<<
>>

. Z.Strukturnye types of asphaltenes with the various maintenance of vanadium


G
For revealing of additional structural features of asphaltenes with the various maintenance of vanadium research of asphaltenes by method IK the Fourier of spectroscopy is carried out. Following spectral factors which are used for the first time for the characteristic of asphaltenes are revealed:
Degree kondensirovannosti aromatic system was estimated as the relation peak intensivnostej strips at 1600 см*1 (fluctuations С=С-of communications of aromatic structures) and at 3050 sm "1 (fluctuations of S-S-communications of benzene rings),
alifatichnost asphaltenes paid off in the form of the relation intensivnostej strips at 2850 sm "1 (fluctuations metalnyh and the methylene fragments) and at 1600 см*1.
Comparison of spectral factors and paramagnetic harak-teristik asphaltenes is resulted in tab. 6.5.
Table 6.5
Paramagnetic and structural characteristics of asphaltenes № p/p the Deposit № HARD CURRENCY. Geol. Age the Maintenance, (n-1018 otn.sp./g) Spectral factors BK CP Кнді Кнд2 Ал2 1 Enorusskinsky 192 С2Ъ 30,09 70,84 0,455 5,744 2,767 2 Enorusskinsky 3826 C2vr 55,67 77,12 0,404 2,989 4,840 3 Enorusskinsky 158 C2vr 42,75 77,35 0,388 4,455 4,323 4 Vishnevo-half-Jansky 8266 C2vr 32,15 99,02 0,447 2,026 3,217 5 Nurlatsky 179 C2vr 46,02 107,70 0,409 3,361 3,905 6 Ilmovsky 683 (1) C2b 77,62 50,12 0,494 3,208 3,543 7 Enorusskinsky 82 Cltl 54,95 91,16 0,412 5,123 4,281 8 Enorusskinsky 1367 Cltl 55,88 85,89 0,433 3,009 3,788 9 Enorusskinsky 84 Clbb 54,44 77,46 0,422 3,01 4,195 10 Enorusskinsky 3609 Clbb 42,73 89,17 0,434 3,274 4,058 11 Enorusskinsky 1301 Clbb 57,37 87,98 0,401 4,000 3,910 12 Alekseevsky 259 Ciksl 17,87 158,40 0,530 3,703 3,175 13 Alekseevsky 30 Ciksl 22,02 201,20 0,514 3,991 2,875 14 Alekseevsky 188 Ciksl 23,94 218,30 0,458 4,383 2,655 15 Alekseevsky 189 Ciksl 18,34 172,40 0,451 3,523 2,400 16 Alekseevsky 20006 Ciksl 17,21 228,40 0,515 3,909 2,784 17 Matrosovsky 163 Clbb 34,52 135,90 0,505 5,676 2,979 18 Matrosovsky 156 Clt 18,82 107,90 0,507 8,614 3,567 19 Vishnevo-half-Jansky 8053 Clbb 55,00 65,27 0,419 3,872 3,703 20 Nurlatsky 42 Clbb 69,83 41,04 0,424 2,844 3,411 21 Nurlatsky 9176 Clbb 55,41 51,59 0,434 2,284 2,920
22 Nurlatsky 1749 Clbb 58,57 60,18 0,410 3,048 3,953 23 Nurlatsky 9222 Clbb 52,19 50,33 0,402 3,130 3,378 24 Tljanchi-Tamaksky 707 Clt 26,55 117,20 0,489 7,680 3,260 25 Tljanchi-Tamaksky 709 Clbb 28,57 119,20 0,502 7,308 3,282 26 Tljanchi-Tamaksky 716 Clbb 26,90 115,30 0,482 6,607 3,248 27 Matrosovsky 169 D3p 9,85 131,30 0,498 4,223 2,717 28 Nurlatsky 1793 D3kn 29,09 137,90 0,501 2,810 2,845 29 Ural 40064 D3sm 26,93 119,90 0,459 4,876 2,822 30 Tljanchi-Tamaksky 715 (2) D3kn 18,97 204,20 0,579 4,447 3,299 31 Tljanchi-Tamaksky 753 D3ev-lv 16,23 186,30 0,492 6,821 2,757 32 Tljanchi-Tamaksky 714 D3p 22,59 144,90 0,495 5,703 2,936 33 Tljanchi-Tamaksky 790 D3p 25,97 159,10 0,592 8,792 2,967 34 Matrosovsky 198 D2vb 6,78 251,50 0,544 5,438 3,302 35 Matrosovsky 194 D2vb 6,42 234,50 0,538 5,746 3,508 36 Matrosovsky 168 D2vb 6,10 233,70 0,517 5,900 3,133 37 Matrosovsky 186 D2vb 4,65 167,90 0,510 4,505 2,877 38 Matrosovsky 180 D2vb 6,74 239,10 0,521 5,667 3,340 39 Matrosovsky 176 D2vb 5,70 261,90 0,516 3,291 2,529 40 Mordovo-Karmalsky 131 P2u 26,29 53,36 0,408 3,857 4,456 41 Mountain 107А P2kz 24,23 95,00 0,478 4,290 3,000 42 Ashalchinsky 195 P2u 29,91 75,67 0,475 6,923 4,567 43 Kamensk 206 P2u 14,29 66,81 0,480 5,000 3,184 44 Averjanovsky 4 P2u 23,86 79,87 0,506 5,169 3,256 45 Ekaterinovsky 6072 Pis 23,04 52,99 - 3,305 4,624
As it was already specified, asphaltenes of native bitumens differ from asphaltenes neftej the big maintenance of diamagnetic components.
Taking into account the evolved files of asphaltenes differing under paramagnetic characteristics (fig.
37), comparison of the spectral characteristics characterising kondensirovannost (PtsdaD^zobo) and alifatichnost (0285 (ut) SHo) asphaltenes has shown, that asphaltenes are divided on two wasps-novnyh of group (fig. 39).
2.00 3.00 4.00 Z.OO
Fig. 39. Comparison kondensirovannosti (D) 60o/D305o) and alifatichnosti (D2850/D1600) asphaltenes neftej
It is scarlet (2850/1600)
Asphaltenes of the first group differ from asphaltenes of the second - on-vyshennoj kondensirovannostju and concerning small alifatichno - styo. Asphaltenes heavy neftej and native bitumens occupy intermediate position on kondensirovannosti and alifatichnosti.
The similar pattern is observed by comparison of spectral factor kondensirovannosti D86o/CDsio "HD75o) with alifatichnostju (D23; o/Di6oo) (fig. 40). If alifatichnost to estimate under relation D ^^ o/D^oo divisions into groups practically does not occur (fig. 41). Iгруппа
P group

Island bo —
ІП
I
go 0.55.
ABOUT
«4Э CO
SH
ISLAND IT —
Island dv —
0.40 —
0.35. 2.CO
3.00
4, CO B.OC
It is scarlet (2850/1600) Fig. 40. Comparison kondensirovannosti (D860 / (D8i0+D75o)) and alifatichnosti (D285 (/Di6oo) asphaltenes neftej about
1Г) with +
About
With aze, —
About to 00
/
/
\
1 V
/
0.43 —

і5
I V h N $ It is scarlet (1375+720/1600)
Fig. 41. Comparison kondensirovannosti (Dg6o / (D8] o+D75o)) and alifatichnosti (Di375+72o/Di6oo) asphaltenes neftej Because of interrelation of structural and paramagnetic characteristics of asphaltenes specific tendencies to dependence of relation SR/VK from relation Кнд1/Ал2 and Кнд2/Ал2 (fig. 42) are observed. The disproportionate kind of the specified tendencies is possibly connected by that VK on a miscellaneous of races-predeleny between polyaromatic and nafteno-aliphatic fragments of structure of various asphaltenes.
16.00-1 and j
І Rch
2 and
і
Rn
And
22 2
2 2 2 2$г 2
1.00 —
4 2
2 4 4 2 2 2 22
4 4
4 4
1-r-t g 1 1 і — | g — 1
0.12
0.16 0.20 Кнд1/Лл2
0.08
0.50 1.1) 0 1.13 2.0 and 2.50 3.03
Кнд2/Лл2 A Fig. 42. Change of relation SR/VK with increase in relation Кнд1/Ал2 () and Кнд2/Ал2 () for asphaltenes neftej and native bitumens
The designated structural files of asphaltenes are shown in tab. 6.6.
Table 6.6
Characteristics of structural files of asphaltenes neftej and native bitumens Type the Deposit № Geol. The maintenance,

(n-10 otn.sp./g) Spectral factors of HARD CURRENCY. Age VK CP Кнді Кнд2 Ал2 1 Matrosovsky 198 D2vb 6,78 251,50 0,544 5,438 3,302 Matrosovsky 194 D2vb 6,42 234,50 0,538 5,746 3,508 Matrosovsky 168 D2vb 6,10 233,70 0,517 5,900 3,133 Matrosovsky 186 D2vb 4,65 167,90 0,510 4,505 2,877 Matrosovsky 180 D2vb 6,74 239,10 0,521 5,667 3,340 Matrosovsky 176 D2vb 5,70 261,90 0,516 3,291 2,529
1 Matrosovsky 169 D3p 9,85 131,30 0,498 4,223 2,717 2 Nurlatsky 1793 D3kn 29,09 137,90 0,501 2,810 2,845 Ural 40064 D3sm 26,93 119,90 0,459 4,876 2,822 Tljanchi-Tamaksky 715 (2) D3kn 18,97 204,20 0,579 4,447 3,299 Tljanchi-Tamaksko e 753 D3ev-lv 16,23 186,30 0,492 6,821 2,757 tljanchi akskoe 714 D3p 22,59 144,90 0,495 5,703 2,936 Tljanchi-Tamaksky 790 D3p 25,97 159,10 0,592 8,792 2,967 Alekseevsky 259 Clksl 17,87 158,40 0,530 3,703 3,175 Alekseevsky 30 Clksl 22,02 201,20 0,514 3,991 2,875 Alekseevsky 188 Clksl 23,94 218,30 0,458 4,383 2,655 Alekseevsky 189 Clksl 18,34 172,40 0,451 3,523 2,400 Alekseevsky 20006 Clksl 17,21 228,40 0,515 3,909 2,784 Matrosovsky 163 Clbb 34,52 135,90 0,505 5,676 2,979 Matrosovsky 156 Clt 18,82 107,90 0,507 8,614 3,567 Tljanchi-Tamaksky 707 Clt 26,55 117,20 0,489 7,680 3,260 Tljanchi-Tamaksky 709 Clbb 28,57 119,20 0,502 7,308 3,282 Tljanchi-Tamaksky 716 Clbb 26,90 115,30 0,482 6,607 3,248 3 Enorusskinsky 82 Cltl 54,95 91,16 0,412 5,123 4,281 Enorusskinsky 1367 Cltl 55,88 85,89 0,433 3,009 3,788 Enorusskinsky 84 Clbb 54,44 77,46 0,422 3,010 4,195 Enorusski certain 3609 Clbb 42,73 89,17 0,434 3,274 4,058 Enorusskinsky 1301 Clbb 57,37 87,98 0,401 4,000 3,910 Vishnevo-half-Jansky 8053 Clbb 55,00 65,27 0,419 3,872 3,703 Nurlatsky 42 Clbb 69,83 41,04 0,424 2,844 3,411 Nurlatsky 9176 Clbb 55,41 51,59 0,434 2,284 2,920 Nurlatsky 1749 Clbb 58,57 60,18 0,410 3,048 3,953 Nurlatsky 9222 Clbb 52,19 50,33 0,402 3,130 3,378 Enorusskinsky 3826 C2vr 55,67 77,12 0,404 2,989 4,840 Enorusskinsky 158 C2vr 42,75 77,35 0,388 4,455 4,323 Ilmovsky 683 (1) C2b 77,62 50,12 0,494 3,208 3,543 4 Enorusskinsky 192 C2b 30,09 70,84 0,455 5,744 2,767 Vishnevo-half-Jansky 8266 C2vr 32,15 99,02 0,447 2,026 3,217 Nurlatsky 179 C2vr 46,02 107,7 0,409 3,361 3,905 Mordovo-Karmalsky 131 P2u 26,29 53,36 0,408 3,857 4,456 Mountain 107А P2kz 24,23 95,00 0,478 4,290 3,000 Ashalchinsky 195 P2u 29,91 75,67 0,475 6,923 4,567 Kamensk 206 P2u 14,29 66,81 0,480 5,000 3,184 Averjanovsky 4 P2u 23,86 79,87 0,506 5,169 3,256 Ekaterinovsky 6072 Pis 23,04 52,99 - 3,305 4,624 Besides communication of the revealed structural files of asphaltenes with geolo-gicheskim age neftej from which they are evolved. There is a communication oso-bennostej the evolved files of asphaltenes with propensity to recombination, the maintenance of vanadium and free radicals, a parity of polyaromatic and nafteno-aliphatic parts in structure of asphaltenes.
Summarising the obtained data it is possible to designate features of the evolved structural files of asphaltenes:
18
File - maintenance CP more than 100 (-10 otn.sp./г),
Maintenance VK less than 15 (-1018 otn.sp./g),
The maintenance of vanadium less than 0,1 mas. %,
Are characterised raised kondensirovannostju aromatic system and depressed alifatichnostju asphaltenes,
Free radicals of polyaromatic fragments of asphaltenes
Are inclined to recombination at allocation of these asphaltenes.
18
File - maintenance CP more than 100 (-10 otn.sp./g),
Maintenance VK from 15 to 40 (-1018 otn.sp./g),
The maintenance of vanadium 0,2 - 0,3 mas. %,
Are characterised concerning high kondensirovannostju aromatic system and depressed alifatichnostju asphaltenes.

File - maintenance CP less than 100 (-10 otn.sp./g),
Maintenance VK more than 40 (-1018 otn.sp./g),
The maintenance of vanadium 0,3 - 0,55 mas. %,
Are characterised concerning low kondensirovannostju and raised alifatichnostju a peripheral part of a molecule of asphaltenes.
T I
File - maintenance CP less than 100 (-10 otn.sp./g),
Maintenance VK from 15 to 50 (-1018 otn.sp./g),
The maintenance of vanadium 0,2 - 0,4 mas. %,
Accumulate bolshee quantity of diamagnetic components in comparison with asphaltenes more high-gravity oils.
Proceeding from features of the studied asphaltenes, (under the vanadium maintenance) it is possible to present a space model of extreme types of asphaltenes as follows.
Asphaltenes And type are characterised by high concentration CP in the central polyaromatic part, peripheral nafteno - aliphatic - the part is less on size. The maintenance in structure of these asphaltenes of vanadium and vanadilovyh complexes rather low. The specified asphaltenes are characterised raised kondensirovannostju, small alifatichnostju and propensity CP to recombination in the course of allocation of asphaltenes. Thus, asphaltenes And type contain large polyaromatic fragments in average structure of a molecule (fig. 43).
Asphaltenes In type in the central polyaromatic part harakte-rizujutsja moderate maintenance CP, peripheral nafteno - the aliphatic part - is more on size. Asphaltenes In type are considerably enriched VK and vanadium, the probability of distortion of a flatness of polyaromatic system therefore is high. These asphaltenes differ concerning high alifatichnostju and depressed kondensirovannostju. Thus, In type there corresponds more volume form of molecules (fig. 43). Therefore at sedimentation of these asphaltenes of recombination practically does not occur, as similar processes are sterically complicated by the "massive" and developed structure of a peripheral part.
If size of a polyaromatic part of average structure of asphaltenes roughly to take over proportional radical concentration. That parity of polyaromatic parts in asphaltenes And - and In - types approximately 3:1, accordingly (taking into account partial rekombina-tsii A-type asphaltenes).

Fig. 43. The Space model of a structure of average structure mo-lekuly asphaltenes And - and V-type
The represented space models do not consider size of molecules of asphaltenes and characterise average unit of structure of asphaltenes.
The investigated asphaltenes of 2nd file occupy intermediate position on a parity in their composition of extreme asphaltenes And - and In - type. Asphaltenes of 4th file, possibly, occupy intermediate position on structure of molecules.
Injected structural typification not only will well be co-ordinated with literary yielded [50, 63] and the received results, but also allows to explain behaviour of asphaltenes in oil disperse systems and feature of occurring processes at their sedimentation and allocation.
So the model of asphaltenes And type allows to explain presence of asphaltenes in neftjah in the form of the agglomerates reminding packs from several beds. And free stable radicals of asphaltenes forming similar agglomerates exist in a dynamic equilibrium:
AND і "+ А2 '« = Ї AND І А2
Balance is supported thanks to presence of solvent which stabilises similar structures in the form of micelles, stable paramagnetism nativnyh oil systems in sheet conditions before technogenic intervention as a result is supported.
After allocation of asphaltenes solvent practically completely leaves from system, hence, there is a displacement of balance towards formation of dimers А1А2 (recombination).
Spatial structure of the asphaltenes enriched by vanadium comes nearer to the spherical. Therefore at sedimentation of these asphaltenes of recombination practically does not occur, as similar processes steri - cheski are complicated.
Thus, by means of methods EPR and IK the Fourier of spectroscopy, is revealed a number of structural features of the asphaltenes differing with the maintenance of vanadium. Basic structural differences of the asphaltenes enriched by vanadium from asphaltenes, with the low maintenance of complexes of vanadium are shown.
The similar division of asphaltenes according to their structural features can become a basis of selection of stabilizers - of destabilizers of oil disperse systems, emulsion breakers etc.
Researches in the field of substances-stabilizers of the VAT are actively made by science team of leading universities of Canada, Mexico and Venesuelly in which there are significant stocks heavy neftej and native bitumens. In a number of works [82, 83] for stabilisation asfaltenovoj phases in an oilstock it is offered to use nativnye petroleum tars, synthetic alkyl phenols and alkylphenolic resins. Efficiency of the specified substances as VAT stabilizers, possibly, svjazanna with presence of phenolic fragments (hydrophilic groups) on external sites of molecules of asphaltenes heavy, sulphurous neftej.
For each group neftej, the evolved files corresponding to asphaltenes, there will be preferable a presence of those or other active fragments in stabilizer structure asfaltenovoj phases.
The structure I should contain the stabilizer:
Mainly aromatic groups
Mainly hydrophilic groups

Fig. 44. Recommendations about composition of chemical structure of stabilizers of oil disperse systems
In particular (fig. 44), stabilisation of the VAT containing asphaltenes which are characterised by sizes DI6OO/I> 305O> 3,0; D285Q/DI6OO< 3,5; содержанием CP > 1020 and VK< 0,3-1020 отн.сп./г, предпочтительно использовать соединения содержащие преимущественно ароматические структуры в своем составе. Если нефтяные дисперсные системы содержат асфальтены, характеризующиеся величинами D1600/D3050 < 5,0; D2850/D16OO > 3,0; maintenance CP< 1020 и ВК > of 0,4*1020 otn.sp./g their stabilisation will be promoted by presence of hydrophilic groups as a part of the stabilizer.
Thus, by results of the yielded chapter it is possible to draw following basic conclusions:
Spectral factors of fragrance and branching of asphaltenes do not correlate with their paramagnetic characteristics.
For the characteristic of asphaltenes spectral factors D1600/D3050 (for degree revealing kondensirovannosti asphaltenes) and D2S50/D1600 (for the characteristic alifatichnosti asphaltenes) for the first time are used.
Asphaltenes of the first file evolved by comparison of a pas-ramagnitnyh and structural characteristics, are characterised by the raised maintenance of free radicals, kondensirovannostju and the depressed maintenance of vanadium (less than 0,1 mas. %), vanadilovyh complexes and alifa-ticheskih fragments, besides, free radicals of polyaromatic fragments of these asphaltenes are inclined to recombination;
Asphaltenes of the second file, differ the moderate maintenance of free stable radicals, vanadilovyh complexes and vanadium, concerning high kondensirovannostju aromatic system and depressed alifatichnostju;
Asphaltenes of the third file are characterised by rather low maintenance of free radicals, weak kondensirovannostju, and also the raised maintenance of vanadium (to 0,55 mas. %), vanadilovyh complexes and aliphatic fragments.
Asphaltenes of the fourth file, differ the low maintenance of free radicals and vanadilovyh complexes, and accumulate bolshee quantity of diamagnetic components in comparison with asphaltenes more high-gravity oils.
Asphaltenes with rather low maintenance of vanadium (less than 0,1 mas. %) have large polyaromatic fragments in molecular composition, to 50 % of free radicals at allocation of the specified asphaltenes rekom - binirujut. The asphaltenes enriched by vanadium (more than 0,3 mas. %), have more volume form of molecules and contain polyaromatic fragments (on which not coupled electrons are localised) in structure interior.
For optimisation of application of chemical reagents-stabilizers of the VAT it is offered to use the connections containing mainly aromatic or hydrophilic groups depending on structural features of asphaltenes neftej.
<< | >>
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 . Z.Strukturnye types of asphaltenes with the various maintenance of vanadium:

  1. 6. STUKTURNYE FEATURES of ASPHALTENES neftej With the VARIOUS MAINTENANCE of VANADIUM
  2. 3.1. Laws of interrelation of the maintenance vanadilovyh complexes with the maintenance of sulphur, asphaltenes and free radicals in neftjah and asphaltenes.
  3. Definition of the maintenance of vanadium
  4. 5.2. Studying of interrelation of the maintenance vanadilovyh complexes isvobodnyh radicals in neftjah and asphaltenes
  5. 2.2.7 Technique of definition of maintenance VK and CP in neftjah and asphaltenes method EPR
  6. 1.2. Vanadium connections in neftjah and their distribution on a compo-nentam
  7. 6.3,3. Behaviour of chrome, vanadium, the titan.
  8. 1.3. Structure of oil asphaltenes
  9. 6.1. Degree of extraction of free stable radicals and vanadilovyh complexes asphaltenes from neftej
  10. 1.3.1. Composition and structure polycyclic and alifaticheskihfragmentov structures of asphaltenes
  11. 6.2. Comparison of spectral characteristics of asphaltenes
  12. orthodox culture in the maintenance of formation of various types of the Russian school in second half XIX - beginnings HH centuries
  13. 4.2. Fenalenilnyj a radical as a part of heavy resin of pyrolysis iosobennosti technogenic asphaltenes
  14. 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
  15. types kontseptov
  16. 1.4.4. Other types of epithets
  17. 3.3.1 Factitive types.
  18. 4.3.1 Factitive types.
  19. 1.4.5. Types of domain boundaries in hexagonal magnetics.
  20. Others. Types 13, 14, 15