CN101906654B - Method for purifying copper electrolyte with minimal chemical reacting dose - Google Patents
Method for purifying copper electrolyte with minimal chemical reacting dose Download PDFInfo
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- CN101906654B CN101906654B CN 201010230354 CN201010230354A CN101906654B CN 101906654 B CN101906654 B CN 101906654B CN 201010230354 CN201010230354 CN 201010230354 CN 201010230354 A CN201010230354 A CN 201010230354A CN 101906654 B CN101906654 B CN 101906654B
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Abstract
The invention relates to a method for purifying copper electrolyte, which belongs to the technical field of wet-process metallurgy. High-purity cathode copper, crude copper sulphate, black copper and nickel are obtained by the following steps of: removing copper by electro-deposition; evaporating and condensing liquid in vacuum after copper removal; crystallizing condensate after the copper removal to obtain copper sulfate; preparing electrolyte from which arsenic is removed; removing arsenic by the electro-deposition; and performing filter pressing on black copper slurry. Due to the adoption of the method of the invention, the electrolyte can be purified during copper electro-deposition and the arsenic is removed in the form of an arsenic-copper alloy, so that the production of hydrogen arsenide is controlled and the technical problem of realizing the purification of the copper electrolyte is solved. The method has the advantages of capability of preventing invalid removal of the copper and effectively controlling the separation of polluting AsH3, simple operation, low energy consumption and suitability for copper electrolytic purification process.
Description
Technical field
What the present invention relates to is a kind of method for purifying copper electrolyte of technical field of wet metallurgy.
Background technology
The method of electrodeposition is mostly adopted in the at home purification dearsenification of electrolytic solution in the cupric electrolysis production process.
Early stage normal operation extremely takes off method, two sections dearsenification methods.The characteristics of these two kinds of methods are that copper is preferentially separated out, and when copper ion concentration was reduced to a certain degree, arsenic just began to separate out, and produced a large amount of AsH
3Gas.Because low, a large amount of copper of dearsenification efficient is disabled and removes, power consumption is high, a large amount of AsH
3The reasons such as γ-ray emission, so these two kinds of methods are eliminated in larger smeltery.
Introduced revulsion from Japan afterwards, domestic well-known large smeltery is these methods of using at present more.Although this method dearsenification efficient increases, but still exist a certain amount of copper be disabled remove, power consumption is high, electrolyzer needs the shortcomings such as peculiar set-up, thereby inevitably increased the dearsenification cost.
The several method that also has in addition domestic rare application: periodic reverse current electrodeposition dearsenification method, limit current density electrodeposition dearsenification method, control cathode electromotive force electrodeposition dearsenification method.This several method exists needs the shortcoming that specific installation disposes, current density is low, the process parameter control accuracy requirement high, power consumption is high, therefore is not widely used.
In recent years, method of dearsenic by parallel circulating continuous electric formation has been invented by certain smeltery, and is more advanced.But any one behind the copper sulfate mother liquor that its two sections copper liberation cell bulking liquors are unspecified element, the decopper(ing) in liquid, the electrolytic solution, the part groove is the terminal point groove, still exists copper and is disabled the shortcoming that removes.
In sum, present employed arsenic removing method in various degree exist copper to be disabled to remove, power consumption height and AsH
3The problem of γ-ray emission.
Summary of the invention
Be disabled and remove and produce AsH in order to overcome electrolyte purification process copper
3Shortcoming, the present invention proposes a kind of method for purifying copper electrolyte.The method is obtained cathode copper, thick copper sulfate, black copper and nickel by electrodeposition decopper(ing) and dearsenification step from copper electrolytic process, solve simultaneously the technical problem of cleaning copper electrolyte.
The scheme that technical solution problem of the present invention adopts is:
1, electrodeposition decopper(ing) step 1: in cuprum-doffing electrolytic tank, inject the copper electrolyte that comes from potroom, make anode with stereotype, as negative electrode, between anode and negative electrode, pass into direct current with stainless steel plate, electrolyte temperature is controlled between 45-65 ℃, and current density is controlled at 190-330A/m
2Between.Under the effect of electric current, cupric ion is deposited on the stainless steel cathode, the fine copper of deposition cupric 99.9935%, arsenic, nickel impurity metal reside in the electrolytic solution, in electrolytic solution, also have the existence of cupric ion, liquid behind the generation decopper(ing), the liquid copper ion concentration is down to 38-40g/L behind the decopper(ing).
2, liquid vacuum evaporation step 2 behind the decopper(ing): liquid behind the decopper(ing) is joined in the vacuum-evaporator, and heating, makes the evaporation of the part moisture in the liquid behind the decopper(ing), make decopper(ing) after liquid concentrated, form concentrated solution behind the decopper(ing).
3, concentrated solution cupric sulfate crystals step 3 behind the decopper(ing): concentrated solution behind the decopper(ing) is joined in the water mold, and the crystallization control liquid temp is between 425-31 ℃, cupric sulphate crystal in the decopper(ing) concentrated solution, form thick copper sulfate and cupric sulfate crystals mother liquor, the copper arsenic in the cupric sulfate crystals mother liquor is than being 1.7-2.5: 1.
4, dearsenification electrolyte quota step 4: the cupric sulfate crystals mother liquor is joined in the dearsenification electrolyte quota groove, and mix with liquid after the dearsenification, be equipped to copper ion concentration at 5-7g/l, ω
Cu: ω
AsBe 1.7-2.5: 1 dearsenification electrolytic solution.
5, electrodeposition dearsenification step: dearsenification electrolytic solution is injected in the dearsenification electrolyzer, makes anode with stereotype, as negative electrode, pass into electric current with stainless steel plate between anode and negative electrode, electrolyte temperature is controlled at 58-65 ℃, and current density is controlled at 160-330A/m
2, under the effect of electric current, the copper in the electrolytic solution and arsenic form the copper arsenic alloy, are called black copper.Isolate black copper and carry out the black copper treatment process, and after the dearsenification after liquid and the press filtration liquid partly enter the nickel treatment process, part is sent potroom back to.Wherein liquid partly is sent in the dearsenification electrolyte quota groove after the dearsenification, is used for being mixed with dearsenification electrolytic solution with the cupric sulphate crystal mother liquor.
6, black copper slurry press filtration step: isolate black copper through the black copper slurry that produces after the electrodeposition dearsenification through press filtration, liquid is sent potroom back to after the press filtration.
Positively effect adopts the inventive method, can purify electrolytic solution in electro deposited copper, and arsenic is removed in the mode of arsenical copper, controls the generation of hydrogen arsenide with this, realizes the cleaning copper electrolyte technical problem with minimum chemical reaction amount.Can avoid the invalid of copper to remove, effectively control the AsH with contaminative
3Separate out, energy consumption simple to operate is low.Suit in the cleaning copper electrolyte process, to use.
Description of drawings:
Fig. 1 is schema of the present invention.
Among the figure, 1. electrodeposition decopper(ing), 2. vacuum-evaporation, 3. water-cooled crystallization, 4. dearsenification electrolyte quota, 5. electrodeposition dearsenification, 6. press filtration.
Embodiment
The blister copper plate obtains fine copper by electrolysis, and in electrolytic process, transfer is deposited as high-purity copper from anode to negative electrode on electrode along with copper.Because contain the foreign metals such as arsenic, nickel in the blister copper, in electrolytic process, these impurity reside in the electrolytic solution, along with the accumulation of impurity, cause power consumption high, chemical ingredients and Quality Down, the chemical reaction amount is large.Based on this state, the present invention adopts following method and step, with the chemical reacting weight of minimum copper electrolyte is purified.
The below is elaborated with technical process shown in Figure 1
1, electrodeposition decopper(ing) step 1: in cuprum-doffing electrolytic tank, inject the copper electrolyte that comes from potroom, make anode with stereotype, as negative electrode, between anode and negative electrode, pass into direct current with stainless steel plate, the control electrolyte temperature is between 45-65 ℃, and the control current density is 190-330A/m
2Between.Under the effect of electric current, the cupric ion in the electrolytic solution is deposited on the stainless steel cathode, forms Cu-CATH-1, arsenic, nickel impurity metal reside in the electrolytic solution, in electrolytic solution, also have a small amount of cupric ion to exist, liquid behind the generation decopper(ing), the liquid copper ion concentration is down to 38-40g/L behind the decopper(ing).
2, liquid vacuum evaporation step 2 behind the decopper(ing): liquid behind the decopper(ing) is joined in the vacuum-evaporator, and heating, makes the evaporation of the part moisture in the liquid behind the decopper(ing), make decopper(ing) after liquid concentrated, form concentrated solution behind the decopper(ing).
3, concentrated solution cupric sulfate crystals step 3 behind the decopper(ing): concentrated solution behind the decopper(ing) is joined in the water mold, and the crystallization control liquid temp is between 5-10 ℃, cupric sulphate crystal in the decopper(ing) concentrated solution, form thick copper sulfate and cupric sulfate crystals mother liquor, the copper arsenic in the cupric sulfate crystals mother liquor is than being 1.7-2.5: 1.
4, dearsenification electrolyte quota step 4: the cupric sulfate crystals mother liquor is joined in the dearsenification electrolyte quota groove, and mix with liquid after the dearsenification, be equipped to copper ion concentration at 5-7g/l, ω
Cu: ω
AsBe 1.7-2.5: 1 dearsenification electrolytic solution.
5, electrodeposition dearsenification step: dearsenification electrolytic solution is injected in the dearsenification electrolyzer, makes anode with stereotype, as negative electrode, pass into electric current with stainless steel plate between anode and negative electrode, electrolyte temperature is controlled at 58-65 ℃, and current density is controlled at 160-330A/m
2, under the effect of electric current, the copper in the electrolytic solution and arsenic form the copper arsenic alloy and are called black copper.Isolate black copper and carry out the black copper treatment process, and after the dearsenification after liquid and the press filtration liquid partly enter the nickel treatment process, part is sent potroom back to.Wherein liquid partly is sent in the dearsenification electrolyte quota groove after the dearsenification, is used for being mixed with dearsenification electrolytic solution with the cupric sulphate crystal mother liquor.
6, black copper slurry press filtration step: isolate black copper through the black copper slurry that produces after the electrodeposition dearsenification through press filtration, liquid is sent potroom back to after the press filtration.
By control bulking liquor internal circulating load and current density, make press filtration after the liquid copper ion concentration be controlled at 0.5-2g/L, establishment AsH
3In the situation about separating out, arsenic is efficiently removed with the form of arsenical copper, and generate Cu as much as possible
2As.
In electrodeposition dearsenification step, under the effect of electric current, part copper is combined with arsenic and is formed arsenical copper, thereby has removed arsenic in electrolytic solution, and prevents that arsenic is combined the generation hydrogen arsenide with hydrogen ion.
In decopper(ing) and dearsenification process, used chemical substance is minimum, the chemical reaction amount is minimum, thereby reaction thoroughly, and idle work consumes little, under the prerequisite that does not add other cleaning copper electrolyte material, by the cupric ion of self and effective combination of arsonium ion in the electrolytic solution, deviate from copper and arsenic wherein, copper electrolyte has been purified, and can reuses.
Dearsenification electrolyzer used in the present invention is the terminal point groove.
Advantage of the present invention:
1, because the present invention follows minimum chemical reacting weight principle, invalid in the dearsenification process, low validity response is reached minimize, the product minimum number has avoided the invalid of copper to remove to greatest extent, thereby effectively reduces dearsenification power consumption and cost.
2, the advantage that the present invention has efficiently, throughput is large, current density can be up to 330A/m
2, dearsenification efficient reaches more than 90%.In the same process situation, required dearsenification electrolyzer is minimum.
3, the present invention can by effective fixed action of copper arsenic alloy, effectively control the AsH with contaminative
3Separate out.
4, the processing parameter of control required for the present invention is few, and is simple to operate.
5, electrolytic solution feed liquid way of the present invention can reduce concentration polarization, improves current density
Claims (2)
1. method for purifying copper electrolyte is characterized in that:
1), electrodeposition decopper(ing) step 1: in cuprum-doffing electrolytic tank, inject the copper electrolyte that comes from potroom, make anode with stereotype, as negative electrode, between anode and negative electrode, pass into direct current with stainless steel plate, the control electrolyte temperature is controlled between 45-65 ℃, and the control current density is 190-330A/m
2Between, under the effect of electric current, cupric ion is deposited on the stainless steel cathode, form 99.9935% cathode copper, arsenic, nickel impurity metal reside in the electrolytic solution, also have the existence of cupric ion in electrolytic solution, liquid behind the generation decopper(ing), the liquid copper ion concentration is down to 38-40g/L behind the decopper(ing);
2), liquid vacuum evaporation step 2 behind the decopper(ing): liquid behind the decopper(ing) is joined in the vacuum-evaporator, and heating, makes the part moisture evaporation in the liquid behind the decopper(ing), make decopper(ing) after liquid concentrated, form concentrated solution behind the decopper(ing);
3), concentrated solution cupric sulfate crystals step 3 behind the decopper(ing): concentrated solution behind the decopper(ing) is joined in the water mold, and the crystallization control liquid temp is between 25-31 ℃, cupric sulphate crystal in the decopper(ing) concentrated solution, form thick copper sulfate and cupric sulfate crystals mother liquor, the copper arsenic in the cupric sulfate crystals mother liquor is than being 1.7-2.5: 1;
4), dearsenification electrolyte quota step 4: the cupric sulfate crystals mother liquor is joined in the dearsenification electrolyte quota groove, and mix with liquid after the dearsenification, be equipped to copper ion concentration at 5-7g/l, ω
Cu: ω
AsBe 1.7-2.5: 1 dearsenification electrolytic solution;
5), electrodeposition dearsenification step: dearsenification electrolytic solution is injected in the dearsenification electrolyzer, makes anode with stereotype, as negative electrode, pass into electric current with stainless steel plate between anode and negative electrode, electrolyte temperature is controlled at 58-65 ℃, and current density is controlled at 160-330A/m
2Under the effect of electric current, copper in the electrolytic solution and arsenic form the copper arsenic alloy and are called black copper, isolate black copper and carry out the black copper treatment process, and after the dearsenification after liquid and the press filtration liquid partly enter the nickel treatment process, part is sent potroom back to, and wherein liquid partly is sent in the dearsenification electrolyte quota groove after the dearsenification, is used for being mixed with dearsenification electrolytic solution with the cupric sulphate crystal mother liquor;
6), black copper slurry press filtration step: isolate black copper through the black copper slurry that produces after the electrodeposition dearsenification through press filtration, liquid is sent potroom back to after the press filtration.
2. a kind of method for purifying copper electrolyte according to claim 1, it is characterized in that: the dearsenification electrolyzer is the terminal point groove.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181668B (en) * | 2011-03-02 | 2013-01-30 | 广西壮族自治区地质矿产测试研究中心 | Method for jointly extracting arsenic from high-arsenic manganese ore tailings |
| CN102345143B (en) * | 2011-10-09 | 2014-01-15 | 中南大学 | Method for separating copper, arsenic and nickel and purifying copper electrolyte |
| CN102633392A (en) * | 2012-05-04 | 2012-08-15 | 山东建筑大学 | Cyclic utilization of waste liquor in small sulfate copper plating process test |
| CN103147094B (en) * | 2013-02-07 | 2015-07-01 | 李东 | Process for deep copper removal through electrodeposition |
| CN106521184A (en) * | 2016-11-04 | 2017-03-22 | 金少平 | Process for extracting copper sulfate through waste copper scraps |
| CN109252189A (en) * | 2018-10-30 | 2019-01-22 | 金川集团股份有限公司 | A kind of method that high purity copper is extracted in waste solution of copper electrolysis purification |
| CN110938842A (en) * | 2019-12-06 | 2020-03-31 | 中国瑞林工程技术股份有限公司 | Copper electrolyte purification method |
| CN112662879A (en) * | 2020-12-11 | 2021-04-16 | 广西金川有色金属有限公司 | Efficient method for extracting nickel sulfate from copper electrolysis waste liquid |
| CN112725844B (en) * | 2020-12-21 | 2023-04-07 | 万载志成实业有限公司 | Electrolyte purification method for electrolytic copper production process |
| CN115074784A (en) * | 2021-03-10 | 2022-09-20 | 中国科学院过程工程研究所 | Method for efficiently removing arsenic through electrolysis in refined copper electrolyte |
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| CN1560289A (en) * | 2004-02-27 | 2005-01-05 | 云南铜业股份有限公司 | Method of dearsenic by parallel circulating continuous electric formation |
| CN101717960A (en) * | 2009-12-07 | 2010-06-02 | 郑雅杰 | Method for purifying copper electrolyte by using chemical reduction method |
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2010
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Patent Citations (2)
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| CN1560289A (en) * | 2004-02-27 | 2005-01-05 | 云南铜业股份有限公司 | Method of dearsenic by parallel circulating continuous electric formation |
| CN101717960A (en) * | 2009-12-07 | 2010-06-02 | 郑雅杰 | Method for purifying copper electrolyte by using chemical reduction method |
Non-Patent Citations (3)
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