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5.2. Studying of interrelation of the maintenance vanadilovyh complexes isvobodnyh radicals in neftjah and asphaltenes


Running forward it is necessary to result a kind of received dependence CP=F (BK) for neftej and asphaltenes, without logarifmirovanija sizes of maintenance VK and CP (fig. 28). Huge distinctions in concentration of paramagnetics in neftjah and asphaltenes complicate visual perception and studying of the received dependences.

Fig.
28. Change of maintenance CP with increase in concentration VK in neftjah and asphaltenes
Therefore further for the characteristic of maintenance VK and CP logarithms of sizes of their abundance (lgBK and lgCP) were used.
For studying of the possible reasons of reduction of the maintenance of free radicals with maintenance increase vanadilovyh complexes in asphaltenes, it is necessary to develop the methodical approach to unification of relative units of measure of concentration of paramagnetics in neftjah and asphaltenes. To bypass the technical complexities connected with calculations of weight neftej in a site of an ampoule which is in area of shooting of data EPR, and "shooting" neftej in thin ampoules or asphaltenes in thick ampoules will be on limits of possibilities of the EPR-SPECTROMETER. The reception allowing with adequate accuracy to translate size characterising maintenance of paramagnetics in neftjah to conformity with similar sizes for asphaltenes has been used.
Us it is offered to manufacture maintenance comparison in oil objects of the general vanadium defined by a method of a straight line ardent atomno - the absorptive spectrometry and the paramagnetic vanadium defined by method EPR. On the basis of concentration sizes in neftjah and asphaltenes of the "general" vanadium and maintenance V4 + (tab. 5.3, 5.4) the dependence graph lgBK — F (lgV) for neftej and asphaltenes (fig. 29) is constructed.
Table 5.3
The maintenance of the general vanadium and vanadilovyh complexes in neftjah № p/p the Deposit № HARD CURRENCY. The geologist, age the Maintenance At, mas. % lgBK, [otn.sp,] lgV, [mas. %] 1 Enorusskinsky 192 С2Ь 0,0399 3,445 2,601 2 Enorusskinsky 53 C2vr 0,0350 3,406 2,544 3 Enorusskinsky 3826 C2vr 0,0370 3,456 2,568 4 Enorusskinsky 51 C2vr 0,0296 3,272 2,471 5 Enorusskinsky 158 C2vr 0,0240 3,292 2,380 6 Enorusskinsky 304 C2vr 0,0270 3,299 2,431 7 Enorusskinsky 54 Cltl 0,0380 3,464 2,580 8 Enorusskinsky 82 Cltl 0,0566 3,519 2,753
Tab. 5.3 continuation
9 Enorusskinsky 84 Clbb 0,0634 3,531 2,802 10 Enorusskinsky 3609 Clbb 0,0220 3,264 2,342 11 Enorusskinsky 1301 Clbb 0,0350 3,450 2,544 12 Enorusskinsky 1304 Clbb, b, vr 0,0360 3,488 2,556 13 Enorusskinsky 1279 Clt 0,0707 3,470 2,849 14 Kijazlinsky 169 C2vr 0,0363 3,333 2,560 15 Kijazlinsky 295 C2vr 0,0310 3,286 2,491 16 Kijazlinsky 291 C2vr 0,0316 3,300 2,500 17 Kijazlinsky 1703 C2vr 0,0279 3,273 2,446 18 Cheremuhovsky 817 C2b 0,0240 3,303 2,380 19 Cheremuhovsky 832 C2b 0,0240 3,300 2,380 20 Cheremuhovsky 821 Cltl 0,0530 3,586 2,724 21 Melnikovsky 3804 C2vr 0,0220 3,196 2,342 22 Melnikovsky 2593 Clbb, tl 0,0440 3,531 2,643 23 Melnikovsky 2586 Clbb 0,0360 3,425 2,556 24 Melnikovsky 2584 Clbb 0,0490 3,569 2,690 25 Melnikovsky 2576 Clbb 0,0520 3,577 2,716 26 Melnikovsky 2587 Clbb 0,0440 3,538 2,643 27 Melnikovsky 2583 Clbb 0,0570 3,597 2,756 28 Melnikovsky 2588 Clbb 0,0310 3,424 2,491 29 Melnikovsky 2574 Clbb 0,0520 3,529 2,716 30 Melnikovsky 254 Clbb 0,0590 3,591 2,771 31 Melnikovsky 242 Clt 0,0440 3,489 2,643 32 Matrosovsky 163 Clbb 0,0293 3,270 2,467 33 Matrosovsky 156 Clt 0,0135 2,960 2,130 34 Matrosovsky 182 Clt 0,0082 2,950 1,914 35 Matrosovsky 169 D3p 0,0032 2,410 1,505 36 Matrosovsky 185 D2vb 0,0019 1,910 1,279 37 Matrosovsky 164 D2vb 0,0015 1,800 1,176 38 Matrosovsky 198 D2vb 0,0015 1,490 1,176 39 Matrosovsky 194 D2vb 0,0007 1,680 0,845 40 Matrosovsky 168 D2vb 0,0009 1,700 0,954 41 Matrosovsky 186 D2vb 0,0011 1,400 1,041 42 Matrosovsky 180 D2vb 0,0020 1,730 1,301 43 Matrosovsky 176 D2vb 0,0004 1,250 0,602 44 Kutushevsky 344 Clbb 0,0480 3,550 2,681 45 Kutushevsky 360 Clbb 0,0310 3,310 2,491 46 Kutushevsky 342 D3kn 0,0120 2,940 2,079
Table 5.4
The maintenance of the general vanadium and vanadilovyh complexes in asphaltenes neftej
№ p/p the Deposit № HARD CURRENCY.
The geologist, age the Maintenance V, mas. % lgBK, [otn.sp.] lgV, [mas. %] 1 Enorusskinsky 192 С2Ь 0,340 1,478 3,532 2 Enorusskinsky 3826 C2vr 0,420 1,746 3,623 3 Enorusskinsky 51 C2vr 0,270 1,649 3,431 4 Enorusskinsky 158 C2vr 0,310 1,631 3,491 5 Enorusskinsky 82 Cltl 0,410 1,740 3,613 6 Enorusskinsky 1367 Cltl 0,440 1,747 3,644 7 Enorusskinsky 84 Clbb 0,430 1,736 3,634 8 Enorusskinsky 3609 Clbb 0,300 1,631 3,477 9 Enorusskinsky 1301 Clbb 0,430 1,759 3,634 10 Enorusskinsky 1304 Clbb, b, vr 0,420 1,740 3,623 11 Cheremuhovsky 817 C2b 0,235 1,586 3,371 12 Matrosovsky 163 Clbb 0,286 1,538 3,456 13 Matrosovsky 156 Clt 0,197 1,275 3,295 14 Matrosovsky 182 Clt 0,256 1,309 3,408 15 Matrosovsky 169 D3p 0,083 0,994 2,919 16 Matrosovsky 185 D2vb 0,055 0,869 2,740 17 Matrosovsky 164 D2vb 0,059 0,680 2,771 18 Matrosovsky 198 D2vb 0,062 0,831 2,792 19 Matrosovsky 194 D2vb 0,054 0,807 2,732 20 Matrosovsky 168 D2vb 0,058 0,785 2,763 21 Matrosovsky 186 D2vb 0,054 0,667 2,732 22 Matrosovsky 180 D2vb 0,048 0,829 2,681 23 Matrosovsky 176 D2vb 0,061 0,756 2,785 24 Kutushevsky 344 Clbb 0,470 1,747 3,672 25 Kutushevsky 360 Clbb 0,424 1,702 3,627 26 Kutushevsky 342 D3kn 0,165 1,305 3,218 27 Ilmovsky 683.1 C2b 0,531 1,890 3,725 28 Nikolaev 926 Civ
f - About
)

AT
Srz.so ate
Oil
At = 1,1 х+0.5 About ' R = 0,97
/
ln
іШіг zoa —
"About
s and

.oo o
about
.o
About, ' about
1.03 at = 1,1 Х-2,0 Asphaltenes r = about, 97
a.ao
1 I 1 1 1 1 1 I
0.00 1.00 200 3.00 4. THE JOINT VENTURE
IgV, [g/t]
Fig. 29. Dependence of the maintenance vanadilovyh complexes from the maintenance
The general vanadium in neftjah and asphaltenes
It is possible to notice, that both for neftej, and for asphaltenes from them dependence of the maintenance vanadilovyh complexes from the maintenance of the general vanadium looks like a straight line. And the tangent of angle of lean of both straight lines coincides. The yielded fact, possibly, testifies that the parity of the paramagnetic and diamagnetic form of vanadium with increase in the maintenance of vanadium in neftjah, in asphaltenes from these neftej remains approximately same.
As a result of the decision of set of equations which describe dependences of maintenance VK on the maintenance of the general vanadium in neftjah and asphalt-nah, the factor of transfer of concentration of paramagnetics in neftjah is revealed
2. 5
To conformity to sizes of the maintenance of paramagnetics in asphaltenes (10 ').
Thus, transfer of scale SR-VK for neftej in scale SR-VK for asphaltenes can be carried out on the equations:
IgBK „= IgBK„ - 2,5 lgCPn = IgCPH - 2,5
Where indexes designate p — translated values,
n - initial values.
After transfer of sizes of paramagnetics characterising the maintenance in neftjah to conformity with similar sizes for asphaltenes, maintenance VK and CP in neftjah also falls into to a mass unit (otn.sp./g] become units of measure podlogarifmicheskih sizes for neftej [).
So, by maintenance comparison in neftjah and asphaltenes of the general vanadium defined method AAS and paramagnetic vanadium defined by method EPR receives the graph of dependence of the maintenance of free radicals from concentration vanadilovyh complexes for neftej and asphaltenes (fig. 30).
Unfortunately for a full pattern of dependence of maintenance CP from maintenance VK in neftjah uneven-age depositions and asphaltenes neftej "do not suffice" oil objects geological age which will be between depositions devona and kembrija, i.e. neftej silura and ordovika. But position of corresponding points is not difficult for foreseeing. As a result dependence lgCP = F (IgBK) for the studied samples neftej uneven-age depositions as a whole has more likely a S-shaped appearance.
In neftjah with low maintenance VK it is observed prjamoproportsio - nalnaja dependence lgCP = F (lgBK) both for neftej, and for asphaltenes. Oil with the high maintenance of vanadium differ that with increase in concentration VK maintenance CP changes a little, for asphaltenes the considered tendency has - a return kind. 3.00-1 with
About

Asphaltenes
RTS
az 2.оо 1.00 —

shchsh
w

Oil 0.00 —
T-zoo
1,00
0,00
1.00
2.00
-3.00 lgBK, [osh.sp,/G]
Fig. 30. Dependence lgCP from lgBK in neftjah and asphaltenes of uneven-age depositions
SHCH-SHCH - є f - top devon-D3
|~| - Centre devon - D2 0-bottom karbon - С1
D - centre karbon - С2 (fig. 30) shows the dependence Analysis, that on co-ordinates of the maintenance of paramagnetics, asphaltenes neftej an average devona concentrate in rather small area. The reason of it, possibly, structural similarity of these asphaltenes, in particular, a similar parity of a polyaromatic and nafteno-aliphatic part in average structure of a molecule of asphaltenes is.
With increase in the maintenance of asphaltenes in neftjah concentration VK in neftjah and in asphaltenes from these neftej (fig. 31) increases.

4. The maintenance of asphaltenes, mzs. % the Maintenance of asphaltenes., mas. %
Fig. 31. Concentration change vanadilovyh complexes with increase in the maintenance of asphaltenes in neftjah
So, in neftjah, enriched by vanadium, with concentration increase vanadilovyh complexes the maintenance of asphaltenes, the maintenance of free radicals in neftjah increases remains to constants, and in average structure of a molecule of asphaltenes decreases.
For neftej with the high maintenance of vanadium structural change of asphaltenes with increase in their maintenance can be represented charted as follows (fig. 32).
For neftej: ВК1< ВК2 < ВКЗ, Для асфальтенов: ВК1 < ВК2 < ВК3 СР1 - СР2 = СРЗ СР1 > СР2> SRZ

poshtar omatache missing a bit a part Nafteno-Alifatichesky cha st
Rice 32. The schematical plotting of structural change of asphaltenes depending on their maintenance in neftjah with high concentration of vanadium
It is impossible to exclude probability of "dilution" of molecules of asphaltenes containing CP molecules VK. But process of allocation of asphaltenes provides their purification from soosadivshihsja resins. Therefore "diluting with" molecules VK by definition also are asphaltenes.
Thus, the tendency to inverse relationship of maintenance CP from maintenance VK in asphaltenes neftej, enriched by vanadium is mainly caused by change of a parity polyaromatic and nafteno - aliphatic parts as a part of average structure of asphaltenes.
It is necessary to notice, that a tangent of angle of lean of direct uniters of a point neftej (fig. 30) with corresponding points of asphaltenes from these neftej for oil objects devona (1,00 - 1,05) more low, than for neftej karbona (1,05 1,40).
Possibly, it is connected by that extraction degree vanadilovyh complexes asphaltenes from neftej devona above, than from neftej karbona. And on the contrary, asphaltenes neftej karbona in bolshej degrees take from neftej free stable radicals, than asphaltenes neftej devona. Result unexpected as maintenance CP in neftjah devona basically is caused by presence of asphaltenes. Deasfaltizaty these neftej practically do not contain the paramagnetic centres.
Asphaltenes neftej an average devona and kembrija have a number of distinctive characteristics;
Rather high maintenance of free radicals and the depressed maintenance vanadilovyh complexes and vanadium in composition,
Dependence of maintenance CP on concentration VK in asphaltenes neftej an average devona in general has a directly proportional appearance,
On co-ordinates of the maintenance of paramagnetics asphaltenes neftej an average devona concentrate in small area (fig. 30),
On a dependence drawing lgCP = F (lgBK) points of asphaltenes neftej an average devona and kembrija are wedged from the tendency characteristic for other asphaltenes (fig. 33).

AT =-0,8031 X + 3,2452 R - 0,71
Possibly, it svjazanno with their structural features.
2.80
Т7
With about
To n
About
About
JW
2.00
1.60
0.00 0,40 0.80 1,20 1.60 2 00
lgBK, [otn.sp./g]
Fig. 33. Change of maintenance CP with concentration increase In To for
Asphaltenes neftej top devona and karbona (average asphaltenes devona
And kembrija are led round)
? - Centre devon - D2, About "bottom karbon - С1,
About - top devon - D3, And - centre karbon - С2
Besides, asphaltenes enriched by vanadium neftej and asphaltenes of native bitumens also have various characteristics and, hence, the structural features which establishment has the practical importance, and can become a basis of the scientific approach to synthesis and selection of the chemical reagents attacking on asfaltenovuju a phase of oil systems.
For an establishment of available structural distinctions of the investigated asphaltenes it is obviously necessary:
To carry out the analysis of degree of extraction of the paramagnetic centres asphaltenes from various neftej, that will allow to reveal localisation of fragments containing not coupled electron in molecular composition of the investigated asphaltenes;
To study distinctions of asphaltenes on the spectral factors characterising kondensirovannost, fragrance, alifatichnost and branching to compare them with paramagnetic characteristics and the vanadium maintenance in asphaltenes.
Summarising the basic results of the yielded chapter it is possible to draw following conclusions:
1. Interaction vanadilovyh complexes with the fragments of the asphaltenes containing not coupled electrons is shown, that, does not result in to formation of diamagnetic complexes, and is caused by nonspecific interactions.
3. The new methodical approach for the analysis of paramagnetics in neftjah and the asphaltenes, consisting in unification of relative units of measure of concentration vanadilovyh complexes and free radicals in neftjah and asphaltenes is offered.
On a dependence drawing lgCP = F (lgBK) points of asphaltenes neftej an average devona and kembrija are wedged from the tendency characteristic for other asphaltenes.
The tendency to inverse relationship of the maintenance of free radicals from the maintenance vanadilovyh complexes in asphaltenes neftej, enriched by vanadium, is mainly caused by change of a parity poly-aromatic and nafteno-alifaticheskoj parts as a part of average structure of asphaltenes.
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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 5.2. Studying of interrelation of the maintenance vanadilovyh complexes isvobodnyh radicals in neftjah and asphaltenes:

  1. 3.1. Laws of interrelation of the maintenance vanadilovyh complexes with the maintenance of sulphur, asphaltenes and free 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. 1.4. Vanadilovye complexes and free stable radicals in neftjah and oil components
  5. 5. The NATURE of INTERRELATION VANADILOVYH of COMPLEXES With ASFALTENOVYMI ASSOCIATES
  6. 2.2.7 Technique of definition of maintenance VK and CP in neftjah and asphaltenes method EPR
  7. 5.1. Research of degree of possible interaction vanadilovyh complexes and asfaltenovyh associates
  8. studying of the phenomenon of internal rotation in n-mononitroalkilnyh radicals
  9. Z.Strukturnye types of asphaltenes with the various maintenance of vanadium
  10. studying of the phenomenon of internal rotation in n-alkilnyh radicals. Rotation of the groups containing free valency.