CN101260539A - Purifying and impurity-removing method for copper electrolytic solution - Google Patents
Purifying and impurity-removing method for copper electrolytic solution Download PDFInfo
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- CN101260539A CN101260539A CNA2008100311448A CN200810031144A CN101260539A CN 101260539 A CN101260539 A CN 101260539A CN A2008100311448 A CNA2008100311448 A CN A2008100311448A CN 200810031144 A CN200810031144 A CN 200810031144A CN 101260539 A CN101260539 A CN 101260539A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a copper electrolyte purification and impurity removal method, wherein, the speed of arsenic antimonates being separated out from copper electrolytes is accelerated by control of the relative mass ratio of antimony/bismuth in anode coppers to be 0.8 to 8.0 percent, the concentration of arsenic in the copper electrolytes to be 4.0 grams per liter to 15 grams per liter, and the concentration ratio of arsenic (III)/arsenic (V) to be 0.01 to 0.15, and then the self purification and impurity removal capacity of the copper electrolytes is further improved; the volume of the electrolytes which are purified by adoption of the prior art for production of a ton of cathode coppers during the electrorefining process of the coppers is driven to be below 0.1m<3>; the impurity concentration in the electrolytes is maintained to be 50 to 250 milligrams per liter for antimony and 60 to 300 milligrams per liter for bismuth. The copper electrolyte purification and impurity removal method has the advantages of simple technology, simple and convenient operation, small reagent dosage, good purification effect, low production cost, no side effect on the main technology and so on.
Description
Technical field
The present invention relates to a kind of purifying and impurity-removing method for copper electrolytic solution.
Background technology
Arsenic in the anode copper, antimony, bismuth impurity enter electrolytic solution in the electrolytic refining process with the anode copper electrochemical dissolution.Because the deposition potential of these impurity and the deposition potential of copper are approaching, when arsenic, antimony, the bismuth concentration in electrolytic solution runs up to a certain degree, will separate out at negative electrode, influence the quality of cathode copper.Therefore, the cupric electrolysis refinery practice will constantly purify electrolytic solution.The traditional technology of cleaning copper electrolyte is: extract part electrolytic solution from electrolyte circulation system; Evaporation, crystallization obtain copper sulfate; Crystalline mother solution electrodeposition decopper(ing) takes off the assorted black copper mud that contains As, Sb, Bi that produces, and decopper(ing) liquid returns electrolyte circulation system; If anode copper is nickeliferous higher, decopper(ing) liquid then elder generation returns the copper electrolyte recycle system again after crude nickle sulphate is reclaimed in electricity evaporation, crystallization.
Copper electrolyte tradition purification process exists the energy consumption height (to purify 1m
3Electrolytic solution power consumption 100-120kwh, steam 0.8-1 ton), operating environment is poor (to be produced a large amount of black copper mud, and discharges obnoxious flavour AsH
3) etc. defective.The clean liquid measure of ton copper of copper electrolyzing refining is normally produced 1 ton of cathode copper and will be purified 0.4-0.6m
3Electrolytic solution, the concentration that just can keep impurity Sb, Bi in the electrolytic solution is all at 300～400mg/L.Along with the develop rapidly of copper metallurgy industry, the high-quality copper ore concentrates is fewer and feweri, and the content of As, Sb, Bi is in rising trend in the mineral products anode copper, and the clean liquid measure of ton copper of copper electrolyzing refining has to increase thereupon.The clean liquid measure of ton copper increases, and not only will increase the cost of copper electrolyzing refining, and can cause the direct yield of electrorefining process copper to descend, and copper, acid are difficult to balance in the electrolytic solution.Therefore, people are seeking new cleaning copper electrolyte technology always, and develop many methods of effectively removing As, Sb, Bi, comprising stannic acid and active carbon purifying copper electrolyte, barium carbonate, the co-precipitation of carbonic acid fine linen remove Bi, organic solvent extraction Sb, Bi contain antimony adsorbents adsorb As, Sb, Bi, and resin absorption Sb, Bi etc.These methods all are to adopt passive mode to remove impurity from copper electrolyte, have ignored the self-purification ability that copper electrolyte itself is had.
Also there is the people in copper electrolyte, to increase arsenic solution or arsenic salt recently, make Sb in the electrolytic solution and Bi and As form precipitation and enter the anode sludge, but this method often only has certain assorted effect of taking off to copper electrolyte adding the arsenic initial stage, along with the prolongation decontamination effect improving of duration of service worse and worse.
Discover that the throw out that the As in the copper electrolyte, Sb, Bi form mainly is the arsenic stibnate.Accelerate the formation speed of arsenic stibnate, can obviously improve the self-purification ability of copper electrolyte, reduce the clean liquid measure of ton copper.Sb (V) is the core element that the arsenic stibnate forms, and does not have Sb (V) just can not produce arsenic stibnate precipitation in the copper electrolyte.As also plays crucial effect: aH to the formation of arsenic stibnate in the copper electrolyte
3AsO
4+ bH[Sb (OH)
6]+cMeO
+→ Me
cAs
aSb
bO
(3a+5b+c/2+1)H
(a+5b-2c+2)XH
2O+cH
++ (a+b+c/2-1-x) H
2O, Me=As (III) wherein, Bi (III) and Sb (III); A 〉=1, b 〉=1, c≤(3a+b).
Summary of the invention
The objective of the invention is to reduce the clean liquid measure of ton copper of copper electrolyzing refining; reduce the production cost of cleaning copper electrolyte, energy-saving and cost-reducing, the protection environment; improve the direct yield of cupric electrolysis refining process process metallic copper, the invention provides a kind of purifying and impurity-removing method for copper electrolytic solution.
Technical scheme of the present invention is:
Relative mass by the Sb/Bi of control in the anode copper is 0.01～0.15 than the concentration ratio that is 0.8～8.0, the concentration of As is As in 4.0g/L～15g/L, the copper electrolyte (III)/As (V) in the copper electrolyte, accelerate the arsenic stibnate and in copper electrolyte, precipitate the speed of separating out, and then improve the ability of copper electrolyte self-purification removal of impurities.Make one ton of cathode copper of the every production of electrolytic refining course of copper adopt the electrolytic solution volume of traditional technology purification by 0.4-0.6m
3Reduce to 0.1m
3Below, impurity concentration maintains Sb 50-250mg/L, Bi 60-300mg/L in the electrolytic solution.
The present invention is by regulating the relative mass ratio of Sb/Bi in the anode copper, improve the concentration of As in the copper electrolyte, reach and in copper electrolyte, go into the concentration ratio that oxygenant reduces As (III)/As (V), impel Sb (III) to be oxidized to Sb (V), quickening As, Sb, Bi form the sedimentary speed of arsenic stibnate in electrolytic solution, to improve the self-purification ability of copper electrolyte, reduce electrolytic refining course of copper impurity Sb, the concentration of Bi in electrolytic solution.
Specific embodiment of the invention process is:
A kind of purifying and impurity-removing method for copper electrolytic solution technological process mainly comprise the relative mass of regulating Sb/Bi in the anode copper than total arsenic concentration in, the control copper electrolyte, add three steps of concentration ratio that oxygenant changes As (III)/As (V) in the electrolytic solution, the relevant parameter of its technological process is: if the relative content of copper metallurgy Sb in raw materials is lower, in copper ore concentrates, allocate an amount of high antimony concentrate into or add a certain amount of high antimony matte, make the relative mass ratio of Sb/Bi in the anode copper increase to 0.8～8.0 in the process of bessemerizing; If the concentration of As is lower in the copper electrolyte, adopt the electrolysis of high arsenic anode copper or add arsenic containing solution in the electrolytic solution or add cupric arsenic salt, make that the concentration of As maintains 4.0g/L～15g/L in the copper electrolyte; In copper electrolyte, extraordinarily go into hydrogen peroxide or peroxosulphuric or chloric acid or perchloric acid and make oxygenant, make the concentration ratio of As in the copper electrolyte (III)/As (V) reduce to 0.01～0.15 by stoichiometric 1.0-3.0.
Technological process improves the concentration of As in the copper electrolyte mainly by the relative mass ratio of regulating Sb/Bi in the anode copper, adds three steps formations of concentration ratio that oxygenant reduces As (III)/As (V) in the electrolytic solution; If in the copper metallurgy material in the relative content of Sb and the copper electrolyte one of concentration of As can satisfy the condition that the arsenic stibnate forms, then technological process is by the relative mass ratio of regulating Sb/Bi in the anode copper, or in the raising copper electrolyte As concentration and add two steps of concentration ratio that oxygenant reduces As (III)/As (V) in the electrolytic solution and constitute; If the relative content of Sb in the copper metallurgy material, and the concentration of As can both satisfy the condition that the arsenic stibnate forms in the copper electrolyte, technological process only needs to add the concentration ratio that oxygenant reduces As (III)/As (V) in copper electrolyte.
The present invention compares with existing technology and has the following advantages and effect:
1. by improving the relative content of Sb in the anode copper, can increase impurity A s, Sb, Bi, reduce the clean liquid measure of ton copper, reduce production costs, reduce emission of harmful substances amounts such as AsH3 in the ratio that electrolytic refining course of copper enters the anode sludge.
2, by keeping As concentration higher in the copper electrolyte, and the adding oxygenant reduces the concentration ratio of As (III)/As (V) in the electrolytic solution, can impel Sb (III) to be oxidized to Sb (V), quickening As, Sb, Bi form the sedimentary speed of arsenic stibnate in electrolytic solution, and then the self-purification ability of raising copper electrolyzing refining electrolytic solution, reduce the clean liquid measure of ton copper, reduce the concentration of impurity Sb, Bi in the electrolytic solution, guarantee the quality of cathode copper.
3. technology is simple, and is easy and simple to handle, and reagent dosage is few, and production cost is low, good purification, and main technology had no side effect.
Embodiment
Below in conjunction with embodiment, the present invention is further described, following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Mineral products anode copper electrolytic refining: circulation of elecrolyte, add hydrogen peroxide continuously by stoichiometric 2.2 times, the concentration ratio that makes As in the electrolytic solution (III)/As (V) is less than 0.05, and add an amount of additive (gelatine, thiocarbamide etc.), the control electrolyte temperature is 65 ± 2 ℃, and the setting current density is 265A/m
2, the clean liquid measure of ton copper is less than 0.1m
3, the result of laboratory test of electrolytic solution, the anode sludge is as follows behind the copper electrolyzing refining one-period:
| Cu | As | Sb | Bi | Ni | Fe | H 2SO 4 | |
| Anode copper, % | 99.39 | 0.19 | 0.031 | 0.028 | 0.038 | 0.003 | ---- |
| Electrolytic solution, g/L | 45.52 | 4.265 | 0.186 | 0.245 | 9.82 | 1.46 | 175.68 |
| The anode sludge, % | 12.34 | 7.65 | 7.16 | 6.87 | --- | --- | ---- |
Embodiment 2
Mineral products anode copper electrolytic refining: circulation of elecrolyte, adding arsenic containing solution makes in the electrolytic solution concentration of As bring up to 9.1g/L by 3.5g/L, and by stoichiometric 1.5 times of continuous peroxosulphuric that add, the concentration ratio that makes As in the electrolytic solution (III)/As (V) is less than 0.12, the kind of additive and add-on are identical with embodiment 1, the control electrolyte temperature is 65 ± 2 ℃, and the setting current density is 285A/m
2, the clean liquid measure of ton copper is less than 0.1m
3, the result of laboratory test of copper electrolyzing refining two all after date electrolytic solution, the anode sludge is as follows:
| Cu | As | Sb | Bi | Ni | Fe | H 2SO 4 | |
| Anode copper, % | 99.39 | 0.19 | 0.045 | 0.027 | 0.038 | 0.003 | ---- |
| Electrolytic solution, g/L | 46.82 | 8.848 | 0.063 | 0.102 | 9.22 | 1.38 | 188.23 |
| The anode sludge, % | 11.42 | 8.31 | 8.05 | 7.42 | --- | --- | ---- |
Embodiment 3
Add high antimony matte in the process of bessemerizing, make the relative mass of Sb/Bi in the anode copper carry out electrolytic refining: circulation of elecrolyte than being increased to 1.81 by 0.433, add chloric acid continuously by stoichiometric 1.2 times, the concentration ratio that makes As in the electrolytic solution (III)/As (V) is less than 0.09, and add an amount of additive (gelatine, thiocarbamide etc.), the control electrolyte temperature is 65 ± 2 ℃, and the setting current density is 255A/m
2, the clean liquid measure of ton copper is less than 0.1m
3, the result of laboratory test of copper electrolyzing refining electrolytic solution, anode sludge after 10 days is as follows:
| Cu | As | Sb | Bi | Ni | Fe | H 2SO 4 | |
| Anode copper, % | 99.27 | 0.21 | 0.105 | 0.058 | 0.033 | 0.003 | ---- |
| Electrolytic solution, g/L | 46.53 | 6.248 | 0.103 | 0.121 | 10.10 | 1.52 | 178.23 |
| The anode sludge, % | 11.42 | 8.41 | 8.65 | 6.52 | --- | --- | ---- |
Claims (6)
1, a kind of purifying and impurity-removing method for copper electrolytic solution, it is characterized in that, in copper electrolyte, precipitate the ability that the speed of separating out improves the removal of impurities of copper electrolyte self-purification by accelerating the arsenic stibnate, the arsenic stibnate precipitates the condition of separating out in copper electrolyte: the relative mass ratio of the Sb/Bi in the anode copper is 0.8～8.0, the concentration of As is 4.0g/L～15g/L in the copper electrolyte, and the concentration ratio of As in the copper electrolyte (III)/As (V) is 0.01～0.15.
2, a kind of purifying and impurity-removing method for copper electrolytic solution according to claim 1, it is characterized in that, under the relative mass of copper metallurgy Sb in raw materials/Bi compares less than 0.8 situation, allocate high antimony concentrate into or add high antimony matte in the process of bessemerizing in copper ore concentrates, making the relative mass ratio of Sb/Bi in the anode copper is 0.8～8.0.
3, a kind of purifying and impurity-removing method for copper electrolytic solution according to claim 1, it is characterized in that, the concentration of As is lower than under the 4.0g/L situation in copper electrolyte, adopt the electrolysis of high arsenic anode copper or add arsenic containing solution or interpolation arsenic salt in electrolytic solution, the concentration that makes As in the copper electrolyte is 4.0g/L～15g/L.
4, a kind of purifying and impurity-removing method for copper electrolytic solution according to claim 1, it is characterized in that, extraordinarily go into hydrogen peroxide or peroxosulphuric or chloric acid or perchloric acid by the stoichiometric 1.0-3.0 of oxidation As (III) and make oxygenant, making the concentration ratio of As in the copper electrolyte (III)/As (V) is 0.01～0.15.
5, a kind of purifying and impurity-removing method for copper electrolytic solution according to claim 1 is characterized in that, one ton of cathode copper of the every production of electrolytic refining course of copper adopts the electrolytic solution volume of traditional technology purification less than 0.1m
3
6, a kind of according to claim 1 or 5 purifying and impurity-removing method for copper electrolytic solution is characterized in that, the concentration Sb 50-250mg/L of impurity, Bi 60-300mg/L in the electrolytic solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100311448A CN101260539A (en) | 2008-04-24 | 2008-04-24 | Purifying and impurity-removing method for copper electrolytic solution |
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| CNA2008100311448A CN101260539A (en) | 2008-04-24 | 2008-04-24 | Purifying and impurity-removing method for copper electrolytic solution |
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| CN101260539A true CN101260539A (en) | 2008-09-10 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104060295A (en) * | 2014-07-14 | 2014-09-24 | 中南大学 | Copper electrolyte adsorption, impurity removal and purification method |
| CN106222696A (en) * | 2016-07-21 | 2016-12-14 | 金川集团股份有限公司 | Except the method for antimony in a kind of copper electrolyte |
| CN109628953A (en) * | 2018-12-26 | 2019-04-16 | 浙江工业大学 | The method of arsenic removal antimony bismuth is gone in a kind of copper electrolyte |
| CN111020634A (en) * | 2019-12-27 | 2020-04-17 | 中南大学 | Method for separating arsenic by copper electrolyte precipitation based on directional crystal form regulation |
| CN111519213A (en) * | 2020-05-09 | 2020-08-11 | 广东飞南资源利用股份有限公司 | Electrolytic purification process for copper electrolyte |
| CN111778520A (en) * | 2020-05-22 | 2020-10-16 | 西北矿冶研究院 | Method for reducing floating anode mud in copper electrolysis process by parallel flow precipitation method |
-
2008
- 2008-04-24 CN CNA2008100311448A patent/CN101260539A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104060295A (en) * | 2014-07-14 | 2014-09-24 | 中南大学 | Copper electrolyte adsorption, impurity removal and purification method |
| CN106222696A (en) * | 2016-07-21 | 2016-12-14 | 金川集团股份有限公司 | Except the method for antimony in a kind of copper electrolyte |
| CN106222696B (en) * | 2016-07-21 | 2018-07-10 | 金川集团股份有限公司 | A kind of method that antimony is removed in copper electrolyte |
| CN109628953A (en) * | 2018-12-26 | 2019-04-16 | 浙江工业大学 | The method of arsenic removal antimony bismuth is gone in a kind of copper electrolyte |
| CN109628953B (en) * | 2018-12-26 | 2020-10-23 | 浙江工业大学 | Method for removing arsenic, antimony and bismuth in copper electrolyte |
| CN111020634A (en) * | 2019-12-27 | 2020-04-17 | 中南大学 | Method for separating arsenic by copper electrolyte precipitation based on directional crystal form regulation |
| CN111519213A (en) * | 2020-05-09 | 2020-08-11 | 广东飞南资源利用股份有限公司 | Electrolytic purification process for copper electrolyte |
| CN111778520A (en) * | 2020-05-22 | 2020-10-16 | 西北矿冶研究院 | Method for reducing floating anode mud in copper electrolysis process by parallel flow precipitation method |
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Open date: 20080910 |