Petroleum ChemistryPetroleum ChemistryНефтехимия0028-24213034-5626The Russian Academy of Sciences65561610.31857/S0028242123030097JCFNPDArticlesСтатьиResearch ArticleCracking of Heavy Oil in Supercritical Water in the Presence of Iron Oxide Nanopowder: Asphaltene Transformations and Process KineticsКрекинг тяжелой нефти в среде сверхкритической воды в присутствии наноразмерного порошка оксида железа: превращение асфальтенов и кинетика процессаSviridenkoN. N.СвириденкоН. Н.nikita26sviridenko@gmail.comInstitute of Petroleum Chemistry, Siberian Branch of Russian Academy of Sciences (IPC SB RAS)Институт химии нефти СО РАН15062023633NO3 (2023)№3 (2023)39140011022025Copyright ©; 2023, Russian Academy of SciencesCopyright ©; 2023, Российская академия наук2023Russian Academy of SciencesРоссийская академия наукhttps://journals.eco-vector.com/0028-2421/article/view/655616

The products of catalytic cracking of heavy crude oil from the Ashalchinskoye oil field (the Almetyevsk district of the Republic of Tatarstan, Russia) were characterized. The effects of a Fe2O3 nanopowder catalyst and the presence of supercritical water (SCW) on the composition and structure of these cracking products were investigated. Cracking over 0.01 wt % Fe2O3 nanopowder in a SCW environment was found to enhance the yield of distillates by more than 34 wt % and to reduce the content of resinous asphaltene materials by a factor of 2.1 compared to the initial crude oil. It was further shown that Fe2O3-nanopowder-catalyzed cracking produces coke-like asphaltenes with a low H/C atomic ratio (no higher than 0.75). Reaction rate constants were evaluated for the thermal and catalytic cracking of the heavy oil from the Ashalchinskoye field.

Проведено исследование зависимости состава и структуры продуктов каталитического крекинга в сверхкритической воде (СКВ) тяжелой нефти Ашальчинского месторождения Альметьевского района республики Татарстан в присутствии наноразмерного порошка (НРП) оксида железа(III). Установлено, что крекинг в присутствии 0.01%-ного НРП оксида железа в среде СКВ позволяет увеличить выход светлых фракций более чем на 34 мас. % и снизить содержание смолисто-асфальтеновых компонентов в 2.1 раза по сравнению с исходной нефтью. Показано, что использование катализатора НРП оксида железа приводит к образованию асфальтенов коксоподобной структуры с низким атомным отношением Н/С (до 0.75). Рассчитаны константы скоростей реакций превращений компонентов тяжелой нефти Ашальчинского месторождения, протекающих при термическом и каталитическом крекингах.

heavy oilnanopowderasphaltenessupercritical waterтяжелая нефтьнаноразмерный порошокасфальтенысверхкритическая водаCanıaz R.O., Arca S., Yaşar M., Erkey C. Refinery bitumen and domestic unconventional heavy oil upgrading in supercritical water // J. of Supercritical Fluids. 2019. V. 152. I. 104569. https://doi.org/10.1016/j.supflu.2019.104569Yakubov M., Abilova G., Tazeeva E., Yakubova S., Tazeev D., Mironov N., Milordov D.A. Comparative analysis of vanadyl porphyrins isolated from resins of heavy oils with high and low vanadium content // Processes. 2021. V. 9. I. 2235. https://doi.org/10.3390/pr9122235Antipenko V.R., Grinko A.A. Parameters of macrostructure of insoluble products obtained by thermolysis of resins and asphaltenes of the Usinskaya oil // Bulletin of the Tomsk Polytechnic University. Geo Аssets Engineering. 2021. V. 332. P. 123-131. https://doi.org/10.18799/24131830/2021/04/3155Korneev D.S., Pevneva G.S., Golovko A.K. Thermal transformations of asphaltenes at a temperature of 120°C // J. of Siberian Federal University. Chemistry. 2019. V. 12. P. 101-117. https://doi.org/10.17516/1998-2836-0110Chen X., Li T., Xin L., Yang Y., Shan H., Yang C. Inductive effect of basic nitrogen compounds on coke formation during the catalytic cracking process // Catalysis Communications. 2016. V. 74. P. 95-98. https://doi.org/10.1016/j.catcom.2015.11.008Nal'gieva Kh.V., Kopytov M.A. Study of the thermolysis products of asphaltenes from the vacuum residue of Usinskoe oil produced in supercritical water // Solid Fuel Chemistry. 2022. V. 56. P. 116-122. https://doi.org/10.3103/S0361521922020070Hosseinpour 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. V. 271. I. 117618. https://doi.org/10.1016/j.fuel.2020.117618Eletskii P.M., Sosnin G.A., Zaikina O.O., Kukushkin R.G., Yakovlev V.A. Heavy oil upgrading in the presence of water // J. of Siberian Federal University. Chemistry. 2017. V. 10. № 4. P. 545-572. https://doi.org/10.17516/1998-2836-0048Eletskii P.M., Mironenko O.O., Kukushkin R.G., Sosnin G.A., Yakovlev V.A. Catalytic steam cracking of heavy oil feedstocks: a review // Catalysis in Industry. 2018. V. 10. № 3. P. 185-201. https://doi.org/10.1134/S2070050418030042Chao K., Chen Y., Li J., Zhang X., Dong B. Upgrading and visbreaking of super-heavy oil by catalytic aquathermolysis with aromatic sulfonic copper // Fuel Processing Technology. 2012. V. 104. P. 174-180. https://doi.org/10.1016/j.fuproc.2012.05.010Sosnin G.A., Zaikina O.O., Eletskii P.M., Yakovlev V.A. Catalytic steam cracking of vacuum residue in presence of dispersed catalysts based on Mo, Ni, Fe, Co, Al metals // Bulletin of the Tomsk Polytechnic University. Geo Аssets Engineering. 2018. V. 329. № 12. P. 145-154. https://doi.org/10.18799/24131830/2018/12/30Urazov K.K., Sviridenko N.N., Iovik Y.A., Kolobova E.N., Grabchenko M.V., Kurzina I.A., Mukhamatdinov I.I. Effect of hydrogen-donor of heavy crude oil catalytic aquathermolysis in the presence of a nickel-based catalyst // Catalysts. 2022. V. 12. I. 1154. https://doi.org/10.3390/catal12101154Vilcaez J., Watanabe M., Watanabe N., Kishita A., Adschiri T. Hydrothermal extractive upgrading of bitumen without coke formation // Fuel. 2012. V. 102. P. 379-385. https://doi.org/10.1016/j.fuel.2012.07.024Sato T., Mori S., Watanabe M., Sasaki M., Itoh N. Upgrading of bitumen with formic acid in supercritical water // J. of Supercritical Fluids. 2010. V. 55. P. 232-240. https://doi.org/10.1016/j.supflu.2010.07.010Vakhin A.V., Aliev F.A., Mukhamatdinov I.I., Sitnov S.A., Kudryashov S.I., Afanasiev I.S., Petrashov O.V., Nurgaliev D.K. Extra-heavy oil aquathermolysis using nickel-based catalyst: some aspects of in situ transformation of catalyst precursor // Catalysts. 2021. V. 11. № 2. P. 189. https://doi.org/10.3390/catal11020189Chen Q., Liu Y., Zhao J. Intensified viscosity reduction of heavy oil by using reservoir minerals and chemical agents in aquathermolysis // Advanced Materials Research. 2011. V. 236-238. P. 839-843. https://doi.org/10.4028/www.scientific.net/AMR.236-238.839Suwaid M.A., Varfolomeev M.A., Al-Muntaser A.A., Abdaljalil N.I., Djimasbe R., Rodionov N.O., Zinnatullin A., Vagizov F.G. Using the oil-soluble copper-based catalysts with different organic ligands for in-situ catalytic upgrading of heavy oil // Fuel. 2022. V. 312. I. 122914. https://doi.org/10.1016/j.fuel.2021.122914Petrukhina N.N., Kayukova G.P., Romanov G.V., Tumanyan B.P., Foss L.E., Kosachev I.P., Musin R.Z., Ramazanova A.I., Vakhin A.V. Conversion processes for high-viscosity heavy crude oil in catalytic and noncatalytic aquathermolysis // Chemistry and Technology of Fuels and Oils. 2014. V. 50. P. 315-326. https://doi.org/10.1007/s10553-014-0528-yКривцов Е.Б., Свириденко Н.Н., Головко А.К. Инициированный крекинга природного битума для увеличения выхода дистиллятных фракций // Изв. Томского политехнического ун-та. 2013. Т. 323. № 3. С. 37-42.Дмитриев Д.Е., Головко А.К. Превращение смол и асфальтенов при термической обработке тяжелых нефтей // Нефтехимия. 2010. Т. 50. № 2. С. 118-125Dmitriev D.E., Golovko A.K. Transformations of resins and asphaltenes during the thermal treatment of heavy oils // Petrol. Chemistry. 2010. V. 50. P. 106-113. https://doi.org/10.1134/S0965544110020040.Fedyaeva O.N., Vostrikov A.A. The products of heavy sulfur-rich oil conversion in a counter supercritical water flow and their desulfurization by ZnO nanoparticles // J. of Supercritical Fluids. 2016. V. 111. P. 121-128. https://doi.org/10.1016/j.supflu.2016.01.020Hosseinpour M., Fatemi S., Ahmadi S.J., Morimoto M., Akizuki M., Oshima Y., Fumoto E. The synergistic effect between supercritical water and redox properties of iron oxide nanoparticles for in situ catalytic upgrading heavy oil with formic acid. isotopic study // Applied Catalysis B: Environmental. 2018. V. 230. P. 91-101. https://doi.org/10.1016/j.apcatb.2018.02.030Chen Y., Wang K., Yang J.-Y., Yuan P.-Q., Cheng Z.-M., Yuan W.-K. Dealkylation of aromatics in subcritical and supercritical water: involvement of carbonium mechanism // Industrial & Engineering Chemistry Research. 2016. V. 55. P. 9578-9585. https://doi.org/10.1021/acs.iecr.6b02323Chibiryaev A.M., Kozhevnikov I.V., Martyanov O.N. Transformation of petroleum asphaltenes in supercritical alcohols - а tool to change H/C ratio and remove S- and N-atoms from refined products // Catalysis Today. 2019. V. 329. P. 177-186. https://doi.org/10.1016/j.cattod.2018.10.066Esfahani F.T., Ehsni M.R., Ivakpour J. A kinetic model for delayed coking process of Iranian vacuum residues // Petrol. Science and Technology. 2019. V. 37. № 19. P. 2049-2057. https://doi.org/10.1080/10916466.2018.1482323Кривцов Е.Б., Гончаров А.В. Влияние добавок стирола на кинетику крекинга компонетнов высокосернистого гудрона // Нефтехимия. 2020. Т. 60. № 3. С. 394-400. https://doi.org/10.31857/S0028242120030119Krivtsov E.B., Goncharov A.V. Effect of Styrene Additives on the Cracking Kinetics of Components of High-Sulfur Vacuum Residue. // Petrol. Chemistry. 2020. V. 60. P. 358-364. https://doi.org/10.1134/S0965544120030111.Al-muntaser A.A., Varfolomeev M.A., Suwai M.A., Feoktistov D.A., Yuan C., Klimovitskii A.E., Gareev B.I., Djimasbe R., Nurgaliev D.K., Kudryashov S.I., Egorova E.V., Fomkin A.V., Petrashov O.V., Afanasiev I.S., Fedorchenko G.D. Hydrogen donating capacity of water in catalytic and non-catalytic aquathermolysis of extra-heavy oil: deuterium tracing study // Fuel. 2021. V. 283. I. 118957. https://doi.org/10.1016/j.fuel.2020.118957Sviridenko N.N., Akimov A.S. Structural changes of asphaltenes during cracking in supercritical water in the presence of disperse catalysts // J. of Supercritical Fluids. 2023. V. 192. I. 105784. https://doi.org/10.1016/j.supflu.2022.105784Hosseinpour M., Fatemi S., Ahmadi S.J. Deuterium tracing study of unsaturated aliphatics hydrogenation by supercritical water in upgrading heavy oil. Part II: Hydrogen donating capacity of water in the presence of iron(III) oxide nanocatalyst // J. of Supercritical Fluids. 2016. V. 110. P. 75-82. https://doi.org/10.1016/j.supflu.2015.12.014