Isolation and Identification of Biphenyls from West Edmond Crude O li

NORMAN G. ADAMSI AND DOROTHY M . RICHARDSON Petroleum Experiment Station, U . S. Bureau o f Mines, Bartlesoille, Okla. The sometimes adverse effects of aromatic hydrocarbons on the combustion characteristics and deposit-forming tendencies of Diesel fuels have stimulated interest in the aromatic hydrocarbon content of such fuels. Ultraviolet spectra of distilled fractions had indicated the probable presence of biphenyls. The present report confirms the presence of biphenyl and 3-methylbiphenyl, and indicates the probable presence of alkylated biphenyls of higher molecular weight. The separation and identification of the t w o biphenyls definitely found are described. As this is the first time these compounds have been reported in virgin stocks from crude oils, it establishes the presence of such a series of aromatic hydrocarbons in crude oil and is, therefore, important not only from a commercial or practical point of view, but also scientifically.

HIS investigation of the presence of biphenyls in a crude oil is part of an extensive Diesel-fuel program being conducted by the Bureau of ;\lines Petroleum Experiment Station, Bartlesd e , Okla. This program involves the determination and study of the composition and properties. including combustion characteristics, of Diesel fuels (1, 3, 4, 6, 7 ) . In an earlier paper by the present authors ( 2 ) the presence of biphenyl and one of its methyl derivatives in close-cut distillation fractions from a crude oil from the West Edmond field in Oklahoma was strongly inferred by ultraviolet spectra. The present study was undertaken to prove the presence of biphenyl and its homologs in a straight-run distillate fuel.


The sequence of operations followed in the investigation was: the biphenyls from their respective fractions, and ( c ) identification of these biphenyls by their infrared spectra. Fractional Distillation of the Crude Oil. The fractional distillation of the crude oil, as described in an earlier paper ( 2 ) ,provided 2-liter fractions, each representing 0.25% of the crude oil, using a column of approximately 80 theoretical plates a t atmospheric pressure. The distillation was conducted a t a pressure of 80 mm. of mercury; it is believed that no significant cracking occurred. Isolation of Biphenyls. The ultraviolet absorption spectrum
Present address, Ethyl Corp., Baton Rouge, La.

(a) E,fficientfractional distillation of the crude oil, ( b ) isolation of

was determined for each of 61 fractions, covering the boiling range of 207" to 290" C. (405" to 554" F.). These fractions exhibited, for the most part, absorption patterns common to alkylbenxenes and alkylnaphthalenes ( 2 ) . Two fractions, Nos. 65 and 79, with corrected boiling pointe near 241 and 262 C: (466" and 504" F.), respectively, however, exhibited spectra radically different from the others, but similar to spectra of biphenyl and its homologs, with absorption maxima centered around 250 mp. I t had been learned previously ( 2 ) that the compounds responsible for these particular spectra could be concentrated by adsorption on silica gel. The biphenyl-containing subfractions from silica gel adsorption of fractlon 65 solidified on cooling, and white crystals were separated and recrystallized repeabedly from alcohol. The concentrate of fraction 79, however, was liquid, as are the three methyl derivatives of biphenyl. As alkylnaphthalenes composed the major contaminants, the concentrate was repeatedly treated with 1,3,5-trinitrobenzene ~olutionfor their removal by complexation. Identification of Individual Biphenyls. The infrared spectrum of the white crystalline material, in solution in carbon disulfide, was determined and compared t o a spectrum obtained similarly from a recrystallized Eastman sample of biphenyl. These comparison spectra are shown in Figure 1. The infrared spectrum of the concentrate from fraction 79 was also determined and compared to those of 2-methyl- and 3methylbiphenyl ( 5 ) furnished by the National Advisory Committee for A4rronautics. These spectra showed that the concentrate contained approximately 75% of the 3-isomer, while the 2isomer could not be identified. The comparison spectra of the concentrate and 3-methylbiphenvl are shown in Figure 2. The spurious absorption around 13 microns and at 12 35 microns is attributed to the residual naphthalenes in the sample because the

Figure 1.

Wave length in Microns Comparison Spectra of Biphenyl


.. N.5-.). 2788-93 (1951). R. Preeented before the Southwest Regional Meeting. 43.5-trinitrobenzene treatments described above. Here the width is the critical dimension in controlling convection.85-mm. 1117-19 (1951). W.December 1962. ANAL. LONGSWORTH The Rockefeller Institute f o r Medical Research.S.3. Mines. and the height determines the resolving power for ions whose mobilities are not very different if countercurrent electrophoresis is not used. of some higher alkylated derivatives of biphenyl is inferred by the ultraviolet spectra of some higherboiling fractions. Oklahoma Acad. Eng.. and incorporated in one of the commercial instruments (S). and Richardson. New York. 1952. and Caudle. The welldefined absorption band at 12. H..the reduction in the volume of solution required for an analysis has in each case been made a t a sacrifice in the resolving power and optical sensitivity of the standard 11-ml. In view of the recent progress in adapting interference methods for recording the refractive index as a function of the height in the channel. in large part.E. APPARATUS ANDPROCEDURE A w = 2 mm. a . Ind.. B. Cell. Tests of the new equipment indicate that the resulting patterns are comparable in quality with those obtained in the conventional apparatus. the optimum appears to be about 2 mm... following a suggestion made in 1939 by Chambers (Z). A well-defined absorption band in the ultra-violet at 252 mp appears superimposed upon an otherwise naphthalenic-type spectrum in 8 fractions with corrected boiling points from 283' to 290' C. G . (4) Puckett. for the reduced dimensions.. is 25 mm.164-77 (1949). ( 5 ) Serijan. D. >I. In the new cell these dimensions are Although the convective circulation of the solution in the channel resulting from the dissipation of the Joule heat decreases with the width. This report describes a cell requiring only 2 ml. the depth determines the optical sensitivity. Natl. The considerations leading to this choice of values are given below. Sci. The presence.. Schwartz. Chem. A . G. T h e quantity of biphenyl is estimated as being 0. 7474 (1948). further recurrences Of highboiling homologs have not been established. as in fractions 65 and 79 ( 2 ) . (3) Hurn. together with the associated autocollimating optical system in which reflection of the light back through the channel of the cell compensates. cell the width.. Proc. 154-66 (1949). From tests on the resolution of the two components of ovalbumin in channels of 3-. Trans.Ark. therefore.A. also.3. a = 10 mm. 30.3. H. I.. and Adams. an optimum width. 1. C. of solution...21 microns. however. In this case.. LTHOUGH several forms of micro. and the clear height. At present. D. and 0. Thus in the autocollimating system described later in this paper a chan- . S .002 to 0. a considerable reduction in the dimension. H. C. In the standard 11-ml. LITERATURE CITED The infrared spectra presented here conclusively confirm the presence of biphenyl and 3-methylbiphenyl in fractions 65 and T9.S. (6) Smith. however... (7) Ward. (541" to 554" F. (9). J. Little Rock. and Nielsen. and h = 70 mm. Comparison Spectra of 3-Methylbiphenyl intensity of these absorption bands progressively decreased with the 1. T. Improved Electrophoresis Apparatus for Small Volumes L. (2) Adams. M . 1953. Aeronaut.. 43. Chem.this sensitivity can be doubled by reflecting the light back through the cell. Y . M. (1) hdams. RECEIVED for review December 29. Tech. Ind. controlling the optical sensitivity.. K. Moreover. 23. IO). G . and Yankauskas. U. J. width. Notes 2557 (Sovember 1951). Bur. Circ. of each side is 86 mm.1074 Wave Numbers in cm-1 ANALYTICAL CHEMISTRY Figure 2. h. does not decrease with removal of naphthalenes and is thought possibly to be caused by a small concentration of 4methylbiphenyl for which a spertrum was not available. G. the ratio of the surface to the volume is thereby increased and electro-osmosis and other wall effects become a disturbing factor in narrow channels.. >I. G. the depth. this biphenyl-type absorption did not dominate the spectrum of the sample. AMERICAX CHEMICAL SOCIETY... Goodman. Advisory Comm. Eng. DISCUSSION OF RESULTS the ultraviolet spectra have not been determined on fractions above this point. There is. The 2-MI. therefore. . of the channel is 3 mm.C m x .and semimicro electrophoresis apparatus are now available (1. Accepted April 6. Rud. X.003yo o f the crude oil. appeared possible. Inform. 129-33 (1951). A. a.. cell. and Smith. N. W. Quart. F.

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