Supramolecular structure and thermal transformations of modified resinous-asphaltene substances

A detailed study of the supramolecular structure of high molecular weight resinous-asphaltene substances (RAS) and the study of their stability to thermal-oxidative degradation processes in the presence of surfactants is a promising scientific direction and can become the basis for the development of additional oil treatment processes and, as a result, the intensification of thermal transformations of oil dispersed systems (ODS). In the work it has been established that the maximum modifying effect, which consists in reducing the amount of asphaltenes by 8–11 % and increasing the concentration of resins, saturated and aromatic hydrocarbons in the composition of the dispersion medium, is achieved by the interaction of ODS with octadecylpropylenediamine, alkyldiamine with the content of ethoxylated groups n = 3–6 and butyl coconut fatty alcohol ester with n = 10. This fact is due to a change in the geometric parameters of asphaltene nanoaggregates due to the adsorption of these surfactants on their surface. Thus, against the background of an increase in the interplanar distances of condensed aromatic layers dm from 3.66 to 3.85 Å and values of the intrachain distance from 5.71 to 5.80 Å, the average diameter of aromatic layers decreases by 0.67–2.36 Å and the average height of their pack by 1.52–2.64 Å, while the average number of layers in a pack is 5. Estimation of the results of thermal analysis indicates that the RAS thermograms have a similar form with three endoeffects with minima in the ranges of ~ 34.7–37.7 °C (I); 325.7–339.3 (II) and 434.8–438.7 °С (III) and one exoeffect with a maximum of ~ 460.5–475.3 °С (IV). With a decrease in the factor of crystallinity and aromaticity of RAS, their resistance to the processes of thermo-oxidative degradation in the temperature region of coke formation increases. The energy of thermal-oxidative destruction for modified systems by surfactants exceeds by 21.6 kJ/mol of this indicator for unmodified RAS and is 62.07 ÷ 66.13 kJ/mol. 

1. Syunyaev Z. I., Safieva R. Z., Syunyaev R. Z. Oil dispersed systems. Moscow, Khimiya Publ., 1990. 226 p. (in Russian).

2. Pokonova Yu. V., Gaile A. A., Spirkin V. G., Chertkov Ya. B., Fakhrutdinov R. Z., Safieva R. Z., Takhistov V. V., Batueva I. Yu. Petroleum Chemistry, Leningrad, Khimiya Publ., 1984. 360 p. (in Russian).

3. Hannisdal A. Particle-Stabilized Emulsions and Heavy Crude Oils. Characterization, Stability Mechanisms and Interfacial Properties [Dissertation]. Trondheim, Norvegian University of Science and Technology, 2006. 152 p.

4. Grin`ko A. A., Golovko A. K. Fractionation of resins and asphaltenes and study of their composition and structure on the example of heavy oil from the Usinsk field. Nefteximiya= Petroleum Chemistry, 2011, vol. 51, no. 3, pp. 204–213 (in Russian).

5. Sjöblom J., Simon S., Xub Zh. Model molecules mimicking asphaltenes. Advanced in Colloid and Interface Science, 2015, vol. 218, pp. 1–16. https://doi.org/10.1016/j.cis.2015.01.002

6. Safieva D. O. Adsorption of asphaltenes on hard surfaces and their aggregation in oil dispersed systems [Dissertation]. Moscow, 2011. 137 p. (in Russian).

7. Safieva R. Z. Chemistry of oil and gas. Oil dispersed systems: composition and properties (part 1). Moscow, RSU of I. M. Gubkina, 2004. 112 p. (in Russian).

8. Mullins O. C., Sheu E. Y., Hammami A., Marshall A. G. Asphaltenes, heavy oils, and petroleomics. New York, Springer, 2007. 669 p. https://doi.org/10.1007/0-387-68903-6

9. Mullins O. C., Sheu E. Y. Structures and Dynamics of Asphaltenes. New York, Plenum Press, 1999. 314 p. https://doi.org/10.1007/978-1-4899-1615-0

10. Mullins O. C., Betancourt S. S., Cribbs M. E., Dubost Fr. X., Creek J. L., Andrews A. B., Venkataramanan L. The Colloidal Structure of Crude Oil and the Structure of Oil Reservoirs. Energy and Fuels, 2007, vol. 21, no. 5, pp. 2785–2794. https://doi.org/doi.org/10.1021/ef0700883

11. Strausz O. P., Mojelsky Th. W., Lown E. M., Kowalewski I., Behar F. Structural Features of Boscan and Duri Asphaltenes. Energy and Fuel, 1999, vol. 13, no. 2, pp. 228–247 https://doi.org/10.1021/EF980245L

12. Strausz O. P., Peng P., Murgich J. About the colloidal nature of asphaltenes and the MW of covalent monomeric units. Energy and Fuels, 2002, vol. 16, no. 4, pp. 809–822. https://doi.org/10.1021/ef0002795

13. Strausz O. P., Safarik I., Strausz O. P., Lown E. M., Morales-Izquierdo A. A critique of asphaltene fluorescence decay and depolarization-based claims about molecular weight and molecular architecture. Energy and Fuels, 2008, vol. 22, no. 2, pp. 1156–1166. https://doi.org/10.1021/ef700320p

14. Evdokimova N. G., Prozorova O. B., Kortyanovich K. V. Methods for studying the properties of bitumen and oil residues. Ufa, Ufa State Petroleum Technological University, 2004. 59 p. (in Russian).

15. Yakavets N. V., Krut’ko N. P., Opanasenko O. N., Yusevich A. I., Malevich N. N. The effect of surfactants on the thermal cracking of heavy oil raw materials. Vestsi Natsyyanal’nai akademii navuk Belarusi. Seryya khimichnykh navuk = Proceedings of the National Academy of Sciences of Belarus. Chemical series, 2014, no. 3, pp. 94–98. (in Russian).

16. Proskuryakova V. A., Drabkina A. E. (ed.). Chemistry of oil and gas. Saint-Petersburg, Khimiya Publ., 1995. 448 p. (in Russian).

17. Dmitriev D. E., Golovko A. K. Transformations of resins and asphaltenes during heat treatment of heavy oils. Nefteximiya = Petroleum Chemistry, 2010, vol. 50, no. 2, pp. 118–125 (in Russian). https://doi.org/10.1134/S0965544110020040

18. Yakavets N. V., Krut’ko N. P. Determination of the component chemical composition of heavy oil dispersions in the presence of surfactants. Neftepromyslovaya khimiya : materialy IX Mezhdunar. (XVII Vseros.) nauch.-prakt. konf. (Ros. gos. un-t nefti i gaza (Nats. issled. un-t) imeni I. M. Gubkina, 30 iyunya 2022 g. [Oilfield chemistry, Materials of the IX International (XVII All-Russian) Scientific and Practical Conference, Moscow, 30 June 2022]. Moscow, 2022, pp. 158–161 (in Russian).

19. Begak O. Yu., Syroezhko A. M. Russian Journal of Applied Chemistry, 2001, vol. 74, no. 6, pp. 696–699. https://doi.org/10.1023/A:1012751808544

20. Begak O. Yu., Syroezhko A. M., Fedorov V. V., Malechkina M. N., Nassonova M. B. Prediction of the Quality of Petroleum Tars and Bitumens by Infrared Spectroscopic and X-ray Diffraction Methods. Russian Journal of Applied Chemistry, 2002, vol. 75, pp. 1173–1177. https://doi.org/10.1023/a:1020745120059

21. Antipenko, V. R., Grin'ko A. A. Macrostructure parameters of insoluble products of thermolysis of resins and asphaltanes of Usinsk oil. Izvestiya Tomskogo politekhnicheskogo universiteta. Inzhiniring georesursov = Bulletin of the Tomsk Polytechnic University. Geo Assets Engineering, 2021, vol. 332, no. 4, pp. 123–131 (in Russian).

22. STB 1333.0-2002. Polymer products for construction. Method for determining durability based on the activation energy of thermal-oxidative destruction of polymer materials. Minsk, 2002. 8 p. (in Russian).

23. Lesueur D. The colloidal structure of bitumen: consequences on the rheology and on the mechanisms of bitumen modification. Advanced in Colloid and Interface Science,, 2009, no. 145, pp. 42–82. https://doi.org/10.1016/j.cis.2008.08.011

24. Akbarzade K., Khammami A., Kharrat A., Chzhan D., Allenson S., Krik D., Kabir Sh., Dzhamaluddin A., Marshal A. Dzh., Rodzhers R. P., Mallins O. K. and Solbakken T. Asphaltenes: problems and prospects. Neftegazovoe obozrenie = Oilfield Review, 2007, vol. 19, no. 2, pр. 28–53 (in Russian).

25. Unger F. G., Andreeva L. N. Fundamental aspects of oil chemistry. The nature of resins and asphaltenes. Novosibirsk, Nauka Publ., 1995. 192 p. (in Russian).

26. Panevchik V. V., Kakoshko E. S. Methodology for assessing the durability of profile polyvinyl chloride products. Vestnik Belorusskogo gosudarstvennogo e`konomicheskogo universiteta = Bulletin of the Belarusian State Economic University, 2014, no. 6, pp. 44–51 (in Russian).

27. Boitsova A. A., Baitalov F., Strokin S. V. Investigation of thermodynamic, kinetic and structural parameters of thermolysis of asphaltenes of heavy Yareg oil. Neftegaz.RU, 2020, no. 3. Available at: https://magazine.neftegaz.ru/articles/pererabotka/536552-issledovanie-termodinamicheskikh-kineticheskikh-i-strukturnykh-parametrov-termoliza-asfaltenov-tyazh (accessed 27 Januare 2023) (in Russian).