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Copper electrolyte purifying technology

A copper electrolyte and purification process technology, which is applied in the separation of impurities and copper electrolyte purification process, can solve the problems of poor working environment, increased electrolyte resistance, and low direct copper recovery rate, and overcome the problem of low purification efficiency Effect

Active Publication Date: 2015-10-07
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There are many defects in the traditional copper electrolyte purification process using electrowinning to remove impurities As, Sb, and Bi: the effective utilization rate of electricity in the electrowinning process is very low, generally less than 20%; the energy consumption is high, and the purification of 1m 3 The electrolyte consumes 100-120kwh of electricity and 0.8-1 ton of steam; the operating environment of the clean liquid is poor, producing a large amount of black copper sludge and black copper plates, and releasing harmful gas AsH 3 ; The direct recovery rate of copper is low, and the black copper sludge and black copper plate produced need to be returned to the fire process system to recycle the copper, causing copper and impurities arsenic, antimony, and bismuth to circulate in the smelting system
However, these methods can only be used to remove impurities such as arsenic, antimony, and bismuth, but cannot remove impurities such as nickel and iron.
Therefore, these methods can only be used as a supplement to electrowinning copper removal and impurity removal, and cannot completely replace the traditional copper electrolyte purification process.
Another reason why these methods cannot replace the traditional process of copper electrolyte purification is that the separation of copper and nickel in the electrolyte can only rely on electrowinning.
[0009] The separation and recovery of nickel in the purification process of copper electrolyte is not only because the recovery of nickel has certain economic value, but more importantly, with the increase of Ni concentration, the resistance of the electrolyte increases, and the unit power consumption of the copper electrolytic refining process increases
The forced freezing and crystallization of the liquid after the second decopper removal can separate some impurities such as nickel and iron, but the separation efficiency is not high. Generally, the crystallization of nickel is less than 60%. 24h, the liquid still contains 15-20g / L Ni after crystallization
In short, the traditional purification process of copper electrolyte has defects such as low purification efficiency, high production cost, and poor working environment.

Method used

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  • Copper electrolyte purifying technology

Examples

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Effect test

Embodiment 1

[0045] Take 1L of copper electrolytic refining electrolyte, add Sb according to the molar ratio of Sb(III) / As(V) 2:1 2 o 3 , and add hydrated Sb according to Sb(IV) / Sb(III) molar ratio 1:7 2 o 4 As an adsorbent, it was stirred and adsorbed at 75°C for 1 hour and then filtered to obtain the loaded adsorbent and the adsorbed liquid. The obtained loaded adsorbent was mixed with water at a solid-to-liquid ratio of 1:6 g / ml, then added with sodium carbonate to adjust the pH to 10.6, stirred and desorbed at 70°C for 3 hours, and filtered to obtain the oxide of antimony hydrate and the desorbed solution. After the desorption solution was stirred and cooled at 10°C for 1 hour, the sodium arsenate product and its crystallized liquid were obtained by filtration. After the obtained adsorbed liquid is pre-decoppered by cooling and crystallizing copper sulfate at 5°C, ammonium sulfate is added according to 1.5 times the theoretical amount of ammonium sulfate double salt formed by Cu and...

Embodiment 2

[0048] Take 5m of the primary decopper solution produced in the copper electrolyte purification process 3 According to 1 times the theoretical amount of ammonium sulfate double salt formed by Cu and Ni, ammonia gas was introduced, stirred at -18°C for 6 hours, and the mixed crystal of copper nickel ammonium sulfate double salt and the solution after nickel removal were obtained by filtration. After the obtained nickel-removed liquid is adsorbed and removed, Sb is added according to the molar ratio of (Sb(III)+Bi(III)) / As(V) 2.5:1 2 o 3 and Bi 2 o 3 The mixture is used as the adsorbent, the Sb in the mixture 2 o 3 with Bi 2 o 3 The molar ratio of Sb(V) / Sb(III) is 4:1, and the hydrated Sb is added according to the Sb(V) / Sb(III) molar ratio of 1:5 2 o 5 , stirred and adsorbed at 85°C for 1.5h, and filtered to obtain the loaded adsorbent and the adsorbed liquid. The obtained adsorbed liquid is returned to the copper electrolysis production system for use; the obtained cop...

Embodiment 3

[0052] Take 1m of the secondary decopper solution produced in the copper electrolyte purification process 3 , according to wherein Cu and Ni form 0.8 times of the theoretical amount of ammonium sulfate double salt, add the nickel ammonium sulfate crystallization solution obtained in Example 2, stir at -5°C for 20h, filter to obtain copper nickel ammonium sulfate double salt mixed crystals and crystallization thereof liquid. The obtained liquid after crystallization is returned to the copper electrolysis production system for use; the obtained copper-nickel ammonium sulfate double salt mixed crystal is added with water at a solid / liquid ratio of 1:5g / ml, stirred and dissolved at 60°C; the obtained dissolved liquid is used as the organic phase selectivity of the P204-kerosene system Extract copper, the concentration of P204 in the organic phase is 10%, load the organic phase with 2mol / L H 4 SO 4 solution as back-extraction. The back-extraction liquid is concentrated to crysta...

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Abstract

The invention discloses a copper electrolyte purifying technology which comprises the following steps: adding a crystallizing agent into copper electrolyte or pre-decoppering post-liquid or adding a crystallizing agent into copper electrolyte after adsorption impurity removal treatment or pre-decoppering post-liquid; crystallizing to obtain copper-nickel compound salt; and separating and recycling copper and nickel from the obtained copper-nickel compound salt to realize purification of the copper electrolyte, wherein in the adsorption impurity removal treatment, an oxide of antimony and / or bismuth and the hydrate thereof are adopted as adsorbents to selectively adsorb the impurities As, Sb and Bi in the copper electrolyte, and the generation of black copper sludge, black copper plates and AsH3 gas can be thoroughly eliminated in a copper electrolyte purifying process. The technology disclosed by the invention has the advantages of simple process, simplicity and convenience in operation, low cost, high efficiency, good operation environment and the like, and is suitable for the industrial production of copper electrolyte purification.

Description

technical field [0001] The invention belongs to the field of hydrometallurgy, and in particular relates to a copper electrolyte purification process, which is suitable for the separation of impurities such as arsenic, antimony, bismuth and nickel in the copper electrolyte. Background technique [0002] In the copper electrolytic scouring process, impurities such as arsenic, antimony, bismuth and nickel in the anode copper are electrochemically dissolved together with the copper into the electrolyte. These impurities exhibit different behaviors during electrorefining and are classified according to their electrochemical order and their solubility in the electrolyte as follows: [0003] The first type of impurities include zinc, iron, nickel, lead, tin, etc. They are more electronegative than copper and thus dissolve electrochemically at the anode. Among them, lead and tin form a sulfate that is insoluble in the electrolyte——PbSO 4 and Sn(OH) 2 SO 4 , the content of these...

Claims

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Application Information

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IPC IPC(8): C22B3/22C22B15/00C25C1/12
CPCY02P10/20
Inventor 王学文王明玉王兴明
Owner CENT SOUTH UNIV
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