DOI: 10.18503/1995-2732-2021-19-3-44-53
Abstract
Problem Statement. The relevance of the research is determined by the need to improve and optimize the existing complex multi-operational technology for processing multicomponent copper anode sludge, in particular, for selective precipitation, concentration and purification of selenium when making a commercial product. The current technology provides for the selenium precipitation on aluminum powder with subsequent treatment by pyro- and hydrometallurgical methods: fusion with a mixture of nitrate and ammonium chloride; leaching with solutions of sodium and ammonium sulfides and sulfites; treatment of Se-Hg slurries with aluminum powder in an alkaline medium to reduce mercury and make it precipitate as a separate phase; leaching of the precipitation with a solution of sulfuric acid; electro-leaching of the precipitation in a solution of sodium hydroxide; dissolution with a sulfite solution in the presence of thiourea or sodium thiosulfate, sodium hydroxide, sodium sulfide to bind mercury; leaching in sodium bisulfite. Objective. The research is aimed at studying kinetics of the initial stage ‒ precipitation of macro- and microcomponents (selenium/mercury) of the leaching solution of copper anode sludge on metallic aluminum, which largely determines the overall speed of the complex technology for producing commercial selenium. Methods Applied. The parameters of the selenium precipitation, depending on the solution temperature, the disk rotation speed, the initial concentration of the components of the solution, are determined by the method of a rotating aluminum disk, which provides the most correct kinetic data due to the equal accessibility of the surface in the diffusion ratio. The precipitation rate of selenium and mercury was judged by the decrease in the concentration of metals over a certain period of time in the liquid phase; the constant of the precipitation/dissolution rate was determined based on the mechanism of reduction of ions of the precipitated metal flowing at limiting current, when metals are deposited on the outer surface of the cathode sections of the disk, which remains constant throughout the entire process. Originality. Under conditions of an equally accessible surface of a rotating disk, we studied the dependences of the specific velocities of selenium and mercury precipitation processes in a wide range of the influencing parameters: the temperature and composition of solutions, the rotation speed of the aluminum disk. The flow modes are established and the details of the mechanism of the studied processes are determined. Findings. Kinetic parameters (W·10-6, g-at/dm2.s; K·10‒6, s‒1; D·10‒11, m2/s) of the selenium/mercury precipitation process tends to increase with an increase in the following system parameters: the concentration of components Se/Hg, Ci = (10–100)/(0.003‒0.2) g/dm3: W = (4.7‒180)/(0.008‒1.4); K = (1.9‒7.6)/(28.6‒73.5); D = (1.5‒89)/(0.006‒1.0); mixing speed of solutions Se/Hg, ω = 17–73 rad/s: W = (156–180)/(1.2‒1.4); K = (6.6‒7.6)/(29-73); D = (69–89)/(0.9‒1.1); temperature of solutions Se/Hg, Т = 293–323оС: W = (156–208)/(0.8‒3.1); K = (6.6‒8.7)/(42–174); D = (69–125)/(0.6‒2.3). Practical Relevance. We have obtained initial data for optimizing the precipitation mode: when the steady process conditions are reached, the rates of selenium reduction, mercury selenide formation, the formation of elemental mercury and aluminum salt of selenic/selenous acid are balanced. Information on the kinetics of precipitation on aluminum allows us to develop technological recommendations for the extraction of selenium from technological solutions.
Keywords
Mercury, selenium, aluminum, precipitation, kinetics, sludge, solution, leaching, sediment, disk, concentration, speed.
For citation
Korolev A.A., Shunin V.A., Timofeev К.L., Maltsev G.I., Voinkov R.S. Kinetics of Mercury and Selenium Precipitation on Aluminum. Vestnik Magnitogorskogo Gosudarstvennogo Tekhnicheskogo Universiteta im. G.I. Nosova [Vestnik of Nosov Magnitogorsk State Technical University]. 2021, vol. 19, no. 3, pp. 44–53. https://doi.org/10.18503/1995-2732-2021-19-3-44-53
1. Nazarenko I.I., Ermakov A.N. Аnaliticheskaya khimiya selena i tellura [Analytical chemistry of selenium and tellurium]. Moscow: Nauka, 1971, 252 p. (In Russ.)
2. Bagnall K. Khimiya selena, tellura i poloniya [Chemistry of selenium, tellurium and polonium]. Moscow: Atomizdat, 1971, 216 p. (In Russ.)
3. Chizhikov D.M., Schastlivy V.P. Selen i selenidy [Selenium and selenides]. Moscow: Nauka, 1964, 320 p. (In Russ.)
4. Kotlyar Yu.A., Meretukov M.A., Strizhko L.S. Metallurgiya blagorodnykh metallov: uchebnik v 2 kn. Kn. 1. [Metallurgy of precious metals: Textbook. In 2 books. Book 1]. Moscow: MISIS, Publishing house "Ore and Metal", 2005, 432 p. (In Russ.)
5. Volkhin A.I., Eliseev E.I., Zhukov V.P., Smirnov B.N. Anodnaya i katodnaya med [Anode and cathode copper]. Chelyabinsk: South Ural Book Publishing House, 2001, 432 p. (In Russ.)
6. Lebed A.B., Naboichenko S.S., Shunin V.A. Proizvodstvo selena i tellura na OAO Uralelektromed: uchebnoe posobie [Production of selenium and tellurium at OJSC Uralelectromed: a textbook]. Yekaterinburg: Ural State University Press, 2015, 112 p. (In Russ.)
7. Soshnikova L.A., Kupchenko M.M. Pererabotka medeelektrolitnykh shlamov [Processing of copper electrolyte sludge]. Moscow: Metallurgiya, 1978, 199 p. (In Russ.)
8. Mastyugin S.A., Volkova N.A., Lastochkina M.A. Shlamy elektroliticheskogo rafinirovaniya medi i nikelya [Sludge of electrolytic refining of copper and nickel]. Yekaterinburg: UrFU, 2013, 256 p. (In Russ.)
9. Kudryavtsev A.A. Khimiya i tekhnologiya selena i tellura [Chemistry and technology of selenium and tellurium]. Moscow: Metallurgiya, 1968, 339 p. (In Russ.)
10. Greiver T.N., Zaitseva I.G., Kosover V.M. Selen i tellur. Novaya tekhnologiya polucheniya i rafinirovaniya [Selenium and tellurium. New technology of production and refining]. Moscow: Metallurgy, 1977, 296 p. (In Russ.)
11. Buketov E.A., Malyshev V.P. Izvlechenie selena i tellura iz medeelektrolitnykh shlamov [Extraction of selenium and tellurium from copper electrolyte sludge]. Alma-Ata: Nauka, 1969, 206 p. (In Russ.)
12. Naboichenko S.S., Mastyugin S.A. Processing of copper electrolyte sludge: evolution of the technology. Izvestiya vysshikh uchebnykh zavedeniy. Tsvetnaya metallurgiya [Universities’ Proceedings. Non-Ferrous Metallurgy], 2012, no. 5, pp. 15‒21. (In Russ.)
13. Melnikov Yu.T., Kravtsova E.D., Krinitsyn D.O. Hydrometallurgical technologies for processing sludge of electrorefining of copper and nickel. Tsvetnye metally [Non-Ferrous Metals], 2017, no.5, pp. 44–49. (In Russ.)
14. Khazieva E.B., Naboichenko S.S., Bolatbayev K.N. Influence of lignosulfonates on the rate of copper precipitation with zinc. Izvestiya vuzov. Tsvetnaya metallurgiya [Universities’ Proceedings. Non-Ferrous Metallurgy], 2015, no. 1, pp. 11‒14. (In Russ.)
15. Bayborodov P.P., Ezhkov A.B., Shuklin A.M. Sposob tsementatsii rtuti iz sulfidno-shchelochnykh rastvorov [Method of mercury precipitation from sulfide-alkaline solutions]. Certificate: SU 195112 A1 USSR, IPC C22B 43/00, 1974.
16. Kozmin Yu.A., Serba N.G., Enns I.I., Kulenova L.N., Korotin A.D., Alibaev B.M., Menyaev A.D., Shonov B.P., Bayanzhanov T.Sh. Sposob izvlecheniya rtuti iz rastvorov tsementatsiey [Method for extracting mercury from solutions by its precipitation]. Patent USSR, no. 584562, IPC C22B 43/00, 1999.
17. Pleskov Yu.V., Filinovsky V.Yu. Vrashchayushchiisya diskovyi elektrod [Rotating disk electrode]. Moscow: Nauka, 1972, 344 p. (In Russ.)
18. Voldman G.M., Zelikman A.N. Teoriya gidrometallurgicheskikh protsessov [Theory of hydrometallurgical processes]. Moscow: Intermet Engineering, 2003. 464 p. (In Russ.)
19. Levich V.G. Fiziko-khimicheskaya gidrodinamika [Physico-chemical hydrodynamics]. Moscow: Fizmatgiz, 1959, 699 p. (In Russ.)
20. Kakovsky I.A., Potashnikov Yu.M. Kinetika protsessov rastvoreniya [Kinetics of dissolution processes]. Moscow: Metallurgy, 1975, 224 p. (In Russ.)
21. Kakovsky I.A., Naboichenko S.S. Termodinamika i kinetika gidrometallurgicheskikh protsessov [Thermodynamics and kinetics of hydrometallurgical processes]. Alma-Ata: Nauka, 1986. 272 p. (In Russ.)