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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
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oils, and for resolving overlapping bands (49B). Grizzle and Coleman obtained absorbance data a t 14 selected frequencies for 52 crude oils. By statistical analysis, they found that 1 2 of these frequencies could be used for the identification of both weathered and unweathered oils. T h e best results were obtained when the reference oil was artificially weathered before comparison with a weathered spill sample (27B). Kawahara and Yang proposed linear discrimination function analysis of ratios of various infrared peaks as a tool for matching an oil spill to a suspected source. They claim 99% accuracy for the method (46B). Mattson had disputed their findings as an oversimplification (60B). T h e use of laser Raman spectroscopy for the identification of oil spills has been hindered by the high fluorescence background which obscures any bands caused by Raman scattering. Ahmadjian and Brown eliminated this problem by adding powdered charcoal to a dilute solution of the sample in pentane. The fluorescent compounds are adsorbed on the charcoal, and no longer interfere with the analysis (4B). Rasmussen obtained gas chromatograms of oils on a 100-ft Dexsil-300 SCOT column. He mathematically treated the chromatograms to obtain "GC patterns" which were characteristic of the oil, and which remained essentially unchanged even after moderate weathering. Several examples are presented to demonstrate the utility of the method (69B). Flanigan and Frame employed a 50-ft SCOT column of either OV-101 or Dexsil-300, and split the effluent between a FID and a N-P detector to obtain fingerprint chromatograms. The N-P mode was especially useful for heavier oils, even after weathering (23B). Grizzle and Coleman studied the correlation of oils by means of the distribution of the n-paraffins. The n-CI1 t o n-Cs5 paraffins were found to be statistically significant for unweathered crudes, while the n-C,, to n-Ciowere best suited for matching weathered samples with unweathered reference oils (28B). Adler and Budinscak fractionated more than 40 crude oils by gel permeation chromatography on polystyrene gels to form a reference library. They were able to classify unknown oils by comparing chromatograms. Mixed oils could not be classified ( I B ) . Saner and Fitzgerald fingerprinted distillate fractions and residual oils using thin-layer chromatograms of the aromatic-polar fraction. This fraction is first isolated by extracting the sample with acidified methanol. Examples correlating spills with suspected sources are shown (79B). Saner and co-workers also fingerprinted crude oils by reverse phase liquid chromatography of the methanol extractables on p-Bondapak-C18. Discrimination between samples was done on the basis of peak height ratios a t 210 and 254 nm (80B). Rogers and others found they could detect useful differences in the liquid chromatograms of heavy petroleum fractions obtained from 25-cm columns of "LiChrospher". They could not, however, distinguish between different coal tars ( 7 I B ) . John and Soutar have studied the variables influencing the results of synchronous excitation spectrofluorometric examinations of crude oils. They find this method adequate to establish the identities of unweathered oils and, when used in conjunction with conventional fluorimetry, promising in the identification of oils in marine spills ( 4 0 B , 4 I B ) . Hertz and co-workers have designed an integrated approach t o oil spill source identification. They combine GC analysis of the head-space gases with GC and HPLC analyses of the liquid portion. Data from major spills are presented and discussed (34B). Yoo has calculated a modified UOP K-factor which links GC and ASTM analyses, and is potentially useful in identifying the source of an oil spill (93B). Ahmadjian and co-workers removed the water from Feathered oil samples by centrifugation at 3700 rpm at 35- 40 C for 0.5 t o 2 h , depending on the viscosity of the sample. Higher temperatures and longer times were required for heavier oils (2%). Geochemical Studies. Kulikova and co-workers extracted recent sediments from the Black, White, and Caspian Seas and isolated the saturate fractions by silica gel chromatography. Increasing diagenesis brought about a decrease in biand tricyclic naphthenes in the upper strata, and in monocyclic naphthenes in the lower strata. and an enrichment in paraffinic compounds. T h e influences of biogenic and geochemical factors were assessed ( 5 1 B ) . Hollerbach and Welte have proposed a separation scheme for organic matter ex-
tracted from sediments. T h e asphaltenes are first removed by Florosil. T h e remaining material is then passed through a silica gel-60 column with hexane, chloroform, and methanol to remove saturates, aromatics, and heterocompounds, respectively (35B). Overton and others extracted the organic compounds from sediments of three outer continental shelf areas around the U S . , obtained chromatogranis on glass capillary columns coated with SE-52, and identified the key peaks. In spiking experiments, they found they were able to distinguish indigenous hydrocarbons from those added by petroleum (67B). McKirdy and Horvath have developed an integrated scheme for the analysis of oil, natural gas, and rocks to assist in the search for more hydrocarbons. They infer composition and geological history from chromatograms of the C,,+ alkanes and infer whether an area is oil- or gas-prone by the Cz-C4 content of the natural gas (57B). Brooks and Thusu have assessed Jurassic sediments as possible source rocks for oils found in the North Sea basin. Chemical maturation studies, and similarities in the composition of the n-paraffins in rock extracts and in the Statfjord and Ekofisk crude oils, confirm that Jurassic rocks a t present depths of 2600-3200 m represent a major source of hydrocarbon generation ( I I B ) . Jones has shown the advantages of using a sophisticated GC/MS system in the characterization of complex mixtures, and has demonstrated its utility in recognizing the sources of crude oils (44B). Huc and coworkers have developed a thin-layer chromatographic analysis for small samples such as the extract from a few grams of rocks. They demonstrate t h a t the results obtained are comparable to those from larger scale analyses (37B). Botneva and others suggest that the direction and range of petroleum migration can be estimated from measurement of three infrared bands (IOB). Safonova and Mileshina found that when petroleum a t TO "Cwas chromatographed through montmorillonite and mudstone, the n-paraffins with low molecular weight and odd carbon numbers were concentrated in the first fraction of the eluate, and the portion sorbed on the rock contained more of the high molecular weight hydrocarbons than the filtrate. When chromatographed through dolomite under similar conditions, the n-pal affins were more intensely held by the rock. These findings may give some insight into migration processes ( 7 8 B ) . Neuman has developed a method for determining oil in reservoirs by neutron activation analysis. The techniques can be used in cased, as well as with uncased, holes ( 6 5 R ) . Levshunova and Telkova determined the light hydrocarbons in Lower Cretaceous formations of the eastern Caucasus, liberating them by thermal desorption and by extraction, and analyzing them by GC. Variations with depth and with lithology were noted (55B). Safonova and Bulekova determined the distribution of n-paraffins in various petroleums and noted t h a t the proportion of ClO-Cl5 n-alkanes increases with increasing age and/or maturity. They attributed variations in the distribution with stratographic horizon and region to the composition of the original organic matter (76B). Il'inskaya and Safonova also used the distribution of n-paraffins for the correlation of bitumens in rocks near oil fields to the produced oils (39B). Sidorov employed infrared measurements to determine the total hydrocarbons in chloroform-extracted bitumens from rock samples. The analysis takes about 30 min, and the results agree well with those from chromatographic determinations (83B). Dubanska, Dubansky, and Hejl have described two pyrolytic methods for the determination of bitumens and gases in geological samples. A Sn bath pyrolyzer is used for samples containing more than bitumens, and an electrically heated gas pipet pyrolyzer is used for samples containing as little as 10 bitumens (20B, 2 I B ) . Espitale and others liberate the organic matter from rock samples by programmed pyrolysis in an inert atmosphere and measure the various products by mass spectroscopy. They point out the application of this technique to petroleum exploration, the estimation of oil yield from shales, and the determination of coal quality (22B). Saxby has studied the demineralization of kerogens from Australian shales and coals, and has determined the effect of each step on the sample. Upon HC1 and H F treatment, the kerogen N content decreases, kerogen solubility increases, and large losses of organic matter occurs ( 8 1 R ) .
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James M. Fraser is manager of the analytical research group of the Union Oil Company of California Science and Technology Division, Brea, Calif. He received his B.S. degree in chemistry from the University of Wisconsin in 1953, and his PhD. degree from there in physical chemistry in 1957. At that time he joined the Pure Oil Company Research Department in Crystal Lake, Ill. He was director of the analytical division of the Pure Oil Company Research Department at the time of the merger of The Pure Oil Company into Union Oil Company of California in 1965. He is a member of the ACS. SAS. and of several ASTM committees. F. C. Trusell Marathon Oil Company Littleton, Colo .
N. H. Flck Texaco, Inc . Beacon, N . Y
N. W. Lambert Union Oil Co. of Calif. Research Department Brea, Calif.
W. E. Halnes Laramle Energy Research Center Energy Research and Development Administration Laramle, Wyo.
J. E. Tacket Marathon Oil Company Littleton, Colo.
M. P T. Bradley The Standard Oil Co . (Ohio) Cleveland, Ohio
D. R. Latham Laramle Energy Research Center Energy Research and Development Administration Laramle, Wyo.
J. W. Loveland Suntech, Inc . Ne wtown Square, Pa
J. D. Beardsley The Standard Oil Co . (Ohio) Cleveland, Ohio
J. Fred Gulf Research & Development Co. Pinsburgh, Pa.
I?. E. Terrell Gulf Research and Development CO . Pittsburgh, Pa.
C. N. White Suntech, Inc , Newton Square, Pa
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Zabrodina and others classified 320 oils, from all of the principal U.S.S.R. fields, into four groups on the basis of the composition of the 200-430 "C fraction and the distribution of n-paraffin and isoprenoid hydrocarbons. From these data, they developed a scheme of genesis and transformation of oil which suggests a consecutive bacterial biodegradation from paraffinic to naphthenic crudes (94B). Gurko and co-workers examined crudes from the Caspian and Baltic shores, and from east Siberia and classified them on the basis of their physical properties and their chemical compositions as determined by GC. T h e crudes are remarkable for their high initial boiling points. The investigators also drew conclusions as to the genetic transformations of the oils (29B). Botneva and co-workers genetically classified crude oils on the basis of the distribution of aromatic compounds boiling above 200 "C (8B). Safonova and Driatskaya correlate crude oils on the basis of some 18 physical and chemical analyses of the whole crude and several additional analyses of distillate fractions (77B). Joly and co-workers, in a regional geochemical study of Middle East crude oils, used structural analytical methods such as GC and MS. They found that density and heteroatom content more related to the thermal history of the source rock, while the naphthene-paraffin ratio, content of steranes and isoprenoids, and distribution of sulfur compounds, were connected to the type of organic matter in the source rock (42B). Marzec and Burczyk have suggested a correlation method based on compositional analyses by liquid chromatography and a partial characterization of the aromatic portion of either NMR spectroscopy or the ndM technique. T h e method was tested on 91 crudes from the Carpathian Flysch region and on 18 crudes from the Lubin region (58B). Chetverikova and co-workers classified dispersed organic matter on the basis of an examination of its nonbitumenous portion by microscopy, elemental analysis, E P R , chemical behavior toward pyridine, petrography, and X-ray analysis. They determined that the main difference between sapropelic and humic substances was the absence of condensed aromatic systems in the former (16B). Whitehead determined the structures of several pentacyclic triterpanes in Nigerian crude oil, and was able to relate them to modern triterpenoids, and to compounds in Green River shale (89B). Van Dorsselaer and others identified various triterpanes of the (17aH)-hopane series and the moretane series as ubiquitous constituents of the alkane fractions of petroleums, oil shales, coals, lignites, and other sediments. They suggest these compounds are formed by the degradation and isomerization of CS5precursors of the (17pH)-hopane series, which occurs in some microorganisms. Variations in the distribution of pentacyclic triterpanes may eventually be useful in developing correlations between crude oils and source rocks (87B). N o n - r o u t i n e Characterizations. Schoolery and Budde explored the use of carbon-13 NMR as a tool for petroleum analysis. This technique has the potential of providing accurate saturate-to-aromatic ratios more rapidly than conventional methods, and has the advantage of distinguishing betueen carbon atoms in the saturate and the aromatic moieties within the same molecule (15B, 82B). Krasodomaki used negative ion mass spectrometry to study the carboxylic acids, either separated from Polish petroleums or prepared by the oxidation of their distillate fractions (50B). Kuz'm ia and co-workers predicted the yields of coke obtained by delayed coking by measurements of absorption coefficients of benzene solutions of the feedstocks a t 400 and 435 nm. The predicted and experimental yields were in good agreement (52B). Roubicek and Splichal determined many of the components of coker distillate by GC (73B). Roof and DeFord designed an apparatus for the chromatographic determination of C3-C, hydrocarbons in stabilizer bottoms. The volatile portion of the sample is vaporized in a hollow column and analyzed by GC. The nonvolatile residue is backflushed from the tube with a liquid solvent. The solvent does not interfere with subsequent determinations (72R). Porro and Terhaar have discussed the instrumentation, and the advantages and disadvantages of double beam fluorescence spectrophotometry in the analysis of petroleum samples. The technique is particularly useful for measuring small differences between two samples of similar fluorescence (68R). Nauruzov and co-workers isolated the resinous components from Mangyshiah crude oil into four fractions by chroma-
tography through large pore silica gel. The fractions were characterized as to molecular weight and elemental composition. UV and IR spectroscopy gave some indication of the compound types present (64B). Sturm and others characterized a heavy crude oil produced by the Solfrac process from the Bartlett Field (Kansas). A combination of techniques including GC, MS, NMK, and GPC were applied to fractions isolated by extraction and by chromatography, to determine the major hydrocarbon and sulfur compound types (85B). McKay and co-workers have analyzed petroleum residues by the techniques originally developed by 'USBM-API Project 60 for the analysis of high boiling distillates. The compositions of residues from four oils are compared ( 5 f i R ) . Miscellaneous. Lee and others tabulated the densities, heat capacities, and UOP characterization factors for distillate fractions of three crude oils ( 5 4 R ) . Rubinstein and Strausx biodegraded Prudhoe Ray crude oil with a yeast and with a mixed bacteria culture, and compared various properties of the degraded oils with those of Athabasha oil sand bitumen. The similarity in properties led them to conclude that oil sand bitumen is formed by the biodegradation of conventional crude, and that the high viscosity, density, and pour point result from the large amount of the polar fraction which is not affected by biodegradation (74B). Bae used DTA and TGA a t high temperatures and pressures to determine the suitability of oils for recovery by fireflooding. Fifteen oils were tested ( 5 B ) . Kasa and Bajnoczy determined traces of oil and oil products in surface waters by exciting a 1,2-dichloroethane extract of the sample a t 260 nm and measuring the fluorescence at 340 nm ( 4 5 B ) . Larson and Weston examined the water extractable material from crude oils by GPC on Sephadex LH-20. Some individual compounds were identified by similar analyses of standard mixtures (53B). Oren and Mackay used GPC to separate the interface fraction of a water-in-petroleum emulsion. The resulting GPC fractions were studied by IR spectroscopy (66B). Milley isolated the natural surfactants in crude oil ti?. conventional chromatography, with kieselguhr as the column packing. The interfacial tensions of the fractions in benzene were measured vs. water, and the chemical properties of each fraction were evaluated by IR spectroscopy and by molecular weight determinations ( 6 3 R ) . Rumsey and Pitt review the methods used by the United Kingdom Coal Research Establishment for characterizing the structure and physical properties of cokes and graphites. Some relationships between the structural parameters of graphites and their physical properties are discussed ( 7 5 B ) . Hernandez and Moreno characterized oil from the Mata-Pionche Field of Mexico and have described the yields and compositions of various distillate fractions (33B). Hatch and Matar have reviewed in general terms the composition of crude oils and the usual means of characterizing them (32B). Yokokawa compared the U.S. Bureau of Mines. the Standard Oil Co., and the U.K. Institute of Petroleum methods for evaluating crude oils. He described equipment requirements, data evaluation, and reliability of data (9219).
Fuels, Gaseous and Liquid J. D. Beardsley The Standard Oil Company (Ohio), Ckveland, Ohio
N a t u r a l , Refinery a n d M a n u f a c t u r e d Gases. Routine analyses and related source data for 233 natural gases from wells and pipelines in the I!.S.A. and Alberta. Canada. are tabulated for 1975 by Moore (SIC) with emphasis on helium. Kubat, Macak, Mizera, and Zachoval (,54C) describe the analysis of natural gas by gas chromatography. The integrator can he used to calculate real density and real calorific values simultaneously. A gas chromatographic device based on the pyroelectric detector was successfully used by Guglya and Korobeinik (35C) for the determination of unsaturated hydrocarbons in the range of 0.001 to 0.0001 vol. % in natural gas from several Soviet fields containing 1 to 7.5% C 2 Ci paraffins. The optimum operating temperatures and threshold
