Isolation of sulfur compounds from petroleums

STRAUSZ ET AL. Isolation of Sulfur Compounds from Petroleum... 

Strausz, O.P. Payzant, J.D. Lown, E.M. Isolation of Sulfur Compounds From Petroleums , this volume. 

A summary of the work on the identification of sulfur compounds in crude oils has been given recently by Ball, Rail, Waddington, and Smith (31), who list the sulfur compounds isolated from petroleum by earlier investigators and, in addition, give several new compounds which have recently been isolated from a Wasson, Tex., crude petroleum by the API Research Project 48. Birch and Norris (5) isolated a substantial number of the thiol (mercaptan) type of sulfur compounds from an Iranian crude petroleum. 

The first section contains overview and introductory material, some historical background, summaries of the present state of knowledge, and other general topics applicable to all fossil fuel These include environmental consequences of fossil fuel combustion, polysulfide chemistry, microbial metabolism of sulfur compounds, and a review of methods for isolating sulfur compounds from petroleum. 

RTLs are being considered for selective extraction either in macro or micro scale. The isolation of target compounds from chemical process systems for instance alcohols from fermentation liquors (Chapeaux et al., 2008 Swatloski et al., 2002 Najdanovic-Visak et al., 2002), aromatic compounds from petroleum products (Arce et al., 2007a,b Arce et al., 2009 Arce et al., 2008), aromatic sulfur-containing compounds (Mochizuki Sugawara, 2008 Alonso et al., 2007 E er et al., 2004) from diesel-fuel represent the use of ILs in large-scale processes. 

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. ... 

In addition to the sulfur compounds listed above, hydrogen sulfide has been found in many crude petroleums. Elemental sulfur has been definitely found in several crude petroleums by API Research Project 48 (23). Although Birch and Norris (5) isolated several disulfides from the spent caustic used in treating gasoline from Iranian petroleum, these compounds may have resulted from the oxidation of the thiols and their presence in the original petroleum is regarded as doubtful. Other types of sulfur compounds, such as thiophenes and aromatic thiols, have been identified in cracked petroleum products, but the presence of such compounds in naturally occurring petroleums has not yet been established. 

Methods based on distillation or mercuric chloride adduct formation (1-5) are tedious and applicable only to the isolation of select, individual compounds. The methods of choice would, instead, isolate the various classes of sulfur-containing compounds from petroleum in high yield and purity. 

As is evident from the focus of this symposium, there is a great interest in sulfur compounds in petroleum. In addition, there is no doubt that microbial metabolism has played a major role in the quantity and quality of the World s petroleum. Yet there is relatively little information on the microbial metabolism of OSC found in petroleum. This paper provided a thorough review of the literature on the topic but it discussed only 20 pure OSC. I am not aware of work which has been done with any other compounds. In their studies of several crude oils, Rail et al. (13) isolated and identified 176 organic sulfur compounds which were grouped into 13 classes. Many more sulfur compounds have been identified since their work. Thus there is much more to be learned about microbial transformations of these compounds. 

Although crude petroleum contains small amounts of oxygen, nitrogen, and sulfur, its major constituents are hydrocarbons—compounds of carbon and hydrogen. Isolating individual hydrocarbon substances from petroleum mixtures is an industrial process of central importance. Moreover, it provides a fascinating story that illustrates how the structures of molecules determines the properties of substances and the behavior of those substances in particular processes. The next three sections present a brief introduction to this story, emphasizing the structure-property correlations. 

Thietanes and 3-thietanones represent the only four-membered sulfur-containing heterocycles of the title group that have been isolated from natural sources. Even in petroleum deposits, where 5- and 6-membered cyclic sulfur compounds are common, thietanes occur only in small amounts. However, thiacyclobutane (1) and thiacyclopentane are both commonly found in shale oil and could be utilized as a possible source of fuel. ... 

Various substituted aromatic compounds can be converted into sulfonyl chlorides by dissolution in five parts of chloroform, dropwise addition of five parts of chlorosulfuric acid at 0°, and keeping for 20 minutes at room temperature. The products are isolated by decomposition with ice, washing of the chloroform layer with water, removal of the solvent, recrystallization of the residue from dry low-boiling light petroleum or from chloroform, and drying in a vacuum over concentrated sulfuric acid. The following benzene-and naphthalene-sulfonyl chlorides were obtained in this way 217... 

Many sulfur-containing organic compounds can be isolated from natural sources such as crude oil, petroleum, gas condensates, and coals <2004MI1>. By chromatographic methods <1999MI58> various polycyclic aromatic sulfur heterocycles (PASHs) (1-7) have been identified from standard samples of coal tar, petroleum crude oil and decant oil. 

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