ANALYTICAL CHEMISTRY, VOL. 51, NO. 5, APRIL 1979
211 R
Petroleum J. M. Fraser Union Oil Company of California, Brea, California 9262 1
This is the 14th review of analytical chemistry in the petroleum industry (1A-13A) sponsored by the Division of Petroleum Chemistry of the American Chemical Society. This review article attempts to cover the most important papers abstracted in Chemical Abstracts, in the American Petroleum Institute Refining Literature Abstracts, and in Anal3 tical Abstracts (London) for the period of July 1976 through June 1978. Thus this review begins where the previous one ended and the general format of previous reviews is continued. References conform t o the Chemical Abstracts "Guide for Abbreviating Periodic Titles". In addition, when a reference publication might not be readily available, the abstract journal reference has been appended to that for the original source. The abbreviations C.A., A.P.I.A., and B.A. are used to identify in order the abstract journals listed above. These abbreviations are followed by the volume number, the abstract number, and the year. The abstract searching was done by D. K. Albert, Standard Ohio Company (Indiana), Amoco Research Center; C. A. Simpson, Mobil Research and Development Corporation; and J. M. Fraser, Union Oil Company of California. The collected abstracts were screened and organized by subject. Each collection of abstracts was then additionally reviewed, screened, and organized by 1 2 authors of the 10 sub-sections which follow. The generous assistance of the abstractors and the authors, many of whom have contributed to previous reviews is very much appreciated and the production of this review is again due to their combined efforts.
trations of polyaromatics are higher in the extracts than they are in the oils (9B). Wise and co-workers used p-Bondapak-NH, to separate polynuclear aromatic hydrocarbons on the basis of the number of condensed rings, and found it gave more distinct separations than other adsorbants (91R). Voznesenskaya and others measured and tahulated a wide variety of physical and chemical properties of the residual oils from four Soviet Union petroleums (88B). The Garrett Gas Train Sulfide Analysis (GGT/S2-)provides a means for quantitatively determining sulfides in a liquid sample. The sample is acidified and the resulting H2S is swept into a Draeger tube for measurement. The method is simple enough to be used in the field (26B). Hajibrahim and others employed HPLC with 5 fim irregular silica gel particles to separate porphyrin mixtures and total nonsaponifiable carotenoid mixtures isolated from curde oils. This technique was also used to fingerprint petroporphyrin distributions in petroleum (30B). S h a l e Oil a n d Coal Liquids. Jones and co-workers have reported a preparative scale fractionation of these fluids on Sephadex LH-20. The gel is used in three different modes: lipophilic-hydrophilic partitioning, molecular size separation, and aliphatic-aromatic separation. The reproducibility of the gravimetric yields is about 2 % (43B). Hurtubise and others prepared concentrates of polynuclear aromatic hydrocarbons from shale oil by column and thin-layer chromatography. Compounds in the column eluate and on the thin-layer plates were identified by their fluorescence spectra (3%'). Hanson and co-workers pyrolyzed oil shales with pulsed lasers and separated the produced gases by GC. The carbonate content of the sample correlates with the CO produced, the Fischer Assay for oil content with the hydrocarbon gases produced, and the hydrogen content of the sample with the ratio of H,-to-CO (31B). Gallegos used mass spectrometric metastable transitions for the identification of steranes and terpanes in shale oil. This technique gives much the same information as is obtained by GC/MS, but in less time (25R Klesment and co-workers studied the behavior of heav shale tar when it is cracked at 3oCt450 "C. Half the tar formed low boiling compounds, the most abundant being the C I 4and CI61-alkenes, and a third of the tar formed coke (48R). Riley has separated such potentially toxic compounds as aromatic and polynuclear aromatic hydrocarbons, thiophenes, and indoles, from shale oil and its waste products by high speed liquid chromatography, but did not attempt identification or quantitative analysis of them (70B) Holmes and co-workers employed the techniques developed by the U.S. Bureau of Mines for API Project 60 to characterize two oils produced by the H-Coal process from Illinois No. 6 coal (36R). Clark and others have reviewed the methods for general class separation of compounds in coal liquids, shale oils, and crude oils (17B). F i n g e r p r i n t i n g a n d Oil S p i l l Identification. Two papers reviewed the variety of analyses used in oil spill identification and discussed their advantages and shortcomings (7B,90B). Flory and others proposed a multimethod approach to matching oils (24R). Infrared spectroscopy has been extensively investigated by Brown and his co-workers for matching spills to their sources. A digitized library of spectra from more than 300 crude oils and the application of statistical methods aid in the matching (6B, 12B). The effects of natural and simulated weathering are also considered (3B. 23B, 14R). Mattson and co-workers have investigated pattern recognition techniques (59R),linear discriminant function analysis (61B), and a multivariate statistical approach (62R)to the problem of fingerprinting oils by infrared spectroscopy. Koeser and Oelert have also discussed computer based systems for fingerprinting crude
Crude Oils F. C. Trusell Marathon Oil Company, Littleton, Colorado
During the preceding two review periods there was a distinct trend away from analyses for the purpose of elucidating the composition of crude oil and its distillate fractions as an end in itself, to analyses for specific applications such as identifying the sources of oil spills, and for geochemical investigations into the origin and migration of crude oil. The continuation of this trend is apparent in the present review. H y d r o c a r b o n a n d Heterocompounds. Smol'yaninova and others determined the hydrocarbon compounds in the various distillate fractions of Samotlorskoe crude oil by physical and chemical methods. Particular attention was given to the gasoline fraction (84B). Svajgl and Kuras have devised a scheme for a hydrocarbon group-type analysis combining liquid chromatography and such conventional determinations as bromine number and aniline point. T h e results approximate those from a mass spectrometric analysis ( 8 6 R ) . Khoroshko and co-workers determined the concentrations of individual hydrocarbons in the gasoline fractions of crude oils from three fields and discussed the implications of their findings ( 4 7 B ) . Dididze and co-workers used a variety of techniques to determine, and to compare, the compositions of the CI4-C1, saturates in three Georgian SSR crude oils. Some significant differences were noted in oils from geographically close locations (19B). Deutsch employed proton NMR to determine the proportions of aromatic compounds, the extent of substitution of aromatic rings, and the methyl groups in non-aromatic compounds, in 34 crude oil fractions boiling between 218 and 439 "C ( 1 8 B ) . Botneva and Nechaeva determined the concentrations of various polycyclic aromatics in crude oils and rock extracts by luminescence spectroscopy. The concen0003-2700/79/0351-211R$05 OO/O
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1979 American Chemical Society
