zldmЗаводская лаборатория. Диагностика материаловIndustrial laboratory. Diagnostics of materials1028-68612588-0187ООО «Издательство «ТЕСТ-ЗЛ»10.26896/1028-6861-2026-92-7-30-36zldm-2884Research ArticleИССЛЕДОВАНИЕ СТРУКТУРЫ И СВОЙСТВ. ФИЗИЧЕСКИЕ МЕТОДЫ ИССЛЕДОВАНИЯ И КОНТРОЛЯTESTING OF STRUCTURE AND PARAMETERS. PHYSICAL METHODS OF TESTING AND QUALITY CONTROLИсследование эффективности термодинамических ингибиторов гидратообразования в условиях осложненной нефтегазодобычиStudy of the effectiveness of thermodynamic inhibitors of hydrate formation in conditions of complicated oil and gas productionРовбоА. С.RovboA. S.

Анна Сергеевна Ровбо

194100, г. Санкт-Петербург, ул. Политехническая, д. 29АФ

Anna S. Rovbo

29AF, ul. Politekhnicheskaya, St. Petersburg, 194100

rovboanna@yandex.ruЯковлеваП. А.YakovlevaP. A.

Полина Андреевна Яковлева

194100, г. Санкт-Петербург, ул. Политехническая, д. 29АФ

Polina A. Yakovleva

29AF, ul. Politekhnicheskaya, St. Petersburg, 194100

КошелевА. Д.KoshelevA. D.

Антон Дмитриевич Кошелев

119049, Москва, Ленинский просп., д. 4, стр. 1

Anton D. Koshelev

4, str. 1, Leninsky prosp., Moscow, 119049

anton.koschelev@vk.comЦветковА. С.TsvetkovA. S.

Антон Сергеевич Цветков

194100, г. Санкт-Петербург, ул. Политехническая, д. 29АФ

Anton S. Tsvetkov

29AF, ul. Politekhnicheskaya, St. Petersburg, 194100

Санкт-Петербургский политехнический университет Петра ВеликогоРоссияPeter the Great St. Petersburg Polytechnic UniversityRussian FederationНИТУ МИСИСРоссияNUST MISISRussian Federation2026260720269273036Copyright © Ровбо А.С., Яковлева П.А., Кошелев А.Д., Цветков А.С., 20262026Ровбо А.С., Яковлева П.А., Кошелев А.Д., Цветков А.С.Rovbo A.S., Yakovleva P.A., Koshelev A.D., Tsvetkov A.S.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.zldm.ru/jour/article/view/2884

Газовые гидраты — кристаллические соединения воды и газа (чаще всего метана), образующиеся при низких температурах и высоком давлении, — могут блокировать потоки в трубопроводах, создавая риски для эксплуатации нефтегазовых месторождений. Цель работы — исследование эффективности термодинамических ингибиторов гидратообразования в системах газ – вода и газ – вода – нефть. Исследовали зоны образования и диссоциации гидратов при давлении до 200 бар и температуре до –40 °C. Эффективность ингибиторов оценивали изохорным методом с применением ступенчатого нагрева, анализировали также влияние состава нефти и газа на формирование гидратных пробок. В качестве ингибиторов гидратообразования использовали ингибиторы термодинамического действия: метанол и моноэтиленгликоль (МЭГ). Исследовали образцы нефти, отличающиеся по плотности (0,78 и 0,85 г/см3). Установлено, что наличие нефти снижает температуру гидратообразования на 11 °C. При добавлении в систему газ – вода – нефть 35 % метанола в исследуемом диапазоне температур образование гидратов отсутствовало. В случае более густой нефти (0,85 г/см3) МЭГ показал меньшую по сравнению с метанолом эффективность вследствие плохой растворимости, низкой скорости диффузионного переноса, ограничения массообмена и др. Полученные результаты могут быть использованы для совершенствования технологии предотвращения гидратообразования при эксплуатации месторождений с осложненной нефтегазодобычей.

Gas hydrates — crystalline compounds of water and gas (most commonly methane) that form at low temperatures and high pressures — can block flow in pipelines, posing risks to the operation of oil and gas fields. The aim of this work is to investigate the effectiveness of thermodynamic hydrate inhibitors in gas – water and gas – water – oil systems. The zones of hydrate formation and dissociation were investigated at pressures up to 200 bars and temperatures down to –40°C. The effectiveness of the inhibitors was evaluated using the isochoric method with stepwise heating; the influence of oil and gas composition on the formation of hydrate plugs was also analyzed. Thermodynamic inhibitors — methanol and monoethylene glycol (MEG) were used as hydrate formation inhibitors. Oil samples with different densities (0.78 and 0.85 g/cm3) were studied. It was found that the presence of oil reduces the hydrate formation temperature by 11°C. When 35% methanol was added to the gas – water – oil system within the studied temperature range, no hydrate formation occurred. In the case of denser oil (0.85 g/cm3), MEG showed lower efficiency compared to methanol due to poor solubility, low diffusion rate, mass transfer limitations, and other factors. The results obtained can be used to improve technologies for preventing hydrate formation during the operation of fields with complex oil and gas production.

газовые гидратыингибиторы гидратообразованиянефтьтермодинамические ингибиторыступенчатый нагревgas hydrateshydrate inhibitorsoilthermodynamic inhibitorsstepwise heatingРабота финансировалась за счет средств бюджета института (учреждения, организации).ReferencesZhang J., Li C., Shi L., et al. The formation and aggregation of hydrate in W/O emulsion containing different compositions: a review / Chem. Eng. J. 2022. Vol. 445. P. 1 – 12. DOI: 10.1016/j.cej.2022.136800Zhang J., Li C., Shi L., et al. The formation and aggregation of hydrate in W/O emulsion containing different compositions: a review / Chem. Eng. J. 2022. Vol. 445. P. 1 – 12. DOI: 10.1016/j.cej.2022.136800Sloan E. D. Natural gas hydrates in flow assurance. — Gulf Professional Publishing, 2010.Sloan E. D. Natural gas hydrates in flow assurance. — Gulf Professional Publishing, 2010.Giavarini C., Hester K. Hydrates seen as a problem for the oil and gas industry. — Springer, 2011.Giavarini C., Hester K. Hydrates seen as a problem for the oil and gas industry. — Springer, 2011.Fingas M., Fieldhouse B. Studies on water-in-oil products from crude oils and petroleum products / Mar. Pollut. Bull. 2012. Vol. 64. No. 2. P. 272 – 283. DOI: 10.1016/j.marpolbul.2011.11.019Fingas M., Fieldhouse B. Studies on water-in-oil products from crude oils and petroleum products / Mar. Pollut. Bull. 2012. Vol. 64. No. 2. P. 272 – 283. DOI: 10.1016/j.marpolbul.2011.11.019Luan H., Liu M., Shan Q., et al. Experimental study on the effect of mixed thermodynamic inhibitors with different concentrations on natural gas hydrate synthesis / Energies. 2024. Vol. 17. No. 9. P. 2078. DOI: 10.3390/en17092078Luan H., Liu M., Shan Q., et al. Experimental study on the effect of mixed thermodynamic inhibitors with different concentrations on natural gas hydrate synthesis / Energies. 2024. Vol. 17. No. 9. P. 2078. DOI: 10.3390/en17092078Semenov A. P., Mendgaziev R. I., Stoporev A. S., et al. Gas hydrate nucleation and growth in the presence of water-soluble polymer, nonionic surfactants, and their mixtures / J. Nat. Gas Sci. Eng. 2020. Vol. 82. P. 103491. DOI: 10.1016/j.jngse.2020.103491Semenov A. P., Mendgaziev R. I., Stoporev A. S., et al. Gas hydrate nucleation and growth in the presence of water-soluble polymer, nonionic surfactants, and their mixtures / J. Nat. Gas Sci. Eng. 2020. Vol. 82. P. 103491. DOI: 10.1016/j.jngse.2020.103491Chen L., Sun C., Chen G., et al. Measurements of hydrate equilibrium conditions for CH4, CO2, and CH4 + C2H6 + C3H8 in various systems by step-heating method / Chin. J. Chem. Eng. 2009. No. 4. P. 635 – 641. DOI: 10.1016/s1004-9541(08)60256-6Chen L., Sun C., Chen G., et al. Measurements of hydrate equilibrium conditions for CH4, CO2, and CH4 + C2H6 + C3H8 in various systems by step-heating method / Chin. J. Chem. Eng. 2009. No. 4. P. 635 – 641. DOI: 10.1016/s1004-9541(08)60256-6Arfanejad A., Poplygin V., Shi X. Study of the formation and dissociation of methane hydrate system in the presence of pure water / Energies. 2025. Vol. 18. No. 11. P. 2849. DOI: 10.3390/en18112849Arfanejad A., Poplygin V., Shi X. Study of the formation and dissociation of methane hydrate system in the presence of pure water / Energies. 2025. Vol. 18. No. 11. P. 2849. DOI: 10.3390/en18112849Semenov A. P., Mendgaziev R. I., Tulegenov T. B., et al. Analysis of the techniques for measuring the equilibrium conditions of gas hydrates formation / Chem. Technol. Fuels Oils. 2022. Vol. 58. No. 5. P. 628 – 636. DOI: 10.1007/s10553-022-01429-wSemenov A. P., Mendgaziev R. I., Tulegenov T. B., et al. Analysis of the techniques for measuring the equilibrium conditions of gas hydrates formation / Chem. Technol. Fuels Oils. 2022. Vol. 58. No. 5. P. 628 – 636. DOI: 10.1007/s10553-022-01429-wFakhreeva A., Nosov V., Voloshin A., et al. Polysaccharides are effective inhibitors of natural gas hydrate formation / Polymers. 2023. Vol. 15. P. 1789. DOI: 10.3390/polym15071789Fakhreeva A., Nosov V., Voloshin A., et al. Polysaccharides are effective inhibitors of natural gas hydrate formation / Polymers. 2023. Vol. 15. P. 1789. DOI: 10.3390/polym15071789Aminnaji M. Improving the accuracy of experimental hydrate equilibrium point determination: a mini-review / Petrol. Petrochem. Eng. J. 2023. Vol. 7. No. 3. DOI: 10.23880/ppej-16000355Aminnaji M. Improving the accuracy of experimental hydrate equilibrium point determination: a mini-review / Petrol. Petrochem. Eng. J. 2023. Vol. 7. No. 3. DOI: 10.23880/ppej-16000355Ito H., Gibo A., Shiraishi S., et al. Renewed measurements of carbon dioxide hydrate phase equilibrium / Int. J. Thermophys. 2023. Vol. 44. Art. 128.Ito H., Gibo A., Shiraishi S., et al. Renewed measurements of carbon dioxide hydrate phase equilibrium / Int. J. Thermophys. 2023. Vol. 44. Art. 128.Kamari E., Oyarhossein M. Experimental determination of hydrate phase equilibrium curve for an Iranian sour gas condensate sample / J. Nat. Gas Sci. Eng. 2012. Vol. 9. P. 11 – 15. DOI: 10.1016/j.jngse.2012.05.004Kamari E., Oyarhossein M. Experimental determination of hydrate phase equilibrium curve for an Iranian sour gas condensate sample / J. Nat. Gas Sci. Eng. 2012. Vol. 9. P. 11 – 15. DOI: 10.1016/j.jngse.2012.05.004Aghajanloo M., Taheri Z., Jafari Behbahani T., et al. Experimental determination and thermodynamic modeling of clathrate hydrate stability conditions in methane + hydrogen sulfide + water system / J. Nat. Gas Sci. Eng. 2020. Vol. 83. P. 103 – 119. DOI: 10.1016/j.jngse.2020.103549Aghajanloo M., Taheri Z., Jafari Behbahani T., et al. Experimental determination and thermodynamic modeling of clathrate hydrate stability conditions in methane + hydrogen sulfide + water system / J. Nat. Gas Sci. Eng. 2020. Vol. 83. P. 103 – 119. DOI: 10.1016/j.jngse.2020.103549PSL Operation manual. Version 193001. https://www.psl- systemtechnik.de (accessed 19.08.2025).PSL Operation manual. Version 193001. https://www.psl- systemtechnik.de (accessed 19.08.2025).Zulu N., Hashemi H., Tumba K. Chemical inhibitors in gas hydrate formation: a review of modelling approaches / Chem. Eng. 2024. Vol. 8. No. 6. P. 124. DOI: 10.3390/chemengineering8060124Zulu N., Hashemi H., Tumba K. Chemical inhibitors in gas hydrate formation: a review of modelling approaches / Chem. Eng. 2024. Vol. 8. No. 6. P. 124. DOI: 10.3390/chemengineering8060124Zhang Q., Kelland M., Lu H. Non-amide kinetic hydrate inhibitors: a review / Fuel. 2022. Vol. 315. P. 123179. DOI: 10.1016/j.fuel.2022.123179Zhang Q., Kelland M., Lu H. Non-amide kinetic hydrate inhibitors: a review / Fuel. 2022. Vol. 315. P. 123179. DOI: 10.1016/j.fuel.2022.123179Yaqub S., Murtaza M., Lal B. Towards a fundamental understanding of biopolymers and their role in gas hydrates: a review / J. Nat. Gas Sci. Eng. 2021. Vol. 91. P. 103892. DOI: 10.1016/j.jngse.2021.103892Yaqub S., Murtaza M., Lal B. Towards a fundamental understanding of biopolymers and their role in gas hydrates: a review / J. Nat. Gas Sci. Eng. 2021. Vol. 91. P. 103892. DOI: 10.1016/j.jngse.2021.103892Brustad S., Løken K.-P., Waalmann J. Hydrate prevention using MEG instead of MeOH: impact of experience from major norwegian developments on technology selection for injection and recovery of MEG / Proc. Offshore Technology Conf. — Houston, Texas, 2005. DOI: 10.4043/17355-msBrustad S., Løken K.-P., Waalmann J. Hydrate prevention using MEG instead of MeOH: impact of experience from major norwegian developments on technology selection for injection and recovery of MEG / Proc. Offshore Technology Conf. — Houston, Texas, 2005. DOI: 10.4043/17355-msVagapov R. K. Assessment of the influence of glycol and alcohol on the morphology and protective properties of iron carbonate during CO2 corrosion of pipelines / Industr. Lab. Mater. Diagn. 2024. Vol. 90. No. 10. P. 32 – 38. DOI: 10.26896/1028-6861-2024-90-10-32-38Vagapov R. K. Assessment of the influence of glycol and alcohol on the morphology and protective properties of iron carbonate during CO2 corrosion of pipelines / Industr. Lab. Mater. Diagn. 2024. Vol. 90. No. 10. P. 32 – 38. DOI: 10.26896/1028-6861-2024-90-10-32-38Vagapov R. K., Zapevalov D. N., Ibatullin K. A. Study of corrosion of gas production infrastructure in the presence of CO2 by analytical control methods / Industr. Lab. Mater. Diagn. 2020. Vol. 86. No. 10. P. 23 – 30. DOI: 10.26896/1028-6861-2020-86-10-23-30Vagapov R. K., Zapevalov D. N., Ibatullin K. A. Study of corrosion of gas production infrastructure in the presence of CO2 by analytical control methods / Industr. Lab. Mater. Diagn. 2020. Vol. 86. No. 10. P. 23 – 30. DOI: 10.26896/1028-6861-2020-86-10-23-30Volkov V. I., Chernyak A. V., Slesarenko N. A., et al. Ion and molecular transport in solid electrolytes studied by NMR / Int. J. Mol. Sci. 2022. Vol. 23. No. 9. P. 5011. DOI: 10.3390/ijms23095011Volkov V. I., Chernyak A. V., Slesarenko N. A., et al. Ion and molecular transport in solid electrolytes studied by NMR / Int. J. Mol. Sci. 2022. Vol. 23. No. 9. P. 5011. DOI: 10.3390/ijms23095011Wang J., Liu H., Zhang Y., et al. The effect of multi-component inhibitor systems on hydrate formation / J. Nat. Gas Sci. Eng. 2024. Vol. 122. DOI: 10.1016/j.jgsce.2024.205214Wang J., Liu H., Zhang Y., et al. The effect of multi-component inhibitor systems on hydrate formation / J. Nat. Gas Sci. Eng. 2024. Vol. 122. DOI: 10.1016/j.jgsce.2024.205214Kashish, Yusuf M., Beg M., et al. Natural gas hydrates: a review of various inhibitors and respective mechanisms / J. Mol. Liq. 2024. Vol. 403. DOI: 10.1016/j.molliq.2024.124809Kashish, Yusuf M., Beg M., et al. Natural gas hydrates: a review of various inhibitors and respective mechanisms / J. Mol. Liq. 2024. Vol. 403. DOI: 10.1016/j.molliq.2024.124809Sira A., Alhajji A., Al-Qasim A. A study on inhibitors for the prevention of hydrate formation in gas transmission pipeline / J. Nat. Gas Chem. 2007. Vol. 16. No. 1. P. 81 – 85. DOI: 10.1016/s1003-9953(07)60031-0Sira A., Alhajji A., Al-Qasim A. A study on inhibitors for the prevention of hydrate formation in gas transmission pipeline / J. Nat. Gas Chem. 2007. Vol. 16. No. 1. P. 81 – 85. DOI: 10.1016/s1003-9953(07)60031-0Liu Y., Duan J., Xu D., et al. Inhibiting effect of a composite formulation of kinetic and thermodynamic inhibitors for gas hydrate formation in high water cut oil-water emulsion / Energy Sci. Eng. 2023. DOI: 10.1002/ese3.1453Liu Y., Duan J., Xu D., et al. Inhibiting effect of a composite formulation of kinetic and thermodynamic inhibitors for gas hydrate formation in high water cut oil-water emulsion / Energy Sci. Eng. 2023. DOI: 10.1002/ese3.1453Paz P., Netto T. On the rheological properties of thermodynamic hydrate inhibitors used in offshore oil and gas production / J. Mar. Sci. Eng. 2020. Vol. 8. No. 11. P. 878. DOI: 10.3390/jmse8110878Paz P., Netto T. On the rheological properties of thermodynamic hydrate inhibitors used in offshore oil and gas production / J. Mar. Sci. Eng. 2020. Vol. 8. No. 11. P. 878. DOI: 10.3390/jmse8110878Bahadori A., Vuthaluru H. Prediction of methanol loss in vapour phase during gas hydrate inhibition using Arrhenius-type functions / J. Loss Prevent. Proc. 2010. Vol. 23. No. 6. P. 902 – 908. DOI: 10.1002/ese3.1156Bahadori A., Vuthaluru H. Prediction of methanol loss in vapour phase during gas hydrate inhibition using Arrhenius-type functions / J. Loss Prevent. Proc. 2010. Vol. 23. No. 6. P. 902 – 908. DOI: 10.1002/ese3.1156Teixeira A., de Oliveira Arinelli L., de Medeiros J., et al. Monoethylene glycol as hydrate inhibitor in offshore natural gas processing: from fundamentals to exergy analysis / Springer Briefs in Petroleum Geoscience & Engineering. 2018. DOI: 10.1007/978-3-319-66074-5Teixeira A., de Oliveira Arinelli L., de Medeiros J., et al. Monoethylene glycol as hydrate inhibitor in offshore natural gas processing: from fundamentals to exergy analysis / Springer Briefs in Petroleum Geoscience & Engineering. 2018. DOI: 10.1007/978-3-319-66074-5

The authors declare that there are no conflicts of interest present.