Petroleum sulfur compounds

Yamada ( 10) reported the isolation of a bacteria capable of utilizing petroleum sulfur compounds like dibenzothiophene. Sagadia (11) isolated a bacteria on benzothiophenes, but due to the toxicity of the compound and the oil components and metals the culture could not reduce the sulfur content of the oil. 

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. 

Reference Data for Hydrocarbons and Petro-Sulfur Compounds, Phillips Petroleum Company, 1962. 

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. 

Thiophene [110-02-17, C H S, and dibenzothiophene [132-65-OJ C22HgS, are models for the organic sulfur compounds found in coal, as well as in petroleum and oil shale. Cobalt—molybdenum and nickel—molybdenum catalysts ate used to promote the removal of organic sulfur (see Coal CONVERSION... 

Petroleum. Apart from its use ia petrochemicals manufacture, there are a number of small, scattered uses of lime ia petroleum (qv) production. These are ia making red lime (drilling) muds, calcium-based lubricating grease, neutralization of organic sulfur compounds and waste acid effluents, water treatment ia water flooding (secondary oil recovery), and use of lime and pozzolans for cementing very deep oil wells. 

The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxyUc acids present in cmde oil. Naphthenic acids [1338-24-5] are classified as monobasic carboxyUc acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentane and cyclohexane derivatives. Naphthenic acids are composed predorninandy of aLkyl-substituted cycloaUphatic carboxyUc acids, with smaller amounts of acycHc aUphatic (paraffinic or fatty) acids. Aromatic, olefinic, hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic acids also contain varying amounts of unsaponifiable hydrocarbons, phenoHc compounds, sulfur compounds, and water. The complex mixture of acids is derived from straight-mn distillates of petroleum, mosdy from kerosene and diesel fractions (see Petroleum). 

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). 

Sulfur constitutes about 0.052 wt % of the earth s cmst. The forms in which it is ordinarily found include elemental or native sulfur in unconsohdated volcanic rocks, in anhydrite over salt-dome stmctures, and in bedded anhydrite or gypsum evaporate basin formations combined sulfur in metal sulfide ores and mineral sulfates hydrogen sulfide in natural gas organic sulfur compounds in petroleum and tar sands and a combination of both pyritic and organic sulfur compounds in coal (qv). 

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. 

Hydrogen sulfide Refinery gases, crude oil, sulfur recovery, various chemical industries using sulfur compounds Petroleum and chemicals Kraft pulping process Foul odor of rotten eggs irritating to eyes and respiratory tract darkening exterior paint... 

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

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. ... 

Sulfur in crude oils is mainly present in the form of organosulfur compounds. Hydrogen sulfide is the only important inorganic sulfur compound found in crude oil. Its presence, however, is harmful because of its corrosive nature. Organosulfur compounds may generally be classified as acidic and non-acidic. Acidic sulfur compounds are the thiols (mercap-tans). Thiophene, sulfides, and disulfides are examples of non-acidic sulfur compounds found in crude fractions. Extensive research has been carried out to identify some sulfur compounds in a narrow light petroleum fraction.Examples of some sulfur compounds from the two types are ... 

Most sulfur compounds can be removed from petroleum streams through hydrotreatment processes, where hydrogen sulfide is produced and the corresponding hydrocarbon released. Hydrogen sulfide is then absorbed in a suitable absorbent and recovered as sulfur (Chapter 4). 

Thiophene (C4H4S) is representative of the organic sulfur compounds that are hydrogenated in the commercial hyditodesulfurization of petroleum naphtha. Estimate both the combined and effective diflfusivities for thiophene in hydrogen at 660 °K and 3.04 MPa in a catalyst with a BET surface area of 168 m2/g, a porosity of 0.40, and an apparent pellet density of 1.40 g/cm3. A narrow pore sized distribution... 

Engineered biocatalysts with altered specificity have been developed. A Rhodococcus strain capable of DBT as well as BT desulfurization has been developed by cloning dsz genes into a strain-containing BT desulfurization pathway. The variety of sulfur compounds in petroleum feedstocks and complexity of the problem may require use of a consortium rather than a single bacterial strain. Alternately, use of multiple bioreactors each with a single dominant strain may be employed to achieve maximum desulfurization [299],... 

Kohler, M. Genz, I.-L. Schicht, B., and Eckart, V., Microbial Desulfurization of Petroleum and Heavy Petroleum Fractions. 4. Anaerobic Degradation of Organic Sulfur Compounds. Zentralbl. Mikrobiol., 1984. 139 pp. 239-247. 

The research was oriented towards the development of biocatalysts for removal of recalcitrant sulfur heterocyclic compounds including benzothiophenes, naphthothio-phenes, and alkylbenzothiophenes. To begin with, they focused on asymmetric sulfur compounds in this class and developed a method for desulfurization of these compounds present in petroleum products [108], The identity of the microorganisms was not disclosed in the abstract but they do claim use of the enzymes as well in the application. 

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