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3.1. Laws of interrelation of the maintenance vanadilovyh complexes with the maintenance of sulphur, asphaltenes and free radicals in neftjah and asphaltenes.


Search of effective ways demetallizatsii an oilstock demands research of interrelation and interaction of metals with high-molecular components of oil - resins and asphaltenes. Revealing of character and interaction degree, in particular, vanadilovyh complexes with the expert - fal tenovymi associates creates preconditions for working out and perfection of extraction ways of concentrating of the oil threw - losoderzhashchih connections.
The lack of knowledge of composition, structure and mutual relations of various components of oil creates preconditions for any interpretation of results of corresponding researches.
Comparison neftej uneven-age depositions under characteristics, componental composition and under the maintenance in composition neftej and vanadium and sulphur asphaltenes is resulted in tab. 3.1.
For neftej with the high maintenance of vanadium characteristicly raised maintenance of sulphur, asphaltenes, the low maintenance hydrocarbonaceous components and a low yield of fractions to 200С. Oil with high gum content and asphaltenes, as a rule, high-viscosity also possess high density. Table 3.1 the Deposit № HARD CURRENCY. The geologist, age the Maintenance, the Elm-bone, the Raft-nost, mas. % ' 10ій otn.sp./g Fraction H.K. -
200C Asf th BS SBS Resins (obshch.) Coal-water-childbirth ^obshch ^neft VAC (J, вкн* vka MM'VC at 20 s g/sm3 Alekseevsky 76 D2gv 39,2 0,5 - - 14,0 95,2 1,0 0,0014 - 0,04 - 6,14 0,9069 Matrosovsky 176 D2vb 32,3 0,4 13,0 7,5 20,5 79,0 1,3 0,0004 0,061 0,06 5,70 7,96 0,8567 Matrosovsky 186 D2vb 35,2 0,6 13,1 4,8 17,9 80,5 1,7 0,0011 0,054 0,08 4,65 7,68 0,8495 Matrosovsky 194 D2vb 37,4 1,2 7,9 3,4 11,4 87,1 1,9 0,0007 0,054 0,15 6,42 6,92 0,8310 Matrosovsky 182 Cjt - 3,2 13,5 23,5 37,0 59,8 2,6 0,0082 0,256 2,82 20,36 - 0,9206 Alekseevsky 30 Ciksl 20,2 4,0 - - 15,0 80,7 2,1 0,0107 - 1,86 22,02 11,30 0,8766 Alekseevsky 188 Ciksl 19,6 4,3 - - 19,0 76,6 1,5 0,0083 - 2,00 23,94 13,10 0,9108 Alekseevsky 189 Qksl 20,6 4,2 - - 22,0 73,5 1,8 0,0093 - - 18,34 11,80 0,9081 Alekseevsky 259 Cjksl - 4,6 - - 25,0 70,0 2,3 - - 1,70 17,87 - 0,9096 Enorusskinsky 1279 Cit 21,1 8,7 10,9 5Д 16,0 74,5 4,3 0,0707 - 9,33 56,06 13,70 0,9300 Enorusskinsky 192 C2b | 17,8 8,9 17,4 8,5 25,9 65,6 3,9 0,0399 0,340 8,81 30,09 14,80 0,9185 * - data after data paramagnetic Characteristics neftej and asphaltenes in a uniform frame of axes
Characteristics and componental composition neftej uneven-age depositions
It is possible to notice, that in oil objects with the low maintenance of asphaltenes the maintenance of vanadium and VK in asphaltenes in hundreds times surpasses that in initial neftjah. In neftjah with the raised maintenance of asphaltenes maintenance VK differs only 10 times from maintenance VK in asphaltenes from these neftej.
Yielded tab. 3.1 show, that such operational and qualitative characteristics of oil as viscosity, the maintenance of light fractions, the sulphur maintenance are defined and depend on the maintenance smolisto - asfaltenovyh substances and vanadium connections. Revealing of features of a structure of asphaltenes neftej, enriched by vanadium, possibly, will allow to increase essentially efficiency of methods of increase in petroreturn, technologies of preparation and oilstock processing.
Paramagnetism research neftej and oil objects is a necessary stage for a choice of rational paths of petroleum refining, and also for the decision of many oil-field problems.
Paramagnetism neftej is caused mainly VK and CP which concentrate in asfal - that parts.
For revealing of the basic interrelations of maintenance VK and CP there were is-sledovany samples neftej differing with geological age, the maintenance of asphaltenes, vanadium and physical and chemical characteristics.
In tab. 3.2 paramagnetic characteristics neftej uneven-age depositions are resulted. In some of them the maintenance of asphaltenes, geological age of containing breeds and corresponding productive horizon is shown.
It is easy to notice, that maintenances VK in investigated neftjah correlates with the maintenance in them of asphaltenes (fig. 14) and with geological age neftej.
Maintenance VK and CP in neftjah uneven-age depositions
Table 3.2. № the Deposit № hard currency. The geologist. A yield the Maintenance, пТ0ь otn.sp. p/p age asf-in, mas. % VK CP 1 Enorusskinsky 192 С2Ъ 8,9 2786,7 3547,3 2 Enorusskinsky 53 C2vr - 2548,9 3068,1 3 Enorusskinsky 3826 C2vr 6,0 2860,0 2171,6 4 Enorusskinsky 51 C2vr 7,8 1869,1 2418,7 5 Enorusskinsky 158 C2vr 6,5 1959,0 2114,5 6 Enorusskinsky 304 C2vr - 1990,3 2669,8 7 Enorusskinsky 54 Cltl - 2908,1 2892,6 8 Enorusskinsky 82 Cltl 9,2 3305,7 2823,7 9 Enorusskinsky 84 Clbb 8,9 3400,0 2817,5 10 Enorusskinsky 3609 Clbb 6,5 1837,4 2633,4 11 Enorusskinsky 1301 Clbb 7,1 2820,0 2524,4 12 Enorusskinsky 1304 Clbb, b, vr 6,4 3072,8 1942,6 13 Enorusskinsky 1279 Clt 8,7 2949,8 3907,2 14 Alekseevsky 259 Clksl 4,6 539,0 2384,0 15 Alekseevsky 30 Clksl 4,0 588,6 2721,6 16 Alekseevsky 188 Clksl 4,3 632,8 3033,3 17 Alekseevsky 20006 Clksl 4,1 296,2 3075,5 18 Alekseevsky 76 D2gv 0,5 13,9 630,6 19 Kijazlinsky 169 C2vr - 2150,3 2761,1 20 Kijazlinsky 295 C2vr - 1932,4 2603,3 21 Kijazlinsky 291 C2vr - 1995,6 2518,4 22 Kijazlinsky 1703 C2vr - 1875,7 2298,1 23 Cheremuhovsky 817 C2b 7,7 2009,6 2894,0 24 Cheremuhovsky 832 C2b - 1995,1 2895,2 25 Cheremuhovsky 821 Cltl - 3851,0 3225,1 26 Melnikovsky 3804 C2vr - 1571,4 2157,0 27 Melnikovsky 2593 Clbb, tl 9,5 3400,0 3145,5 28 Melnikovsky 2586 Clbb 6,4 2660,5 2481,3 29 Melnikovsky 2584 Clbb - 3706,2 3140,0 30 Melnikovsky 2576 Clbb - 3774,4 3656,2 31 Melnikovsky 2587 Clbb - 3452,3 2840,5 32 Melnikovsky 2583 Clbb - 3950,1 3315,7 33 Melnikovsky 2588 Clbb - 2655,4 2179,7 34 Melnikovsky 2574 Clbb - 3382,5 2669,8 35 Melnikovsky 254 Clbb - 3902,6 3233,0
Continuation of tab. 3.2,
36 Melnikovsky 242 Clt - 3080,0 2211,7 37 Матросовское* 163 Clbb 6,4 1862,1 3630,8 38 Матросовское* 156 Clt 5,8 912,0 2630,3 39 Матросовское* 182 Clt 3,2 891,3 2754,2 40 Матросовское* 169 D3p 1,5 257,0 3311,3 41 Матросовское* 185 D2vb. 2,0 81,3 2818,4 42 Матросовское* 164 D2vb 1,4 63,1 2398,8 43 Матросовское* 198 D2vb 0,5 30,9 1148,2 44 Матросовское* 194 D2vb 1,3 47,9 1698,2 45 Матросовское* 168 D2vb 0,8 50,1 1513,6 46 Матросовское* 186 D2vb 0,6 25,1 724,4 47 Матросовское* 180 D2vb 0,9 53,7 2089,3 48 Матросовское* 176 D2vb 0,4 17,8 758,6 49 Кутуптевское* 344. Clbb 10,0 3548,1 4466,8 50 Кутушевское* 360 Clbb 4,4 2041,7 3630,8 51 Кутушевское* 342 D3kn 3,0 870,9 3548,1 52 Verhne-Chehonsky - Є 0,1 0,003 0,645 * - paramagnetic characteristics neftej are resulted in work [101] in sp/sm

The maintenance of asphaltenes, mas. % of a Fig. 14. Change of maintenance VK with increase in the maintenance asphalt-is new in neftjah uneven-age depositions
It is necessary to notice, that oil Verhne-Chehonsky deposits (Eastern Siberia) - most ancient of studied, and falls into to depositions kembrija (middle age about 570 million years). The specified oil is characterised by the lowest, among the studied oil objects, the maintenance of asphaltenes, VK and COMPARE Age of the most ancient depositions investigated neftej deposits of Tatarstan (D2) averages about 400 million years. For these neftej characteristicly depressed maintenance of asphaltenes and rather low concentration VK also COMPARE
In neftjah dependence of maintenance CP on maintenance VK not proslezhi-vaetsja (fig. 15).
? - Centre devon - D2, About "bottom karbon - С1,
About - top devon - D3, А* centre karbon - С2
№ n about
(D
I
To
To it About,
(d
P about
ABOUT
ABOUT Q
About about
і
2qj0q 40.00 t0,00 so.00
Maintenance VK, otn.sp./g
Fig. 17. Change of maintenance CP with increase in concentration VK in asphaltenes neftej uneven-age depositions and native bitumens (і)
&
fct about
U
olo
0.00
? - Centre devon - D2, About - top devon - D3,
About - bottom karbon - С1, And - centre karbon - С2 As a whole, with reduction of geological age of productive layers maintenance CP decreases and maintenance VK in asphaltenes corresponding neftej (tab. 3.4 increases.).
Table 3.4.
Paramagnetic characteristics of asphaltenes neftej the uneven-age
Deposition Geological age Maintenance CP, 10 "otn.sp./g Maintenance VK, 1018otn.sp./G kembry - With 540 2 centre devon - D2 170-300 5-7 top devon - D3 110-220 10-34 bottom karbon - С1 40-150 17-70 centre karbon - С2 40-110 37 108 perm - R 50-100 14-49
For asphaltenes neftej different productive layers it is possible to reveal various tendencies of interrelation VK and CP (fig. 18, 19). 1. Y - 32 X + 42,3 R = 0,7

I [1 J 1 1
SH 7JU TO
The maintenance In To, sggn.sp./G
Y =-1,8X 4 188,0 * = 0} 2 0
ABOUT

•Sfflflq — і
IN IN
And
j
About
CLT імла About
rts "sscutt —
About
5
N
May -
& Them.
et
About
About
And
asha -
I 1*1
Maintenance VK, otn.a_/g
If for asphaltenes neftej an average devona the tendency to dependence CP=F (BK) directly proportional for asphaltenes neftej top devona the tendency to an inverse ratio of considered dependence (fig. 18) is observed. Similar tendencies to inverse relationship of maintenance CP from maintenance VK are observed for asphaltenes neftej bottom and centre karbona (fig. 19).
Y =-2ЈX + 209,8 R 0, Й5

1 1 1 ^ 1
la 1:;:: the visa
Maintenance VK ^ otn.sp. Л1
Fig. 19. Dependence CP = F (VK) for asphaltenes neftej About - bottom karbon - With І, D - centre karbon - С2
Y =-0,8 X + 119,7 R = 0,58

1—1—Г 1—I—1—1
09 IEJ3S HJ0 az (nanosecond
Maintenance Btl, otn. mJr
Fig. 18. Dependence CP = F (VK) for asphaltenes neftej? - Centre devon - D2, About - top devon - D3
The fact of the tendency to direct dependence CP = F (VK) for asphaltenes neftej an average devona can be a consequence of basic structural difference of these asphaltenes from the others.
At calculation of the maintenance of paramagnetics in asphaltenes, the signal size is led to weight of the taken shot. Hence, passing to a molecular scale, it is possible to offer data under maintenance VK and CP to fall into to "average structure of asphaltenes. Specified units of structure of asphaltenes are averaged in the sense that the parity of the condensed aromatic part and branched out nafteno - an aliphatic part (fig. 20), characteristic for each asphaltenes, in considered average structure of asphaltenes remains invariable. Thus all average structures of asphaltenes should be identical weight as paramagnetic characteristics fall into to a mass unit.

Fig. 20. Hypothetical structure of a molecule of asphaltenes of conditionally times-granichennaja on polyaromatic and nafteno-aliphatic parts
As free stable radicals, and vanadilovye complexes are not dispersed on all sample (powder) of the evolved asphaltenes, and localised on certain sites of molecular composition of asphaltenes. Therefore the formulation average structure of asphaltenes for mental association with the fixed sizes of concentration VK and CP in asphaltenes is represented to the most convenient.
It is necessary to notice, that vanadyl an ion can enter as into composition asfaltenovoj structures containing CP, and whether - to co-ordinate large gandy free of COMPARE Molecular weights oil vanadilporfiri - new complexes make 500 a.e.m. Weights of molecules of asphaltenes are estimated as 700-1500 a.e.m.
From maintenance VK in asphaltenes it is possible to explain observable return tendencies to dependence of maintenance CP following reasons:
Asphaltenes neftej with raised maintenance VK contain the big concentration VK in a substance mass unit. Possibly, there is "dilution" of molecules containing CP molecules VK;
The oil, containing various quantity VK differ with conditions zaleganija, and asphaltenes of these neftej have structural distinctions. Probably, the tendency to inverse relationship of maintenance CP from maintenance VK in asphaltenes neftej is mainly caused by change of a parity polyaromatic and nafteno-alifaticheskoj parts as a part of average structure of asphaltenes;
Probably, strengthening VK in asphaltenes can result in to formation of diamagnetic complexes between flat molecules VK and flat fragments of asphaltenes.
Thus, for an establishment of character of interrelation VK with asphalt new associates and the nature of the tendency to inverse relationship of maintenance CP from maintenance VK in asphaltenes it is obviously necessary:
To investigate asphaltenes of petrosimilar systems about possibility of their use as the simplified models of structures containing stable radicals,
To reveal degree of possible interaction VK and CP,
To develop the methodical approach to unification of relative units of measure of concentration of paramagnetics in neftjah and asphaltenes, and to carry out the analysis of interdependence of the maintenance in them of paramagnetics.
Thus, by results of the yielded chapter it is possible to draw following basic conclusions:
For neftej with the high maintenance of vanadium characteristicly raised maintenance of sulphur, asphaltenes, the low maintenance hydrocarbonaceous components and a low yield of fractions to 200С. Oil with high gum content and asphaltenes, as a rule, high-viscosity also possess high density.
In neftjah dependence of the maintenance of free radicals on concentration vanadilovyh complexes is not traced.
For asphaltenes neftej karbona and top devona return tendencies of change of radical concentration with maintenance increase vanadilovyh complexes are characteristic, for asphaltenes neftej an average devona the specified tendency looks like a straight line.
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A source: Tagirzjanov, Marseilles Ilgisovich. ASPHALTENES VANADIJSODERZHASHCHIH neftej (on an example of oil objects of deposits of Tatarstan) the Dissertation on competition of a scientific degree of a Cand.Chem.Sci. Kazan - 2003. 2003

More on topic 3.1. Laws of interrelation of the maintenance vanadilovyh complexes with the maintenance of sulphur, asphaltenes and free radicals in neftjah and asphaltenes.:

  1. 5.2. Studying of interrelation of the maintenance vanadilovyh complexes isvobodnyh radicals in neftjah and asphaltenes
  2. 3. CHARACTER of INTERRELATION of MAINTENANCE VANADILOVYH of COMPLEXES, SULFUR And FREE RADICALS In neftjah IASFALTENAH.
  3. 6.1. Degree of extraction of free stable radicals and vanadilovyh complexes asphaltenes from neftej
  4. 2.2.7 Technique of definition of maintenance VK and CP in neftjah and asphaltenes method EPR
  5. 1.4. Vanadilovye complexes and free stable radicals in neftjah and oil components
  6. Z.Strukturnye types of asphaltenes with the various maintenance of vanadium
  7. 6. STUKTURNYE FEATURES of ASPHALTENES neftej With the VARIOUS MAINTENANCE of VANADIUM
  8. 5. The NATURE of INTERRELATION VANADILOVYH of COMPLEXES With ASFALTENOVYMI ASSOCIATES
  9. 1.3. Structure of oil asphaltenes
  10. 1.3.1. Composition and structure polycyclic and alifaticheskihfragmentov structures of asphaltenes