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6.1. Degree of extraction of free stable radicals and vanadilovyh complexes asphaltenes from neftej


Studying of asphaltenes neftej represents special interest and an individual scientific direction in oil chemistry. Researches in this area are especially actual in connection with constantly increasing share heavy neftej and native bitumens in balance of extraction.
The specified objects are considerably enriched smolisto-asfaltenovymi by components owing to what their extraction and processing puts forward a complex of problems.
In Volgo-Ural neftegazonosnoj deposit provinces vanadienosnyh oil objects are connected, as a rule, with coal and Perm depositions paleozoja. All oil objects enriched by vanadium, are characterised by the high maintenance of asphaltenes, resins, sulfurs. Oil objects are characterised by different stability of asphaltenes to sedimentation, stability of water oil emulsions etc. Specified distinctions, are a consequence of many factors (a mineralization and acidity of sheet waters, influence of a complex of reagents applied on a craft, etc.). One of the major - is structural difference of these asphaltenes neftej. A number of structural features of asphaltenes is obviously possible for revealing by means of methods EPR and IK the Fourier of spectroscopy.
In the previous chapter a number of differences in paramagnetic characteristics of asphaltenes neftej devona and kembrija from other asphaltenes has been noted. The conclusion about the inverse relationship nature in asphaltenes neftej allows to assume, that in structure of asphaltenes with the raised maintenance of free radicals the polyaromatic part prevails.
Space models offered in the literature for the description of structure of asphaltenes assume an arrangement of polyaromatic fragments (on which not coupled electrons are localised) as in internal area of molecules of asphaltenes [30, 32, 58, 59, 62], and on an external part of "volume" molecules of asphaltenes [57, 82]. It is possible to assume, that if the aromatic sites containing not coupled electrons, are on an external surface of molecules at sedimentation of asphaltenes CP will be inclined to the mutual recombination. If polyaromatic sites are localised in the internal (closed) part of molecules of asphaltenes recombination CP at sedimentation of asphaltenes will be sterically complicated.
For research of the designated question calculation and the analysis of degree of extraction of the paramagnetic centres by asphaltenes from various neftej have been carried out. Calculation was made on the basis of paramagnetic characteristics for neftej (after unification of relative sizes of the maintenance of paramagnetics in neftjah and asphaltenes as it is described in the previous chapter) and asphalt-is new from these neftej (taking into account the maintenance of asphaltenes in neftjah).
Degree of extraction of a paramagnetic (%) = Pja • And / P „
Where the Pas - the paramagnetic maintenance (CP, VK) in asphaltenes, otn.sp./g;
And - the maintenance of asphaltenes, %;
Pn - the paramagnetic maintenance in neftjah, otn.sp.
On a share deasfaltizatov neftej it is necessary no more than 20 % from general maintenance CP in neftjah. However maintenance VK in them can reach 80 % that is connected with the big gum content in a number of studied neftej.
Results of calculation of degree of extraction of vanadium, VK and CP from neftej are shown by asphaltenes in tab.
6.1. As a matter of convenience oil objects are built in decreasing order their geological age. Accuracy of results is insignificant, however the received values allow to estimate distribution of paramagnetics after allocation of asphaltenes from neftej in a solid kind.
Table 6.1 № p/p the Deposit № hard currency. The geologist, age the Yield asf-in, mas. % Degree of extraction, % V VK CP 1 In erhne-Chehonskoe - Є odes - 56 67 2 Matrosovsky 185 D2vb 2,0 58 58 66 3 Matrosovsky 164 D2vb 1,4 55 34 39 4 Matrosovsky 198 D2vb 0,5 21 35 35 5 Matrosovsky 194 D2vb 1,2 93 51 52 6 Matrosovsky 168 D2vb 0,8 52 31 39 7 Matrosovsky 186 D2vb 0,6 30 35 44 8 Matrosovsky 180 D2vb 0,9 22 36 33 9 Matrosovsky 176 D2vb 0,4 61 41 44 10 Matrosovsky 169 D3p 1,5 39 18 19 11 Kutushevsky 342 D3kn 3,0 41 22 33 12 Enorusskinsky 1279 Clt 8,7 - 52 68 13 Matrosovsky 156 Clt 5,8 85 38 75 14 Matrosovsky 182 Clt 3,2 99 23 44 15 Alekseevsky 259 Ciksl 4,6 - 48 97 16 Alekseevsky 30 Ciksl 4,0 - 47 94 17 Alekseevsky 188 Ciksl 4,3 _ 51 98 18 Alekseevsky 20006 Ciksl 4,1 - 75 96 19 Kijazlinsky 352 Clbb, t 5,6 - 38 93 20 Melnikovsky 2586 Clbb 6,4 - 36 53 21 Matrosovsky 163 Clbb 6,4 63 38 76 22 Kutushevsky 344 Clbb 10,0 98 50 67 23 Kutushevsky 360 Clbb 4,4 60 34 37 24 Melnikovsky 2593 Clbb, tl 9,5 - 44 55 25 Enorusskinsky 3609 Clbb 6,5 89 48 70 26 Enorusskinsky 1301 Clbb 7,1 87 46 78 27 Enorusskinsky 84 Clbb 8,9 60 45 77 28 Enorusskinsky 1304 Clbb, b, vr 6,4 75 36 64 29 Enorusskinsky 82 Cltl 9,2 67 48 94 30 Enorusskinsky 1367 cm 6,0 85 45 - 31 Cheremuhovsky 817 C2b 7,7 75 47 83 32 Enorusskinsky 192 C2b 8,9 76 30 56 33 (Enorusskinsky 3826 C2vr 6,0 68 37 67 34 (Enorusskinsky 51 C2vr 7,8 71 59 95 35 (Enorusskinsky 158 C2vr 6,5 84 45 75
Degree of extraction of the general vanadium basically above, than paramagnetic V4 + (fig. 34а). In some cases asphaltenes take mainly paramagnetic form of vanadium, and the most part diamagneticly -

Fig. 34. Balance of degree of extraction: the general V/BK () and SR/VK ()
Degree of extraction CP also above, than extraction degree In To (rice 346). Rather small degrees of extraction by asphaltenes V and VK are characteristic for neftej which resins contain significant amounts va - nadijsoderzhashchih connections. However for a number of asphaltenes the depressed degrees of extraction CP (to 30 %) though maintenance CP in deasfal - tizatah does not exceed 20 % from initial maintenance CP in neftjah are characteristic.
From yielded tab. 6,1 follows that the underestimated degrees of extraction ha-rakterny basically for asphaltenes neftej devona, on deasfaltizaty specified neftej it is necessary no more than 5 % from general maintenance CP in neftjah. The elicited facts of "understating" of degree of extraction CP in some investigated objects can be explained partial (to 50 %) recombination CP at allocation of asphaltenes from an oil disperse system.
For asphaltenes characterised by the underestimated degree of extraction CP from neftej characteristicly low maintenance VK (tab. 6.2).
Table 6.2
Degree of extraction V, VK, CP asphaltenes from neftej and paramagnetic characteristics of asphaltenes № p/p the Deposit № HARD CURRENCY. The geologist, age Degree of extraction, % the Maintenance, nl01K Otn.sp./g V VK CP VK CP 1 In erhne-Chehonskoe - Є - 56 67 1,8 539,7 2 Matrosovsky 185 D2vb 58 58 66 7,4 295,5 3 Matrosovsky 164 D2vb 55 34 39 4,8 209,9 4 Matrosovsky 198 D2vb 21 35 35 6,8 251,5 5 Matrosovsky 194 D2vb 93 51 52 6,4 234,5 6 Matrosovsky 168 D2vb 52 31 39 6,1 233,7 7 Matrosovsky 186 D2vb 30 35 44 4,7 167,9 8 Matrosovsky 180 D2vb 22 36 33 6,7 239,1 9 Matrosovsky 176 D2vb 61 41 44 5,7 261,9 10 Matrosovsky 169 D3p 39 18 19 9,9 131,3 11 Kutushevsky |342 D3kn 41 22 33 20,2 122,2 12 Enorusskinsky 1279 Clt - 52 68 56,1 96,0 13 Matrosovsky 156 Clt 85 38 75 18,8 107,9 14 Matrosovsky 182 Clt 99 23 44 20,4 120,2 15 Alekseevsky 259 Clksl - 48 97 17,9 158,4 16 Alekseevsky 30 Clksl - 47 94 22,0 201,2 17 Alekseevsky 188 Clksl - 51 98 23,9 218,3 18 Alekseevsky 20006 Clksl - 75 96 18,3 172,4 19 Kijazlinsky 352 Clbb.t - 38 93 53,7 81,3 20 Melnikovsky 2586 Clbb - 36 53 47,6 64,8 21 Matrosovsky 163 Clbb 63 38 76 34,5 135,9 22 Kutushevsky 344 Clbb 98 50 67 55,9 94,8 23 Kutushevsky 360 Clbb 60 34 37 50,3 95,3 24 Melnikovsky 2593 Clbb, tl - 44 55 49,8 57,4 25 Enorusskinsky 3609 Clbb 89 48 70 42,7 89,2 26 Enorusskinsky 1301 Clbb 87 46 78 57,4 88,0 27 Enorusskinsky 84 Clbb 60 45 77 54,4 77,5 28 Enorusskinsky 1304 Clbb, b, v 75 36 64 55,0 61,2 29 Enorusskinsky 82 Cltl 67 48 94 55,0 91,2 30 Enorusskinsky 1367 Cltl 85 45 - 55,9 85,9 31 Cheremuhovsky 817 C2b 75 47 83 38,5 99,0 32 Enorusskinsky 192 C2b 76 30 56 30,1 70,8 33 Enorusskinsky 3826 C2vr 68 37 67 55,7 77,1 34 Enorusskinsky 51 C2vr 71 59 95 44,6 93,0 35 Enorusskinsky 158 C2vr 84 45 75 42,8 77,4
Degree of extraction V, VK and CP asphaltenes from neftej
The analysis of yielded tab. 6.2 allows to position characteristic paramagnetic signs of asphaltenes characterised by the underestimated degree of extraction CP (fig. 35),

VK, OTH.CrtJr CP, otn.sil
Fig. 35. Dependence of degree of extraction CP on maintenance VK () and CP () in asphaltenes
The specified asphaltenes are characterised by maintenance VK less than 15 (•1018 otn.sp./g) and maintenance CP more than 100 (*1018 otn.sp./g) (fig. 36).
Went
I a h
Si
ABOUT
1ЭДВЗ
G
іша ota і &ла elm
VK, otn.sp./g
Fig. 36. The area of paramagnetic characteristics of asphaltenes for which is characteristic the underestimated degree of extraction CP from neftej
About - top devon - D3 „
And - centre karbon - С2
? - Centre devon - D2, About bottom karbon - С1,
Distinction of the investigated asphaltenes in sizes of degree of extraction CP and as consequence in propensity of asphaltenes to recombination can be explained distinction in spatial structure of the last.
The asphaltenes characterised by the raised maintenance of free radicals against the low maintenance vanadilovyh of complexes are inclined to recombination. Possibly, in structure of the specified asphaltenes the central polyaromatic part prevails, and peripheral nafteno - the aliphatic part of structure does not interfere with recombination (fig. 20).
The vanadium maintenance, communicates and correlates with the maintenance in asphaltenes as polyaromatic, and nafteno-alifaticheskoj the parts, which inseparably linked with fragments of heteroorganic structures and actually with a polyaromatic part. The designated structural parts form a uniform molecule with all structural variety inherent in it spatially-. Vanadium connections connected with a polyaromatic part, can result in to a deviation from a flatness of the condensed aromatic system. The deviation can be a consequence of communication of vanadium with atoms S and About, a part of not aromatic ring compounds.
Being reverted to results of the previous chapter it is possible to note, what exactly because of part recombination (to 50 %) free radicals of a point of asphaltenes neftej an average devona and kembrija are wedged from the tendency lgCP = F (lgBK) characteristic for other asphaltenes (fig. 33). At recalculation of data under maintenance CP for these asphaltenes taking into account their recombination corresponding points on a drawing lgCP-F (lgBK) "lay down" on the tendency characteristic for other asphaltenes.
Asphaltenes with rather high maintenance VK and low maintenance CP not rekombinirujut (tab. 5.2) that testifies to localisation of polyaromatic fragments in molecular composition interior, unlike the literary data assuming placement ar about - matimeskih of fragments on an external part of structure of "volume" molecules
Asphaltenes [57, 63].
The analysis of paramagnetic characteristics of asphaltenes neftej and PB pozvo - і
ljaet to evolve four basic structural files (fig. 37) [122] paramagnetics differing by the maintenance and propensity to recombination CP at allocation of asphaltenes from neftej.

0.00 20 Л0 40.00 60.00 60.00
Maintenance BE, otn.sp./g of a Fig. 37 Basic files of asphaltenes differing with the maintenance of paramagnetics and propensity to recombination
? - Centre devon - D2, About "bottom karbon - С1,
About - top devon - D3, And - centre karbon - С2
For revealing of additional structural features of asphaltenes with the various maintenance of vanadium it is obviously necessary to study distinctions of asphaltenes on the spectral factors characterising kondensirovannost, fragrance, alifatichnost and it is branched out! just and to compare them with paramagnetic characteristics of asphaltenes. That will help to increase differentiation of asphaltenes on structural distinctions and to divide them into structural types.
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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 6.1. Degree of extraction of free stable radicals and vanadilovyh complexes asphaltenes from neftej:

  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. 5.2. Studying of interrelation of the maintenance vanadilovyh complexes isvobodnyh radicals in neftjah and asphaltenes
  3. 1.4. Vanadilovye complexes and free stable radicals in neftjah and oil components
  4. 3. CHARACTER of INTERRELATION of MAINTENANCE VANADILOVYH of COMPLEXES, SULFUR And FREE RADICALS In neftjah IASFALTENAH.
  5. 5.1. Research of degree of possible interaction vanadilovyh complexes and asfaltenovyh associates
  6. 6. STUKTURNYE FEATURES of ASPHALTENES neftej With the VARIOUS MAINTENANCE of VANADIUM
  7. 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
  8. 5. The NATURE of INTERRELATION VANADILOVYH of COMPLEXES With ASFALTENOVYMI ASSOCIATES
  9. studying of the phenomenon of internal rotation in n-alkilnyh radicals. Rotation of groups, free of free valency.
  10. studying of the phenomenon of internal rotation in n-alkilnyh radicals. Rotation of the groups containing free valency.