INDUSTRIAL AND ENGINEERING CHEMISTRY
May 1952
(11) Lambert, J. M., and Sanders, H. L., IND.ENO.CHEM.,42, 1388 (1950). (12) McBain, J. W., “Advances in Colloid Science, I,” Kraemer, E. D., ed., p. 99,New York, Interscience Publishers, Inc., 1942. (13) McBain, J. W., and Green, A. A,, J. Am. Chem. Soc., 68, 1731 (1946). --, \--
(14) McBain, J. W., and Hoffman, 0. A., J . Phys. & Colloid Chem., 53,39 (1949). (15) McBain, J. W.,Merrill, R. C., and Vinograd, J. R., J . Am. Chem. Soc., 63,670(1941). (16) McBain, J. W.,Wilder, A. G., and Merrill, R. C., J . Phys. & Colloid Chem., 52, 12 (1948). (17) Merrill, R. C.,and Getty, R., Ibid., 52, 774 (1948). (18)Reich, I.,and Snell, F. D., IND.ENG.CREM.,41,2797(1949).
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(19) Rideal, E. K., “Wetting and Detergency,” 2nd ed., British section, New York, Chemical Publishing Co., Inc., 1939. (20) Robineon, C., Zbid. (21) Snell, F.D.,Chem. Eng. News, 27,2256 (1949). (22) Snell, F. D., IND. ENO.CHEM.,24,76 (1932). (23) Zbid., 25, 162 (1933). (24) Snell, F. D.,and Reich, I., J . SOC.Chem. I n d . (London),6 8 , 98 (1949). (25) Vold, R. D.,and Konecny, C. C., J . Phgs. & Colloid Chem., 53, 1262 (1949). (26) Weatherburn, A. S., Rose, G: R., and Bayley, C. H., Can. J . Research, F28,213,363(1950). RECEIVED for review June 2 1 , 1951.
.%CCEPTED
Deoemher 5, 1951.
Chemical State of Vanadium in Santa Maria Valley Crude Oil J
DAVIS A. SKINNER Research and Process Department, Research Division, Union Oil Co. of California, Brea, Calif.
T
HE presence of vanadium in certain crude oils and other bituminous materials from all over the world has been recognized for some time. A number of years ago vanadium was detected in crude oil from Sant,a Maria Valley in California. This paper represents a phase of an investigation which was initiated by interest in this crude as a source of recoverable vanadium. The objectives of the study were to determine the physical and chemical state of vanadium in the crude and the properties of the vanadium bearer. It was also desired that information be developed on the origin of the vanadium bearer and the manner in which it was introduced into the crude. These considerations are not only of academic interest, but have a definite practical aspect as well. In a progress report of the Bmerican Petroleum Institute, Project 43 (1946-47),i t was euggested that more research is needed on the trace elements in petroleum to possibly fingerprint source beds as an aid in prospecting, particularly in new basins. Katchenkov (6) has shown that a correlation exists between the micro elements of petroleum and geologic eras and periods. Treibs (IO)has pointed out that when certain metal-porphyrin complexes are found in petroleum, the upper temperature limits to which the oil has been subjected can be easily established. PRELIMINARY EXAMINATION
I n oil field practice in the Santa Maria Valley field, wet crude flowing from the wells is composited and then subjected to electrical dehydrating and desalting operations before being transported through the pipelines to refining installations. I n the electrical dehydration the wet crude is subjected to a high tension alternating current field to coalesce the water globules, and the water which separates is removed. The relatively dry crude is then desalted by agitation with a suitable quantity of fresh water at about 125” C. to effect solution of the remaining water-soluble salts. The resulting oil-water mixture is again electrically dehydrated as before. Electrical potentials employed may be of the order of 16,000 volts or more. These field operations succeed in removing about 85% of the water-soluble chlorides from Santa Maria Valley crude, but only about one third of the total mineral content is affected. Representative samples of crude oil were obtained from each lease in the Santa Maria Valley field. Samples were also obtained of a composite before and after it had passed through the dehydrators and desalters, respectively. Simultaneously, the water streams entering and leaving these systems were also
sampled. Analyses of the samples a-ere made to determine if the field treatments affected the vanadium content of the crude. EXPERIMENTAL TECHNIQUE. Samples of water from the dehydrators and desalters, as well as of the fresh water used in the desalters, were evaporated to dryness and the residues wereanalyzed on an Applied Research Laboratory, 1.5-meter emission spectrograph, using an Applied Research Laboratory comparator-densitometer for evaluation of the spectral lines. Samples of crude oil from each of the leases as well as the dehydrated! and desalted composite crude samples were analyzed spectroscopically for vanadium by the quenched electrode technique (9)These spectrographic analytical findings were checked by chemical analyses using a colorimetric method (IS). ANALYTICAL RESULTS.Very little difference was found in the vanadium content of the crude oil samples from the various Santa Maria Valley leases. The composite crude averaged about 0.022% vanadium, expressed as the metal. Table I shows the analytical results for the water streams involved. No vanadium was found to be entering or leaving the field treating operations via water streams.
TABLEI. SPECTROGRAPHIC ANALYSESOF RESIDUESFROM EVAPORATING WATERSTREAMS (From dehydrating and desalting Santa Maria Valley crude) Grams ---Metallio Constituents of Residue-Solid/ ModSample Liter Majora erateb Slightc Traced From dehydrator 17 44 Na ,. B, Mg, Sr SI, Fe, Cu, Ca From desalter 3 16 Na Rlg, Ca B, Si, Sr Fe, Cu, TI A1 Cr Raw water to de0.74 Ka, M g , Si Fe, Sr B, 6 11,Ti, salter Ca Al, Cr, &In
.
a
2 10%.
b
From 1 to 10%. FromO.l t o 1.0%.
d
