THERMAL TRANSFORMATIONS OF MALTENES AND OILS FROM HEAVY METHANE BASE CRUDES
Abstract
The paper considers changes of composition of oils and maltenes during thermal cracking process. The oils and maltenes (mixture Oils+Resins) were isolated from crudes from two oil fields: Zyuzeevskoye (Republic of Tatarstan) and Zuunbayanskoye (Mongolia). Both crudes relate to methane type, but differ by content of saturated, aromatic hydrocarbons, resins, asphaltenes and sulfur. Cracking of oils and (O+R) mixtures was carried out at 450 °С for 120 min in isothermal mode. Data on the mass balance of process, composition of gaseous and liquid cracking products were obtained. It was shown the С1-С5 hydrocarbons are predominate in the composition of gaseous cracking products of oils and (O+R) mixtures. Independent of cracking object their content changes in a series: C1 > C2 > C3 > С4-С5. The dynamics of group hydrocarbon composition changes in thermolysates was studied. It was shown the thermal transformations of hydrocarbons steer in the direction of destruction reactions during cracking of oils with high content of saturated hydrocarbons, as it indicated by gaseous products yield. Condensation reactions are dominated during cracking of oils, in composition of which aromatic hydrocarbons are prevail. It was shown the addition of resins into the complex multicomponent mixture of hydrocarbons leads to directivity change of cracking free radical reaction behavior. Differences in structural-group characteristics of average resins molecules reflect not only on the yield of solid and gaseous cracking products of (O+R) mixture, but also affect on the directivity of hydrocarbons thermal transformations. Moreover it is impossible to exclude the effect of differences in the content of saturated and aromatic hydrocarbons in the composition of oils on the components thermal transformations during cracking process of (O+R) mixtures.
For citation:
Voronetskaya N.G., Pevneva G.S. Thermal transformations of maltenes and oils from heavy methane base crudes. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 8. P. 59-67. DOI: 10.6060/ivkkt.20246708.4t.
References
Wang F., Wei Q., Li K., Biney B. W., Liu H, Chen K., Wang Z., Guo A. Coke formation of heavy oil during thermal cracking: New insights into the effect of olefinicbond-containing aromatics. Fuel. 2023. V. 336. P. 127-138. DOI: 10.1016/j.fuel.2022.127138.
Ancheyta J., Speight J.G. Hydroprocessing of Heavy Oils and Residua. SPb: TSOP “Professiya”. 2012. 384 p.
Ayala M., Hernandez-Lopez E.L., Perezgasga L., Vazquez-Duhalt R. Reduced coke formation and aromaticity due to chloroperoxidase-catalyzed transformation of asphaltenes from Maya crude oil. Fuel. 2012. V. 92. N 1. P. 245-249. DOI: 10.1016/j.fuel.2011.06.067.
Luo P., Gu Y. Effects of asphaltene content on the heavy oil viscosity at different temperatures. Fuel. 2007. V. 86. P. 1069–1078. DOI: 10.1016/j.fuel.2006.10.017.
Chen X., Li T., Xin L., Yang Y., Shan H., Yang Ch. Inductive effect of basic nitrogen compounds on coke formation during the catalytic cracking process. Catal. Commun.. 2016. V. 74. P. 95-98. DOI: 10.1016/j.catcom.2015.11.008.
Nalgieva K.V., Kopytov M.A. Characteristics of resin and asphaltene destruction products in supercritical water. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 11. P. 25-31 (in Russian). DOI: 10.6060/ivkkt.20236611.11t.
Pevneva G.S., Voronetskaya N.G. Composition of thermal cracking products of SARA fractions from heavy methane crude oil. Chemistry for Sustainable Development [Khimiya v Interesah Ustoichivogo Razvitiya]. 2023. V. 31. N 2. P. 226-232. DOI: 10.15372/CSD2023460.
Halikova D.A., Petrov S.M., Bashkirtseva N.Yu. Review of the advanced technologies for processing of heavy highly viscous crude oils and natural bitumen. Vestn. Kazan. Tekhnol. Un-ta. 2013. N 3. P. 217–221 (in Russian).
Rogel E., Witt M. Asphaltene characterization during hydroprocessing by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry. Energy Fuels. 2017. V. 31. N 4. P. 3409–3416. DOI: 10.1021/acs.energyfuels.6b02363.
Kapadia P.R., Kallos M.S., Gates I.D. A review of py-rolysis, aquathermolysis, and oxidation of Athabasca bi-tumen. Fuel Proc. Technol. 2015. V. 131. P. 270–289. DOI: 10.1021/ef900206n.
Chiaberge S., Guglielmetti G., Montanari L., Salvalaggio M., Santolini L., Spera S., Cesti P. Investigation of Asphaltene Chemical Structural Modification Induced by Thermal Treatments. Energy Fuels. 2009. V. 23. N 9. P. 4486–4495. DOI: 10.1021/ef900206n.
Li N., Zhang X., Zhang Q., Chen L., Ma L., Xiao X. Reactivity and structural changes of asphaltenes during the supercritical water upgrading process. Fuel. 2020. V. 278. 118331. DOI: 10.1016/j.fuel.2020.118331.
Nal’gieva K.V., Kopytov M.A., Cheshkova T.V., Krivtsov E.B., Mamontov G.V. Transformation of asphaltenes isolated from heavy crude oil during catalityc and non catalytic aquathermolysis. Neft.Gaz.Novatsii. 2021. V. 247. N 3. P. 13-16 (in Russian).
Nal’gieva K.V., Kopytov M.A. Study of the thermolysis products of asphaltenes from the vacuum residue of Usinskoe oil produced in supercritical water. Solid Fuel Chem. 2022. V. 56. N 2. P. 116-122. DOI: 10.3103/S0361521922020070.
Korneev D.S., Pevneva G.S., Voronetskaya N.G. Effects of the composition and molecular structure of heavy oil asphaltenes on their reactivity in thermal decomposition processes. Petrol. Chem. 2021. V. 61. N 2. P. 152-161. DOI: 10.1134/S0965544121020158.
Boytsova A.A., Baytalov F., Strokin S.V. Study of thermodynamic, kinetic and structural parameters of heavy Yaregskaya crude oil aspaltenes thermolysis. Neftegaz.RU. 2020. N 3. P. 47-51 (in Russian).
Korneev D.S., Pevneva G.S. Composition of the prod-ucts of low-temperature destruction of asphaltenes of heavy oil and oil residues. Chemistry for Sustainable Development [Khimiya v Interesah Ustoichivogo Razvitiya]. 2020. V. 28. N 3. P. 252-257 (in Russian). DOI: 10.15372/KhUR2020226.
Trejo F., Ancheyta J., Morgan T.J., Herod A.A., Kandiyoti R. Characterization of Asphaltenes from Hy-drotreated Products by SEC, LDMS, MALDI, NMR, and XRD. Energy Fuels. 2007. V. 21. P. 2121-2128. DOI: 10.1021/ef060621z.
Neyfel'd A.L., Savinykh Yu.V., Kopytov M.A., Orlov-sky V.M. Electron beam impact on petroleum asphaltenes. J. Siber. Fed. Univ. Chem. 2023. V. 16. N 1. P. 59-65.
Sviridenko N.N., Akimov A.S. Characteristics of products of thermal and catalytic cracking of heavy oil asphaltenes under supercritical water conditions. J. Supercrit. Fluids. 2023. V. 192. 105784. DOI: 10.1016/j.supflu.2022.105784.
Cheshkova T.V., Sagachenko T.A., Min R.S., Kovalen-ko E.Yu. Biogenic oxidation of resin-asphaltene compo-nents of heavy oil. Part1: Asphaltenes. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 11. P. 110-118. DOI: 10.6060/ivkkt.20236611.12t (In Russian).
Volkova G.I., Kalinina T.V., Morozova A.V. Changes of the asphaltenes structural parameters under the influ-ence of ultrasonic waves. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2019. V. 62. N 12. P. 71-77 (in Russian). DOI: 10.6060/ivkkt.20196212.6016.
Urazov Kh.Kh., Sviridenko N.N. Influence of In Situ Formed Nickel- and Cobalt-Containing Catalysts on the Mechanism of Conversion of Heavy Oil Asphaltenes. Solid Fuel Chem. 2023. V. 57. N 1. P. 76–81. DOI: 10.3103/S0361521923020155.
Pevneva G.S., Voronetskaya N.G., Grin’ko A.A., Golovko A.K. Influence of resins ad asphaltenes on thermal transformations of hydrcarbons of paraffin-base heavy crude oil. Petrol. Chem. 2016. V. 56. N 8. P. 690-696. DOI: 10.1134/ S0965544116080144.
Pevneva G.S., Voronetskaya N.G., Korneev D.S., Golovko A.K. Study of hydrocarbon thermal conversion in heavy naphthene-base oil. AIP Conf. Proceed. Proceed. of the Adv. Mater. with Hierarchical Struct. for New Technol. and Reliable Struct. 2018. P. 020237. DOI: 10.1063/1.5083480.
Pevneva G.S., Voronetskaya N.G., Korneev D.S., Golovko A.K. Mutual influence of resins and oils in crude oil from the Usinskoe oilfield on the direction of their thermal transformations. Petrol. Chem. 2017. V. 57. N 8. P. 739-745. DOI: 10.1134/S0965544117080126.
Russian Ministry of Natural Resources Order N 3-r dated 01.02 2016. Prilozheniya 1-3.
Pevneva G.S., Voronetskaya N.G., Sviridenko N.N. Cracking of Maltenes of Naphthenic Petroleum in the Presence of WC/Ni–Cr. Petrol. Chem. 2020. V. 60. N 3. P. 373-379. DOI: 10.1134/S0965544120030160.
Pevneva G.S., Voronetskaya N.G., Kopytov M.A. Study of coke formation in SARA fractions by means of thrmogravimetry. Chemistry for Sustainable Development [Khimiya v Interesah Ustoichivogo Razvitiya]. 2022. V. 30. N 4. P. 395-401. DOI: 10.15372/CSD2022396.
Don A.R., Voronetskaya N.G., Grin’ko A.A. Golovko A.K. Effect of resinasphaltene substances on thermal transformations of hydrocarbons from natural bitumen. Vestn. TGU. 2015. N 393. P. 244-249 (in Russian). DOI: 10.17223/15617793/393/39.
Ivanova L.V., Gordadze G.N., Koshelev V.N. Determing mass content of solid paraffins by capillary gas-liquid chromatigraphy. Trudy Gubkin Univer. Nefti Gaza. 2011. V. 264. N 3. P. 61-68 (in Russian).
Dmitriev D.E., Golovko A.K. Transformations of resins and asphaltenes during the thermal treatment of heavy oils. Petrol. Chem. 2010. V. 50. N 2. P. 106-113. DOI: 10.1134/S0965544110020040
Smirnov M.B., Vanyukova N.A., Brodskii E.S. A new type of aromatic petroleum hydrocarbons: phenyl-substituted tri- and tetracycloaromatics. Petrol. Chem. 2020. V. 60. N 3. P. 270-277. DOI: 10.1134/S0965544120030202.
