Method of Obtaining of Metal Oxide Anodes That Do Not Contain Noble Metals

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DOI https://doi.org/10.15407/pmach2022.04.046
Journal Journal of Mechanical Engineering – Problemy Mashynobuduvannia
Publisher A. Pidhornyi Institute for Mechanical Engineering Problems
National Academy of Science of Ukraine
ISSN  2709-2984 (Print), 2709-2992 (Online)
Issue Vol. 25, no. 4, 2022 (December)
Pages 46-57
Cited by J. of Mech. Eng., 2022, vol. 25, no. 4, pp. 46-57

 

Authors

Volodymyr H. Mykhailenko, A. Pidhornyi Institute of Mechanical Engineering Problems of NASU (2/10, Pozharskyi str., Kharkiv, 61046, Ukraine), e-mail: port342017@gmail.com, ORCID: 0000-0003-3082-6148

Oleksii V. Antonov, A. Pidhornyi Institute of Mechanical Engineering Problems of NASU (2/10, Pozharskyi str., Kharkiv, 61046, Ukraine), ORCID: 0000-0001-6319-535X

Olha I. Lukianova, A. Pidhornyi Institute of Mechanical Engineering Problems of NASU (2/10, Pozharskyi str., Kharkiv, 61046, Ukraine), ORCID: 0000-0001-7235-7293

Yevhen F. Lukianov, A. Pidhornyi Institute of Mechanical Engineering Problems of NASU (2/10, Pozharskyi str., Kharkiv, 61046, Ukraine), ORCID: 0000-0001-8839-091X

Oleksandr Ye. Khinievich, A. Pidhornyi Institute of Mechanical Engineering Problems of NASU (2/10, Pozharskyi str., Kharkiv, 61046, Ukraine), ORCID: 0000-0003-1902-534X

Tamara S. Vitkovska, A. Pidhornyi Institute of Mechanical Engineering Problems of NASU (2/10, Pozharskyi str., Kharkiv, 61046, Ukraine), ORCID: 0000-0001-6890-0441

 

Abstract

In the mining and industrial regions of Ukraine, a large amount of mine and quarry waters is formed. Due to high mineralization, they cannot be discharged into natural hydrographic objects without deep processing, including demineralization. Most of such waters are significantly contaminated with concentrates of sulfides and dissolved iron compounds, which hinder their further purification. At the same time, thermal power plants located in these regions consume a significant amount of scarce drinking water for their needs. Deep processing of mine and quarry waters allows to clean them and obtain feed water for heating systems, boilers of TPPs and CHPs. A method of obtaining stable inert titanium-based anodes with an active coating of PbO2, which do not contain noble metals and their compounds, has been developed. The method consists in protecting titanium from passivation with an oxide film by thermally applying a MnO2 coating, and later applying to the base with this coating a thin layer of PbO2 from an alkaline complex electrolyte containing 2.5 mol/dm3 NaOH, 0.6 mol/dm3 EDTA, ethylene glycol additive and is a saturated PbO. The main 3–5 mm thick layer of coating is applied from the nitrate electrolyte, which includes Pb(NO3)2 1 mol/dm3, Cu(NO3)2 0.4 mol/dm3, Al(NO3)3 0.2 mol/dm3 and the gelatin additive. A method of extending the service life of an alkaline electrolyte by reduction of Pb (IV) compounds during the contact with the active surface of metallic plumbum is described. The conducted resource tests of this anode for 1400 hours proved its stability when processing solutions containing a mixture of sodium sulfate and sodium chloride. On the basis of this anode, the technology of electrochemical deironing of mine waters and removal of sulfides from them before demineralization was developed and experimentally tested. This technology is the only possible method of reagent-free iron removal and removal of sulfides from waters with high mineralization. Such anodes significantly expand the scope of application of electrochemical processes. They can be used not only for water treatment in thermal power generation, but also for the treatment of wastewater of various mineral and organic composition, chemical and technological processes for obtaining oxidants, etc.

 

Keywords: inert anodes, PbO2, MnO2, removal of iron and sulfides, water treatment, purification of mine and quarry waters.

 

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References

  1. Mykhaylenko, V., Yurchenko, V., Antonov, O., Lukianova, O., & Gil, Z. (2021). Advanced technologies for processing liquid waste of galurgical productions environmental problems. Environmental Problems, vol. 6, no. 1, pp. 1–6. https://doi.org/10.23939/ep2021.01.001.
  2. Slesarenko, O. A., Zharskiy, I. M., Letsko, V. V., & Voropayev, L. Ye. (1990). Sposob izgotovleniya anoda s pokrytiyem iz dioksida margantsa [Method for manufacturing an anode coated with manganese dioxide]: Certificate of authorship SU 1546516. Published on 02/28/1990 (in Russian).
  3. Kebadze, Zh. M., Dzhaparidze, L. N., Pruidze, V. P., Dinkevich, F. E., Kalinovskiy, Ye. A., Chakhunashvili, T. A., & Kakuriya, L. Sh. (1993). Sposob izgotovleniya titan-dioksidnomargantsevogo anoda dlya proizvodstva elektroliticheskogo dioksida margantsa [Method for manufacturing a titanium-manganese dioxide anode for the production of electrolytic manganese dioxide]: RF patent no. 1788088. Published on 01/15/1993 (in Russian).
  4. Kokarev, G. A., Bobrin, S. V., Kodintsev, I. M., Mikhaylov, V. V., Abramchuk, A. P., Mazanko, V. F., Falchenko, V. M., Mazanko, A. F., Lvovich, F. (1999). Sposob izgotovleniya anoda dlya elektroliticheskogo polucheniya dioksida margantsa [A method of manufacturing an anode for the electrolytic production of manganese dioxide]: RF patent no. 1426144. Published on 07/10/1999 (in Russian).
  5. Smirnitskaya, I. V. (2010). Polucheniye metallooksidnogo elektroda na osnove oksidov kobalta, margantsa i nikelya [Obtaining a metal oxide electrode based on oxides of cobalt, manganese and nickel]: Ph.D. dissertation. South Russian State Technical University (Novocherkassk Polytechnic Institute), Novocherkassk, 15 p. (in Russian).
  6. Dzhaparidze, L. N., Chakhunashvili, T. A., Kalinovskiy, Ye. A., Kebadze, Zh. M., Dinkevich, F. E., Kervalishvili, Z. Ya., Rossinskiy, Yu. K., Grinberg, N. V., Rokva, T. V., Strikha, E. M., Drozdenko, V. A., & Bogdanov, E. A. (1991). Sposob izgotovleniya anoda dlya elektroliticheskogo polucheniya dioksida margantsa [A method of manufacturing an anode for the electrolytic production of manganese dioxide]: Certificate of authorship SU 1661247. Published on 07/07/1991 (in Russian).
  7. Kladiti, S. Yu. (2015). Elektroosazhdeniye oksidnykh materialov, modiffitsirovannykh soyedineniyami molibdena (VI) i ikh funktsionalnyye svoystva [Electrodeposition of oxide materials modified with molybdenum (VI) compounds and their functional properties]: Ph.D. dissertation. Russian University of Chemical Technology named after D. I. Mendeleev, Moscow, 121 p. (in Russian).
  8. Devilliers, D., Dinh, T. M. T., Mahe, E., & Xuan, L. (2003). Preparation and use of Ti/PbO2 anodes for the oxidation of Cr(III). https://www.electrochem.org/dl/ma/203/pdfs/2271.pdf.
  9. Shmychkova, O.B., Luk’yanenko, T. V., Amadelli, R., & Velichenko, A. B. (2017). The electrochemical oxidation of 4-nitroaniline and 4-nitrophenol on modified PbO2-electrodes. Bulletin of Dnipropetrovsk University. Series Chemistry, vol. 25, iss. 1, pp. 27–35. https://doi.org/10.15421/081705.
  10. Sauer, L., Kralik, D., Izak, P., Slouka, Z., & Pribyl, M. (2022). Effects of aqueous systems and stabilization membranes on the separation of an antibiotic precursor in a microextractor. Separation and Purification Technology, vol. 292, paper ID 121050. https://doi.org/10.1016/j.seppur.2022.121050.
  11. Tong, S., Zhang, T., & Ma, C. (2008). Oxygen evolution behavior of PTFE-F-PbO2 electrode in H2SO4 solution. Chinese Journal of Chemical Engineering, vol. 16, iss. 6, pp. 885–889. https://doi.org/10.1016/S1004-9541(09)60011-2.
  12. Grimmig, R., Gillemot, P., Stucki, S., Gunther, K., Baltruschat, H., & Witzleben, S. (2022). Operating an ozone-evolving PEM electrolyser in tap water: A case study of water and ion transport. Separation and Purification Technology, vol. 292, paper ID 121063. https://doi.org/10.1016/j.seppur.2022.121063.
  13. Wang, Y.-H. & Chen, Q. -Y. (2013). Anodic materials for electrocatalytic ozone generation. International Journal of Electrochemistry, vol. 2013, article ID 128248. https://doi.org/10.1155/2013/128248.
  14. Girenko, D. V. & Gruzdeva, Ye. V. (2011). Fiziko-khimicheskiye svoystva dioksida svintsa, osazhdennogo iz metansulfonatnogo elektrolita [Physical and chemical properties of plumbum dioxide deposited from methanesulfonate electrolyte]. Voprosy khimii i khimicheskoy tekhnologii – Issues of Chemistry and Chemical Technology, no. 4 (1), pp. 1239–132 (in Russian).
  15. Antonov, O. V., Mykhailenko, V. H., & Tulskyi, H. H. (2008). Vdoskonalennia tekhnolohii oderzhannia pliumbum dvooksydnoho pokryttia z luzhnykh elektrolitiv [Improvement of the technology of obtaining plumbum dioxide coating from alkaline electrolytes]. Visnyk Kharkivskoho natsionalnoho tekhnichnoho universytetu «KhPI». Tematychnyi vypusk: Khimiia, khimichna tekhnolohiia i ekolohiia – Bulletin of Kharkiv National Technical University “KhPI”. Thematic issue: Chemistry, chemical technology and ecology, no. 16, pp. 8–11 (in Russian).
  16. Dzhafarov, E. A. (1967). Elektroosazhdeniye, svoystva i primeneniye dvuokisi svintsa [Electrodeposition, properties and application of plumbum dioxide]. Baku: Publishing House of the Academy of Sciences of the Azerbaijan SSR, 101 p. (in Russian).

 

Received 26 October 2022

Published 30 December 2022