Method for purifying copper electrolyte by regulating valence state

A copper electrolyte and electrolyte technology, applied in the field of purifying copper electrolyte, can solve the problems of long extraction process, low current efficiency and high cost of returning materials, and achieve good impurity removal effect, low current efficiency and high cost of returning materials Effect

Inactive Publication Date: 2012-11-21
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Purification of copper electrolyte by electrowinning has the following disadvantages: ① using insoluble anode for electrolysis, high cell voltage, low current efficiency, and high energy consumption; ② highly toxic arsine gas is precipitated at the end of electrowinning; Higher black copper needs to be further processed. If it is returned to smelting, not only the cost of returning materials will be high, but also lead to a vicious cycle of arsenic, antimony, and bismuth in the smelting system; ④ Excessive copper removal causes copper acid imbalance
Its disadvantage is that the resin exchange capacity is limited, and the Cl produced by the analysis - Contaminated electrolyte
The extraction method is strong for As extraction, but weak for antimony and bismuth, the extraction process is long, the loss of extraction agent is large, and the cost is high
The precipitation effect of the precipitation method is not ideal, the amount of precipitant is large, and the operation is complicated
The patented technology for copper arsenite purification of copper electrolyte still has the following two problems: (1) the preparation of copper arsenite generally uses the highly toxic chemical arsenic as raw material, which requires strict management; (2) as the electrolysis proceeds, the As accumulates with it, arsenic removal still needs to be done
Directly use sulfur dioxide to reduce and purify the copper electrolyte, which has a certain removal effect on arsenic, but has a low removal rate on antimony and bismuth

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0007] In 1800mL copper electrolyte, pass through SO 2 restore, SO 2 The gas flow rate was 600mL / min, and the reduction was performed at 45°C for 5h; another 1200mL of copper electrolyte was added, hydrogen peroxide was added, and the reaction was carried out at 25°C for 0.5h. The composition of the copper electrolyte was shown in Table 1.

[0008] Mix the reduced electrolyte with the oxidized electrolyte, at this time the copper electrolyte n 5价As : n 总As and n 5价Sb : n 总Sb Both are 0.4. Heating and evaporation, when the copper electrolyte volume is concentrated from 3000mL to 1200mL, after cooling crystallization and filtration, the removal rate of copper is 85%, the removal rate of total arsenic is 62.4%, the removal rate of antimony is 60%, and the removal rate of bismuth The rate is 91%.

[0009] Table 1 Composition of copper electrolyte / g L -1

[0010] Cu As Sb Bi h 2 SO 4 32 10 0.75 0.45 203

Embodiment 2

[0012] In 1500mL copper electrolyte, feed sulfur dioxide at a flow rate of 500mL / min, and reduce at 30°C for 5.5h; take another 1500mL copper electrolyte, add hydrogen peroxide, and react at 25°C for 0.5h.

[0013] Mix the reduced electrolyte with the oxidized electrolyte, at this time the copper electrolyte n 5价As : n 总As and n 5价Sb : n 总Sb Both are 0.50. Heating, evaporating and concentrating, cooling and crystallizing at 10°C, and then filtering to obtain 1.2 L of filtrate. The composition of the copper electrolyte before and after purification is shown in Table 2. It can be seen from the calculation of the experimental results that the removal rate of copper is 86%, the removal rate of total arsenic is 62.01%, the removal rate of total antimony is 68%, and the removal rate of bismuth is 91.05%.

[0014] Table 2 Composition of copper electrolyte / g L -1

[0015] Composition of copper electrolyte Total arsenic total antimony Cu Bi Before pur...

Embodiment 3

[0017] In 1600mL copper electrolyte, pass through SO 2 restore, SO 2 The gas flow rate was 600mL / min, and the reduction was performed at 45°C for 5h; another 400mL of copper electrolyte was added, hydrogen peroxide was added, and the reaction was carried out at 25°C for 0.5h. The composition of the copper electrolyte was shown in Table 3.

[0018] Mix the reduced electrolyte with the oxidized electrolyte, at this time the copper electrolyte n 5价As : n 总As and n 5价Sb : n 总Sb Both are 0.2. Heating and evaporation, when the copper electrolyte volume is concentrated from 2000mL to 800mL, after cooling crystallization and filtration, the removal rate of copper is 83%, the removal rate of total arsenic is 86%, the removal rate of antimony is 52%, and the removal rate of bismuth The rate is 87%.

[0019] Table 3 Composition of copper electrolyte ρ / g L -1

[0020] Cu As Sb Bi h 2 SO 4 32 12 0.62 0.32 220

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Abstract

A method for purifying copper electrolyte by regulating valence state comprise the following steps: introducing sulfur dioxide in part of copper electrolyte, reducing pentavalent As and pentavalent Sb in the copper electrolyte into trivalent As and trivalent Sb; adding oxidizer into the other part of copper electrolyte, thus oxidizing trivalent As and trivalent Sb in the copper electrolyte into pentravalent As and pentravalent Sb; then mixing the reduced copper electrolyte and oxidized copper electrolyte, and adjusting the valence state ratio of the pentravalent As to the pentravalent Sb in the copper electrolyte, thus leading n pentravalent As: n total As and n pentravalent Sb in the mixed copper electrolyte to be 0.05-0.8; and after adjusting the valence state ratio of As to Sb in the copper electrolyte, removing Cu, As, Sb and Bi in the electrolyte by concentration and crystallization, thus purifying the electrolyte. In the invention, the method of regulating the valence state of As and Sb is adopted for purifying the copper electrolyte, so that the defect of black copper slag and arsenic hydride generated by electrodeposition is eliminated, the process is simple and the energyconsumption is low.

Description

technical field [0001] The invention relates to a method for purifying copper electrolyte. Background technique [0002] During the copper electrolytic refining process, As, Sb, and Bi impurities in the anode copper enter the copper electrolyte with a certain distribution ratio and accumulate gradually. They not only deposit on the cathode, but also form floating anode slime, affecting the quality of cathode copper. Therefore, the removal of As, Sb, and Bi impurities is the main goal of copper electrolyte purification. The copper electrolyte purification process widely adopts the electrowinning method, and the electrowinning method is divided into intermittent decopper method, periodic reverse current electrolysis method, limiting current density method, and induced decopper and arsenic removal method. In addition to electrowinning, there are ion exchange, extraction, chemical precipitation, and chemical reduction. [0003] Purification of copper electrolyte by electrowin...

Claims

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Application Information

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Patent Type & AuthorityPatents(China)
IPC IPC(8): C25C1/12C25C7/06
CPCY02P10/20
Inventor郑雅杰彭映林周文科
OwnerCENT SOUTH UNIV