Satbayev University, Institute of Metallurgy and Ore Beneficiation, Almaty, Kazakhstan:

A. S. Sharipova, Senior Researcher, Candidate of Technical Sciences, e-mail: a_sharipova@mail.ru
K. A. Linnik, Engineer
A. N. Zagorodnyaya, Principal Researcher, Doctor of Technical Sciences
N. Bakhytuly, Junior Researcher

This paper examines the process of selenium precipitation from the slime generated by the sulphuric acid plant of the Balkhash Copper Smelter. Contrary to similar tailings generated by non-ferrous metals industry, such slime has a high concentration of selenium (12.5–4.6 wt. %). By utilizing it in the production process, one can raise the output of selenium by more than 30% compared with the amount of selenium recovered by the smelter from copper anode slimes. The slime that was used in the experiments had been separated from the slurry produced as a result of scrubbing of metallurgical gases generated by copper smelting and matte converting processes. The slime was rinsed with water to remove sulphuric acid from it and then dried at 105 ^oC. With the help of new-generation analytical equipment, the slime was analyzed for qualitative, quantitative and material compositions. 15 elements with significantly varying concentrations were detected. The main components include lead (51.17 wt. %) and selenium (12.49 wt. %), which are present in the form of lead sulphates and elemental selenium. Other lead and mercury compounds are also present as disseminations – i.e. different salts of selenium acids. Considering the forms in which lead and selenium are mainly found in the slime, lead was initially converted into carbonates by sodium carbonate leaching, and then nitric acid was used to make lead transfer from the cake into the solution. The authors looked at the effect produced by the sodium carbonate concentration (50–200 g/dm³), solid-to-liquid ratio (1:(2–6)), process duration (20–120 min) and temperature (20–70 ^oC) at constant slime feed and stirrer RPM on the behaviour of lead and selenium. Optimum conditions were identified in which both elements almost completely remain in the carbonate cake, and only 0.019% Pb and 0.17% Se get extracted into the solution. Different quantities of three carbonate-containing compounds of lead and seven selenium compounds were found in the cake. When the carbonate cake is leached with nitric acid, almost all of the lead transfer to the solution, while selenium remains in the cake as an elementary substance and mercury selenides. As compared with the slime, the concentration of selenium in the cake increased by 5.6 times.
This research was funded by the Science Board of the Ministry of Science and Education of the Republic of Kazakhstan under the following programme: Development and Implementation of Innovative Technology Ensuring a Higher Recovery of Non-Ferrous, Noble, Rare and Rare Earth Metals, as well as Fulfillment of Production Targets by Industrial Companies of the Republic of Kazakhstan Set for 2018–2020.

1. Zagorodnyaya A. N. Slime from sulfuric acid shop of Balkhash coppersmelting factory – alternative source for production of selenium at the enterprise. Review. Kompleksnoe ispolzovanie mineralnogo syrya. 2018. No. 4. pp. 46–53. DOI: 10.31643/2018/6445.29.
2. Kulchitskiy N. A., Naumov A. V. Current status of the market of selenium and selenium-based compounds. Izvestiya vuzov. Tsvetnaya metallurgiya. 2015. No. 3. pp. 43–47.
3. Global and Russian selenium and tellurium market 2018. Available at: https://www.metalresearch.ru/pdf/World_Rus_Se_Te_mark.pdf
4. Kenzhaliev B. K., Trebukhov S. A., Volodin V. N. et al. Selenium extraction out of metallurgical production middlings. Kompleksnoe ispolzovanie mineralnogo syrya. 2018. No. 4. pp. 56–64. DOI: 10.31643/2018/6445.30.
5. Khrapunov V. E., Trebukhov S. A., Marki I. A. et al. Selenium recovery from slime of sulfuric acid production by vacuum method. Kompleksnoe ispolzovanie mineralnogo syrya. 2014. No. 4. pp. 42–48.
6. Kenzhaliyev B. K., Trebukhov S. A., Nitsenko A. V. et al. Determination of technological parameters of selenium recovery from metallurgical production middlings in a vacuumdistillation unit. International Journal of Mechanical and Production Engineering Research and Development (IJMPERD). 2019. Vol. 9, Iss. 6. pp. 87–98.

7. Karelov S. V., Mamyachenkov S. V., Naboychenko S. S. et al. Comprehensive processing of lead-tin cakes. Tsvetnye Metally. 1994. No. 2. pp. 17–20.
8. Karelov S. V., Mamyachenkov S. V., Naboychenko E. S. Copper smelter wastes and their prospective recycling. Tsvetnye Metally. 2000. No. 9. pp. 47–49.
9. Chinkin V. B., Kozlov P. A. Extraction of lead from lead cakes obtained as a result of Waelz oxide processing: Process analysis. Tsvetnaya metallurgiya. 2001. No. 10. pp. 21–23.
10. Tarasov A. V., Beser A. D., Chinkin E. V. A study aimed at developing a process to recycle lead cakes while recovering lead, zinc, copper and precious metals. Tsvetnaya metallurgiya. 2002. No. 10. pp. 26–32.
11. Karelov S. V., Sergeev V. A., Mamyachenkov S. V., Anisimova O. S. Purification of lead trilonate solutions while recovering the solvent. Tsvetnaya metallurgiya. 2008. No. 3. pp. 13–16.
12. Karelov S. V., Sergeev V. A., Panshin A. M. et al. Hydrometallurgical technology for processing of lead cakes of zinc production using complex-forming reagents. Tsvetnye Metally. 2009. No. 6. pp. 29–31.
13. Mamyachenkov S. V., Anisimova O. S., Sergeev V. A., Karelov S. V. Alternative hydrometallurgical processing of lead-containing middlings. Proceedings of the 2 nd International Congress “Non-Ferrous Metals – 2010”. Krasnoyarsk, 2-4 September 2010. pp. 206–213.
14. Tarasov A. V. Metallurgical processing of secondary lead material. Moscow : Gintsvetmet, 2003. 224 p.
15. Areshina N. S., Kasikov A. G., Malts I. E. Understanding the possibility to obtain additional selenium products from copper-nickel middlings and waste. Proceedings of the National Science Conference with International Participants “Research and Developments in the Area of Chemistry and Technology of Functional Materials”. Apatity, 2010. pp. 27–29.
16. Kasikov A. G., Areshina N. S., Malts I. E. Hydrometallurgical processing of copper-nickel smelter gas scrubbing waste. Proceedings of the 2^nd International Congress “Non-Ferrous Metals – 2010”. Krasnoyarsk, 2–4 September 2010. pp. 721–727.
17. Areshina N. S., Kasikov A. G., Malts I. E., Zenkevich T. R. Selenium recovery from scrubbing gas products at the Kola Mining and Metallurgical Company JSC. Tsvetnye Metally. 2011. No. 11. pp. 62–65.
18. Zagorodnyaya A. N., Linnik K. A., Sharipova A. S., Akchulakova S. T. Preparation of slime from the sulphuric acid plant of the Balkhash Copper Smelter for the study of the material composition of selenium. Khimicheskaya tekhnologiya. 2019. No. 10. pp. 462–468. DOI: 10.31044/1684-5811-2019-20-10-462–468.
19. Abisheva Z. S., Zagorodnyaya A. N., Bukurov T. N. et al. Comprehensive processing of copper-sulfide ores resulting in the production of rare metal concentrates. Proceedings of the XXI International Mineral Processing Congress. Rome, Italy, July 2000. Vol. B. pp. 1022–1029.
20. Abisheva Z. S., Zagorodnyaya A. N., Sharipova A. S. et al. Comprehensive processing of lead slimes generated by the copper industry. Tsvetnye Metally. 2002. No. 3. pp. 33–36.
21. Bukurov T. N., Abisheva Z. S., Zagorodnyaya A. N. et al. Comprehensive processing of copper sulphide ores to produce rare metal concentrates. Vestnik KazNRTU. 2002. No. 5. pp. 176–177.
22. Abisheva Z., Zagorodnyaya A., Bukurov T. et al. The recovery of rhenium and radiogenic osmium from copper processing by-products. Proceedings of the Copper-Cobre 2003 5-th International Conference. Santiago, Chile, 30 November – 3 December 2003. Vol. VI, Book 2. pp. 645–657.
23. GOST 5100–85. Technical soda ash. Specifications. Introduced: 01.01.1986.
24. GOST 4461–77. Reagents. Nitric acid. Specifications. Introduced: 01.01.1979.
25. Nakomoto K. Infrared and Raman spectra of inorganic and coordination compounds. New York : John Wiley and Sons, 2009. p. 419.
26. Silverstein R., Bassler G., Morrill T. Spectrometric identification of organic compounds. Moscow : Mir, 1977. 592 p.
27. Farmer V. C. The Infrared spectra of minerals. London : Mineralogical society, 1974. 539 р.
28. Kazitsyna L. A., Kupletskaya N. B. Application of UV, IR and NMR spectroscopy in organic chemistry. Moscow : Vysshaya shkola, 1971. 264 p.
29. Bolshakov G. F., Glebovskaya E. A., Kaplan Z. G. Infrared spectra and X-ray diffraction patterns of heterorganic compounds. Leningrad : Khimiya, 1967. 168 p.
30. Moenke H. Mineralspektren. Berlin : Academie Verlag, 1962. 394 р.
31. HR Aldrich FT-IR Collection Edition II. Available at: https://www.thermofisher.com/order/catalog/product/834-016201#/834-016201 (Accessed: 08.04.2021).
32. Sharipova A. S. Comprehensive processing of lead dusts generated by the copper industry to produce ammonium perrhenate and non-ferrous metal compounds: Extended abstract of PhD thesis. Almaty, 2009. 22 p.