Investigation of Vanadium Content in Crude Oils of Western Siberia by the Radioactivation Method
Abstract Generated abstract
This study determines the distribution of vanadium in crude oils from several Western Siberian fields and in selected oil components, using radioactivation analysis for high sensitivity and reduced sample preparation losses. Vanadium was measured in whole oils, asphaltenes, silica gel resins, distillation fractions, and chromatographically separated hydrocarbon groups from South Cheremshan oil. The results indicate that vanadium occurs in nearly all but the lightest fractions, with nonuniform distribution, enrichment in resins and asphaltenes, and increased concentrations in heavier fractions above 350°C. A notable rise in some middle boiling fractions is interpreted as possibly reflecting volatile vanadium compounds or organometallic forms, while the highest component value reported for South Cheremshan oil occurs in the second aromatic hydrocarbon group of the 250 to 300°C fraction.
Full Text
STUDY OF VANADIUM CONTENT IN OILS OF WESTERN SIBERIA BY THE RADIOACTIVATION METHOD
S. I. Smolyaninov, R. P. Meshcheryakov, G. G. Glukhov,
V. G. Ozeredenko, L. M. Ryzhova, G. N. Aleshin
(Presented by the organic section of the scientific-methodological seminar of the Chemical Engineering Faculty)
The study of vanadium content in oils, their components, and commercial petroleum products is of considerable theoretical and practical interest [1–5].
Studies carried out at Tomsk Polytechnic Institute [6] have shown that vanadium can be present in practically all fractions of oils, with the exception of the very lightest. These data were obtained using the radioactivation method of analysis, which has exceptionally high sensitivity and eliminates losses of vanadium in the process of sample preparation [7].
The present work gives the results of determining vanadium in crude oils and in asphaltenes and silica-gel resins extracted from them from the Klyuchevskoye, Ozernoye, and Yuzhno-Cheremshanskoye fields of Tomsk Oblast, and in a typical oil representing a mixture of commercial oils from the Nizhnevartovsk arch in proportions corresponding to the 1975 production level. In addition, the vanadium content was determined in ITK fractions of Yuzhno-Cheremshanskoye and typical oils, as well as in aromatic and methane-naphthenic hydrocarbons of Yuzhno-Cheremshanskoye oil obtained by chromatographic separation.
Some characteristics of the oils studied are presented in Table 1, and the results of the experiments in Tables 2–6.
These results show that vanadium is detected in almost all oil fractions, and its distribution is nonuniform. For
Table 1
Characteristics of the initial oils
| Oil field | Density, g/cm³ | Ash content, % | Molecular weight | Kinematic viscosity \(v_{20}^{2}\), cSt | Sulfur content, % | Asphaltene content, % | Silica-gel resin content, % |
|---|---|---|---|---|---|---|---|
| Klyuchevskoye | 0.8335 | 0.020 | 181.50 | 4.99 | — | 1.36 | 4.29 |
| Ozernoye | 0.8370 | 0.002 | 190.04 | 4.81 | 0.43 | 1.67 | 5.42 |
| Yuzhno-Cheremshanskoye | 0.8395 | 0.035 | 175.50 | 5.06 | — | 3.59 | 7.15 |
| Typical oil | 0.8599 | 0.026 | 205.00 | 8.66 | — | 1.47 | 9.90 |
| Sovetskoye | 0.8370 | 0.051 | 179.00 | 5.64 | 0.85 | 1.40 | 7.50 |
| Samotlorskoye | 0.8457 | 0.029 | 191.00 | 7.39 | 0.96 | 1.00 | 7.80 |
Table 2
Vanadium content in oils of Western Siberia
| Oil field | Average vanadium content, % wt. · 10^-3 |
|---|---|
| South-Cheremshanskoye | 1.76 |
| Klyuchevskoye | 0.62 |
| Ozernoye | 3.45 |
| Typical oil | 4.12 |
Table 3
Vanadium content in resins and asphaltenes of oils of Western Siberia
| Oil | Vanadium content, % wt. · 10^-2 in asphaltenes | Vanadium content, % wt. · 10^-2 in resins |
|---|---|---|
| Sovetskaya | 2.560 | 1.970 |
| Samotlor | 9.240 | 5.180 |
| South-Cheremshanskaya | 6.030 | 2.000 |
| Klyuchevskaya | 8.300 | 3.960 |
| Ozernaya | 12.040 | 6.580 |
Table 4
Vanadium content in aromatic and methane-naphthenic hydrocarbons of South-Cheremshanskaya oil
| Fraction, °C | Average vanadium content, % wt. · 10^-4, methane-naphthenic | Average vanadium content, % wt. · 10^-4, group I aromatics | Average vanadium content, % wt. · 10^-4, group II aromatics | Average vanadium content, % wt. · 10^-4, group III aromatics | Average vanadium content, % wt. · 10^-4, group IV aromatics |
|---|---|---|---|---|---|
| 200—250 | 0.657 | 1.875 | 5.855 | 6.305 | — |
| 250—300 | 1.126 | 9.210 | 46.150 | 6.870 | — |
| 300—350 | 0.598 | 5.785 | 14.190 | 11.580 | 6.160 |
| 350—400 | 0.795 | 1.680 | 7.320 | 2.030 | 0.994 |
Table 5
Vanadium content in fractions of typical oil
| Temperature limits for fraction collection, °C | Vanadium content, % wt. · 10^-4 (average) | Temperature limits for fraction collection, °C | Vanadium content, % wt. · 10^-4 (average) |
|---|---|---|---|
| Gas to C₄ | — | 362—380 | 2.9050 |
| 32—67 | absent | 380—393 | 2.1650 |
| 67—92 | absent | 393—410 | 7.0350 |
| 92—107 | absent | 410—424 | 4.3800 |
| 107—126 | 0.0256 | 424—445 | 7.0900 |
| 126—144 | 0.0247 | residue | 8.7410 |
| 144—160 | 0.0548 | ||
| 160—176 | 0.0512 | ||
| 176—193 | 0.2860 | ||
| 193—208 | — | ||
| 208—224 | 0.1460 | ||
| 224—245 | 0.2180 | ||
| 245—259 | 0.3510 | ||
| 259—276 | 0.1750 | ||
| 276—295 | — | ||
| 295—311 | 0.3960 | ||
| 311—330 | 0.8400 | ||
| 330—348 | 1.6250 | ||
| 348—362 | 2.8000 |
Table 6
Vanadium content in fractions of South-Cheremshan oil
| Temperature limits for fraction collection, °C | Vanadium content, % wt.·10⁻⁴ (average) | Temperature limits for fraction collection, °C | Average vanadium content, % wt.·10⁻⁴ |
|---|---|---|---|
| Gas to C₄ | — | 380—401 | 0.9760 |
| 25—53 | absent | 401—423 | 5.5260 |
| 53—62 | absent | 423—438 | 1.4120 |
| 62—85 | absent | 438—450 | 1.3260 |
| 85—99 | 0.0273 | residue | 1.7170 |
| 99—114 | 0.0352 | ||
| 114—127 | 0.0542 | ||
| 127—143 | 0.0529 | ||
| 143—157 | 0.3020 | ||
| 157—173 | 0.6550 | ||
| 173—193 | 0.5080 | ||
| 193—206 | 0.3100 | ||
| 206—225 | 0.1950 | ||
| 225—263 | 0.5510 | ||
| 263—286 | 0.6310 | ||
| 286—306 | 0.5300 | ||
| 306—324 | 0.5640 | ||
| 324—350 | 0.6340 | ||
| 350—380 | 0.7860 |
For the fractions of South-Cheremshan and typical oils, an increase in vanadium content in the fraction boiling interval of 120—150°C is characteristic. It is possible that vanadium is present in the middle fractions in the form of some compound with an organic moiety or in the form of an inorganic compound of the type VОBr₃ with \(t_{\text{b.p.}} = 130^\circ\)C, VCl₄ with \(t_{\text{b.p.}} = 150^\circ\)C, or VOCl₃ with \(t_{\text{b.p.}} = 127^\circ\)C.
Possessing a known volatility, these compounds could have entered the lighter fractions. The increase in vanadium content can be explained in the heavy fractions (\(>350^\circ\)C) by the concentration of vanadium with the resinous substances of Western Siberian oils. The maximum content among the components of South-Cheremshan oil falls on the second group of aromatic hydrocarbons of the 250—300°C fraction.
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