<<
>>

5.1. Research of degree of possible interaction vanadilovyh complexes and asfaltenovyh associates


For carrying out of check of possibility of formation of chemical bonds between vanadilovymi complexes and sites of asphaltenes containing not coupled electrons, and also revealings of quantitative characteristics of the discussed phenomena interaction modelling vanadilovyh complexes and models of free radicals in a benzene solution has been made.
As models oil VK concentrates expressly evolved from Ashalchinsky oil vanadilporfirinov (fig.
26а) which are characterised by rather low maintenance of free radicals in the composition were used. Maintenance VP (in a concentrate) defined spektrofotometricheski has made 7,6 mas. %. Techniques of allocation and maintenance definition vanadilporfirinov are described in an experimental part.
As models of fragments of the asphaltenes characterised on-lichiem not coupled electron (fig. 266) and absence VK, asphaltenes from hydrocarbonaceous systems of a technogenic origin have been used. In the previous chapter possibility of use of technogenic asphaltenes as models of the structures containing not coupled electrons was specified. Technogenic asphaltenes are evolved from the rests of processes of pyrolysis and synthesis ethyl benzol and Open Society "Нижнекамскнефтехим" - heavy resin of pyrolysis and polialkilbenzolnoj resins. Besides technogenic asphaltenes the oil asphaltenes characterised by low maintenance VK also have been used.


Fig. 26. And - a structure fragment vanad silt of pores firinovogo a complex — a fragment of structure of asphaltenes containing CP
Results EPR on change fixing intensivnostej signals VK and CP (taking into account width of a signal) corresponding solutions of modelling samples before mixture are resulted in tab. 5,1.
Table 5.1
Paramagnetic characteristics of solutions of asphaltenes before introduction vanadilovyh complexes Benzene solutions the expert-faltenov 1 mas. % the Maintenance of paramagnetics, otn.ed. * before introduction of concentrate VK CP VK To the ambassador TO the ambassador Technogenic asphaltenes TSP 10,4 9,8 0 116,7 PABS 94,4 94,7 0 117,0 Oil asphaltenes matrosovskie, 164 58,3 58,0 sl. 116,5 matrosovskie, 186 47,1 47,0 sl. 117,0 matrosovskie, 176 72,2 72,4 sl. 117,2 Entered additive concentrate VK 0,3 - 117,0 - * - conditions of shooting of spectrums EPR differed from conditions for neftej, therefore the received sizes have units of measure — otn.ed, 1
As a whole by results of the yielded modelling it is possible to ascertain, that significant change of integrated signal strength CP after addition to a solution of asphaltenes of concentrate VP does not occur. "Flare" of signals CP and VK after mixture that is a consequence of exchange interaction between them is observed.
The flare of signal CP with increase in maintenance VK is characteristic also for the investigated asphaltenes neftej (fig. 27).

Maintenance VK, OTN.SP./G
Fig. 27. Change of width of signal CP () with increase in concentration VK in asphaltenes neftej
The similar tendency is a consequence of a various sort of nonspecific interactions (including exchange, 7Г-7і-стекинга, etc.) between vanadilovymi complexes and sites of asphaltenes on which lokalizo-vany free stable radicals [105, 121].
According to work [99] at oil fractionation on components there is a destruction of a part of diamagnetic complexes CP and VK, and they mo - gut to be formed again at preparation of "modelling" oil of the evolved components.
Extraction division testifies to absence of chemical interaction between VK and sites of asphaltenes containing CP (with formation of diamagnetic complexes) (acetone and atsetilatsetonom) asphaltenes neftej made in work [101]. It is shown, that in the received fractions the total maintenance of the paramagnetic centres corresponds to their maintenance in initial asphaltenes. The processed results of extraction division are presented to tab. 5.2.
Table 5.2
Abundance CP and VK in fractions of asphaltenes Initial asphaltenes Atsetilatseton Acetone the rest ekst eakt the rest ekst eakt CP VK CP VK CP VK CP VK CP VK otn.ed.'ug * makarovskie 38 11 26 3 10 7 36 9 1 1 zjuzeevskie 23 21 21 9 2 5 24 18 0 2 sabanchinskie 52 14 32 1 14 10 55 11 1 2 Kamensk 32 11 60 5 7 5 40 10 0 1 ashalchinskie 36 10 21 4 7 6 34 11 2 2 * - the presented sizes of maintenance VK and CP are calculated from data of work [101] therefore have units of measure - otn.ed.'ug
If at asphaltenes there are diamagnetic complexes VK and CP after extraction of asphaltenes they should partially will collapse, that will lead bolshemu to maintenance CP and VK in the received extracts and the corresponding rests in comparison with initial asphaltenes. However the raised maintenance of free radicals in extracts and the corresponding rests agrees to yielded tab. 5.2 is observed only for asphaltenes of Kamensk bitumen (possibly enriched by labile components). The maintenance vanadilovyh complexes practically in all objects corresponds to their maintenance in extracts and the rests.
Thus, the tendency to inverse relationship of maintenance CP from maintenance VK in asphaltenes neftej not result of interaction VK and CP with formation of diamagnetic complexes, and is caused by other reasons. The received results prove perspectivity of application of extraction methods of concentrating vanadijsoderzhashchih connections from CAB.
<< | >>
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 5.1. Research of degree of possible interaction vanadilovyh complexes and asfaltenovyh associates:

  1. 5. The NATURE of INTERRELATION VANADILOVYH of COMPLEXES With ASFALTENOVYMI ASSOCIATES
  2. 6.1. Degree of extraction of free stable radicals and vanadilovyh complexes asphaltenes from neftej
  3. 5.2. Studying of interrelation of the maintenance vanadilovyh complexes isvobodnyh radicals in neftjah and asphaltenes
  4. 3. CHARACTER of INTERRELATION of MAINTENANCE VANADILOVYH of COMPLEXES, SULFUR And FREE RADICALS In neftjah IASFALTENAH.
  5. 3.1. Laws of interrelation of the maintenance vanadilovyh complexes with the maintenance of sulphur, asphaltenes and free radicals in neftjah and asphaltenes.
  6. Physical and chemicalmethods of research kompleksonov and their complexes
  7. Research of conformational changes of complexes from protein VirE2-VirE1 the method of normal fashions
  8. PANCHENKO VLADISLAV JUREVICH. LEGAL INTERACTION AS the KIND of SOCIAL COMMUNICATIONS: TEORETIKO-LEGAL RESEARCH. The dissertation on competition of a scientific degree of the doctor of juridical science. Moscow - 2016, 2016
  9. 3.1. Maintenance with medical products of the citizens, suffering socially significant diseases and the diseases representing Danger to associates
  10. Abramova Natalia Stepanovna. ELECTROCATALYTIC REACTIONS of COMPLEXES of NICKEL (II) And COBALT (II) With ERIOCHROME BLACK T ON the MERCURY DRIPPING ELECTRODE. The dissertation on competition of a scientific degree of a Cand.Chem.Sci. Krasnodar - 2017, 2017
  11. § 3.1. Legal bases of interaction between the Russian Federation and the European Union in the field of research and space use
  12. § 3.1. Legal bases of interaction between the Russian Federation and the European Union in the field of research and space use
  13. ABRAMOVA NATALIA STEPANOVNA. ELECTROCATALYTIC REACTIONS of COMPLEXES of NICKEL (II) And COBALT (II) With ERIOCHROME BLACK T ON the MERCURY DRIPPING ELECTRODE. The dissertation AUTOABSTRACT on competition of a scientific degree of a Cand.Chem.Sci. Krasnodar - 2017, 2017
  14. § 2. Advantages of electronic interaction before traditional forms of interaction within the limits of the relations labour and directly connected with them
  15. CHAPTER 2. EMPIRICAL RESEARCH OF EFFICIENCY OF INTERACTION OF SCHOOL AND THE FAMILY IN DUHOVNOYONRAVSTVENNOM EDUCATION OF YOUNGER SCHOOLBOYS IN POLYCULTURAL EDUCATIONAL
  16. the CHAPTER I. THEORETICAL BASES of RESEARCH of INTERACTION of LAW-ENFORCEMENT BODIES With INSTITUTES of the CIVIL SOCIETY In SPHERE of COUNTERACTION narkotizatsii of the POPULATION
  17. 1.4. Vanadilovye complexes and free stable radicals in neftjah and oil components