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Features of the n-alkanes crystalline phase content in paraffin oil components and their deposits

UDK: 622.276.1/.4
Key words: crystallization, wax, paraffin, asphalt-resinous substances, phase transitions, crude oil disperse system
Authors: D.A. Ibragimova, A.G. Safiulina, A.I. Lakhova, N.Yu. Bashkirtseva (Kazan National Research Technological University, RF, Kazan), S.M. Petrov (Kazan (Volga) Federal University, RF, Kazan), Yu.M. Ganeeva (Institute of Physical and Organic Chemistry A.E.Arbuzov RAS, RF, Kazan)

High-molecular n-alkanes within В high paraffin oils of remaining hard-to-recover reserves are studied. Oil paraffin hydrocarbons redistribution between oils and their heavy deposits В in the downhole equipment is presented. The presence of n-alkanes in the oils asphaltenes and their deposits is shown. В Asphaltenes, extracted from the oils and their asphaltene deposits, were investigated by high-temperature gas chromatography and differential scanning calorimetry, with the help of which it was succeeded to find В the presence of high n-alkanes С4059 and higher ones in their composition judging by В the crystallization temperature В detected in the crystalline phase. The highest molecular weight n-alkanes, whose molecular mass distribution peak falls on В С5458 , were found in asphaltenes of oils with low paraffin wax content. The data В on the crystalline phase content in oils, heavy oil deposits, asphaltenes samples, isolated from oils and heavy oil deposits, as well as on the crystallization temperature are presented. High-molecular oil paraffin hydrocarbons В can serve as crystallization centers of the complex structural units in oil dispersion system and flocculate at the system unbalance В at achieving the critical concentration. Paraffin hydrocarbons, containing В in the asphaltenes, are able to migrate and accumulate within the oil heavy deposits under certain thermodynamic conditions, as evidenced by the different compositions of n-alkanes in the oil asphaltenes and В in their deposits. Different kind of В the heat capacity temperature dependences is stated for oils, the presence of paraffin wax crystal phase is revealed. Comparative analysis of differential scanning calorimetry data of samples indicates contradictory dependence В of В the crystallization temperature and В crystalline phase content on the molecular mass distribution of n-alkanes, containing В in their composition, and correlates with the molecular mass distribution of solid n-alkanes in the asphaltenes, that В determines the differences in the structural organization of the dispersed phase in heavy oil deposits.

References

1. Altunina L.K., Serebrennikova O.V., Russkikh I.V., Stakhina L.D., Features of hydrocarbon

distribution in the viscous oil-aqueous phase system during testing

of oil displacement fluids, Petroleum Chemistry, 2015, V. 55, no. 1, pp. 32–37.

2. Ostroukhov S.B., Soboleva E.F., Soboleva N.D., Peculiarities of crude oil composition

of the Volgograd Volga Region (In Russ.), Neftyanoe khozyaystvo =

Oil Industry, 2016, no. 3, pp. 64–67.

3. Bissada (Adry) K.K., Tan J., Szymezyk E. et al., Group-type characterization

of crude oil and bitumen, Part II: Efficient separation and quantification of

normal-paraffinsiso-paraffins and naphthenes, Fuel, 2016, V. 173, pp. 217–221.

4. Cheng P., Xiao X.M., Gai H.F. et al., Characteristics and origin of carbon isotopes

of n-alkanes in crude oils from the western Pearl River Mouth Basin,

South China sea, Marine and Petroleum Geology, 2015, V. 67, pp. 217–229.

5. Do T.X., Lim Y.-il, Lee J., Lee W., Effect of normal paraffins separation from

naphtha on reaction kinetics for olefins and aromatics production, Computers

& Chemical Engineering, 2015, V. 74, pp. 128–143.

6. Yusupova T.N., Ganeeva Yu.M., Khalikova D.A., Romanov G.V., Rapid assessment

of the paraffin composition of asphaltene-resin-paraffin deposits by

thermal analysis and differential scanning calorimetry data (In Russ.),

Neftekhimiya = Petroleum Chemistry, 2012, V. 52, no. 1, pp. 17–21.

7. Klinov A.V., D'yakonov G.S., Malygin A.V., Nurgalieva A.A., Description of

caloric properties of n-alkanes on the basis of a spherically symmetric

Lennard-Jones potential (In Russ.), Vestnik Kazanskogo tekhnologicheskogo

universiteta, 2010, no. 11, pp. 446–452.

8. Ganeeva Y.M., Yusupova T.N., Romanov G.V. et al., The composition and

thermal properties of waxes in oil asphaltenes, Journal of Thermal Analysis

and Calorimetry, 2015, V. 122, no. 3, pp. 1365–1373.

9. Yusupova T.N., Barskaya E.E., Ganeeva Yu.M. et al., Identification of wax deposits

in the bottom-hole formation zone and wellbore in reducing of the

pressure (In Russ.), Neftyanoe khozyaystvo = Oil Industry, 2016, no. 1, pp. 39–41.

10. Rogel E., Ovalles C., Vien J., Moir M., Asphaltene characterization of

paraffinic crude oils, Fuel, 2016, V. 178, pp. 71–76.

High-molecular n-alkanes within В high paraffin oils of remaining hard-to-recover reserves are studied. Oil paraffin hydrocarbons redistribution between oils and their heavy deposits В in the downhole equipment is presented. The presence of n-alkanes in the oils asphaltenes and their deposits is shown. В Asphaltenes, extracted from the oils and their asphaltene deposits, were investigated by high-temperature gas chromatography and differential scanning calorimetry, with the help of which it was succeeded to find В the presence of high n-alkanes С4059 and higher ones in their composition judging by В the crystallization temperature В detected in the crystalline phase. The highest molecular weight n-alkanes, whose molecular mass distribution peak falls on В С5458 , were found in asphaltenes of oils with low paraffin wax content. The data В on the crystalline phase content in oils, heavy oil deposits, asphaltenes samples, isolated from oils and heavy oil deposits, as well as on the crystallization temperature are presented. High-molecular oil paraffin hydrocarbons В can serve as crystallization centers of the complex structural units in oil dispersion system and flocculate at the system unbalance В at achieving the critical concentration. Paraffin hydrocarbons, containing В in the asphaltenes, are able to migrate and accumulate within the oil heavy deposits under certain thermodynamic conditions, as evidenced by the different compositions of n-alkanes in the oil asphaltenes and В in their deposits. Different kind of В the heat capacity temperature dependences is stated for oils, the presence of paraffin wax crystal phase is revealed. Comparative analysis of differential scanning calorimetry data of samples indicates contradictory dependence В of В the crystallization temperature and В crystalline phase content on the molecular mass distribution of n-alkanes, containing В in their composition, and correlates with the molecular mass distribution of solid n-alkanes in the asphaltenes, that В determines the differences in the structural organization of the dispersed phase in heavy oil deposits.

References

1. Altunina L.K., Serebrennikova O.V., Russkikh I.V., Stakhina L.D., Features of hydrocarbon

distribution in the viscous oil-aqueous phase system during testing

of oil displacement fluids, Petroleum Chemistry, 2015, V. 55, no. 1, pp. 32–37.

2. Ostroukhov S.B., Soboleva E.F., Soboleva N.D., Peculiarities of crude oil composition

of the Volgograd Volga Region (In Russ.), Neftyanoe khozyaystvo =

Oil Industry, 2016, no. 3, pp. 64–67.

3. Bissada (Adry) K.K., Tan J., Szymezyk E. et al., Group-type characterization

of crude oil and bitumen, Part II: Efficient separation and quantification of

normal-paraffinsiso-paraffins and naphthenes, Fuel, 2016, V. 173, pp. 217–221.

4. Cheng P., Xiao X.M., Gai H.F. et al., Characteristics and origin of carbon isotopes

of n-alkanes in crude oils from the western Pearl River Mouth Basin,

South China sea, Marine and Petroleum Geology, 2015, V. 67, pp. 217–229.

5. Do T.X., Lim Y.-il, Lee J., Lee W., Effect of normal paraffins separation from

naphtha on reaction kinetics for olefins and aromatics production, Computers

& Chemical Engineering, 2015, V. 74, pp. 128–143.

6. Yusupova T.N., Ganeeva Yu.M., Khalikova D.A., Romanov G.V., Rapid assessment

of the paraffin composition of asphaltene-resin-paraffin deposits by

thermal analysis and differential scanning calorimetry data (In Russ.),

Neftekhimiya = Petroleum Chemistry, 2012, V. 52, no. 1, pp. 17–21.

7. Klinov A.V., D'yakonov G.S., Malygin A.V., Nurgalieva A.A., Description of

caloric properties of n-alkanes on the basis of a spherically symmetric

Lennard-Jones potential (In Russ.), Vestnik Kazanskogo tekhnologicheskogo

universiteta, 2010, no. 11, pp. 446–452.

8. Ganeeva Y.M., Yusupova T.N., Romanov G.V. et al., The composition and

thermal properties of waxes in oil asphaltenes, Journal of Thermal Analysis

and Calorimetry, 2015, V. 122, no. 3, pp. 1365–1373.

9. Yusupova T.N., Barskaya E.E., Ganeeva Yu.M. et al., Identification of wax deposits

in the bottom-hole formation zone and wellbore in reducing of the

pressure (In Russ.), Neftyanoe khozyaystvo = Oil Industry, 2016, no. 1, pp. 39–41.

10. Rogel E., Ovalles C., Vien J., Moir M., Asphaltene characterization of

paraffinic crude oils, Fuel, 2016, V. 178, pp. 71–76.



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