A mineralogical study of the deportment and reaction of silver during copper electrorefining

The majority (>95 pct) of the silver in copper anodes occurs in metastable solid solution in the copper matrix; only a small percentage is present in solid solution in Cu₂(Se,Te) inclusions, as a constituent of complex Cu-Pb-As-Sb-Bi oxides or as tiny grains of Ag-Cu alloy. During elec-trorefining, the silver in the copper matrix dissolves, but it is rapidly removed from the elec-trolyte by a variety of reactions. Part of the silver is precipitated in elemental form by cuprous ion, but some of this metallic silver subsequently redissolves. Some of the dissolved silver precipitates as a complex Cu-Ag-Pb-As-Se oxidate phase which agglomerates the particles in the anode slimes, and some reacts with the Cu₂(Se,Te) inclusions liberated from the anode to form, sequentially, silver-bearing copper selenide, AgCuSe, copper-bearing silver selenide, and Ag₂Se. Several selenide species are present in the anode slimes, and individual selenide particles com-monly consist of more than one selenide species. Because of the diversity and complexity of the silver-bearing phases present, the Ag/Se ratio in the anode is only an approximate indicator of the selenide species present in the anode slimes.     

A Mineralogical overview of the behavior of nickel during copper electrorefining

Nickel-bearing copper anodes and anode slimes were studied using a variety of mineralogical and chemical techniques. In anodes containing <;0.3 pct Ni, the nickel occurs only in solid solution in the copper matrix. This nickel dissolves simultaneously with the copper during electrorefining, but a small amount reprecipitates as copper-nickel sulfate or a complex Ni-bearing Cu-Ag-As-Se-S oxidate phase in the anode slimes. In anodes containing >0.3 pct Ni, NiO crystals also form. The presence of the Cu-Ni-Sb oxide, kupferglimmer, in the anode depends on its antimony content. Kupferglimmer is prevalent in nickel-rich anodes with high Sb contents (>200 ppm) but is not found in similar anodes with Sb contents <200 ppm. Various Cu-Ni and Ca-Cu-Ni silicate inclusions are present. Depending on the iron content of the anode, Fe-bearing NiO, NiFe₂O₄, and other Ni-bearing iron oxide phases also may be present. All of the oxidate nickel phases remain largely undissolved during electrorefining and concentrate in the anode slimes.     

The corrosion of lead anodes in copper electrowinning

The steady-state corrosion rate of 0.4 pct As-10 pct Sb-Pb anodes in H₂SO₄ copper electro-winning electrolytes was studied. The corrosion rate increases markedly with increasing acid strength and current density, although the corrosion per pound of copper electrowon is affected only slightly by current density. Several ions such as Cu⁺², Mg⁺², Al⁺³, SiO₃ ^-2 and Na+ have no effect on the corrosion while Fe+S and Ni+2 ions have moderate inhibiting effects. Strong corrosion inhibition is brought about by introducing small amounts of Co*2 into the solution or by substituting a Ca-Pb alloy for the conventional antimonial lead anodes.     

Phase equilibria and thermodynamic properties of the Cu<Subscript>2</Subscript>O-CaO-Na<Subscript>2</Subscript>O system in equilibrium with copper

The liquidus surfaces of the Cu₂O-CaO, Cu₂O-Na₂O, and Cu₂O-CaO-Na₂O phase diagrams in equilibrium with metallic Cu were measured by thermal analysis at compositions varying from approximately 0 to 35 wt pct Na₂O and 0 to 15 wt pct CaO. Solubilities in the solid binary terminal solutions were also measured by wavelength dispersive X-ray spectrometer analysis. Copper oxide activities in binary liquid slags were determined from the measured oxygen content of the metallic copper equilibrated with the slags. The ternary system is a simple eutectic system. No ternary compounds were observed. The Cu₂O-CaO binary eutectic was measured at 1140 °C±10 °C at 10±1 wt pct CaO and the Cu₂O-Na₂O binary eutectic was measured at 803 °C±15 °C at 28±2 wt pct Na₂O. The liquid slag was thermodynamically modeled with the modified quasi-chemical model, while the solid Cu₂O-rich solution was treated as Henrian ideal. All data from the present work and from the literature (phase diagrams and activities) for the binary systems were evaluated simultaneously by least-squares optimization in order to obtain the best model parameters. With only these binary parameters, the calculated ternary liquidus surface is in very good agreement with the measurements. Finally, using the model, the liquidus projection of the Cu₂O-CaO-Na₂O system in equilibrium with Cu was calculated as well as the oxygen content of the equilibrated Cu as a function of slag composition.     

Mineralogical characterization of a copper anode and the anode slimes from the la caridad copper refinery of mexicana de cobre

A detailed mineralogical study was carried out to characterize a copper anode, the anode-face slimes, the slimes on the bottom of the refining cell, and the autoclave-leached slimes from the La Caridad refinery of Mexicana de Cobre. The objective was to identify possible Pb-Sb-Bi and As-Sb-Bi interactions that could control the Sb and Bi concentrations of the electrolyte. Although some Pb, As, Sb, and Bi can be found in solid solution in the copper crystals of the anode, these elements are mostly present as Cu-Pb-As oxide and Cu-Pb-As-Sb-Bi oxide inclusions at the grain boundaries. During electrorefining, the Pb, As, Sb, and Bi in solid solution dissolve. Part of the Pb, As, Sb, and Bi in the oxide inclusions also dissolves, but part reacts in situ to form PbSO₄ and Pb₅(AsO₄)₃(OH,Cl). Some of the dissolved elements reprecipitate as PbSO₄, SbAsO₄, Sb-As oxide, Sb-As-Bi oxide, Pb₅(AsO₄)₃(OH,Cl), and an oxidate phase of mainly Cu-Ag-AsO₄-SO₄ composition. Thus, high As contents facilitate the precipitation of Sb and Bi from the electrolyte. Although Pb-Sb oxide and Pb-Bi oxide species were only rarely detected, a high Pb content in the anode may retard the dissolution of the Cu-Pb-As-Sb-Bi oxide inclusions, thereby retaining some Sb and Bi in the raw anode slimes. Autoclave leaching dissolves part of As, Sb, and Bi, but the SbAsO₄ and Sb-As-Bi oxide species remain in the leach residue. The Pb is converted almost entirely to PbSO₄, which is present as subhedral crystals in the autoclave leach residue.     

碲处理控制Y15易切削钢中MnS夹杂物形貌

 为了研究碲对钢中MnS夹杂物形貌的影响,针对Y15高硫易切削钢,利用SEM-EDS扫面电镜,结合FactSage热力学计算,分析了不同碲质量分数对钢中MnS夹杂物形貌、尺寸、长宽比的影响,同时探讨了稀散金属碲对MnS夹杂物形貌控制的机理。研究结果表明,钢液中加碲后,在MnS夹杂物的外环形成了碲、锰、铁的复合相。钢中加碲后MnS夹杂物的形貌和分布大幅度改变,当碲硫比为0.05时,链状MnS夹杂物大幅度减少,球状MnS夹杂物数量增加;当碲硫比增加到0.2时,链状MnS夹杂物基本消失;当碲硫比增加到0.5时,MnS夹杂物形貌的变化不再明显。钢中加碲显著降低了MnS夹杂物的长宽比,控制MnS夹杂物长宽比最合适的碲硫比为0.2。FactSage计算结果表明,MnTe的生成温度为1 900 ℃,在MnS的析出温度下,MnTe是作为液态夹杂物存在的。在凝固过程中,MnTe和MnS发生固溶现象,由于MnTe为液态,两者形成的固溶体会趋于球形生长。     

Mineralogical characterization of silver flotation concentrates made from zinc neutral leach residues

Silver flotation concentrates prepared from high-silver (1480 ppm Ag) and low-silver (300 ppm Ag) neutral leach residues have been examined mineralogically to determine the phases present and to elucidate the behavior of silver during zinc processing. The flotation concentrates consist principally of sphalerite although lesser amounts of zinc ferrite and PbSO₄, as well as traces of other phases, also are present. In the high-silver flotation concentrate, silver occurs mostly as Ag₂S or (Ag, Cu)₂S rims on sphalerite although (Ag, Cu)₂S inclusions within sphalerite also are present. Trace amounts of a Cu-Ag-S-Cl phase are present on rare copper oxide grains, and this silver-bearing phase may be a fine mixture of Ag₂S, AgCl, and Cu₂S. In the low-silver flotation concentrate, silver occurs mostly as Ag₂S although traces of silver-bearing CuS and Cu₂S also are present. The Ag₂S occurs as <1 μm particles disseminated in elemental sulfur-silica gel patches, as discontinuous rims or isolated patches on sphalerite grains, and as tiny free particles. Silver chloride was not detected. These studies suggest that silver dissolves during neutral leaching and subsequently reacts with sphalerite or other sulfides to form silver sulfide.     

Mineralogical characterization of silver flotation concentrates made from zinc neutral leach residues

Silver flotation concentrates prepared from high-silver (1480 ppm Ag) and low-silver (300 ppm Ag) neutral leach residues have been examined mineralogically to determine the phases present and to elucidate the behavior of silver during zinc processing. The flotation concentrates consist principally of sphalerite although lesser amounts of zinc ferrite and PbSO₄, as well as traces of other phases, also are present. In the high-silver flotation concentrate, silver occurs mostly as Ag₂S or (Ag, Cu)₂S rims on sphalerite although (Ag, Cu)₂S inclusions within sphalerite also are present. Trace amounts of a Cu-Ag-S-Cl phase are present on rare copper oxide grains, and this silver-bearing phase may be a fine mixture of Ag₂S, AgCl, and Cu₂S. In the low-silver flotation concentrate, silver occurs mostly as Ag₂S although traces of silver-bearing CuS and Cu₂S also are present. The Ag₂S occurs as <1 μm particles disseminated in elemental sulfur-silica gel patches, as discontinuous rims or isolated patches on sphalerite grains, and as tiny free particles. Silver chloride was not detected. These studies suggest that silver dissolves during neutral leaching and subsequently reacts with sphalerite or other sulfides to form silver sulfide.     

Reactions of dense MgO with calcium ferrite-based slags at 1573 K

The drop-quench technique was used to investigate the solubility of dense MgO in calcium ferrite-based slags (CaO 20 wt pct) under oxygen potentials from 10⁻⁸ to 10⁻⁴ atm at 1573 K. The effect of copper oxide in the slag on the solubility of MgO was also examined in a CO₂ atmosphere. The results showed that MgO solubility in copper-free calcium ferrite slags was generally less than 2 wt pct and it increased with the addition of Cu₂O (up to 28.5 wt pct). It was found that magnesiowustite or magnesioferrite may form at the slag-refractory interface depending on the prevailing oxygen potential. The activity of MgO was estimated through equilibrium between the slag and the solid solution phases. The activity coefficient of MgO was found to be essentially independent of the oxygen potential within the range studied and to decrease from approximately 15 for the copper-free slag to 7 for slags with 28.5 wt pct Cu₂O.     

Effect of Slag Basicity on Phase Equilibria and Selenium and Tellurium Distribution in Magnesia-Saturated Calcium Iron Silicate Slags

New measurements have been made on the phase equilibria of magnesia-saturated CaO-FeO_x-SiO₂ slags at 1573 K (1300 °C) and an oxygen partial pressure of 10⁻⁹ atm. The thermodynamic behavior of selenium (Se) and tellurium (Te) in the slag and the stability of oxide mineral phases within the slag were examined as a function of slag composition. The measured equilibrium distribution of Se and Te between the slag and the copper showed nonlinear dependence on the slag basicity, reaching maxima at CaO/(CaO + SiO₂) ratios of about 0.2 and 1 and a minimum at a ratio of about 0.5. The solubility of the copper oxide in the bulk slag also passed through a minimum value at a ratio of about 0.5. Results from drop-quench experiments confirmed the stability of various oxide solid solution phases at 1573 K (1300 °C) that had virtually no solubility for Se and Te. The deduced capacity of the liquid slag for Se was found to be independent of basicity in relatively basic slags, and decreased sharply as SiO₂ replaced CaO in relatively acidic slags.     

On the nature of the Fe-bearing particles influencing hard anodizing behavior of AA 7075 extrusion products

The deleterious effects of Fe-bearing constituent particles on the fracture toughness of wrought Al alloys have been known. Recent studies have shown that the presence of Fe-bearing constituent particles is also detrimental to the nature and growth of the hard anodic oxide coating formed on such materials. The present study, using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA), was made to examine the influence of the nature of the Fe-bearing particles on the hard anodizing behavior of AA 7075 extrusion products containing varying amounts of Si, Mn, and Fe impurities. It was found that, in the alloy containing 0.25 wt pct Si, 0.27 wt pct Mn, and 0.25 wt pct Fe, the Fe-bearing constituent particles are based on the Al₁₂(FeMn)₃Si phase (bcc with a=1.260 nm). These particles survive the hard anodizing treatment, add resistance to the electrical path, causing a rapid rise in the bath voltage with time, and cause a nonuniform growth of the anodic oxide film. In the materials containing 0.05 wt pct Si, 0.04 wt pct Mn, and 0.18 wt pct Fe, on the other hand, the formation of the Al₁₂(FeMn)₃Si-based phase is suppressed, and two different Fe-bearing phases, based on Al-Fe-Cu-Mn (simple cubic with a=1.265 nm) and Al₇Cu₂Fe, respectively, form. Neither the Al-Fe-Cu-Mn-based phase nor the Al₇Cu₂Fe-based phase survive the hard anodizing treatment, and this results in a steady rise in the bath voltage with time and a relatively uniform growth of the anodic oxide film. Consideration of the size of the Fe-bearing particles reveals that the smaller the particle, the more uniform the growth of the anodic oxide film.     

Study of the mechanism of anodic dissolution of Cu2S

The anodic dissolution of Cu₂S in sulfuric acid solutions was studied under galvanostatic and potentiostatic conditions. The anodic products were studied by mineralogical and X-ray diffraction methods. In every case, the formation of a digenite Cu_1-8S layer is observed at the surface of Cu₂S according to 5Cu₂S → 5Cu_1.8S + Cu⁺⁺ + 2e A copper concentration gradient appears through the digenite layer whose thickness remains constant as soon as a Cu_1.1S layer appears at its own surface according to 3Cu_1.8S → 4Cu_1.1S + Cu++ + 2e If the electrolysis conditions are such that the anodic potential remains low, the next reaction to occur is 10Cu_1.1S → HCu⁺⁺ + 10S + 22e But if under galvanostatic conditions, the current density is high enough at a given temperature to reach the sharp rise in anodic potential, or if under potentiostatic conditions the potential is kept high, two other reactions are possible: 10Cu_1.1S → 10CuS + Cu⁺⁺ + 2e followed by CuS → Cu⁺⁺ + S + 2e Moreover, at high anodic potential, the following reaction occurs also to some extent CuS + 4H₂O ? Cu⁺⁺ + SO₄ ⁼ + 8H⁺ +8e resulting in a decrease in anodic current efficiency for the copper dissolution. From a more practical point of view, it was shown that it is possible to deplete virtually completely the copper content of the anode (residue at less than 0.5 pct Cu)keepingthe electrode potential at a low value (less than +650 mV/ENH). Providing the temperature is high enough (75°C at least), the mean current density remains near to 2 A/dm², a suitable value to obtain good cathodic deposits.     

Fluidised-bed anodic dissolution of chalcocite

The anodic dissolution of chalcocite (Cu₂S) has been investigated using a fluidised-bed anode technique. Results obtained for a variety of electrolytes and experimental conditions indicate that the fluidised-bed anodic dissolution of chalcocite occurs via the formation of an intermediate copper sulphide, viz., “blue-remaining” covellite, Cu_1.1S.In sulphuric acid electrolyte the dissolution of chalcocite is inhibited after about 50% copper extraction by the vigorous evolution of oxygen gas at the platinum feeder anode.In both sulphuric acid-sodium chloride and sulphuric acid-potasium bromide electrolytes, the dissolution of chalcocite occurs to 95% copper extraction in two stages. The first stage involves the formation of Cu_1.1S, as is the case for the sulphuric acid electrolyte, while the second stage is attributed to the reaction between chloride (or bromide) and Cu_1.1S.     

微量碲对38MnVS6钢中MnS夹杂物塑性变形的影响

摘要：为探究微量碲改质对钢中硫化物塑性变形的影响机制,对38MnVS6非调质钢中MnS夹杂物进行了微量碲改质工业试验,并探讨了碲对钢中MnS夹杂物的改质机制和塑性变形行为的影响。结果表明,微量碲改质能明显降低试验钢铸坯中硫化物的长宽比,碲改质后不同变形量的轧材中硫化物评级亦有所改善;钢中碲主要固溶于MnS,形成Mn(S,Te)固溶夹杂物,当碲浓度达到析出过饱和度时,以MnTe形式析出于MnS表面并形成MnS MnTe夹杂物;碲良好的硫化物形态调控效果是由于形成显微硬度更高、相对塑性更低的Mn(S,Te)夹杂物;而夹杂物在大变形量轧制条件下的真应变增幅减小导致碲改质后试样中夹杂物的相对塑性反而有所增加;长条状硫化物夹杂在轧制时可能发生先碎化再经历Ostwald熟化的过程。     

On the nature of the Fe-bearing particles influencing hard anodizing behavior of AA 7075 extrusion products

The deleterious effects of Fe-bearing constituent particles on the fracture toughness of wrought A1 alloys have been known. Recent studies have shown that the presence of Fe-bearing, constituent particles is also determental to the nature and growth of the hard anodic oxide coating formed on such materials. The present study, using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA), was made to examine the influence of the nature of the Fe-bearing particles on the hard anodizing behavior of AA 7075 extrusion products containing varying amounts of Si, Mn, and Fe impurities. It was found that, in the alloy containing 0.25 wt pct Si, 0.27 wt pct Mn, and 0.25 wt pct Fe, the Fe-bearing constituent particles are based on the Al₁₂(FeMn)₃Si phase (bcc with α=1.260 nm). These particles survive the hard anodizing treatment, add resistance to the electrical path, causing a rapid rise in the bath voltage with time, and cause a nonuniform growth of the anodic oxide film. In the materials containing 0.05 wt pct Si, 0.04 wt pct Mn, and 0.18 wt pct Fe, on the other hand, the formation of the Al₁₂(FeMn)₃Si-based phase is suppressed, and two different Fe-bearing phases, based on Al−Fe−Cu−Mn-based (simple cubic with a=1.265 nm) and Al₇Cu₂Fe, respectively form. Neither the Al−Fe−Cu−Mn-based phase nor the Al₇Cu₂Fe-based phase survive the hard anodizing treatment, and this results in a steady rise in the bath voltage with time and a relatively uniform growth of the anodic oxide film. Consideration of the size of the Fe-bearing, particles reveals that the smaller the particle, the more uniform the growth of the anodic oxide film.     

Effect of silicon on the rate of de-sulphurization of liquid Fe-S alloys by argon-hydrogen at 1550°C

Abstract

The passivation of copper anodes due to precipitation of copper sulfate on the anode surface was investigated as a function of electrolyte composition and temperature, and of anode composition. The slime layer present on the anode surface was shown to be the primary factor in causing passivation by inhibiting the diffusion of copper ions. Factors such as temperature, free acid level, Ni²⁺ and Cu²⁺ ion levels were also important in so far as they affected the mass transfer characteristics of Cu²⁺ ions and the solubility of copper sulfate.

Résumé

La passivation des anodes de cuivre due à la précipitation du sulfate de cuivre sur la surface de l'anode a été étudiée en fonction de la composition et la température de l'électrolyte et aussi en fonction de la composition de l'anode. Nous avons montré que la couche d'impuretés présente sur la surface de l'anode est la cause première de la passivation car elle empêche la diffusion des ions cuivre. D'autres facteurs tels que la température, le niveau d'acide libre, le niveau d'ions Ni²⁺ et Cu² sont également importants en ce qu'ils affectent les caractéristiques de transport de matière des ions Cu²⁺ et la solubilitédu sulfate de cuivre.     

Phase Equilibria of “Cu2O”-“FeO”-CaO-MgO-Al2O3 Slags at PO2 of 10-8.5 atm in Equilibrium with Metallic Copper for a Copper Slag Cleaning Production

Limited data are available on phase equilibria of the multicomponent slag system at the oxygen partial pressures used in the copper smelting, converting, and slag-cleaning processes. Recently, experimental procedures have been developed and have been applied successfully to characterize several complex industrial slags. The experimental procedures involve high-temperature equilibration on a substrate and quenching followed by electron probe X-ray microanalysis. This technique has been used to construct the liquidus for the “Cu₂O”-“FeO”-SiO₂-based slags with 2 wt pct of CaO, 0.5 wt pct of MgO, and 4.0 wt pct of Al₂O₃ at controlled oxygen partial pressures in equilibrium with metallic copper. The selected ranges of compositions and temperatures are directly relevant to the copper slag-cleaning processes. The new experimental equilibrium results are presented in the form of ternary sections and as a liquidus temperature vs Fe/SiO₂ weight ratio diagram. The experimental results are compared with the FactSage thermodynamic model calculations.     

Effect of ferrosilicon addition on the composition of inclusions in 16Cr-14Ni-Si stainless steel melts

The silicon deoxidation equilibrium between the 16Cr-14Ni-1.5Mn-Si melts and the CaO-SiO₂-8MgO-5CaF₂ (basicity=1.8) slag at 1743 K was investigated to understand the effect of aluminum and silicon contents on the composition of inclusions. Therefore, the ferrosilicon alloys with different aluminum content were chosen based on the preceding objective. In addition, the phase stability diagram of the inclusions was computed using commercial thermodynamic software based on the Gibbs energy minimization principles. The content of MnO in the inclusions sharply decreases with increasing silicon content when the steel melts were deoxidized by the ferrosilicon alloys containing high aluminum (FeSi-H). The content of SiO₂ in the inclusions slightly increases with increasing silicon content when the FeSi-L is used, while a maximum value is shown at [Si]=1.5 pct when the FeSi-H is used. The content of MgO in the inclusions increases by increasing the content of silicon, regardless of the kinds of ferrosilicon alloys. The use of the FeSi-L as a deoxidizer could suppress the formation of Al₂O₃ in the inclusions, while the content of Al₂O₃ increases with increasing silicon content when the FeSi-H is used. When the FeSi-H is used as a deoxidizer, the inclusions are the glassy type with the composition of Mn-silicates at [Si]≤1.3 pct, while the Mg(Ca)-silicates with the composition of the forsterite phase are observed in the steel composition of [Si]=3.3 pct. When the steel melts were deoxidized by the FeSi-L alloys, the inclusions are the glassy-type Mn-silicates at [Si]=0.8 pct, while the Mn-silicates containing the cristobalite phase are observed at [Si]=1.5 to 2.4 pct. In the composition of [Si]=3.3 pct, the Mg-silicates with the composition of the rhodonite phase are observed. The log(X _SiO2/X _MnO) of the inclusions linearly increases by increasing the log [a _Si · a _O / a _Mn] with the slope close to unity when the FeSi-L is used as a deoxidizer, while the slope of the line is about 2 times greater than that of the expected value when FeSi-H is used. The log (X _MgO/X _MnO) of the inclusions linearly increases by increasing the log [a _Mg/a _Mn] with slopes greater than the expected value of unity.     

Development of Kinetic Model for Reactions Between Cu-Containing Multicomponent Slag and Liquid Sulfide Using Coupled Reaction Model

Copper smelting slag contains less than 2 mass pct of Cu oxide and 30–50 mass pct of Fe_xO. Each year, the grade of copper ore decreases, while the amount of slag generated in the copper smelting process increases. In this study, a coupled reaction model to simulate the reaction between multicomponent slag and FeS-based matte was developed using reported thermodynamic data and double-film theory for the recycling of copper smelting slag. The activity coefficients of oxides in the multicomponent slag were calculated using a regular solution. The activity coefficients of Cu₂O in the slag and those of FeS, Cu₂S, and CaS in the FeS-based matte used previously reported data. The behaviors of Cu in slag and matte were confirmed by comparing the simulated results and the reported solubility of Cu in the slag in the temperatures ranging from 1473 K to 1573 K. In addition, the effect of the input amount of FeS on the copper content of the slag was verified by comparing the results of reaction model to experimental results. Using the reaction model, the influences of the initial ratio of FeO/SiO₂ of the slag, temperature, and matte composition on the behaviors of Cu in the slag and matte were investigated.     

Copper-Sulfate Pentahydrate as a Product of the Waste Sulfuric Acid Solution Treatment

The aim of this study is synthesis of copper-sulfate pentahydrate from the waste sulfuric acid solution-mother liquor generated during the regeneration process of copper bleed solution. Copper is removed from the mother liquor solution in the process of the electrolytic treatment using the insoluble lead anodes alloyed with 6 mass pct of antimony on the industrial-scale equipment. As the result of the decopperization process, copper is removed in the form of the cathode sludge and is precipitated at the bottom of the electrolytic cell. By this procedure, the content of copper could be reduced to the 20 mass pct of the initial value. Chemical characterization of the sludge has shown that it contains about 90 mass pct of copper. During the decopperization process, the very strong poison, arsine, can be formed, and the process is in that case terminated. The copper leaching degree of 82 mass pct is obtained using H₂SO₄ aqueous solution with the oxygen addition during the cathode sludge chemical treatment at 80?°C?±?5?°C. Obtained copper salt satisfies the requirements of the Serbian Standard for Pesticide, SRPS H.P1. 058. Therefore, the treatment of waste sulfuric acid solutions is of great economic and environmental interest.