen sulfide, methyl mercaptane, dimethyl sulfide and dimethyl disulfide. These can be determined separately using FTIR and gas chromatographic techniques. 

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.

Figure 14.5 Chi OinatograplTic separation of (a) sulfur compounds, and (b) hydrocarbons, obtained by using the system illustrated in Figure 14.4.

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 overhead product is totally liquefied in the overhead condensers. A portion of the overhead liquid is pumped and returned to the tower as reflux. The remainder is sent to a treating unit to remove H2S and other sulfur compounds. The mixed Cj s and C s stream can then be fed to an ether or an alkylation unit. It can be fed to a depropanizer tower where the Cj s are separated from C4 s. The Cj s are processed for petrochemical feedstock and the C4 s are alkylated. 

Products from the reactor are recovered in the main fractionator a J the gas plant. The main fractionator recovers the heaviest produc, such as light cycle and decanted oil, from the gasoline and ligh r products. The gas plant separates the main fractionator overhead vap< s into gasoline, Cj s, C4 s and fuel gas. The products contain sulfur compounds and need to be treated prior to being used. A combination of amine and caustic solutions are employed to sweeten these products... 

SFC-FID is widely used for the analysis of (nonvolatile) textile finish components. An application of SFC in fuel product analysis is the determination of lubricating oil additives, which consist of complex mixtures of compounds such as zinc dialkylthiophosphates, organic sulfur compounds (e.g. nonylphenyl sulfides), hindered phenols (e.g. 2,6-di-f-butyl-4-methylphenol), hindered amines (e.g. dioctyldiphenylamines) and surfactants (sulfonic acid salts). Classical TLC, SEC and LC analysis are not satisfactory here because of the complexity of such mixtures of compounds, while their lability precludes GC determination. Both cSFC and pSFC enable analysis of most of these chemical classes [305]. Rather few examples have been reported of thermally unstable compounds analysed by SFC an example of thermally labile polymer additives are fire retardants [360]. pSFC has been used for the separation of a mixture of methylvinylsilicones and peroxides (thermally labile analytes) [361]. 

Phosphorous- and sulfur-containing compounds separated by GC have been determined with both He and N2 MIP-MS systems with low ng to pg detection limits [335], Halogenated compounds and organotins can be determined by GC-MIP-MS, at low to sub-pg detection limits. 

Conventional wastewater treatment techniques consist of physical/chemical treatments, including oil separation, dissolved gas flotation, and ammonia distillation (for removal of free cyanides, free sulfides, and ammonia) followed by biological treatment (for organics removal) and residual ammonia nitrification. Almost all residuals from coke-making operations are either recovered as crude byproducts (e.g., as crude coal tar, crude light oil, ammonium sulfate, or other sulfur compounds)... 

Kremer L, Spicer LD. 1973. Gas chromatographic separation of hydrogen sulfide, carbonyl sulfide, and higher sulfur compounds with a single pass system. Anal Chem 45 1963-1964. 

This reaction is the reverse of the initial ketyl radical formation by the benzophenone triplet and is therm Q4ynamically favorable. The experiments using optically active alcohols as source of hydrogen atoms show, however, that under normal conditions this reaction is unimportant. This is probably due to other, more efficient pathways for reaction of the ketyl radicals or perhaps to diffusion rates which separate the radicals before reverse transfer can occur. That this reaction can be important in some cases even without the presence of sulfur compounds was shown by studying the photoreduction of benzophenone in optically active ethers.<68) Although the reaction of benzophenone in methyl 2-octyl ether is only 0.17 times as fast as that in isopropanol, ethers can be used as sources of hydrogen atoms for photoreduction ... 

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