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1.2. Vanadium connections in neftjah and their distribution on a compo-nentam


Conditions in which the majority of deposits is formed, promote passing of processes of accumulation of metals on migratory mechanisms. The basic forms of a finding of vanadium are vanadilovye complexes among which an essential share represent vanadilporfiriny.
According to literary data [5, 6], vanadium - and nikelsoderzhashchie connections in the majority neftej on the average on 30-40 % are presented pores - firinovymi by complexes.
According to work [7], other part metallo - containing connections is in neftjah in the form of salts of organic acids and in the form of chelates with the mixed ligands. This part metallosoder - zhashchih connections neftej it is accepted to name metallic connections neporfirinovoj structures. metalloporfirinovye complexes, as well as the basic part of oil metallic connections, kontsen-trirujutsja in smolisto-asfaltenovyh components and heavy petroleum residue. On data [8, 9] the maximum maintenance of vanadium, on the average, the maintenance 10 times exceeding it in petroleum crude, is observed in asphaltenes, and vanadilporfirinovyh complexes - in resins.
Among metallic connections neftej by present time the fullest composition and chemical structure only metallopor - firinovyh complexes (fig. 2) are studied.

Fig. 2, Structural skeleton vanadilporfirinovogo a complex
Vanadium connections neporfirinovogo character are offered for dividing into some groups depending on type of linkage of metals [10].
Among set vanadijsoderzhashchih connections possibility of presence and such in which the vanadium ion co-ordinates round itself a little mono-and bidentatnyh ligands [11] is not excluded.
Nickel, as well as vanadium, in neftjah is in the form porfirinovyh and neporfirinovyh complexes. By the nature and those, and other connections are similar. The low molecular weight part of resins and asphaltenes contains nickel in a kind porfirinovyh complexes. At molecular weight increase the share neporfirinovyh connections of nickel [12] grows.
It is found, that the parity vanadyl - and nikelporfirinov depends on an oil base. In vysokosernistyh neftjah the most part of porphyrins is presented vanadilovymi by complexes, in malosernistyh neftjah routinely prevail nikelporfiriny (NP) [13].
Concentration VP even for one region varies in wide limits, complexes with nickel are propagated more evenly. So, for neftej Western Siberia concentration VP changes from 0,05 to 20 mg/100 of g, NP - from 0,01 to 0,3 mg/100 of g [14], for neftej the Perm Prikamye - accordingly from 0,10 to 520 and from 0,25 to 20 mg/100 of g [15]. Concentration VP in Paleozoic neftjah Tatarstan varies from 60 to 172 mg/100 of g [16], and NP - from 4 to 29 mg/100 of g [17]. Authors of work [18] divide asphalts of deposits of basin of the Dead Sea (Israel) into two genetic types according to maintenance VP: less than 1 mg and more 30 mg on 100 g of asphalt.
According to [19-21] maximum concentration of vanadium it is necessary on asphaltenes. But as the general maintenance of asphaltenes in oil is routine less, than gum content the basic share of vanadium after division, as a rule, is necessary on silikagelevye resins. For example, in neftjah to Western Siberia [20, 22] and California of initial quantity of [23 55-88 % of vanadium 11-38 % on asfaltenovye are necessary on pitchy and only to fraction.
Knowledge of microelement composition of a high-molecular part of oil as the most enriched by heterocomponents, can have essential value for a perspectivity estimation demetallizatsii an oilstock and possible negative effects at petroleum refining [24].
Developed in IOFH KazNTS the Russian Academies of Sciences of a technique [17] have shown, that the share of vanadium connected with porfirinovymi by complexes in oil objects of Tatarstan, makes 10-40 %. Benzene resins accumulate 10-55 % of vanadium that does not exceed 10 % from the potential maintenance of this metal in raw materials, vanadium complexes practically are totally presented by connections neporfirinovoj structures. Spirto-BENZENE resins accumulate 1085 % of vanadium, 20-70 which % are presented by connections porfirinovoj structures that makes 10-80 % VP, from their potential maintenance in oil. The upper bound of distribution and the vanadium and nickel maintenance is characteristic for vysokosmolistyh neftej. Asphaltenes accumulate 10-80 % of vanadium, 10-40 which % are presented by connections porfirinovoj structures that makes to 60 % VP from their potential maintenance in oil.
Vanadium and VP concentrate as a part of polar fractions of resins and asphaltenes. Nickel, on the contrary, accumulates as a part of their non-polar fractions. Absolute concentration of vanadium increases among: non-polar fractions of resins - polar fractions of resins - asphaltenes, and nickel among: polar fractions of resins - non-polar fractions of resins - asphaltenes.
Excessively high values of the molecular weights measured by some methods asfaltenovyh components (4000-22000 a.e.m.) and concentrating in their high-polymeric fractions of the basic part of metals specifies, that evolved asfaltenovye components are large polymolecular associates in which formation the trace elements connecting separate macromolecules at the expense of donor-acceptor interactions should play the important role. In particular, elements Fe and V, not connected electrons having in an internal cover, at the expense of the exchange
Interactions also can organise large associates.
For this reason studying of interrelation of structural features of asphaltenes with the vanadium maintenance in neftjah and asphaltenes can make essential impact at the decision of existing problems of extraction and oil preparation.
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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 1.2. Vanadium connections in neftjah and their distribution on a compo-nentam:

  1. Definition of the maintenance of vanadium
  2. 5.2. Studying of interrelation of the maintenance vanadilovyh complexes isvobodnyh radicals in neftjah and asphaltenes
  3. 6.3,3. Behaviour of chrome, vanadium, the titan.
  4. Z.Strukturnye types of asphaltenes with the various maintenance of vanadium
  5. 1.4. Vanadilovye complexes and free stable radicals in neftjah and oil components
  6. 2.2.7 Technique of definition of maintenance VK and CP in neftjah and asphaltenes method EPR
  7. 6. STUKTURNYE FEATURES of ASPHALTENES neftej With the VARIOUS MAINTENANCE of VANADIUM
  8. 3. CHARACTER of INTERRELATION of MAINTENANCE VANADILOVYH of COMPLEXES, SULFUR And FREE RADICALS In neftjah IASFALTENAH.
  9. 3.1. Laws of interrelation of the maintenance vanadilovyh complexes with the maintenance of sulphur, asphaltenes and free radicals in neftjah and asphaltenes.
  10. § 2. Reception of the information on connections between subscribers and (or) user's devices: concept and value of investigatory action
  11. 5.4.2 Choice of a variant of central connections of integral mesh structural coatings
  12. spectrums of reference-point connections
  13. § 2. Tactics of manufacture of reception of the information on connections between subscribers and (or) user's devices
  14. 1.4 Toxic action rtutorganicheskih connections on animals and the person