ipolytechiPolytech JournaliPolytech Journal2782-40042782-6341Irkutsk National Research Technical University10.21285/1814-3520-2024-4-623-633DFVWFGipolytech-890Research ArticleМЕТАЛЛУРГИЯMETALLURGYКаталитическое влияние карбидообразующих оксидов на процесс графитизации углеродных изделий, эксплуатируемых в металлургииCatalytic effect of carbide-forming oxides on the graphitization of carbon objects used in metallurgyhttps://orcid.org/0000-0002-9570-2309ЕрохинаО. О.ErokhinaО. О.

Ерохина Ольга Олеговна, специалист по маркетинговым исследованиям

660123, г. Красноярск, Траспортный проезд, 1

Olga O. Erokhina, Market Researcher

1, Transportny Proezd, Krasnoyarsk 660123

o.o.erokhina@gmail.comПироговаН. А.PirogovaN. A.

Пирогова Надежда Алексеевна, младший научный сотрудник

196247, г. Санкт-Петербург, Ленинский просп., 151, оф. 635

Nadezhda A. Pirogova, Junior Researcher

151, Leninsky pr., office 635, Saint-Petersburg 196247

Pirogova-n@gidrometall.ruОАО «Красцветмет»РоссияJSC “Krastsvetmet”Russian FederationНИЦ «Гидрометаллургия»РоссияNietz TechnologiesRussian Federation202404012025284623633Copyright © Ерохина О.О., Пирогова Н.А., 20242024Ерохина О.О., Пирогова Н.А.Erokhina О.О., Pirogova N.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://ipolytech.elpub.ru/jour/article/view/890

Цель – провести изучение вопроса о возможности использования карбидообразующих оксидов в качестве катализаторов для процесса графитизации изделий, используемых в металлургии. Проведен анализ опубликованных данных о роли катализаторов (карбидообразующих металлов и их оксидов) для процесса графитизации углеграфитовых материалов. Показано, что данные катализаторы процесса графитизации могут в значительной степени снижать температуру графитизации. При этом сохраняются физико-химические свойства, характерные для углеграфитовых материалов, графитизированных без использования катализаторов. Выявлено, что в случае с сыпучими материалами при использовании катализаторов температура графитизации может быть снижена до 1200–1500ºС (против 2000ºС и более). Приведено описание механизма каталитической графитизации, включающего две реакции: взаимодействие между металлом (или его оксидом) с углеродом с образованием карбида; последующее образование чистого металла и карбидоподобного графита при повышении температуры. Полученная графитовая фаза является центром кристаллизации. Выявлена основная проблема использования катализаторов при производстве графитизированных изделий – удаление продуктов реакции, в том числе металлов. Показано, что подшихтовку катализатором можно производить на стадии смешения и формовки, вследствие чего часть продуктов реакции будет удаляться еще на этапе обжига заготовки. Предполагается, что механизм удаления продуктов реакции будет сопоставим с удалением золы из графитизируемой заготовки. При этом доказана эффективность содержания карбидообразующих оксидов в изделии даже в незначительном количестве (до 5 масс. %). Вследствие этого, а также при учете возможности подбора катализатора, в зависимости от условий дальнейшей эксплуатации возможно снижение негативного влияния избыточного содержания оксидов в шихте. Таким образом, использование катализаторов для процесса графитизации электродов, эксплуатируемых в металлургии, является перспективным способом снижения температуры процесса, однако требуется подбор оптимального содержания оксидов и корректировка режимов электротермических процессов с целью адаптации технологии для крупногабаритных изделий.

The paper aims to study the possibility of using carbide-forming oxides as catalysts for the graphitization of objects used in metallurgy. Published data on the role of catalysts (carbide-forming metals and their oxides) for the graphitization of carbon materials was analyzed. These graphitization catalysts are shown to be able to significantly reduce the graphitization temperature. The physicochemical properties characteristic of carbon materials graphitized without the use of catalysts are preserved. It was revealed that in the case of bulk materials, the graphitization temperature can be reduced to 1200–1500℃ with the use of catalysts (as opposed to 2000ºС and above). The mechanism of catalytic graphitization involving two reactions is described: interaction between a metal (or its oxide) and carbon with the formation of carbide; subsequent formation of pure metal and carbide-like graphite with increasing temperature. The resulting graphite phase constitutes the crystallization nucleus. The main problem associated with the use of catalysts in the production of graphitized objects was identified—the removal of reaction products, including metals. It is shown that additional catalyst charging can be performed at the stage of mixing and forming, which results in the removal of a part of the reaction products at the stage of baking. The mechanism of removing reaction products is expected to be comparable to ash removal from the piece to be graphitized. It was proven effective for objects to contain carbide-forming oxides, even in insignificant amounts (up to 5 wt%). Due to this, as well as given the possibility of catalyst selection, the negative effect of excessive oxide content in the charge can be reduced depending on further operating conditions. Thus, the use of catalysts for the graphitization of electrodes used in metallurgy is a promising way to reduce the process temperature. However, it is required to select the optimal oxide content and adjust the conditions of electrothermal processes in order to adapt the technology for large-sized products.

карбидообразующие оксидыграфитизациякатализуглеграфитовые материалыграфитизированные электродыграфитизированные катодыграфитизированные анодыcarbide-forming oxidesgraphitizationcatalysiscarbon-graphite materialsgraphitized electrodesgraphitized cathodesgraphitized anodesReferencesFeng Gao, Naixiang Feng, Qingren Niu, Hua He, Liguo Han, Jianzhuang Yang. Study on graphitization of cathode carbon blocks for aluminum electrolysis // Light Metals / eds. C.E. Suarez. Сham: Springer, 2012. P. 1355–1357. https://doi.org/10.1007/978-3-319-48179-1_234.Feng Gao, Naixiang Feng, Qingren Niu, Hua He, Liguo Han, Jianzhuang Yang. Study on graphitization of cathode carbon blocks for aluminum electrolysis. In: Suarez C.E. (eds.). Light Metals. Сham: Springer; 2012, p. 1355-1357. https://doi.org/10.1007/978-3-319-48179-1_234.Moghadam H.A., Jabbari M., Daneshmand S., Jazi S.R., Khosravi A. Effects of TiO2/SiC/SiO2 coating on graphite electrode consumption in sublimation and oxidation states as determined by EAF simulation and experimental methods // Surface and Coatings Technology. 2021. Vol. 420. P. 127340. https://doi.org/10.1016/j.surfcoat.2021.127340.Moghadam H.A., Jabbari M., Daneshmand S., Jazi S.R., Khosravi A. Effects of TiO2/SiC/SiO2 coating on graphite electrode consumption in sublimation and oxidation states as determined by EAF simulation and experimental methods. Surface and Coatings Technology. 2021;420:127340. https://doi.org/10.1016/j.surfcoat.2021.127340.Saitov A.V., Bazhin V.Yu. Features of using modified carbon-graphite lining materials in aluminum electrolyzers // Refractories and Industrial Ceramics. 2018. Vol. 59. No. 3. P. 278–286. https://doi.org/10.1007/s11148-018-0221-5.Saitov A.V., Bazhin V.Yu. Features of using modified carbon-graphite lining materials in aluminum electrolyzers. Refractories and Industrial Ceramics. 2018;59(3):278-286. https://doi.org/10.1007/s11148-018-0221-5.Zhu Yaming, Liu Huimei, Xu Yunliang, Hu Chaoshuai, Zhao Chunlei, Cheng Junxia, et al. Preparation and characterization of coal-pitch-based needle coke (part III): the effects of quinoline insoluble in coal tar pitch // Energy & Fuels. 2020. Vol. 34. Iss. 7. P. 8676–8684. https://doi.org/10.1021/acs.energyfuels.0c01049.Zhu Yaming, Liu Huimei, Xu Yunliang, Hu Chaoshuai, Zhao Chunlei, Cheng Junxia, et al. Preparation and characterization of coal-pitch-based needle coke (Part III): The effects of quinoline insoluble in coal tar pitch. Energy & Fuels. 2020;34(7):8676-8684. https://doi.org/10.1021/acs.energyfuels.0c01049.Ragan S., Marsh H. Science and technology of graphite manufacture // Journal of Materials Science. 1983. Vol. 18. P. 3161–3176. https://doi.org/10.1007/BF00544139.Ragan S., Marsh H. Science and technology of graphite manufacture. Journal of Materials Science. 1983;18:3161- 3176. https://doi.org/10.1007/BF00544139.Уббелоде А.Р. Графит и его кристаллические соединения / пер. с англ.; под ред. Е.С. Головиной и О.А. Цухановой. М.: Мир, 1965. 256 с.Ubbelohde A.R. Graphite and its crystal compounds. Oxford: Clarendon Press; 1960, 217 р. (Russ. еd.: Grafit i ego kristallicheskiye soyedineniya. Moscow: Mir; 1965, 256 р.)Perruchoud R., Fischer W., Meier M., Mannweiler U. Coke selection criteria for abrasion resistant graphitized cathodes // Light Metals / eds. S.J. Lindsay. Сham: Springer, 2011. P. 1067–1072. https://doi.org/10.1007/978-3-319-48160-9_181.Perruchoud R., Fischer W., Meier M., Mannweiler U. Coke selection criteria for abrasion resistant graphitized cathodes. In: Lindsay S.J. (eds.). Light Metals. Сham: Springer; 2011, p. 1067-1072. https://doi.org/10.1007/978-3-319-48160-9_181.Belitskus D. Effect of anthracite properties and formulation on properties of bench scale cathode blocks for aluminum smelting // Metallurgical Transactions B. 1976. Vol. 7. P. 543–549. https://doi.org/10.1007/BF02698586.Belitskus D. Effect of anthracite properties and formulation on properties of bench scale cathode blocks for aluminum smelting. Metallurgical Transactions B. 1976;7:543-549. https://doi.org/10.1007/BF02698586.Oberlin A., Boichard S., Oshida K. Landmarks for graphitization // Tanso. 2006. Vol. 224. P. 281–298. https://doi.org/10.7209/tanso.2006.281.Oberlin A., Boichard S., Oshida K. Landmarks for graphitization. Tanso. 2006;224:281-298. https://doi.org/10.7209/tanso.2006.281.Frohs W., Roeßner F. Expansion of carbon artifacts during graphitization – an industrial issue // Tanso. 2015. Вып. 267. P. 77–83. https://doi.org/10.7209/tanso.2015.77.Frohs W., Roeßner F. Expansion of carbon artifacts during graphitization – an industrial issue. Tanso. 2015;267:77-83. https://doi.org/10.7209/tanso.2015.77.Kuznetsov D.M., Korobov V.K. A comparison of properties of electrodes graphitized by the Acheson and Castner methods // Refractories and industrial ceramics. 2001. Vol. 42. No. 9-10. P. 355–359. https://doi.org/10.1023/A:1014022730724.Kuznetsov D.M., Korobov V.K. A comparison of properties of electrodes graphitized by the Acheson and Castner methods. Refractories and industrial ceramics. 2001;42(9-10):355-359. https://doi.org/10.1023/A:1014022730724.Ōya A., Yamashita R., Ōtani S. Catalytic graphitization of carbons by borons // Fuel. 1979. Vol. 58. Iss. 7. P. 495–500. https://doi.org/10.1016/0016-2361(79)90167-4.Ōya A., Yamashita R., Ōtani S. Catalytic graphitization of carbons by borons. Fuel. 1979;58(7):495-500. https://doi.org/10.1016/0016-2361(79)90167-4.Marsh H., Warburton A.P. Catalysis of graphitisation // Journal of Applied Chemistry. 1970. Vol. 20. No. 4. P. 133–142. https://doi.org/10.1002/jctb.5010200409.Marsh H., Warburton A.P. Catalysis of graphitization. Journal of Applied Chemistry. 1970;20(4):133-142. https://doi.org/10.1002/jctb.5010200409.Чалых Е.Ф. Технология и оборудование электродных и электроугольных предприятий. М.: Металлургия, 1972. 423 с.Chalykh E.F. Technology and equipment of electrode and electric coal enterprises. Moscow: Metallurgiya; 1972, 423 р. (In Russ.).Ōya A., Marsh H. Phenomena of catalytic graphitization // Journal of Materials Science. 1982. Vol. 17. P. 309– 322. https://doi.org/10.1007/BF00591464.Ōya A., Marsh H. Phenomena of catalytic graphitization. Journal of Materials Science. 1982;17:309-322. https://doi.org/10.1007/BF00591464.Ōya A., Ōtani S. Catalytic graphitization of carbons by various metals // Carbon. 1979. Vol. 17. Iss. 2. P. 131– 137. https://doi.org/10.1016/0008-6223(79)90020-4.Ōya A., Ōtani S. Catalytic graphitization of carbons by various metals. Carbon. 1979;17(2):131-137. https://doi.org/10.1016/0008-6223(79)90020-4.Bitencourt C.S., Luz A.P., Pagliosa C., Pandolfelli V.C. Role of catalytic agents and processing parameters in the graphitization process of a carbon-based refractory binder // Ceramics International. 2015. Vol. 41. Iss. 10-A. P. 13320–13330. https://doi.org/10.1016/j.ceramint.2015.07.115.Bitencourt C.S., Luz A.P., Pagliosa C., Pandolfelli V.C. Role of catalytic agents and processing parameters in the graphitization process of a carbon-based refractory binder. Ceramics International. 2015;41(10-A):13320-13330. https://doi.org/10.1016/j.ceramint.2015.07.115.Yokokawa C., Hosokawa K., Takegami Y. A kinetic study of catalytic graphitization of hard carbon // Carbon. 1967. Vol. 5. Iss. 5. P. 475–480. https://doi.org/10.1016/0008-6223(67)90024-3.Yokokawa C., Hosokawa K., Takegami Y. A kinetic study of catalytic graphitization of hard carbon. Carbon. 1967;5(5):475-480. https://doi.org/10.1016/0008-6223(67)90024-3.Nugroho A., Nursanto E.B., Pradanawati S.A., Oktaviano H.S., Nilasary H., Nursukatmo H. Fe based catalysts for petroleum coke graphitization for Lithium Ion battery application // Materials Letters. 2021. Vol. 303. P. 130557. https://doi.org/10.1016/j.matlet.2021.130557.Nugroho A., Nursanto E.B., Pradanawati S.A., Oktaviano H.S., Nilasary H., Nursukatmo H. Fe based catalysts for petroleum coke graphitization for Lithium-ion battery application. Materials Letters. 2021;303:130557. https://doi.org/10.1016/j.matlet.2021.130557.Thompson E., Danks A.E., Bourgeois L., Schnepp Z. Iron-catalyzed graphitization of biomass // Green Chemistry. 2014. Vol. 17. No. 1. P. 551–556. https://doi.org/10.1039/C4GC01673D.Thompson E., Danks A.E., Bourgeois L., Schnepp Z. Iron-catalyzed graphitization of biomass. Green Chemistry. 2014;17(1):551-556. https://doi.org/10.1039/C4GC01673D.Фещенко Р.Ю., Ерохина О.О., Литаврин И.О., Рябошук С.В. Повышение окислительной стойкости графитированных электродов дуговых печей // Черные металлы. 2023. № 7. P. 31–36. https://doi.org/10.17580/chm.2023.07.03.Feshchenko R.Y., Erokhina O.O., Litavrin I.O., Ryaboshuk S.V. Improvement of oxidation resistance of arc furnace graphite electrodes. Chernye Metally. 2023;7:31-36. https://doi.org/10.17580/chm.2023.07.03.Notton G., Caluianu I., Colda I., Caluianu S. Influence d’un ombrage partiel sur la production électrique d’un module photovoltaïque en silicium monocristallin // Journal of Renewable Energies. 2010. Vol. 13. Iss. 1. С. 49–62. https://doi.org/10.54966/jreen.v13i1.177.Notton G., Caluianu I., Colda I., Caluianu S. Influence d’un ombrage partiel sur la production électrique d’un module photovoltaïque en silicium monocristallin. Journal of Renewable Energies. 2010;13(1):49-62. https://doi.org/10.54966/jreen.v13i1.177.Немчинова Н.В., Хоанг В.В., Апончук И.И. Изучение химического состава рафинировочных шлаков кремниевого производства для поиска путей их рациональной переработки // Вестник Иркутского государственного технического университета. 2021. Т. 25. № 2. С. 252–263. https://doi.org/10.21285/1814-3520-2021-2-252-263. EDN: ESAGII.Nemchinova N.V., Hoang V.V., Aponchuk I.I. Research into the chemical composition of refinery slag from silicon production for its efficient recycling. Proceedings of Irkutsk State Technical University. 2021;25(2):252-263. (In Russ.). https://doi.org/10.21285/1814-3520-2021-2-252-263. EDN: ESAGII.Bachmatiuk A., Börrnert F., Grobosch M., Schffel F., Wolff U., Scott A., et al. Investigating the graphitization mechanism of SiO2 nanoparticles in chemical vapor deposition // Acs Nano. 2009. Vol. 3. Iss. 12. P. 4098–4104. https://doi.org/10.1021/nn9009278.Bachmatiuk A., Börrnert F., Grobosch M., Schffel F., Wolff U., Scott A., et al. Investigating the graphitization mechanism of SiO2 nanoparticles in chemical vapor deposition. Acs Nano. 2009;3(12):4098-4104. https://doi.org/10.1021/nn9009278.Mochida I., Ohtsubo R., Takeshita K., Marsh H. Catalytic graphitization of graphitizable carbon by chromium, manganese and molybdenum oxides // Carbon. 1980. Vol. 18. Iss. 1. P. 25–30. https://doi.org/10.1016/0008-6223(80)90077-9.Mochida I., Ohtsubo R., Takeshita K., Marsh H. Catalytic graphitization of graphitizable carbon by chromium, manganese and molybdenum oxides. Carbon. 1980;18(1):25-30. https://doi.org/10.1016/0008-6223(80)90077-9.Mochida I., Ohtsubo R., Takeshita K., Marsh H. Catalytic graphitization of non-graphitizable carbon by chromium and manganese oxides // Carbon. 1980. Vol. 18. Iss. 2. P. 117–123. https://doi.org/10.1016/0008-6223(80)90019-6.Mochida I., Ohtsubo R., Takeshita K., Marsh H. Catalytic graphitization of non-graphitizable carbon by chromium and manganese oxides. Carbon. 1980;18(2):117-123. https://doi.org/10.1016/0008-6223(80)90019-6.Zhang Yude, Li Yan, Zhang Qian, Li Guangzhen. Graphitization of anthracite catalyzed by single metal oxides and its enhanced electrical conductivity // International Journal of Coal Preparation and Utilization. 2024. Vol. 44. Iss. 9. P. 1227–1245. https://doi.org/10.1080/19392699.2023.2270925.Zhang Yude, Li Yan, Zhang Qian, Li Guangzhen. Graphitization of anthracite catalyzed by single metal oxides and its enhanced electrical conductivity. International Journal of Coal Preparation and Utilization. 2024;44(9):1227- 1245. https://doi.org/10.1080/19392699.2023.2270925.Gomez-Martin A., Schnepp Z., Ramirez-Rico J. Structural evolution in iron-catalyzed graphitization of hard carbons // Chemistry of Materials. 2021. Vol. 33. Iss. 9. P. 3087–3097. https://doi.org/10.1021/acs.chemmater.0c04385.Gomez-Martin A., Schnepp Z., Ramirez-Rico J. Structural evolution in iron-catalyzed graphitization of hard carbons. Chemistry of Materials. 2021;33(9):3087-3097. https://doi.org/10.1021/acs.chemmater.0c04385.Wang Keliang, Cao Yuhe, Wang Xiaomin, Kharel P.R., Gibbons W., Luo Bing, et al. Nickel catalytic graphitized porous carbon as electrode material for high performance supercapacitors // Energy. 2016. Vol. 101. P. 9–15. https://doi.org/10.1016/j.energy.2016.01.059.Wang Keliang, Cao Yuhe, Wang Xiaomin, Kharel P.R., Gibbons W., Luo Bing, et al. Nickel catalytic graphitized porous carbon as electrode material for high performance supercapacitors. Energy. 2016;101:9-15. https://doi.org/10.1016/j.energy.2016.01.059.Ōya A., Ōtani S. Influences of particle size of metal on catalytic graphitization of non-graphitizing carbons // Carbon. 1981. Vol. 19. Iss. 5. P. 391–400. https://doi.org/10.1016/0008-6223(81)90064-6.Ōya A., Ōtani S. Influences of particle size of metal on catalytic graphitization of non-graphitizing carbons. Carbon. 1981;19(5):391-400. https://doi.org/10.1016/0008-6223(81)90064-6.Liu Yuanchao, Liu Qinglei, Gu Jiajun, Kang Danmiao, Zhou Fengyu, Zhang Wang, et al. Highly porous graphitic materials prepared by catalytic graphitization // Carbon. 2013. Vol. 64. P. 132–140. https://doi.org/10.1016/j.carbon.2013.07.044.Liu Yuanchao, Liu Qinglei, Gu Jiajun, Kang Danmiao, Zhou Fengyu, Zhang Wang, et al. Highly porous graphitic materials prepared by catalytic graphitization. Carbon. 2013;64:132-140. https://doi.org/10.1016/j.carbon.2013.07.044.Casado A., Torralba J.M., Milenkovic S. Wettability and infiltration of liquid silicon on graphite substrates // Metals. 2019. Vol. 9. Iss. 3. P. 300. https://doi.org/10.3390/met9030300.Casado A., Torralba J.M., Milenkovic S. Wettability and infiltration of liquid silicon on graphite substrates. Metals. 2019;9(3):300. https://doi.org/10.3390/met9030300.Roger J., Chollon G. Mechanisms and kinetics during reactive infiltration of molten silicon in porous graphite // Ceramics International. 2019. Vol. 45. Iss. 7-A. P. 8690–8699. https://doi.org/10.1016/j.ceramint.2019.01.191.Roger J., Chollon G. Mechanisms and kinetics during reactive infiltration of molten silicon in porous graphite. Ceramics International. 2019;45(7-A):8690-8699. https://doi.org/10.1016/j.ceramint.2019.01.191.Lewis I.C. Chemistry of pitch carbonization // Fuel. 1987. Vol. 66. Iss. 11. P. 1527–1531. https://doi.org/10.1016/0016-2361(87)90012-3.Lewis I.C. Chemistry of pitch carbonization. Fuel. 1987;66(11):1527-1531. https://doi.org/10.1016/0016-2361(87)90012-3.Cao Haiyue, Li Kuo, Zhang Hao, Liu Qinfu Investigation on the mineral catalytic graphitization of anthracite during series high temperature treatment // Minerals. 2023. Vol. 13. Iss. 6. P. 749. https://doi.org/10.3390/min13060749.Cao Haiyue, Li Kuo, Zhang Hao, Liu Qinfu Investigation on the mineral catalytic graphitization of anthracite during series high temperature treatment. Minerals. 2023;13(6):749. https://doi.org/10.3390/min13060749.Patel P., Hyland M., Hiltmann F. Influence of internal cathode structure on behavior during electrolysis part II: Porosity and wear mechanisms in graphitized cathode material // Light Metals / eds. A. Tomsett, J. Johnson. Сham: Springer, 2016. P. 1017–1022. https://doi.org/10.1007/978-3-319-48200-2_136.Patel P., Hyland M., Hiltmann F. Influence of internal cathode structure on behavior during electrolysis part II: Porosity and wear mechanisms in graphitized cathode material. In: Tomsett А., Johnson J. (eds.). Light Metals. Сham: Springer; 2016, p. 1017-1022. https://doi.org/10.1007/978-3-319-48200-2_136.Arnesen K., Aarhaug T.A., Einarsrud K.E., Tranell G.M. Influence of atmosphere and temperature on polycyclic aromatic hydrocarbon emissions from green anode paste baking // ACS Omega. 2023. Vol. 8. Iss. 20. P. 18116– 18121. https://doi.org/10.1021/acsomega.3c01411.Arnesen K., Aarhaug T.A., Einarsrud K.E., Tranell G.M. Influence of atmosphere and temperature on polycyclic aromatic hydrocarbon emissions from green anode paste baking. ACS Omega. 2023;8(20):18116-18121. https://doi.org/10.1021/acsomega.3c01411.Kim Changkyu, Kwon Woong, Lee Moon Hee, Woo Jong Seok, Jeong Euigyung. Correlation between Pitch Impregnation pressure and pore sizes of graphite block // Materials. 2022. Vol. 15. Iss. 2. P. 561. https://doi.org/10.3390/ma15020561.Kim Changkyu, Kwon Woong, Lee Moon Hee, Woo Jong Seok, Jeong Euigyung. Correlation between pitch impregnation pressure and pore sizes of graphite block. Materials. 2022;15(2):561. https://doi.org/10.3390/ma15020561.

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