Method of electrolytic refining of copper in block-series of baths of box type

FIELD: metallurgy.

SUBSTANCE: invention refers to metallurgy, particularly to methods of electro-chemical refining of copper out of anodes with impurities of other metals. The method consists in electrolysis with anode dissolution of copper and its sedimentation on a cathode under effect of electric current with cathode density of current 220-330 A/m2. Also there is performed a direct flow circulating supply of copper containing solution with colloid and concentration of free sulphuric acid 120-180 g/dm3. Electrolysis is carried out at 50-65°C temperature of solution at rate of its circulation from 12 to 30 dcm3/min. Concentration of copper in solution is maintained within ranges 35-65 g/dcm3. Voltage in the bath during electrolysis is supported at 0.25-0.6 V at daily withdrawal of part of volume of solution from block-series of baths constituing 1-4 % from the total volume; it is made up with condensate or copper containing solution.

EFFECT: increased efficiency of electrolysis process production and upgraded quality of cathode copper of MOOK grade produced out of materials with considerable amount of impurities in raw material.

1 ex

 

The invention relates to the field of metallurgy, in particular to methods for electrochemical refining of copper anodes with impurities of other metals, such as lead, Nickel, iron, arsenic, antimony, lead, gold, silver, platinum and palladium, and can be used in the electrolytic refining of non-ferrous metals, particularly copper, in aqueous solutions.

The known method for electrochemical refining of copper, used for the production of pure copper using bathing box type including the electrolysis of copper and preparatory operations. The preparatory operations include loading and unloading of the baths of electrodes, filling the bath electrolyte and removing it after electrolysis. The cleaning of the slurry and anode scrap, supply of electricity and other operations. The electrolysis of copper is carried out in a combined direction of circulation of the electrolyte and the electrical circuit with a voltage of 1-3, the circulation rate of 15-50 DM3/min (see RF patent №2187579, CL C25C 1/12 2000).

The disadvantage of this method of refining copper are high speed circulation of the solution (50 DM3/min), which leads to mixing of the sludge formed at the bottom of the baths from the dissolution of the anode and the deposition in the body of copper cathode. The result is reduced quality copper, leads to loss of precious metals, which the sludge, as well as the complexity of practical application because of the impossibility of feeding electrolyte into the space between the electrodes. In addition, the distance between the surfaces of adjacent electrodes is 55-65 mm and its increase leads to additional power consumption and performance degradation due to the reduction in the number of electrodes in the bath. Judging by the values of the voltage at the baths, is 1-3 In this way, use standard bath size 4×1 m

Also there is a method of electrochemical recovery of copper from sulfate solutions, including cathodic deposition of copper from solution with a copper concentration of less than 40 g/l, at a cathode current density 86-258 a/m2and the concentration of sulfuric acid 160-200 g/l temperature of electrolyte 50-65°C (see RF patent №2033481, CL C25C 1/12 for 1992).

The disadvantages of these methods is that it can be used to extract copper from solutions only with insoluble anodes and may not be used for the electrolytic process, because when the content of copper in the solution is not more than 40 g/l, sediment quality copper cathode can be obtained only at low current densities less than 200 a/m2and a low content of impurities in the electrolyte solution.

The closest in technical essence to the invention is a method elektroliticheskoj the refining of copper per unit-series baths box type, used to group mediatisierung plants, especially plants of the former USSR, described in the book [Kapustin, Sat, Bensimon "Refining of copper". Moscow, metallurgy, 1992, p.123]. Method of electrolytic refining of copper includes the deposition of copper cathode under the influence of the electric current density 170-300 a/m2from the electrolyte solution in which copper 36-45 g/DM3, sulfuric acid 120-200 g/DM3, impurities 1-7 g/DM3surfactants of 20-200 g/T. the circulation Rate is equal to 0.6-25 DM3/min, and the temperature of the electrolyte is equal to 50-65°C.

The disadvantage of these methods is the inability to obtain high-quality copper brand M00k at current density of 300 a/m2and refining of anode copper with a copper content below 99,0%. The circulation rate 12-30 DM3/insufficient min) to stabilize the solution in the whole volume of the electrolysis bath at a current density of 300 a/m2. In the process of electrolysis near-cathode layer is depleted of copper ions, which affects the chemical composition of the cathode Deposit. The increase in the circulation rate of over 30 DM3/min leads to resuspension of sludge, which leads to loss of precious metals.

The technical objective of the proposed method is to increase the performance of the process of electrolysis with high quality copper cathode mark M00k when Rafi the funding of copper with a high content of impurities.

The specified technical task is achieved by the fact that in the proposed method, electrolytic refining of copper per unit-series baths box type, including electrolysis with anodic dissolution of copper and its deposition on the cathode under the action of electric current from the cathode current density 220-330 a/m2, straight-through flow of copper-bearing solution with a colloid and a concentration of free sulfuric acid 120-180 g/DM3with a temperature of 50-65°C. at a speed of circulation of the solution, from 12 DM3/min to 30 DM3/min, the concentration of copper in the solution is maintained within the range of 35 to 65 g/DM3the electrolysis is carried out at a voltage in a bath of 0.25 to 0.6, with a daily output part of the solution volume of the block of the series of baths, which is 1-4% of the total volume and fill it with condensate or copper-containing solution.

Example

The proposed method is electrolytic refining of copper in the bath is performed in the following way. Block series (consisting, for example, from 40 baths), is filled with electrolyte (copper-containing sulfuric acid solution with a copper concentration 35-65 g/DM3free sulfuric acid 120-180 g/DM3. Inside each bath set parallel to each other alternating between an anode and cathode plates, so that they were in contact with one pole of the power source. The anodes will the tive in the form of copper plates, the cathode is a copper base or matrix (for example, titanium or stainless steel). After filling baths include circulation of the electrolyte and heat the electrolyte to a temperature of 50-65°C. the Circulation of the electrolyte is accomplished in the following way - the electrolyte is fed through a pocket at one end of each bath with speed 12-30 DM3/min, the motion perpendicular to the plane of the electrodes of the bath and removed through the pocket on the other end of the bath. After heating the electrolyte to a predetermined temperature includes a source of DC power and put the necessary amperage to ensure that the current density in the range 220-330 a/m2.

In the process of electrolysis in a bath set voltage from 0.25 to 0.6 depending on current load and chemical composition of the electrolyte. In addition, the electrolysis process is the accumulation of impurities (Nickel, arsenic, iron, and others), the resulting chemical dissolution of copper are removed from the bath electrolyte for recycling, for example for the production of sulphate of copper and Nickel. At the same daily amount of the output of copper-bearing solution from the block series is 1.0 to 4.0% of the total circulating volume of the electrolyte. To replenish the required volume of solution is used, the condensate, for example, after the vacuum evaporation crystallization is stanovic in the production of sulphate of copper and Nickel, or copper-containing solution formed, for example, as a result of washing the surface of the cathodes condensate.

Using the proposed method allows the refining of anode copper in a wide limit of its chemical composition (98,0% copper content up to 99.7%). However, regardless of the quality of anode copper to produce high quality copper cathode, to preserve the performance of the electrolysis bath. Selection of technological regimes is based on the quality of anode copper.

For example, for the refining of anode copper with a copper content of 98.5%-98,7% at current density of 300 a/m2and obtain copper cathodes for high grade M00k it is necessary to maintain the concentration of copper in solution within 58-62 g/DM3to maintain the speed of circulation of the electrolyte within 20-25 DM3/min, to carry out the daily output of the electrolyte of 1.6-2% of the total volume of solution per unit-series to make its replenishment condensate. The voltage on the tub is 0.35-0,46 Century

Thus, this method is electrolytic refining of copper expands the technical ability to receive high-quality copper with the deterioration of the quality of the copper raw materials, reduces the cost of copper production, as it does not require additional energy and fluxes to increase the depth of refining copper. When the volume increases performance mediatisierung furnaces and less subtle harmful emissions into the atmosphere during fire refining of copper.

Method of electrolytic refining of copper per unit-series baths box type, including electrolysis with anodic dissolution of copper and its deposition on the cathode under the action of electric current from the cathode current density 220-330 a/m2, straight-through flow of copper-bearing solution with a colloid and a concentration of free sulfuric acid 120-180 g/DM3with a temperature of 50-65°C. at a speed of circulation of the solution from 12 to 30 DM3/min, wherein the copper concentration in the solution is maintained within the range of 35-65 g/DM3the electrolysis is carried out at a voltage in a bath of 0.25-0.6 V and the daily output part of the solution volume of the block of the series of baths, which is 1-4% of the total volume, and fill it with condensate or copper-containing solution.



 

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