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Study of the Vanadium Content in Tomsk Crude Oils and Their Fractions by the Radioactivation Method

S. I. SMOLYANINOV, R. P. MESHCHERYAKOV, G. G. GLUKHOV
Submitted 1976 | SovietRxiv: ru-197601.13198 | Translated from Russian

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STUDY OF VANADIUM CONTENT IN TOMSK CRUDES AND THEIR FRACTIONS BY THE RADIOACTIVATION METHOD

S. I. SMOLYANINOV, R. P. MESHCHERYAKOV, G. G. GLUKHOV,
V. V. CHERNOV, V. G. OZEREDENKO

(Presented by the Scientific-Methodological Seminar of the Organic Departments)

Vanadium contained in crude oil and petroleum products has a negative effect on the processes of oil refining and on the operational properties of fuels.

The presence of vanadium in oils causes corrosion of equipment, which significantly shortens its service life and increases the cost of petroleum products. A vanadium content in feedstock of \(10^{-4}\%\) increases the degree of corrosion by 30% [1—2].

It is well known that heavy metals contained in cracking feedstock, such as vanadium, nickel, copper, iron, and others, during catalytic cracking are deposited on the surface of the catalyst and poison it, reducing selectivity [1].

Vanadium is always present in crude oil; its content amounts to up to 40% of the ash [3].

The accumulation of vanadium in oils is associated both with the nature of the original parent material and with the conditions of its accumulation and transformation [4—7].

Thus, interest in vanadium is based on its possible role in the genesis of petroleum, on its influence on oil-refining and petrochemical processes, and on the use of petroleum products [8].

From the foregoing it is clear that the determination and study of vanadium in oils is of great practical and theoretical importance.

There are a variety of methods for determining vanadium in oils and petroleum products—EPR [9], spectral [10], X-ray

Oil field Petroleum-bearing horizon Well No. Depth of well, m Specific gravity, \(\rho_4^{20}\) Molecular weight Kinematic viscosity, cSt Flash point in closed crucible, °C Pour point, °C, with heat treatment Pour point, °C, without heat treatment
Samotlor A-1 14 1694 0.8525 213 4.48 −14 −43 −9
Sovetskoe A-1 47 1658 0.8629 228 7.87 −15 −36 −6
Olenye Yu-1 121 2544 0.8350 174 5.14 — — −28
Typical crude oil (mixture of oils from the Nizhnevartovsk region) — — — 0.8605 190 8.66 — — −14

spectroscopy [11], colorimetric [12], neutron-activation [13], and others.

Most of these methods are based on preliminary thermal treatment of the sample, with the assumption that vanadium compounds are nonvolatile and thermally stable.

The studies we carried out to determine vanadium by a radioactivation method using a nuclear reactor made it possible to establish the presence of vanadium in the light fractions of Tomsk crude oils. It follows from this that ideas about the practical nonvolatility of vanadium compounds may be fundamentally erroneous. Thus, there arises the need to conduct detailed studies in this direction.

In the present work, data are given on the vanadium content in crude oils, their fractions, petroleum resins, and asphaltenes from a number of new fields in Western Siberia, determined by the radioactivation method. The procedure and characteristics of this method were described by us earlier [14].

Samples of crude oils from the Sovetskoye, Samotlor, and Olenye fields and of a typical oil, as well as 3% fractions of Samotlor and typical oils, were studied. The characteristics of the indicated objects are given in Table 1.

The data on determining the vanadium content in crude oils are presented in Table 2, and in ITC fractions—in Table 3. For the Olenye field oil,

Table 2

Vanadium content in crude oils of Western Siberia

Field Vanadium content, wt. %
Samotlor 0.00144
Olenye 0.00106
Sovetskoye 0.00137
Typical oil 0.00133

the vanadium content in resins and asphaltenes was determined. The analyses showed that petroleum resins and asphaltenes contain, respectively, 0.00138 and 0.01715 wt. % vanadium.

As a result of the studies carried out, the presence of vanadium in low-boiling fractions was confirmed.

It is not yet possible to say in what form vanadium is present in these fractions, owing to the absence of work in this direction. Thus,

Table 1

of the original crude oils

Paraffin content, % Paraffin melting temperature, °C Ash content, % Coking value, % Asphaltene content, % Silica-gel resin content, % Mechanical impurities content, % Vanadium content, % Sulfur content, % Salts, mg NaCl/liter of oil
5.64 54 0.017 3.155 1.09 8.85 0.09 0.0014 0.95 20
4.39 48 0.012 1.900 0.79 9.88 0.046 0.00028 0.75 25
1.30 — 0.004 3.200 2.15 6.08 — 0.0005 0.58 —
3.37 — 0.026 1.930 1.47 9.66 absent 0.0013 1.33 —

Vanadium content in TBP fractions of West Siberian oils, wt. %

Table 3

Oleni oil: boiling limits of fractions, °C Oleni oil: vanadium content ·10⁻³ wt. % Samotlor oil: boiling limits of fractions, °C Samotlor oil: vanadium content ·10⁻³ wt. % Typical oil: boiling limits of fractions, °C Typical oil: vanadium content ·10⁻³ wt. %
Gas to C₄ — Gas to C₄ — Gas to C₄ —
21—53 — 28—56 — 32—62 —
53—72 — 56—76 — 62—75 0,030
72—90 0,025 76—92 0,013 75—86 0,044
90—101 0,020 92—112 0,017 86—120 0,018
101—116 0,025 112—129 0,017 120—137 0,009
116—131 0,016 129—146 0,027 137—152 0,015
131—145 0,025 146—167 — 152—171 0,033
145—161 0,013 167—183 0,015 171—187 0,015
161—176 0,033 183—199 0,013 187—203 0,007
176—193 0,048 199—217 0,019 203—212 0,011
193—208 0,051 217—240 0,027 212—228 0,005
208—216 0,056 240—251 0,019 228—250 0,011
216—230 0,014 251—274 0,017 250—264 0,014
230—254 0,018 274—291 0,023 264—280 0,005
254—273 0,043 291—310 0,026 280—304 0,010
273—290 0,017 310—322 0,028 304—314 0,012
290—310 0,032 322—335 0,030 314—324 0,024
310—330 0,019 335—362 0,078 324—340 0,028
330—348 0,036 362—382 0,115 340—362 0,026
348—362 0,043 382—392 0,070 362—382 0,029
362—382 0,017 392—411 0,030 382—402 0,037
382—400 0,081 411—433 0,084 402—414 0,049
400—410 0,042 433—450 0,220 414—433 0,044
410—440 0,172 Residue 15,600 433—445 0,061
Residue 7,150 Residue 8,000

Rostoker W. [15] indicates that compounds such as VOCl₃ \((t_{\text{bp}} = 127^\circ\text{C})\), VCl₄ \((t_{\text{bp}} = 152^\circ\text{C})\), and VOBr₃ \((t_{\text{bp}} = 130^\circ\text{C})\) may also be classified as readily volatile compounds; their presence in oils may be assumed.

The results of the distribution of vanadium among TBP fractions of oils show that vanadium is distributed among them unevenly.

When considering the analysis data for TBP fractions, it may be noted that, with increasing molecular weight of the hydrocarbons, the vanadium content increases. For the light fractions of all oils, an overall uniform distribution of vanadium is characteristic.

Conclusions

  1. Vanadium was determined in a number of oils and their fractions from West Siberian fields by the radioactivation method.

  2. The radioactivation method has very substantial advantages over the certified colorimetric method: the greatest sensitivity among all methods currently known \((10^{-9}\%\) versus \(10^{-4}\%)\), rapidity of determination (0.5 versus 4–5 hours), a small sample weight (down to fractions of a gram), and, most importantly, the absence of losses of volatile compounds, which may be significant.

  3. The vanadium content in oils determined by the radioactivation method gave a result several times greater than that obtained by the standard method, which makes it possible to raise the question of the need to revise the latter.

  4. In determining vanadium in the fractions, it was found that vanadium is distributed among them unevenly.

  1. Determination of the vanadium content in resins and asphaltenes showed that up to 45% by weight of the vanadium accumulates in them.
  2. Vanadium is concentrated mainly in the asphaltenes.

REFERENCES

  1. P. H. Emmett. Catalysis in the Petrochemical and Petroleum-Refining Industries. Moscow, Gostoptekhizdat, 1963.

  2. V. A. Gruze, D. R. Stevens. Petroleum Refining Technology. Moscow, “Khimiya,” 1964.

  3. V. N. Kholodov. Vanadium. Moscow, “Nauka,” 1968.

  4. S. M. Manskaya, T. V. Drozdova. Geochemistry of Organic Matter. Moscow, “Nauka,” 1964.

  5. S. M. Katchetkov. Minor Chemical Elements in Sedimentary Rocks and Petroleum. Moscow, “Nauka,” 1959.

  6. Kh. K. Kasymov. Microcomponents of Oils of Western and Southern Uzbekistan. FAN, Tashkent, 1967.

  7. D. I. Zulfugarli. Azerbaijan Chemical Journal, No. 5, 7–10, 1959.

  8. B. V. Losikov. Chemistry and Technology of Fuels and Oils, No. 4, 25–29, 1958.

  9. A. V. Ilyasov. Chemistry and Technology of Fuels and Oils, No. 9, 10–14, 1962.

  10. L. G. Mashireva, K. I. Zimina. Chemistry and Technology of Fuels and Oils, No. 2, 13–15, 1961.

  11. C. D. Dvengs, X. H. Danning. Anal. Chem., vol. 32, 1137–1141, 1960.

  12. E. Sendel. Colorimetric Methods for the Determination of Metals. Moscow, “Mir,” 1964.

  13. G. Bowen, D. Gibbons. Radioactivation Analysis. Moscow, Atomizdat, 1968.

  14. S. I. Smolyaninov, R. P. Meshcheryakov, G. N. Yurova, G. G. Glukhov, N. M. Smolyaninova. In: Questions of the Geology and Quality of Oils, Gases, and Gas Condensates of Western Siberian Fields. Tomsk University Press (in press).

  15. U. Rostoker. Metallurgy of Vanadium. Moscow, Foreign Literature Publishing House, 1959.

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[v1] 1976

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Study of the Vanadium Content in Tomsk Crude Oils and Their Fractions by the Radioactivation Method