ИСПОЛЬЗОВАНИЕ СВЕРХКРИТИЧЕСКИХ ФЛЮИДОВ В НЕФТЕПЕРЕРАБОТКЕ

На сегодняшний день в мире нефтяная промышленность по своей деятельности особое внимание уделяет развитию новых подходов переработки, повышению энергоэффективности и снижению эксплуатационных затрат. Обзор рассматривает современные методы переработки тяжелых нефтей с использованием сверхкритических флюидов. Основное внимание уделяется сверхкритической флюидной экстракции, которые позволяют эффективно извлекать углеводороды и удалять нежелательные примеси. В обзоре рассмотрены кинетика взаимодействия сверхкритических флюидов, а также влияние температуры, давления и растворителей на эффективность сверхкритической флюидной экстракции. Ключевые особенности данного метода являются глубина очистки, селективность процессов, высокая избирательность, снижение отходов, возможность регенерации растворителей, сокращение выбросов и уменьшение негативного воздействия на окружающую среду. Однако в использовании сверхкритических флюидов в нефтяной промышленности имеются определенные ограничения, включая высокие энергозатраты, необходимость сложного оборудования и технологические сложности при масштабировании процессов, что требует дальнейших исследований и оптимизации параметров. Рассмотрены перспективы интеграции сверхкритической флюидной технологий в нефтеперерабатывающую промышленность, включая комбинированные методы с катализаторами и модификаторами растворителей. Установлено, что внедрение сверхкритической флюидной технологий в нефтяную отрасль может значительно повысить эффективность переработки тяжелых углеводородных систем, способствуя созданию более экологичных и экономически устойчивых технологий.

1. Knez Z., Markocic E., Leitgeb M., Primozic M., Knez H.M., Skerget M. Industrial applications of supercritical fluids: A review // Energy. – 2014. – Vol. 77. – P. 235-243.

2. Ortiz F., Kruse A. The use of process simulation in supercritical fluids applications // Reaction Chemistry and Engineering. – 2020. – Vol. 5. – P. 424-451.

3. Ahmad T., Masoodi F.A., Rather S.A., Wani S.M., Gull A. Supercritical Fluid Extraction: A Review // Journal of Biological and Chemical Chronicles. – 2019. – Vol. 5, No. 1. – P. 114-122.

4. Manjare S.D., Dhingra K. Supercritical fluids in separation and purification: A review // Materials Science for Energy Technologies. – 2019. – Vol. 2. – P. 463-484.

5. Prasada S.K., Sangwai J.S., Byun H.S. A review of the supercritical CO₂ fluid applications for improved oil and gas production and associated carbon storage // Journal of CO₂ Utilization. – 2023. – Vol. 72. 102479.

6. Manjare S.D., Dhingra K. Supercritical fluids in separation and purification: A review // Materials Science for Energy Technologies. – 2019. – Vol. 2. – P. 463-484.

7. Knapik E., Chruszcz-Lipska K. Chemistry of Reservoir Fluids in the Aspect of CO₂ Injection for Selected Oil Reservoirs in Poland // Energies. – 2020. – Vol. 13. 6456.

8. Boyère C., Jérôme C., Debuigne A. Input of supercritical carbon dioxide to polymer synthesis: An overview // European Polymer Journal. – 2014. – Vol. 61. – P. 45-63.

9. Tutek K., Masek A., Kosmalska A., Cichosz S. Application of Fluids in Supercritical Conditions in the Polymer Industry // Polymers. – 2021. – Vol. 13. 729.

10. Daneshyan S., Sodeifian G. Utilization of CO₂ in supercritical conditions for the synthesis of cyclic poly (N-isopropylacrylamide) via emulsion and homogeneous reactions // Scientific Reports. – 2022. – Vol. 12. 17459.

11. Билалов Т.Р., Мазанов С.В., Хайрутдинов В.Ф., Гумеров Ф.М. Описание и обобщение растворимости веществ в сверхкритических флюидах: учебное пособие. – Казань: Изд-во КНИТУ, 2020. – 129 с.

12. La H. Extraction of Bitumen from Athabasca Oil Sand Slurry Using Supercritical Carbon Dioxide: Master’s Thesis. – University of Alberta, 2011. – 41 p.

13. Kamal G., Sumit A., Anil K. Industrial applications of supercritical fluid extraction: A review // International Journal of Chemical Studies. – 2017. – Vol. 5. – P. 336-340.

14. Koch T.J., Desset S.L., Leitner W. Catalytic supercritical fluid extraction: Selective hydroformylation of olefin mixtures using scCO₂ solubility for differentiation // Green Chemistry. – 2010. – Vol. 12. – P. 1719-1721.

15. Al-Marzouqi A.H., Zekri A.Y., Jobe B., Dowaidar A. Supercritical fluid extraction for the determination of optimum oil recovery conditions // Journal of Petroleum Science and Engineering. – 2007. – Vol. 55. – P. 37-47.

16. Marchetto F., Aziz A.A. A Review of Supercritical Fluid Extraction Technology and Application // Journal Teknologi (Sciences & Engineering). – 2014. – Vol. 69, No. 6. – P. 27-31.

17. URACA Company. High-Pressure Pumps [Electronic resource]. – Available online: https://www.uraca.com/ru/sistemy-i-izdelija/nasosy/ (accessed on 29 November 2021).

18. Bilalov T.L., Gumerov F.M. Calculation of the solubility of aromatic hydrocarbons in supercritical media based on the entropy method of similarity theory // Theoretical Foundations of Chemical Engineering. – 2019. – Vol. 4. – P. 387-401.

19. Carmela S.R. Experiments and Modeling of Supercritical CO₂ Extraction of Lipids from Microalgae: Master’s Thesis. – University of Padua, 2014. – 164 p.

20. Rój E. Supercritical CO₂ Extraction and Its Applications. – Polish Foundations of the Opportunities Industrialization Centers “OIC Poland”, Lublin, Poland, 2014.

21. Sun Y.X., Wang X.L., Meng Y.Z., Tian J.L., Lu C.H. Fracture propagation mechanism and application of supercritical CO₂ fracturing in shale: A review // Petroleum Science. – 2025.

22. Pereira C.G., Meireles M.A.A. Supercritical Fluid Extraction of Bioactive Compounds: Fundamentals, Applications and Economic Perspectives // Food and Bioprocess Technology. – 2010. – Vol. 3, No. 3. – P. 340–372.

23. Lyadova A.S., Petrukhina N.N. Extraction and Refining of Heavy Crude Oils: Problems and Prospects // Russian Journal of Applied Chemistry. – 2018. – Vol. 91, No. 12. – P. 1912-1921.

24. Magomedova R.N., Pripakhaylo A.V., Maryutina T.A. Solvent demetallization of heavy petroleum feedstock using supercritical carbon dioxide with modifiers // The Journal of Supercritical Fluids. – 2017. – Vol. 119. – P. 150-158.

25. Li N., Jin Z., Zhang S., Wang H., Yang P., Zou Y., Zhou T. Micro-mechanical properties of shale due to water/supercritical carbon dioxide-rock interaction // Petroleum Exploration and Development. – 2023. – Vol. 50, No. 4. – P. 1001-1012.

26. Pripakhaylo A.V., Magomedova R.N., Maryutina T.A. Separation of Heavy Oil into Narrow Fractions by Supercritical Fluid Extraction Using a CO₂-Toluene Mixture // Journal of Analytical Chemistry. – 2019. – Vol. 74. – P. 401-409.

27. Kwek W., Khan M.K., Sarkar B., Kim J. Supercritical methanol as an effective medium for producing asphaltenes-free light fraction oil from vacuum residue // The Journal of Supercritical Fluids. – 2017. – Vol. 133. – P. 184-194.

28. More S.R., Yadav G.D. Effect of Supercritical CO₂ as Reaction Medium for Selective Hydrogenation of Acetophenone to 1-Phenylethanol // ACS Omega. – 2018. – Vol. 3. – P. 7124-7132.

29. Koch T.J., Desset S.L., Leitner W. Catalytic supercritical fluid extraction: Selective hydroformylation of olefin mixtures using scCO₂ solubility for differentiation // Green Chemistry. – 2010. – Vol. 12. – P. 1719-1721.

30. Webb P., Sellin M.F., Kunene T.E., Williamson S., Slawin A., Cole-Hamilton D.J. Continuous Flow Hydroformylation of Alkenes in Supercritical Fluid Ionic Liquid Biphasic Systems // Journal of the American Chemical Society. – 2003. – Vol. 125. – P. 15577-15588.

31. Makaryan I.A., Kostin A.Y., Sedov I.V. The Use of SCF Technologies in the Chemical and Petrochemical Industries (Review) // Petroleum Chemistry. – 2020. – Vol. 60, No. 3. – P. 270-282.

32. Tu H., Guo P., Jia N., Zhou D., Zhou X., Wang Z. Determination of the Diffusion Coefficient of Supercritical CO₂ in Low-Permeability Formation Cores // Energy & Fuels. – 2020. – Vol. 34. – P. 2001-2014.

33. Voisin T., Erriguible A., Ballenghien D., Mateos D., Kunegel A., Cansell F., Aymonier C. Solubility of inorganic salts in sub and supercritical hydrothermal environment: Application to SCWO processes // The Journal of Supercritical Fluids. – 2017. – Vol. 120. – P. 18-31.

34. Li Y., Wang S. Supercritical Water Oxidation for Environmentally Friendly Treatment of Organic Wastes // Advanced Supercritical Fluids Technologies. – 2020. – P. 1-28.

35. Hui K., Tang J., Lu H., Xi B., Qu C., Li J. Status and prospect of oil recovery from oily sludge: A review // Arabian Journal of Chemistry. – 2020. – Vol. 13. – P. 6523-6543.

36. Chen Z., Chen Z., Yin F., Wang G., Chen H., He C., Xu Y. Supercritical water oxidation of oil-based drill cuttings // Journal of Hazardous Materials. – 2017. – Vol. 332. – P. 205-213.

37. Ma B., Wang R., Ni H., Wang K. Experimental study on harmless disposal of waste oil-based mud using supercritical carbon dioxide extraction // Fuel. – 2019. – Vol. 252. – P. 722-729.

38. Wei H., He H., Zhang Y. Optimization of oil-based drilling cuttings treatment process by supercritical CO₂ fluid using response surface methodology // Chinese Journal of Environmental Engineering. – 2017. – Vol. 11. – P. 6050-6055.

39. Khayrutdinov V.F., Gabitova A.R., Gumerov F.M., Gabitov R.F., Kurdyukov A.I. Extraction of Petroleum Products and Asphaltene-Resin Mixtures from Highly Watered Oil Sludge with Supercritical Fluid Method // Russian Journal of Physical Chemistry. – 2019. – Vol. 13. – P. 1128-1130.

40. Gumerov F.M., Khayrutdinov V.F., Farakhov M.I. Mathematical modeling of technology for disposal of oil sludge with the use of liquid and supercritical fluid extraction processes // Journal of Engineering and Applied Science. – 2016. – Vol. 11. – P. 2024-2027.

41. Djimasbe R., Varfolomeev M.A., Almuntaser A.A., Yuan C., Suwaid M.A., Feoktistov D.A., Rakhmatullin I.Z., Milovankin A.A., Murzakhanov F., Morozov V., Gafurov M., Farhadian A., Davletshin R.R. Deep Insights into Heavy Oil Upgrading Using Supercritical Water by a Comprehensive Analysis of GC, GC-MS, NMR, and SEM − EDX with the Aid of EPR as a Complementary Technical Analysis // ACS Omega. – 2021. – Vol. 6. – P. 135-147.

42. Pavlova P.L., Minakov A.V., Platonov D.V., Zhigarev V.A., Guzei D.V. Supercritical Fluid Application in the Oil and Gas Industry: A Comprehensive Review // Sustainability. – 2022. – Vol. 14. 698.

43. Иманбаев Е.И., Онгарбаев Е.К., Тилеуберди Е. Использование сверхкритических флюидов для извлечения природных битумов из нефтебитуминозных пород // Горение и плазмохимия. – 2020. – Т. 18. – С. 218-226.

44. Maa B., Wang R., Ni H., Wang K. Experimental Study on Harmless Disposal of Waste Oil-Based Mud Using Supercritical Carbon Dioxide Extraction // Fuel. – 2019. – Vol. 252. – P. 722-729.

45. Khairutdinov V. F., Akhmetzyanov T. R., Gumerov F. M., Khabriev I. Sh., Farakhov M. I. Supercritical Fluid Propane–Butane Extraction Treatment of Oil-Bearing Sands // Theoretical Foundations of Chemical Engineering. – 2017. – Vol. 51, No. 3. – P. 299-306.

46. Zhao X., Wang L., Liu S., Luo X., Zhang M., Fu F., Gao X., Yan T. Dissolution Behavior of Polycyclic Aromatic Hydrocarbons in Heavy Oil in the Presence of Supercritical Cyclohexane // ACS Omega. – 2024. – Vol. 9. – P. 252-263.

47. Yan T., Wu L., Wang L., Fu F., Fang T. Desulfurization of Sulfur-Containing Compounds in Heavy Oil in the Presence of Supercritical Methanol // Energy Fuels. – 2020. – Vol. 34. – P. 2958–2968.

48. Гумеров Ф.М., Хайрутдинов В.Ф., Ахметзянов Т.Р., Габитов Ф.Р., Зарипов З.И., Фарахов М.И., Мухутдинов В. Сверхкритическая флюидная пропан-бутановая экстракционная обработка нефтяных шламов // Сверхкритические Флюиды: Теория и Практика. – 2016. – Т. 11, № 2. – С. 75-83.

49. Гумеров Ф.М., Фарахов М.И., Хайрутдинов В.Ф., Габитов Ф.Р., Зарипов З.И., Хабриев И.Ш., Ахметзянов Т.Р. Увеличение функциональности карбонатного щебня посредством сверхкритической флюидной импреграции битуминозными соединениями // Сверхкритические Флюиды: Теория и Практика. – 2015. – Т. 10, № 2. – С. 4-15.

50. Cosseya H. L., Guigarda S. E., Underwooda E., Stiverb W. H., Mc Millanc J., Bhattacharya S. Supercritical Fluid Extraction of Bitumen Using Chemically Modified Carbon Dioxide // The Journal of Supercritical Fluids. – 2019. – Vol. 154. 104599.

51. Félix G., Djimasbe R., Tirado A., Varfolomeev M.A., Anchyta J. Kinetic Study for the Ashalcha Heavy Crude Oil Upgrading at Supercritical Water Conditions // Fuel. – 2025. – Vol. 380. 133145.

52. Radfarnia H. R., Khulbe C., Little E. C. Supercritical Water Treatment of Oil Sludge, A Viable Route to Valorize Waste Oil Materials // Fuel. – 2015. – Vol. 159. – P. 653-658.

53. Sato T., Sumita T., Itoh N. Effect of CO Addition on Upgrading Bitumen in Supercritical Water // The Journal of Supercritical Fluids. – 2015. – Vol. 104. – P. 171-176.

54. Sun G., Li C., Yang S., Yang F., Chen Y. Experimental Investigation of the Rheological Properties of a Typical Waxy Crude Oil Treated with Supercritical CO2 and the Stability Change in Its Emulsion // Energy Fuels. – 2019. – Vol. 33. – P. 4731-4739.

55. Kozhevnikov I., Nuzhdin A., Martyanov O. Transformation of Petroleum Asphaltenes in Supercritical Water // Journal of Supercritical Fluids – 2010. – Vol. 55. – P. 217-222.

56. Hosseinpour M., Soltani M., Noofeli A., Nathwani J. An Optimization Study on Heavy Oil Upgrading in Supercritical Water Through the Response Surface Methodology (RSM) // Fuel. – 2020. – Vol. 271. 117618.

57. Moiseeva E.G., Lakhova A.I., Petrov S.M., Bashkirtseva N.Y. Conversion of High-Viscosity Oil of Ashalchinsk Deposit in the Presence of Activated Carbon and Supercritical Aqueous Fluid // Chemistry and Technology of Fuels and Oils. – 2021. – Vol. 57. – P. 746-752.

58. Antipenko V.R., Fedyaeva O.N., Grinko A.A., Vostrikov A.A. Structural Parameters of Resins and Asphaltenes of Natural Asphaltite and Products of Its Conversion in Supercritical Water // AIP Conf. Proc. – 2020. – Vol. 2310. 020022.

59. Fakher S., Ahdaya M., Elturki M., Imqam A. Critical Review of Asphaltene Properties and Factors Impacting Its Stability in Crude Oil // Journal of Petroleum Exploration and Production Technology. – 2020. – Vol. 10. – P. 1183-1200.

60. Liu B., Li J., Qi C., Li X., Mai T., Zhang J. Mechanism of Asphaltene Aggregation Induced by Supercritical CO2: Insights from Molecular Dynamics Simulation // RSC Adv. – 2017. – Vol. 7. – P. 50786-50793.

61. Gregoli A. A., Oko U. M., Leder F. Process for Converting Heavy Crudes, Tars, and Bitumens to Lighter Products in the Presence of Brine at Supercritical Conditions // US Patent No. 4,818,370. – 1989.

62. Brill T. B., Savage P. E. Kinetics and Mechanisms of Hydrothermal Organic Reactions // D.A. Palmer, R. Fernandez-Prini, A.H. Harvey (Eds.), Aqueous Systems at Elevated Temperatures and Pressures: Physical Chemistry in Water, Steam and Hydrothermal Solutions. – Elsevier, Amsterdam, The Netherlands, 2004. – P. 643-675.

63. Akiya N., Savage P. E. Role of Water in Formic Acid Decomposition // AIChE Journal. – 1998. – Vol. 44. – P. 405-415.

64. Savage P. E., Gopalan S., Mizan T. I., Martino C. J., Brock E. E. Reactions at Supercritical Conditions: Applications and Fundamentals // AIChE Journal. – 1995. – Vol. 41. – P. 1723-1778.

65. Moore J. W., Pearson R. G. Kinetics and Mechanism. – 3rd ed. – Wiley, New York, 1981.

66. Sandler S. I. Chemical and Engineering Thermodynamics. – 2nd ed. – Wiley, New York, 1989.

67. Van Eldik R., Asano T., LeNoble W. J. Activation and Reaction Volumes in Solution 2 // Chem. Rev. – 1989. – Vol. 89. – P. 549-688.

68. Johnston K. P., Haynes C. Extreme Solvent Effects on Reaction Rate Constants at Supercritical Fluid Conditions // AIChE Journal. – 1987. – Vol. 33. – P. 2017-2026.

69. Eckert C.A., Hsieh C.K., McCabe J.R. Molecular Thermodynamics for Chemical Reactor Design // AIChE J. – 1974. – Vol. 20. – P. 20-36.

70. Huppert G.L., Wu B.C., Townsend S. H., Klein M.T., Paspek S.C. Hydrolysis in Supercritical Water: Identification and Implication of a Polar Transition State // Industrial & Engineering Chemistry Research. – 1989. – Vol. 28. – P. 161-165.

71. Connors K. A. Chemical Kinetics: The Study of Reaction Rates in Solution. – VCH Publishers, New York, 1990.

72. Ederer H.J., Kruse A., Mas C., Ebert K.H. Modelling of the Pyrolysis of Tert-Butylbenzene in Supercritical Water // The Journal of Supercritical Fluids. – 1999. – Vol. 15. – P. 191-204.

73. Froment G. F., Bischoff K. B. Chemical Reactor Analysis and Design. – 2nd ed. – Wiley, New York, 1990.

74. Miksa D., Brill T.B. Spectroscopy of hydrothermal reactions. 17. Kinetics of the surface catalyzed water gas shift reaction with inadvertent formation of Ni(CO)₄ // Industrial & Engineering Chemistry Research. – 2001. – Vol. 40. – P. 3098-3103.