Устойчивое извлечение высокочистого ванадия из отработанных ванадиевых катализаторов для применения в водородной энергетике

В статье приведены результаты исследований по переработке отработанных ванадийсодержащих катализаторов с извлечением пентаоксида ванадия и других соединений ванадия, носителя на основе четырехзамещенного кремния, позволяющего локализовать извлечение ванадиевых катализаторов для производства серной кислоты из вторичного сырья, а также предупредить загрязнение окружающей среды токсичными соединениями ванадия.
Проведен элементный анализ состава отработанных ванадиевых катализаторов (ОВК) и ИК-спектроскопические исследования твердого остатка, а также определен качественный и количественный фазовый состав продукта выщелачивания, полученного методом высаливания (определялся методом порошкового дифракционного анализа на дифрактометре).
Показано, что при использовании перекиси водорода в качестве окислителя, выщелачивание при более высокой температуре обладает преимуществами.
Установлено, что переработкой отработанных ванадийсодержащих катализаторов гидрометаллургическим способом раствором серной кислоты можно извлекать в раствор более 90 % ванадия и получить пятиокись ванадия высокой чистоты, пригодной для приготовления ванадиевого катализатора для получения водорода термохимическим разложением воды.

1. . Мухленов И. П., Добкина Е. И., Дерюшкина В. И., Сороко В. Е. Технология катализаторов. – Л., Химия, 1989, 272 с.

2. . American Environmental Protection Agency. Annual Report on the Environmental Impact of Catalysis and Waste Catalysis Management. – Washington, D. C.: U. S. EPA, 2020. – 132 p.

3. . U. S. Census Bureau. Global Trends in Automotive Industry Waste and Catalyst Recycling. – Washington, D. C.: U. S. Department of Commerce, 2021. – 110 p.

4. . Винаров И. В., Владимирова О. В., Починок И. В., Янкелевич Р. Г. Регенерация ценных компонентов отработанного катализатора окисления SO2-СВД // Комплексное использование минерального сырья. – 2019. – № 6 (168). – С. 77.

5. . Петров В. Н. Способы переработки отработанных ванадиевых катализаторов // Разное: химия. – 06.09.2016. – № 1473182646.

6. . Biswas R. K., Wakihara M., Taniguchi M. Recovery of vanadium and molybdenum from heavy oil desulphurization waste catalyst // Hydrometallurgy. – 1985. – № 14. – С. 219-230.

7. . Park K. H., Mohabatra B. R., Reddy. Selective recovery of molybdenum from spent HDS catalyst using oxidative soda ash leach/carbon adsorption method // Journal of Hazardous Materials. – 2006. – С. 311-316.

8. . Mihashi T., Motomura H., Takeuchi H. Recovering processes of valuable metals from spent petroleum hydrodesulphurization catalysts: Patent JP № 57022119. – 1982.

9. . Zeng L. A literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurization catalysts // Hydrometallurgy. – 2009. – Vol. 98, № 1-2. – Pp. 10-20.

10. . Parkinson G. S., Ishio. Recyclers try new ways to process spent catalyst // Chemical Engineering. – 1994. – № 1. – Pp. 25-31.

11. . Villarreal M. S., Kharisov B. I., Torres-Martinez L. M., Elizondo V. N. Recovery of vanadium and molybdenum from spent petroleum catalyst of PEMEX // Industrial & Engineering Chemistry Research. – 1999. – Pp. 4624-4628.

12. . Серегин А. Н. Рециклинг ванадия из отработанных катализаторов // Вторичные металлы. – 2008. – № 4. – С. 70-72.

13. . Сирина Т. П., Красненко Т. И. Технология переработки ОВК, получающихся при производстве серной кислоты // Тезисы докладов VII Всероссийского совещания, 16-20 сентября 1996 г., Пермская обл., г. Чусовой. – 1996. – С. 78.

14. . Ivam M. V., Jessica P., Julio C. A. Hydrometallurgical route to recover molybdenum, nickel, cobalt and aluminum from spent hydrotreating catalysts in acid medium // Journal of Hazardous Materials. – 2008.

15. . Gaballah I. M., Djona M. Recovery of Co, Ni, Mo and V from unroasted spent hydrorefining catalysts by selective chlorination // Metallurgical and Materials Transactions B. – 1995. – Vol. 26, № 1. – Pp. 41-50.

16. . Флейтлих И. Ю., Равдоникас И. В., Денисов В. В. Получение пятиокиси ванадия из отработанных ванадиевых катализаторов сернокислотного производства с применением экстракции // Сборник тезисов докладов Всесоюзного совещания «Исследования по технологии экстракционного разделения неорганических веществ», 1986. Апатиты. – С. 19-20.

17. . Garcia J., Lozano M., Vivancos D., Mulero. Leaching of vanadium from sulfuric acid manufacture spent catalysts // Rev. Met. CENIM. – 2001. – № 1. – Pp. 18-23.

18. . Молчанова Т. В., Овчаренко Е. В. Извлечение ванадия из руд: патент России № 2644720 // Бюл. изобр. – 2018.

19. . Винаров И. В., Янкелевич Р. Г., Владимирова О. В., Починок И. В. Способ извлечения V2O5 из отработанных ванадиевых катализаторов: патент России № 1162093 // Бюл. № 19. – 1981.

20. . Винаров И. В., Владимирова О. В., Починок Р. Г., Янкелевич Р. Г. Регенерация ценных компонентов отработанного катализатора окисления SO2-СВД // Комплексное использование минерального сырья. – 2013. – Т. 19, № 6 (168). – С. 77.

21. . Козлов В. А. Новые технологии в утилизации отработанных ванадиевых катализаторов // Электронный ресурс. – Режим доступа: ntokakz >jornal – 10 / Kozlov.doc. – 2004.

22. . Козлов В. А., Рабинович Е. М., Ахметова К. Ш. и др. Технология комплексной утилизации отработанных ванадиевых катализаторов сернокислотного производства // Тезисы докладов VII Всероссийского совещания (Международная конференция 16-21 сентября 1996 г.) «Химия, технология и применение ванадиевых соединений», г. Чусовой. – 1996. – С. 64.

23. . Жарский И. М., Орехова С. Е., Кирило И. И. Использование электрохимического метода для переработки дезактивированных ванадиевых катализаторов // Теория и практика современных электрохимических производств: сб. тез. докл. Том II. – СПб.: СПбГТИ (ТУ), 2010. – С. 20-21.

24. . Крышелович Е. В. и др. Интенсификация процесса выделения соединений ванадия из растворов выщелачивания ванадийсодержащих промышленных отходов // Тезисы докладов IV Международной конференции Рос. Хим. Общества им. Д. И. Менделеева «Химическая технология и биотехнология новых материалов и продуктов», 2012. – С. 202-203.

25. . Дадаходжаев А. Т., Халмухаммедов А. А., Салаватов Ф. Р., Хасанов У. Х. Способ выделения ванадия из отработанных катализаторов: патент № IAP 02915 // 2002.

26. . Петухов О. Ф., Каримов А. К., Тураев Ф. Э., Ашуров О. Т., Рузиев Б. Т. Разработка и опытно-промышленные испытания технологии получения пятиокиси ванадия из отработанных ванадиевых катализаторов // НГМК Горный журнал. – 2017. – № 1.

27. . Инфракрасная спектроскопия: прибор IR-Perkin Elmer, 2000 кВт · ч, США. – 2010.

28. . Рентгеновский порошковый дифрактометр XRD-6100. Shimadzu Corporation, Япония. – 2007.

29. . Bowen Li, Shefford P. Baker, Huahang Zhai, Sergio Neves Monteiro, Rajiv Soman, Faqin Dong, Zhinghong Li, Ruigang Wang. On vanadium oxide dissolution in Sodium carbonate solutions. Advances in Powder and Ceramic Materials Science. Springer. – 2020. – 178 p.

30. . Болотов А. Г., Сошников В. В. Способ приготовления ванадиевого электролита с использованием асимметричного электролизера: пат. RU 2251763 C2 Российская Федерация. №2003102140; заявл. 23.01.2003; опубл. 10.05.2005. – 6 с.

31. . Петухов О. Ф., Шмакина О. Ф., Очилова И. Д., Коваленко В. И. Исследования сорбции ванадия из сульфатных растворов // Горный вестник Узбекистана. – 2017. – Т. 68. – № 1. – С. 111-114.

32. . Дадаходжаев А. Т., Мураткулов О. К., Якибова Д. Х., Каримов А. К. «Опытно-промышленные испытания переработки отработанного ванадиевого катализатора (ОВК)». Tashkent international congress on modern sciences-III, Tashkent Chemical-Technological Institute, April 22-23, 2024, Tashkent.

33. . Kedelbayev B. Sh., Dadahodjaev A. T., Tashkazaev R. A. Resource-saving technology for processing of spent vanadium catalysts with vanadium pentoxide production and integrated utilization of secondary products // Journal of Ecological Engineering. – 2025; 26(11):258-268.

34. . Li Y., Tan X., Yang W., Bo X., Su Z., Zhao T., Smith S. C., Zhao C. Vanadium Oxide Clusters Decorated Metallic Cobalt Catalyst for Active Alkaline Hydrogen Evolution // Cell Rep. Phys. Sci. – 2020; 1:100275. 10.1016/j.xcrp.2020.100275.

35. . Devarayapalli K. C., Lee K., Do H. B., Dang N. N., Yoo K., Shim J., Prabhakar Vattikuti S. V. Mesostructured g-C3N4 Nanosheets Interconnected with V2O5 Nanobelts as Electrode for Coin-Cell-Type-Asymmetric Supercapacitor Device. Mater // Today Energy. – 2021; 21:100699. 10.1016/j.mtener.2021.100699.

36. . Javed M. S., Najim T., Hussain I., Batool S., Idrees M., Mehmood A., Imran M., Assiri M. A., Ahmad A., Ahmad Shah S. S. 2D V2O5 Nanoflakes as a Binder-Free Electrode Material for High-Performance Pseudocapacitor // Ceram. Int. – 2021; 47:25152-25157. 10.1016/j.ceramint.2021.05.181.

37. . Zhou P., Zhai G., Lv X., Liu Y., Wang Z., Wang P., Zheng Z., Cheng H., Dai Y., Huang B. Boosting the Electrocatalytic HER Performance of Ni3N-V2O3 via the Interface Coupling Effect // Appl. Catal., B. – 2021; 283:119590. 10.1016/j.apcatb.2020.119590.

38. . Peng Hu, Ping Hu, Tuan Duc Vu, Ming Li, Shancheng Wang, Yujie Ke, Xianting Zeng, Liqiang Mai, Yi Long. Vanadium Oxide: Phase Diagrams, Structures // Synthesis, and Applications. – 2023 Mar 27; 123(8):4353-4415. doi: 10.1021/acs.chemrev.2c00546

39. . Patricio González-Navarrete, Juan Andrés, Monica Calatayud. Can Supported Reduced Vanadium Oxides form H2 from CH3OH? A Computational GasPhase Mechanistic Study // The Journal of Physical Chemistry A. – 2017; 122:4.

40. . Ludivine K. Bidi, Alix Desjonquères, Guillaume Izzet, Geoffroy Guillemot. H2 Evolution at a Reduced Hybrid Polyoxometalate and Its Vanadium-Oxo Derivative Used as Molecular Models for Reducible Metal Oxides // Inorgani,Chemistry. – 2023;62 (5):1935-1941. https://doi.org/10.1021/acs.inorgchem.2c01741

41. . Боресков Г. К. Гетерогенный катализ. – М., Изд-во «Наука», 1989, 302 с.

42. . Дадаходжаев А. Т. и др. Разработка сернокислотного катализатора из отработанного ванадиевого катализатора // Экология и промышленность России. – 2023. – № 8. – Т. 27, с. 32-35.

43. . Патент РУз № IAP7744 «Способ приготовления катализатора». 30.04.2023 г.

44. . Патент РУз № IAP03097 от 22.06.2002. «Способ приготовления катализатора для конверсии оксида углерода».

45. . Hassan S. F., Smith J. Environmental and Health Effects of Vanadium Pentoxide // Environmental Research. – 2018. – Vol. 164. – Pр. 54-62.

46. . Adriano D. C. Trace Elements in Terrestrial Environments: Biogeochemistry, Bioavailability, and Risks of Metals. – Springer, 2001. – 866 p.

47. . Alloway B. J. Heavy Metals in Soils. – 2nd ed. – Glasgow: Blackie Academic & Professional, 1995. – 368 p.

48. . Barochová M., Uhlířová H., et al. Ecotoxicity of vanadium pentoxide and its accumulation in the aquatic food chain // Chemosphere. – 2014. – Vol. 112. – Pр. 27-33.

49. . Lamsal C.; Ravindra N. M. Vanadium Oxides: Synthesis, Properties, and Applications. In Semiconductors: Synthesis, Properties and Applications; Pech-Canul M. I., Ravindra N. M., Eds. // Springer International Publishing, 2019; pp 127-218.

50. . Патент RU 2080176 C1. Катализатор для окисления SO- в SO- / А. Т. Дадаходжаев и др. – Опубл. 20.05.1997. – Бюл. № 14. – 3 с.

51. . American Environmental Protection Agency. Annual Report on the Environmental Impact of Catalysis and Waste Catalysis Management. Washington, D. C.: U. S. EPA, 2020. – 132 p.

52. . U. S. Census Bureau. Global Trends in Automotive Industry Waste and Catalyst Recycling. – Washington, D. C.: U. S. Department of Commerce, 2021. – 110 p.

53. . Moskalyk R. R., Alfantazi A. M. Processing of Vanadium: a Review // Miner. Eng. – 2003; 16:793-805. 10.1016/S0892-6875(03)00213-9.

54. . Sutradhar M., Da Silva J. A. L., Pombeiro A. J. L. Chapter 1 Introduction: Vanadium, Its Compounds and Applications. In Vanadium Catalysis // The Royal Society of Chemistry. – 2021, pp 1-11.

55. . Langeslay R. R., Kaphan D. M., Marshall C. L., Stair P. C., Sattelberger A. P., Delferro M. Catalytic Applications of Vanadium: A Mechanistic Perspective // Chem. Rev. – 2019; 119:2128-2191. 10.1021/acs.chemrev.8b00245.

56. . Liu M., Su B., Tang Y., Jiang X., Yu A. Recent Advances in Nanostructured Vanadium Oxides and Composites for Energy Conversion // Adv. Energy Mater. – 2017; 7:1700885. 10.1002/aenm.201700885.

57. . Wu C., Xie Y. Promising Vanadium Oxide and Hydroxide Nanostructures: from Energy Storage to Energy Saving // Energy Environ. Sci. – 2010; 3:1191-1206. 10.1039/c0ee00026d.

58. . Kianfar E. Recent. Advances in Synthesis, Properties, and Applications of Vanadium Oxide Nanotube // Microchem. J. – 2019; 145:966-978. 10.1016/j.microc.2018.12.008.

59. . Wu C., Feng F., Xie Y. Design of Vanadium Oxide Structures with Controllable Electrical Properties for Energy Applications // Chem. Soc. Rev. – 2013; 42:5157-5183. 10.1039/c3cs35508j.

60. . McNulty D., Buckley D. N., O’Dwyer C. Synthesis and Electrochemical Properties of Vanadium Oxide Materials and Structures as Li-Ion Battery Positive Electrodes // J. Power Sources. – 2014; 267:831-873. 10.1016/j.jpowsour.2014.05.115.

61. . Armer C. F., Yeoh J. S., Li X., Lowe A. Electrospun Vanadium-Based Oxides as Electrode Materials // J. Power Sources. – 2018; 395:414-429. 10.1016/j.jpowsour.2018.05.076.

62. . Mounasamy V., Mani G. K., Madanagurusamy S. Vanadium Oxide Nanostructures for Chemiresistive Gas and Vapour Sensing: a Review on State of the Art. Microchim // Acta. – 2020; 187:253. 10.1007/s00604-020-4182-2.

63. . Livage J. Hydrothermal Synthesis of Nanostructured Vanadium Oxides // Materials. – 2010; 3:4175-4195. 10.3390/ma3084175.

64. . Artiglia L., Agnoli S., Granozzi G. Vanadium Oxide Nanostructures on Another Oxide: The Viewpoint from Model Catalysts Studies // Coord. Chem. Rev. – 2015; 301-302;106-122. 10.1016/j.ccr.2014.12.015.

65. . Zhu K., Wei S., Shou H., Shen F., Chen S., Zhang P., Wang C., Cao Y., Guo X., Luo M., Zhang H., Ye B., Wu X., He L., Song L., et al. Defect Engineering on V2O3 Cathode for long-Cycling Aqueous Zinc Metal Batteries // Nat. Commun. – 2021; 12:6878. 10.1038/s41467-021-27203-w.

66. . Corr S. A., Grossman M., Furman J. D., Melot B. C., Cheetham A. K., Heier K. R., Seshadri R. Controlled Reduction of Vanadium Oxide Nanoscrolls: Crystal Structure, Morphology, and Electrical Properties // Chem. Mater. – 2008; 20:6396-6404. 10.1021/cm801539f.

67. . Zhou C., Wu C., Liu D., Yan M. Cover Feature: Metal-Organic Framework Derived Hierarchical Co/C@V-O- Hollow Spheres as a Thin, Lightweight, and High-Efficiency Electromagnetic Wave Absorber // Chemistry – A European Journal. – 2019. – Vol. 25, No. 9. – https://doi.org/10.1002/chem.201900125

68. . Waltersson K., Forslund B., Wilhelmi K. -A., Andersson S., Galy J. The Crystal Structure of V3O7 // Acta. Crystallogr. B. – 1974; 30:2644-2652. 10.1107/S0567740874007722.

69. . An Q., Sheng J., Xu X., Wei Q., Zhu Y., Han C., Niu C., Mai L. Ultralong H2V3O8 Nanowire Bundles as a Promising Cathode for Lithium Batteries // New J. Chem. – 2014; 38:2075-2080. 10.1039/C3NJ01134H.

70. . Li C., Isobe M., Ueda H., Matsushita Y., Ueda Y. Crystal Growth and Anisotropic Magnetic Properties of V3O7 // J. Solid State Chem. – 2009; 182:3222-3225. 10.1016/j.jssc.2009.09.011.

71. . А. С. Хасанов, Б. Р. Вохидов, Г. Ф. Мамараимов. Разработка технологии получения ванадия из минерального и техногенного сырья // Universum: технические науки: электронный научный журнал. – 2022; 12(105):43-47.

72. . Винаров И. В., Владимирова О. В., Починок И. В., Янкелевич Р. Г. Регенерация ценных компонентов отработанного катализатора окисления SO2 – СВД // Комплексное использование минерального сырья. – 1992.– № 6(168). – С. 77.

73. . Г. Ф. Мамараимов, А. С. Хасанов, Б. Р. Вохидов. Извлечения ванадия из техногенных ресурсов // Universum: технические науки: электронный научный журнал. – 2022. – № 12(105). – C. 53-57.

74. . Винаров И. В. Регенерация ценных компонентов отработанного катализатора окисления SO2 – СВД [Текст] / И. В. Винаров, О. В. Владимирова, И. В. Починок, Р. Г. Янкелевич // Комплексное использование минерального сырья. – 1992. – № 6 (168). – С. 77.

75. . Vokhidov B. R., Kayumov O. A. & Mamaraimov G. F. Development technology for producing vanadium five oxide from mineral and technogenic raw materials // Sanoatda raqamli texnologiyalar. – 2023; 1(1):33-39.

76. . Xasanov A. S., Voxidov B. R. & Qayumov O. A. Mineral va texnogen xom ashyolardan vanadiy boyitmasini olish texnologiyasini ishlab chiqish // Oriental renaissance: Innovative, educational, natural and social sciences. – 2022; 2(9):319-326.

77. . Аймбетова И. О. Исследование кинетики сорбции оксида ванадия // Вестник НИА РК. – 2008. – Том 3. – С. 80-88.

78. . Вохидов Б. Р., Каюмов О. А. Исследование способа извлечения ванадия из техногенных отходов (ОВК-отработанный ванадиевый катализатор) // Universum: технические науки. – 2023; 10(115):13-18.

79. . Жарский И. М., Орехова С. И., Курило И. И., Крылишович Е. В. Восстановление ванадийсодержащих соединений в растворах выщелачивания // Химия и технология. – 2011. – Том 3. – С. 3-7.

80. . Жучков В. И., Алыбаев Ж. А., Бекенова Г. К., Джуманкулова С. К. Обзор состояния и перспектива развития ванадиевого производства в республике Казахстан // Металлург. – 2020. – Том 1. – С. 69-74.

81. . Nishant Beriwal, Lekha Sharma, Anil Verma. Powering a vanadium redox flow battery using spent vanadium catalyst: Extraction of direct-use V(IV)/V(III) vanadium precursors // Journal of Cleaner Production. – 2023. – Volume 429, 139568. https://doi.org/10.1016/j.jclepro.2023.139568.

82. . L. Cao et al. A review of electrolyte additives and impurities in vanadium redox flow batteries // J. Energy Chem. – 2018.

83. . G. Du et al. The nucleation kinetics of ammonium metavanadate precipitated by ammonium chloride // J. Cryst. Growth. – 2016.

84. . R. K. Gautam et al. Uniquely designed surface nanocracks for highly efficient and ultra-stable graphite felt electrode for vanadium redox flow battery // Mater. Chem. Phys. – 2020.

85. . R. Gilligan et al. The extraction of vanadium from titanomagnetites and other sources // Miner. Eng. – 2020.

86. . D. Lee et al. Recovery of vanadium and cesium from spent sulfuric acid catalysts by a hydrometallurgical process // Green Chem. – 2022.

87. . Nityanand Singh, Kedhareswara. Sairam Pasupuleti, Sruthi Ambili, Jaebeom Lee, Moon-Deock Kim, Jin-Young Lee. Sustainable vanadium recovery from SAM spent catalysts: A hydrometallurgical approach for high-purity V-O₅ production and gas sensing applications // Sustainable Materials and Technologies. – 15 July 2026. – Volume 48. – e01995. https://doi.org/10.1016/j.susmat.2026.e01995.

88. . Zarei-Jelyani M., Loghavi M. M., Babaiee M. et al. The significance of charge and discharge current densities in the performance of vanadium redox flow battery // Electrochim Acta. – 2023; 443:141922.

89. . S. Goldstein, X. Vitart. General comments about the efficiency of the iodinesulphur cycle coupled to a high temperature gas cooled reactor // Alternative Energy and Ecology (ISJAEE). – 2004. – № 3.

90. . Елагин Ю. П. Роль энергетики в водородной экономике // Атомная энергетика за рубежом. – 2006. – № 8.

91. . Miller A. I. Launching hydrogen // Nuclear Engineering International. – 2005, v. 50, No 612, pр. 16-19.

92. . Mehdi Mehrpooya, Roghayeh Habibi. A review on hydrogen production thermochemical water-splitting cycles // Journal of Cleaner Production. – 2020. – Volume 275, 123836. https://doi.org/10.1016/j.jclepro.2020.123836.

93. . Z. Abdin et al. Hydrogen as an energy vector. Renew // Sustain. Energy Rev. – 2020.

94. . C. Acar et al. Comparative assessment of hydrogen production methods from renewable and non-renewable sources // Int. J. Hydrogen Energy. – 2014.

95. . S. Bai et al. Experimental study on the purification of HIx phase in the iodine–sulfur thermochemical hydrogen production process // Int. J. Hydrogen Energy. – 2013.

96. . M. T. Balta et al. Energy and exergy analyses of magnesium-chlorine (Mg-Cl) thermochemical cycle // Int. J. Hydrogen Energy. – 2012.

97. . Yanpeng Mao, Yibo Gao, Wei Dong, Han Wu, Zhanlong Song, Xiqiang Zhao, Jing Sun, Wenlong Wang. Hydrogen production via a two-step water splitting thermochemical cycle based on metal oxide – A review // Applied Energy. – 2020; 267:114860. https://doi.org/10.1016/j.apenergy.2020.114860.

98. . A. Kogan. Direct solar thermal splitting of water and on site separation of the products. II. Experimental feasibility study // Int J Hydrogen Energy. – 1998.

99. . Jonathan R. Scheffe et al. Oxygen exchange materials for solar thermochemical splitting of H2O and CO2: a review // Mater Today. – 2014.

100. . Seyed Ehsan Hosseini et al. Hydrogen production from renewable and sustainable energy resources: Promising green energy carrier for clean development // Renew Sustain Energy Rev. – 2016.

101. . S. Abanades et al. Screening of water-splitting thermochemical cycles potentially attractive for hydrogen production by concentrated solar energy // Energy. – 2006.

102. . Y. Tadokoro et al. Technical evaluation of UT-3 thermochemical hydrogen production process for an industrial scale plant // Int J Hydrogen Energy. – 1997.

103. . E. D. Teo et al. A critical pathway energy efficiency analysis of the thermochemical UT-3 cycle // Int J Hydrogen Energy. – 2005.

104. . K. Damen et al. A comparison of electricity and hydrogen production systems with CO2 capture and storage. Part A: Review and selection of promising conversion and capture technologies. Progress in energy and combustion // Science. – 2006.

105. . Wu Zhou, Shuangjiang Li, Yang Yang, Jiachao Yao, Pengfei Chen, Jian Liu,Yang Wu, Zhi Li, Fangming Jin. Hydrogen production technologies from water decomposition: A review // Next Energy. – 2025; 8:100270. https://doi.org/10.1016/j.nxener.2025.100270.

106. . Z. Abdin, A. Zafaranloo, A. Rafiee, W. Mérida, W. Lipiński, K. R. Khalilpour. Hydrogen as an energy vector. Renew // Sustain. Energy Rev. – 2020; 120: 109620. 10.1016/j.rser.2019.109620.

107. . F. Safari, I. Dincer. A review and comparative evaluation of thermochemical water splitting cycles for hydrogen production // Energy Convers. Manag. – 2020; 205:112182. 10.1016/j.enconman.2019.112182.

108. . C. Hong, J. Ji, J. Huang, Y. Zhang, L. Li. NiMo/NiFe-LDH heterostructured electrocatalyst for hydrogen production from water electrolysis // Mater. Lett. – 2025; 379:137664. 10.1016/j.matlet.2024.137664.

109. . X. Zhang, S. H. Chan, H. K. Ho, S. -C. Tan, M. Li, G. Li, J. Li, Z. Feng. Towards a smart energy network: the roles of fuel/electrolysis cells and technological perspectives // Int. J. Hydrog. Energy. – 2015; 40:6866-6919. 10.1016/j.ijhydene.2015.03.133.

110. . M. A. Laguna-Bercero. Recent advances in high temperature electrolysis using solid oxide fuel cells: a review // J. Power Sources. – 2012; 203:4-16. 10.1016/j.jpowsour.2011.12.019.

111. . H. Liu, J. Høgh, P. Blennow, X. Sun, Y. Zong, M. Chen. Assessing fluctuating wind to hydrogen production via long-term testing of solid oxide electrolysis stacks // Appl. Energy. – 2024; 361:122938. 10.1016/j.apenergy.2024.122938.

112. . M. S. Khan, M. Abid, C. Chen, J. H. Zaini, T. Ratlamwala, A. A. Alqahtani Sustainable hydrogen storage and methanol synthesis through solar-powered Co-electrolysis using SOEC // Energy Storage. – 2024; 6:70095. 10.1002/est2.70095.

113. . J. E. Funk. Thermochemical hydrogen production: past and present // Int. J. Hydrog. Energy. – 2001; 26:185-190. 10.1016/S0360-3199(00)00062-8.

114. . O. Oruc, I. Dincer. Assessing the potential of thermo-chemical water splitting cycles: a bridge towards clean and sustainable hydrogen generation // Fuel. – 2021; 286:119325. 10.1016/j.fuel.2020.119325.

115. . Chengxi Wang, Hanqing Ni, Vincent Ji, Jilin Lei, Wei Deng, Peng Song, Taihong Huang, Xiaowei Zhang. Review: Vanadium pentoxide, based catalysts for photocatalytic water splitting // Journal of Materials Science. – 2026; 8.

116. . Tao Hai, Ammar. k. Alazzawi, Yongfeng Ju, Dan Wang, Suqi Wang. International Integration of vanadium-chlorine thermochemical cycle with a nano-particle aided solar power tower for power and hydrogen cogeneration // Journal of Hydrogen Energy. – 2024. – Volume 52, Part C. – Pages 580-593. https://doi.org/10.1016/j.ijhydene.2023.05.005.

117. . Al Amayreh H. H., Khalaf A., Hawwari M. I., Hourani M. K., Al Bawab A. The Recovery of vanadium pentoxide (V2O5) from spent catalyst utilized in a sulfuric acid production plant in Jordan // Materials. – 2023; 16(19):6503. https://doi.org/10.3390/ma16196503.

118. . Blum R. -P., Niehus H., Hucho C., Fortrie R., Ganduglia-Pirovano M. V., Sauer J., Shaikhutdinov S., Freund H. -J. Surface metal-insulator transition on a vanadium pentoxide (001) single crystal // Physical Review Letters. – 2007; 99(22):226103. https://doi.org/10.1103/PhysRevLett.99.226103.

119. . Chen X. -M., Li H. -Y., Wei C. -C., Cheng J., Diao J., Xie B., Pan F. Selective chemical etching of vanadium slag enables highly efficient and clean extraction of vanadium // ACS Sustainable Chemistry & Engineering. – 2025; 13(3):1327-1335. https://doi.org/10.1021/acssuschemeng.4c08516.

120. . Choi I. -H., Moon G., Lee J. -Y., Jyothi R. K. Extraction of tungsten and vanadium from spent selective catalytic reduction catalyst for stationary application by pressure leaching process // Journal of Cleaner Production. – 2018; 197:163-169. https://doi.org/10.1016/j.jclepro.2018.06.196.

121. . EL Hasbaoui N., EL Hadrami A., Essifi K., Assaoui J., Brahmi R. Recycling of spent catalysts used in sulfuric acid production // Moroccan Journal of Chemistry. – 2025; 13(1):405-423. https://doi.org/10.48317/IMIST.PRSM/MORJCHEM-V13I1.51501.

122. . . Elmaataouy E., Nahi H., Chari A., Bouzzite M., Alami J., Dahbi M. A Sustainable Recycling Route from Spent Sulfuric Acid Catalysts to Vanadium Pentoxide Precursor for the Production of Low-CostNa3V2(-PO4)3 @C Na‐Ion Batteries // ChemistrySelect. – 2024. – Vol. 9, No. 33. – e202402163. – https://doi.org/10.1002/slct.202402163

123. . Fu Z., He W., Rao Y., Du G., Wang N., Wang S. A highly selective and low-discharge method for vanadium extraction from vanadium slag: Low calcification roasting-sodium bicarbonate leaching // Separation and Purification Technology. – 2025; 361:131584. https://doi.org/10.1016/j.seppur.2025.131584.

124. . Guardiani M., Ozturk A. T., Ognyanova A., De Michelis I., Ferella F., Veglio F. (2007). Preliminary results of metal extraction from spent sulfuric acid catalyst by acid leaching. 7th International Scientific Conference on Modern Management of Mine Producing, Geology and Environmental Protection, SGEM 2007. https://www.scopus.com/inward/record.uri?eid=2-s2.0-84890291550&partnerID=40&md5=f440f949bfa810da0d8c1bae31176cb4

125. . Hugo Calderón & Diana Endara. Recovery of vanadium from acid and basic leach solutions of spent vanadium pentoxide catalysts // Journal of Geological Resource and Engineering. – 2016; 4(4). https://doi.org/10.17265/2328-2193/2015.04.006.

126. . Imtiaz M., Rizwan M. S., Xiong S., Li H., Ashraf M., Shahzad S. M., Shahzad M., Rizwan M., Tu S. (). Vanadium, recent advancements and research prospects: A review // Environment International. – 2015; 80:79-88. https://doi.org/10.1016/j.envint.2015.03.018.

127. . Ju Z. -J., Wang C. -Y., Yin F. Dissolution kinetics of vanadium from black shale by activated sulfuric acid leaching in atmosphere pressure // International Journal of Mineral Processing. – 2015; 138:1-5. https://doi.org/10.1016/j.minpro.2015.03.005.

128. . Kurniawan K., Kim S., Bae M., Lee H., Lee J. A review on the metallurgical recycling process of vanadium from secondary resources // Mineral Processing and Extractive Metallurgy Review. – 2024; 45(7):697-727. https://doi.org/10.1080/08827508.2023.2243007.

129. . Mazurek K. Recovery of vanadium, potassium and iron from a spent vanadium catalyst by oxalic acid solution leaching, precipitation and ion exchange processes // Hydrometallurgy. – 2013; 134-135:26-31. https://doi.org/10.1016/j.hydromet.2013.01.01.

130. . Mazurek K., Białowicz K., Trypuć M. Recovery of vanadium, potassium and iron from a spent catalyst using urea solution // Hydrometallurgy. – 2010; 103(1-4):19-24. https://doi.org/10.1016/j.hydromet.2010.02.008.

131. . Mikoda B., Potysz A., Kucha H., Kmiecik E. Vanadium removal from spent sulfuric acid plant catalyst using citric acid and Acidithiobacillus thiooxidans // Archives of Civil and Mechanical Engineering. – 2020; 20(4):132. https://doi.org/10.1007/s43452-020-00136-9.

132. . Nannan X., Yimin Z., Tao L., Jing H., Hong L., Fang C. Mechanism of vanadium extraction from stone coal via hydrating and hardening of anhydrous calcium sulfate // Hydrometallurgy. – 2016; 166:48-56. https://doi.org/10.1016/J.HYDROMET.2016.08.013.

133. . Nasimifar A., Mehrabani J. A review on the extraction of vanadium pentoxide from primary, secondary, and co-product sources // International Journal of Mining and Geo-Engineering, Online First. – 2022. https://doi.org/10.22059/ijmge.2022.319012.594893.

134. . Petranikova M., Tkaczyk A. H., Bartl A., Amato A., Lapkovskis V., Tunsu C. Vanadium sustainability in the context of innovative recycling and sourcing development // Waste Management. – 2020; 113:521-544. https://doi.org/10.1016/j.wasman.2020.04.007.

135. . Romanovskaia E., Romanovski V., Kwapinski W., Kurilo I. Selective recovery of vanadium pentoxide from spent catalysts of sulfuric acid production: Sustainable approach // Hydrometallurgy. – 2021; 200:105568. https://doi.org/10.1016/j.hydromet.2021.105568.

136. . Singh N., Kang H. -N., Jyothi R. K., Jha M. K., Pasupuleti K. S., Lee J. -Y. Hydrometallurgical approach to recover vanadium and aluminum from the sulfuric acid manufacturing spent catalyst // Mineral Processing and Extractive Metallurgy Review. – 2025; 1-12. https://doi.org/10.1080/08827508.2025.2456027.

137. . Singh N., Kumar Jyothi R., Pasupuleti K. S., Lee J. -Y. Recovery of aluminum, vanadium, and nickel from waste desulfurization catalyst residue by roasting and water leaching // Journal of Industrial and Engineering Chemistry. – 2025; 143:632-644. https://doi.org/10.1016/j.jiec.2024.09.011.

138. . Tarasov V. P., Gorelikov E. S., Zykova A. V., Petrunin K. O. Review of modern scientific developments in the field of extraction of vanadium oxide from petrochemical catalysts // NonFerrous Metals. – 2022; 27-31. https://doi.org/10.17580/nfm.2022.01.04.

139. . Vinco J. H., Romano Espinosa D. C., Soares Tenório J. A. Purification of vanadium-bearing solutions: A comprehensive review // Minerals Engineering. – 2025; 227. https://doi.org/10.1016/j.mineng.2025.109289.

140. . Wang B., Yang Q. Recovery of V2O5 from spent SCR catalyst by H2SO4 – ascorbic acid leaching and chemical precipitation // Journal of Environmental Chemical Engineering. – 2022; 10(6):108719. https://doi.org/10.1016/j.jece.2022.108719.

141. . Wu L., Dai C., Wang H., Wang J., Dong Y. Leaching of vanadium, potassium, and iron from spent catalyst of the manufacture of sulfuric acid // Journal of Materials Research and Technology. – 2021; 11:905-913. https://doi.org/10.1016/j.jmrt.2021.01.072.

142. . Yang, G., Wu, X., Guan, W., Fang, K., Wu, G., Zhang, G., Wang, M., Wu, S., Li, Q. Recovery of vanadium from high-iron chlorination titanium-white waste acid using D2EHPA/iso-octanol: From laboratory to pilot test // Chemical Engineering Journal. – 2024; 492:152030. https://doi.org/10.1016/j.cej.2024.152030.

143. . Tejeda-Iglesias M., Szuba J., Koniuch R. & Ricardez-Sandoval L. A. Optimization and modelling of an industrial-scale sulfuric acid plant under uncertainty // Ind. Eng. Chem. Res. – 2018; 57(24):8253-8266.

144. . Kuznetsova S. M., Dobkina E. I., Nefedova L. A. & Lavrishcheva S. A. Vanadium catalysts promoted with magnesium compounds for production of sulfuric acid // Russ. J. Appl. Chem. – 2002; 75:1816-1819.

145. . Marafi M. & Stanislaus A. Spent catalyst waste management: A review Part I – Developments in hydroprocessing catalyst waste reduction and use // Resour. Conserv. Recycl. – 2008; 52:859-873.

146. . Wahoud A. Sulfuric acid baking and leaching of spent sulfuric acid catalyst // Period. Polytech. Chem. Eng. – 2011; 55:31-34.

147. . Ossias R., Hale M. & Lindsay N. Federal register // Fed. Regist. – 2010; 75:56928-56935.

148. . Schlesinger W. H., Klein E. M. & Vengosh A. Global biogeochemical cycle of vanadium // Proc. Natl. Acad. Sci. – 2017. https://doi.org/10.1073/pnas.1715500114.

149. . Yuan R. et al. A critical review on extraction and refining of vanadium metal // Int. J. Refract. Met. Hard Mater. – 2021; 101:105696.

150. . Gao M., Xue X., Li L., Yang H. & Chen D. Leaching behavior and kinetics of vanadium extraction from vanadium-bearing steel slag // Metall. Res. Technol. – 2019; 116:407.

151. . Qian Y., Gallagher F. J., Feng H., Wu M. & Zhu Q. Vanadium uptake and translocation in dominant plant species on an urban coastal brown fi eld site // Sci. Total Environ. – 2014; 476-477:696-704.

152. . Romanovskaia E., Romanovski V., Kwapinski W. & Kurilo I. Surface metal-insulator transition on a vanadium pentoxide (001) single crystal // Hydrometallurgy. – 2022; 200:105568.

153. . Blum R. et al. Surface metal-insulator transition on a vanadium pentoxide (001) single crystal // Phys. Rev. Lett. – 2007; 99:226103.

154. . Wexler P., Judson R., De Marcellus S., De Knecht J. & Leinala E. Health effects of toxicants: Online knowledge support // Life Sci. – 2016; 145:284-293.

155. . Mohanty J., Rath P. C., Bhattacharya I. N. & Paramguru R. K. The recovery of vanadium from spent catalyst: A case study // Mineral Process. Extr. Metall. – 2011; 120:56.

156. . Erust C., Akcil A., Bedelova Z., Anarbekov K. & Baikonurova A. Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids: Laboratory and semi-pilot tests // Waste Manag. – 2016; 49:455-461.

157. . Aarabi-Karasgani M., Rashchi F., Mostou N. & Vahidi E. Leaching of vanadium from LD converter slag using sulfuric acid // Hydrometallurgy. – 2010; 102:14-21.

158. . Problems P. Leaching of zinc from low grade oxide ore // Physicochem. Probl. Mineral Process. – 2013; 49:547-555.

159. . Chen Y. et al. Green chemical engineering mild and efficient recovery of lithium-ion battery cathode material by deep eutectic solvents with natural and cheap components // Green Chem. Eng. – 2023; 4:303-311.

160. . Mazurek K. Hydrometallurgy recovery of vanadium, potassium and iron from a spent vanadium catalyst by oxalic acid solution leaching, precipitation and ion exchange processes // Hydrometallurgy. – 2013; 134-135:26-31.

161. . Mohanty C. et al. Citric acid mediated leaching kinetics study and comprehensive investigation on extraction of vanadium (V) from the spent catalyst // Sep. Purif. Technol. – 2021; 276:119377.

162. . 162. Kim C. J. et al. Leaching kinetics of lanthanum in sulphuric acid from rare earth element (REE) slag // Hydrometallurgy. – 2014; 146:133-137.

163. . 163. Meshram P., Pandey B. D. & Mankhand T. R. Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries // Waste Manag. – 2016. https://doi.org/10.1016/j.wasman.2015.12.018.

164. . Landau M. V., Vradman L. & Gedanken A. Ultrasonically controlled deposition – precipitation // J. Catal. – 2001; 36:22-36.

165. . Zeng L. & Cheng C. Y. Hydrometallurgy a literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurisation catalysts Part II: Separation and purification Hydrometallurgy a literature review of the recovery of molybdenum and vanadium from spent hydr // Hydrometallurgy. – 2009; 98:10-20.

166. . Mahandra H., Singh R. & Gupta B. Hydro-metallurgy recovery of vanadium (V) from synthetic and real leach solutions of spent catalyst by solvent extraction using Cyphos IL 104 // Hydrometallurgy. – 2020; 196:105405.

167. . Bal Y., Bal K., Cote G. & Lallam A. Characterization of the solid third phases that precipitate from the organic solutions of Aliquat R 336 after extraction of molybdenum (VI) and vanadium (V) // Hydrometallurgy. – 2004; 75:123-134.

168. . Padh B., Das M. & Reddy B. R. A roastleach process for the recovery of vanadium from vanadium-bearing gasifier slag (VBGS) using citric acid as a green reagent: Leaching studies and statistical analysis for sustainable processing // Hydrometallurgy. – 2023; 216:1-11.

169. . Tsaramyrsi M., Kavousanaki D., Raptopoulou C. P., Terzis A. & Salifoglou A. Systematic synthesis, structural characterization, and reactivity studies of vanadium (V)-citrate anions [VO2(C6H6O7)]2 2−, isolated from aqueous solutions in the presence of different cations // Inorg. Chim. Acta. – 2001; 320:47-59.

170. . Manaa E. -S. A., Kouraim M. N., Youssef M. A. M., Bakry A. R. & El-Desoky E. Hydrothermal leaching of nickel, uranium and the remaining vanadium from alkali treated boiler ash residue using citric acid // Egypt. J. Chem. – 2020; 63:2445-2455.

171. . Mirazimi S. M. J., Rashchi F. & Saba M. A new approach for direct leaching of vanadium from LD converter slag // Chem. Eng. Res. Des. – 2015; 94:131-140.

172. . Chen X., Lan X., Zhang Q., Ma H. & Zhou J. Leaching vanadium by high concentration sulfuric acid from stone coal // Trans. Nonferrous Met. Soc. China. – 2010; 20:123-126.

173. . Nazari E., Rashchi F., Saba M. & Mirazimi S. M. J. Simultaneous recovery of vanadium and nickel from power plant fly-ash: Optimization of parameters using response surface methodology // Waste Manag. – 2014; 34(12):2687-2696.

174. . Li Q., Liu Z. & Liu Q. Kinetics of vanadium leaching from a spent industrial V2O5/TiO2 catalyst by sulfuric acid // Ind. Eng. Chem. Res. – 2014; 53:2956-2962.

175. . Lai Y. D. & Liu J. C. Leaching behaviors of Ni and V from spent catalyst // J. Hazard. Mater. – 1997; 53(1-3):213-224.

176. . Wan J. et al. Direct leaching of vanadium from vanadium-bearing steel slag using NaOH solutions: A case study // Miner. Process. Extr. Metall. Rev. – 2020; 42(4):257-267.

177. . Rout P. C., Mishra G. K., Mohapatra D., Padh B. & Reddy B. R. Selective leaching and recovery of V as iron vanadate from industrially generated Mo-V residue // Trans. Nonferrous Met. Soc. China. – 2018; 28:2368-2374.