STRUCTURAL ORGANIZATION OF ASPHALTENES OF NAPHTHENIC AND AROMATIC TYPES OF OILS
Abstract
The products of oxidative degradation of asphaltenes from naphthenic and aromatic oils from the Russian and Novoportovskoye fields, respectively, using hydrogen peroxide in the presence of acetic acid, were studied. It was found that naphthenic asphaltene contains twice as many oxidized compounds as aromatic asphaltene. According to infrared spectroscopy data, both types of asphaltenes have aliphatic, aromatic, and oxygen-containing groups in their structures. Compounds associated with naphthenic oils have a higher proportion of aromatic structures, while compounds associated with aromatic oils have a greater proportion of aliphatic groups and sulfoxide groups. n-alkanes, steranes, hopanes, and n-alkanec acids as methyl esters were identified in the oxidized products from both types of oil. Using geochemical coefficients, we found that the occlusion of asphaltene oils from both types occurred under reducing sedimentation conditions, but at different stages of organic matter transformation. Using XRD and SGA methods, we showed that the reduction in occluded compounds results in a change in the composition and structure of asphaltene components. Due to the oxidation reaction, the molecular weight of asphaltenes decreases and the distribution of heteroatoms changes. The crystal-like pack formations in the macromolecular structure of asphaltenes become more compact, and the size of the average molecule decreases because of a decrease in the number of structural blocks, naphthenic rings, and carbon atoms in the paraffin fragments.
For citation:
Ostapenko D.V., Cheshkova T.V., Sagachenko T.A., Min R.S. Structural organization of asphaltenes of naphthenic and aromatic types of oils. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2025. V. 68. N 8. P. 92-100. DOI: 10.6060/ivkkt.20256808.10t.
References
Ali M.F., Siddiqui M.N., Al-Hajji A.A. Structural studies on residual fuel oil asphaltenes by RICO method. Petrol. Sci. Technol. 2004. V. 22. P. 631–645. DOI: 10.1081/ LFT-120034205.
Cheshkova T.V., Sergun V.P., Kovalenko E.Y., Gerasimova N.N., Sagachenko T.A., Min R.S. Resins and asphaltenes of light and heavy oils: their composition and structure. Energy Fuels. 2019. V. 33. N 9. P. 7971–7982. DOI: 10.1021/acs.energyfuels.9b00285.
Snowdon L.R., Volkman J.K., Zhang Z., Tao G., Liu P. The organic geochemistry of asphaltenes and occluded biomarkers. Organic Geochem. 2016. V. 91. P. 3-15. DOI: 10.1016/j.orggeochem.2015.11.005.
Cheng B., Zhao Ji., Jang Ch., Tian Y., Liao Z. Geo-chemical Evolution of Occluded Hydrocarbons inside Geomacromolecules: A Review. Energy Fuels. 2017. V. 31. N 9. P. 8823-8832. DOI: 10.1021/acs.energyfuels.7b00454.
Ganeeva Y.M., Barskaya E.E., Okhotnikova E.S., Yusupova T.N. Features of the composition of compounds trapped in asphaltenes of oils and bitumens of the Bavly oil field. Energy Fuels. 2021. V. 35. N 3. P. 2493-2505. DOI: 10.1021/acs.energyfuels.0c03022.
Pan Y., Liao Y., Zheng Y. Effect of biodegradation on the molecular composition and structure of asphaltenes: Clues from quantitative Py–GC and THM–GC. Org. Geo-chem. 2015. V. 86. P. 32-44. DOI: 10.1016/j.orggeochem.2015.06.002.
Cheshkova T.V., Ostapenko D.V., Sagachenko T.A., Min R.S. The composition of compounds occluded by asphaltenes of oils of various chemical nature. Zhurn. Sib. Feder. Un-ta. Khim. 2024. V. 17. N 4. P. 539-545 (in Russian). DOI: 10.15372/CSD2024545.
Ostapenko D.V., Cheshkova T.V., Sagachenko T.A., Min R.S. The composition of compounds occluded by asphaltenes of heavy oils. KhIUR. 2024. V. 2. P. 174-180 (in Russian). DOI: 10.15372/KhUR2024545.
Kashirtsev V.A. Hydrocarbons occluded by asphaltenes. Russ. Geol. Geophys. 2018. V. 59. N 8. P. 975-982. DOI: 10.1016/j.rgg.2018.07.017.
Zhao J., Liao Z.W., Zhang L.H., Creux P., Yang C.P., Chrostowska A., Zhang H.Z., Graciaa A. Comparative studies on compounds occluded inside asphaltenes hierarchically released by increasing amounts of H2O2/CH3COOH. Appl. Geochem. 2010. V. 25. N 9. P. 1330-1338. DOI: 10.1016/j.apgeochem.2010.06.003.
Borisov D.N., Foss L.E., Shabalin K.V., Musin L.I., Musin R.Z. Oxidative cleavage of asphaltenes under mild conditions. Chem. Technol. Fuels Oils. 2019. V. 55. N 5. P. 552-556. DOI: 10.1007/s10553-019-01065-x.
Kovalenko E.Y., Sagachenko T.A., Min R.S., Ogorodnikov V.D., Perevezentsev S.A. Peculiarities of com-position and structure of asphaltene components of bituminous oils. Khim. Tverd. Topliva. 2023. V. 2-3. P. 35-40 (in Russian). DOI: 10.31857/S0023117723020081.
Peng P., Morales-Izquierdo A., Lown E.M., Strauaz O.P. Rutheniumions catalyzed oxidation of an immature asphaltene: structural features and biomarker distribution. Energy. 1999. V. 13. N 1. P. 248-265. DOI: 10.1021/EF980235K.
Kayukova G.P., Mikhailova A.N., Kosachev I.P., Morozov V.I., Eskin A.A. Effect of the natural minerals py-rite and hematite on the transformation of Domanik rock organic matter in hydrothermal processes. Petrol. Chem. 2019. V. 59. N 1. P. 24-33. DOI: 10.1134/S0965544119010080.
Tian Y.K., Zhao J., Yang C.P., Liao Z.W., Zhang L.H., Zhang H.Z. Multiple – soursed features of marine oils in the Tarim Basin, NW China-Geochemical evidence from occluded hydrocarbons inside asphaltenes. J. Asian Earth Sci. 2012. V. 54-55. P. 174-181. DOI: 10.1016/j.jseaes.2012.04.010.
Gordadze G.N., Giruts M.V., Koshelev V.N., Yusupova T.N. Distribution Features of Biomarker Hydrocarbons in Asphaltene Thermolysis Products of Different Fractional Compositions (Using as an Example Oils from Carbonate Deposits of Tatarstan Oilfields). Petrol. Chem. 2015. V. 55. N 1. P. 22-31. DOI: 10.1134/S0965544115010053.
Cheshkova T.V., Sagachenko T.A., Min R.S., Kovalenko E.Y. Biogenic oxidation of tar-asphaltene components of heavy oil. Message 1. Asphaltenes. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 11. P. 110-118 (in Russian). DOI: 10.6060/ivkkt.20236611.12t.
Cheshkova T.V., Sagachenko T.A., Min R.S., Kovalen-ko E.Y. Biogenic oxidation of tarasphaltene components of heavy oil. Message 2. Resins. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 11. P. 119-125 (in Russian). DOI: 10.6060/ivkkt.20236611.13t.
Acevedo S., Castillo J. Asphaltenes: Aggregates in terms of A1 and A2 or island and archipielago structures. ACS Omega. 2023. N 8. P. 4453−4471. DOI: 10.1021/acsomega.2c06362.
Miller V.K., Ivanova L.V., Mansur G., Uertas Budilova S.K., Koshelev V.N., Primerova O.V. The structural fea-tures of resins and asphaltenes of crude oils from Udmurtia oilfields. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2021. V. 64. N 10. P. 113–118 (in Russian). DOI: 10.6060/ivkkt.20216410.6370.
