Mendeleev University of Chemical Technology of Russia, Moscow, Russia

V. A. Brodskiy, Associate Professor of the Department of Technology of Inorganic Substances and Electrochemical Processes, Candidate of Chemical Sciences, e-mail: brodskii.v.a@muctr.ru
I. S. Maksimov, postgraduate student of the Department of Technology of Inorganic Substances and Electrochemical Processes, e-mail: vanyamaks@mail.ru
D. Yu. Zhukov, Director of Ecokhimproject Technological Center, Candidate of Technical Sciences, e-mail: zhukov.d.i@muctr.ru
A. V. Kolesnikov, Acting Head of the Department of Technology of Inorganic Substances and Electrochemical Processes, Associate Professor, Candidate of Technical Sciences, e-mail: kolesnikov.a.v@muctr.ru

The article describes an X-ray fluorescence analysis conducted to study a composition of bronze production slag from copper melting. Copper content is up to 48.742% at., zinc content is 33.405% at. The authors optimized the parameters of bronze slag leaching with a sulfuric acid concentration of 0.1 mol/l. After sulfuric leaching a copper cake underwent copper-ammonia leaching, and copper-chloride pickling (period: 20–40 minutes, copper limit concentration: 35.0–55.5 g/l, respectively). Copper extraction from leaching solutions was conducted using extraction solvents D2EGFK, DKh-510A, LIX 54-I at their concentration of 50–100%. The article compares efficiency of extraction processes for copper-ammonia and copper-chloride solutions. In both cases, the highest efficiency was attributed to extraction agents LIX-54-I with a concentration of 50% in kerosene, included into the class of β-diketones and containing 1-phenyl-decan-1,3-dione isomers with various structures of the alkyl group. Subsequent electroextraction of copper from the resulting re-extracting solutions was conducted at set optimal cathode current density (ik) of 0.6 A/dm², maximum current copper yield achieved 65%. Thus, the article presents the determined optimal conditions for extracting copper and zinc from bronze production dust and slag by electrochemical and extraction methods and describes the opportunity to use pickling solutions, extraction solvents and sulfuric acid electrolyte as reusable solutions.

1. The Russian Academy of Sciences. Scientific and technical aspects of environment protection. Review. VINITI. 2020. No. 6. 122 p.
2. V. V. Panin, D. Yu. Voronin, L. N. Krylova, Yu. S. Karabasov. Method of processing of sulphide-oxidised copper ores. Patent RF, No. 2337159, C1. IPC C22B 15/00, C22B 3/08. Applied: 16.04.2007. Published: 27.10.2008. 6 p.
3. Dave nport W. G., King M., Schlesinger M., Biswas A. K. Extractive metallurgy of copper. Pergamon, 2002. 434 p.
4. Steblevskaya N. I., Medokov M. A., Belobeletskaya M. V., Smolkov A. A. et al. Liquid-liquid extraction in hydrometallurgy and technology of inorganic materials production. Vestnik DVO RAN. 2006. No. 5. p. 38.
5. Altushkin I. A., Cherepovitsyn A. E., Korol Yu. A. Practical implementation of the sustainable development mechanism in establishing and forming the mining and metallurgical holding of the copper industry in Russia. Moscow: Ore and Metals Publishing House, 2016. 227 p.
6. Sele znev A. I., Balinov S. V., Emelyanov Yu. E., Shketova A. E. et al. Assessing the opportunity of extracting copper and nickel from sulphide products by a heap bacterial leaching method. Prospects for development of the processing technology for hydrocarbon, plant and mineral resources : Proceedings of the 4^th All-Russian Scientific and Practical Conference with International Participation (Irkutsk, 24–25 April 2014). Irkutsk : IrGTU, 2014. pp. 13, 14.
7. Martirosyan V. A., Lisovskaya Yu. O., Sasuntsyan M. E. A comprehensive mineralogical study on copper and molybdenum slag from operating metallurgical plants of Armenia. Vestnik gosudarstvennogo inzhenernogo universiteta Armenii (politekhnik). Seriya: Khimicheskie i prirodookhrannye tekhnologii. 2014. Vol. 17, No. 1. pp. 86–95.
8. Kordosky G. A. Copper recovery using leach/solvent extraction/electrowinning technology: Forty years of innovation, 2.2 million tonnes of copper annually. Journal of the Southern African Institute of Mining and Metallurgy. 2002. Vol. 102, No. 8. pp. 853–862.
9. Travkin V. F., Dilman S. V., Solodov A. I. Separation of emulsion in mixingsettling facilities for copper extraction. Tsvetnye Metally. 1983. No. 6. pp. 24.
10. Laskori n B. N., Popov I. F., Ulyanov B. C. Copper extraction from heap leaching solutions. II Extraction and sorption in non-ferrous metallurgy : Transactions. Alma-Ata : Nauka, 1975. pp. 16–21.
11. Pradhan S., Mishra S. A review on extraction and separation studies of copper with various commercial extractants. Metall. Res. Technol. 2015. Vol. 112. 202.
12. Reddy B. R., Rao S. V., Park K. H. Solvent extraction separation and recovery of cobalt and nickel from sulphate medium using mixtures of TOPS 99 and TIBPS extractants. Miner. 2009. Vol. 22, No. 5. pp. 500–505.
13. Agrawal A ., Kumari S., Manoj M. K., Pandey B. D. et al. Separation and recovery of copper and nickel from copper bleed stream by solvent extraction route. Proceedings of the International Symposium on Solvent Extraction. Bhubaneswar, 2002. pp. 26, 27.
14. Aluguacil F. J. Recovery of copper from ammoniacal ammonium sulfate medium by LIX 54. Journal of Chemical Technology and Biotechnology. 1999. Vol. 74, No. 12. pp. 1171–1175.
15. Mickler W. The characterization of the active components in commercial-diketone-type extractants LIX 54 and MX 80. Separation Science and Technology. 1992. Vol. 27, No. 89. pp. 1171–1179.
16. Dziwinski E. Composition of copper extractant LIX 54-100. Solvent Extraction and Ion Exchange. 1996. Vol. 14, No. 2. pp. 219–226.
17. Zapatero M. J. Isolation and characterization of the active component in commercial extractant LIX 54. Analytical Sciences. 1989. Vol. 5. pp. 591–596.
18. Zhu T. Extracti on and ion exchange. Beijing: Metallurgical Industry Press, Chinese. 2005. pp. 280–281.
19. Kordosky G. A. β-Diketone copper extractants: structure and stability. International Solvent Extraction Conference. Cape Town, South Africa. 2002. pp. 360–365.
20. G. I. Elagin. Copp er ammonia pickling solution recovery method. Patent RF, No. 2041973, C1. IPC C25C 1/12, C23F 1/46, C23G 1/36. Applied: 26.02.1993. Published: 20.08.1995. 6 p.
21. Turaev D. Yu. A ne w regeneration method for hydrochloric copper-chloride solutions of pickling copper. Uspekhi v khimii i khimicheskoy tekhnologii. 2020. Vol. 34, No. 4. pp. 150–151.
22. Hourn M., Turner D. W. Commercialisation of Albion process. Alta-2012-Gold Conference. Burswood Convention Centre Perth. Australia. 2012.
23. Zaytsev P. V., Shneerson Ya. M. Autoclave processing of copper-bearing materials. Tsvetnye Metally. 2016. No. 1. pp. 26–31.
24. Shakhalov A. A. Autoclave processing of off-grade copper concentrates using hydrothermal treatment : thesis. … of Candidate of Technical Sciences. Yekaterinburg, 2020.
25. Bell M., Hoey M., Liu M. Design, construction and commissioning of the Sepon Copper POX II circuit. Proceedings of ALTA 2010 Nickel Cobalt Copper Conference. Perth, 2010.
26. Mwale M. Development o f effective solvent-extraction process control – low cost implementation value-addition to hydrometallurgical copper operations. Processing of 60 S.A.B.M. Conference. 2011. pp. 353–366.
27. GOST 4167–74. Reagents. Cupric chloride 2-aqueous. Specifications. Introduced: 01.01.1975.
28. GOST 3773–72. Reagents. Ammonium chloride. Specifications. Introduced: 01.07.1973.
29. GOST 3760–79. Reagents. Ammonia water. Specifications. Introduced: 01.07.1980.
30. GOST 3118–77. Reagents. Hydrochloric acid. Specifications. Introduced: 01.01.1979.
31. Maksimov I. S., Yavorskiy A. R., Brodskiy V. A. Processing metallurgical dust from bronze production by leaching and electrolysis methods. Technologies of processing wastes to manufacture new products: Proceedings of the 5^th All-Russian Scientific and Practical Conference. Kirov, 14–15 November 2023. Kirov, 2023. pp. 46–50.
32. Trifonova V. B., Kondrateva E. S., Gubin A. F., Kolesnikov V. A. Determining optimal conditions of electrical deposition of copper from sulfuric re-extracting solutions, when manufacturing printed boards. Uspekhi v khimii i khimicheskoy tekhnologii. 2016. Vol. 30, No. 3. pp. 26, 27.