CN105274564A - Method for recovering copper and cyanide through electrodeposition of high-concentration waste liquid containing copper and cyanide - Google Patents
Method for recovering copper and cyanide through electrodeposition of high-concentration waste liquid containing copper and cyanide Download PDFInfo
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- CN105274564A CN105274564A CN201410233711.3A CN201410233711A CN105274564A CN 105274564 A CN105274564 A CN 105274564A CN 201410233711 A CN201410233711 A CN 201410233711A CN 105274564 A CN105274564 A CN 105274564A
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- copper
- cyanide
- prussiate
- recovery
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Abstract
The present invention discloses a treatment method for concurrently recovering copper and cyanide from high-concentration waste liquid containing copper and cyanide. The treatment method is characterized in that an electrodeposition method is used, an inhibitor (such as sulfite, thiosulfate, hypophosphite and the like) is added to inhibit oxidation decomposition of the cyanide at the anode so as to achieve the cyanide recovery, electrodeposition is performed at the cathode to obtain copper and the alloy thereof so as to achieve recovery of copper, zinc and the like in the wastewater, the treated wastewater can return to the cyanidation leaching process, and the leaching of gold and silver is not affected. With the method of the present invention, the effective recovery of the valuable elements in the cyanidation plant wastewater, electroplating wastewater containing cyanogen, and other waste liquids containing copper and cyanide can be achieved.
Description
Technical field
The invention belongs to Non-ferrous Metallurgy and field of environment protection, belong to a kind for the treatment of process simultaneously reclaiming copper and prussiate from cupric cyanide bearing waste solution.
Background technology
Gold has a very important role in fields such as national economy, finance, science and technology, in reply economic crisis, ensures also to play key player in economic security of the country.At present, extraction of gold by cyanidation is still the main method of golden production, calculates by the average Gold Content 5g/t of ore, and annual the produced cyanide wastewater of China can reach 1.4 hundred million tons more than.Due to the prussiate containing severe toxicity in the sewage of cyanide plant discharge and other valuable element, if directly discharge not only will have a strong impact on environmental safety, also cause the waste of resource, process must be managed.At present, the main process of cyaniding sewage is broadly divided into two classes: cyanide oxidation destroys and eliminates toxicity by a class, and metal ion forms throw out removal makes waste water be purified, and the comparatively normal method adopted has chlorination and SO
2-air methods etc., adopt the method for purifying treatment can not synthetical recovery valuable element, and the chlorination the most often adopted also to there is reagent consumption more, the higher problems such as reprocessing that still need of sewage residual chlorine after process; But for gold industry, Cyanide in Waste Water compound is also a kind of important secondary resource, therefore when processing cyaniding sewage, the prussiate in waste water regenerates by more employing absorption method, waste water after process returns use, but the copper-bearing mineral of association in gold mine can stripping in cyanidation-leaching process, the cyanide complex forming copper enters in solution, and constantly accumulate in the use procedure of cyaniding solution circulated, the more important thing is that the existence of copper in leach liquor also can reduce the dissolution rate of gold significantly, increase the consumption of prussiate, leaching efficiency is declined.In addition because Some Enterprises adopts zinc dust precipitation technique to carry gold, this makes simultaneously containing a large amount of zinc in sewage, and in leach liquor, the existence of zinc also can consume prussiate in a large number, increases and leaches reagent cost.Therefore, the recycle of cyaniding sewage be realized, just must select copper, zinc in suitable technique removal waste water.At present, industrial the most frequently used regeneration recovery method is acidization and zinc sulfate-sulfuric acid process.Acidization, full name is acidifying volatilization-alkali absorption method (AVR method).The method be by sulfuric acid acidation and protection alkali; free cyanide and the metal complex such as copper, zinc prussiate are decomposed and generates hydrogen cyanide gas; generate sodium cyanide recycle through air stripping, alkali liquor absorption, copper, zinc etc. are formed to be removed containing cyanogen complex precipitate.This treatment process is serious to equipment acid etching, and alkali liquor absorption tower very easily blocks again, and produces the prussic acid of severe toxicity in treating processes, there is serious potential safety hazard.Zinc sulfate-sulfuric acid process first in waste water, adds zinc sulfate, is that free cyanide and the metal complex such as copper, zinc prussiate are converted into zinc cyanide precipitation, then adopts vitriolization to zinc cyanide precipitate and separate, return use with after alkali liquor absorption regeneration.This technique acid consumption is little, and therefore processing cost is lower, but is still for the recovery of prussiate the technique adopting acidifying volatilization-alkali liquor absorption, therefore still cannot avoid the inherent defect of acidization.Electrolytic process Treatment of Cyanide-containing Wastewater is adopted industrially to be applied, but traditional electrolytic process treatment process is to destroy for the purpose of prussiate, only can reclaim the metallic element in waste water, therefore and be not suitable for the process of gold mine cyanide wastewater especially high cyanide containing wastewater this certainly will cause the waste of a large amount of prussiate; Electrodeposition-acidization is combined with acidization at electrolytic process, directly obtains metallic copper by electrolysis, realizes the efficient recovery of valuable metal element, then by acidization recovery of cyanide.But this technique still fails fundamentally to solve many drawbacks of acidization recovery of cyanide.Membrane electrolysis is oxidized by using diaphragm sell thus avoiding prussiate to enter positive column, and after galvanic deposit, electrolytic solution can directly return leaching operation, and the recovery achieving prussiate also fundamentally avoids the defect of acidization recovery.But because barrier film is expensive and work-ing life is short, also fail to realize large-scale industrial application.
More above-mentioned technique is known, and reclaiming valuable metal element by galvanic deposit is effective means the most, and in electrodeposition process, how to avoid prussiate, at anode, oxidation occurs be the key adopting electrodip process recovery of cyanide.The present invention, by adding inhibitor galvanic deposit cyanide wastewater under without the need to the condition of barrier film, had both reclaimed metal, had inhibit again the anodic oxidation of prussiate, achieved the efficient recovery of prussiate, fundamentally avoided the drawback of acidifying recovery of cyanide technique.
Summary of the invention
In the problems existed for current electrolysis art breading cupric cyanide wastewater, the invention provides a kind for the treatment of process simultaneously reclaiming copper and prussiate from cupric cyanide bearing waste solution, it is characterized in that without the need to adopting barrier film, by prussiate in the suppression electrolytic processes such as interpolation hypophosphite, sulphite, thiosulphate in the oxygenolysis of anode, thus realize the recovery to prussiate; Negative electrode substrates obtains Copper and its alloy, realizes the recovery to Cu in waste water.The method, except being applied to the process of gold mine cyanide wastewater, also effectively can process cyanide-containing electroplating water.
After adding inhibitor, the contingent reaction of anode is:
H
2PO-2+3OH
—=HPO2-3+2H
2O+2eE
0=﹣1.65V（1）
HPO2-3+3OH
—=PO3-4+2H
2O+2eE
0=﹣1.05V（2）
SO2-3+2OH
—=SO2-4+2H
2O+2eE
0=﹣0.95V（3）
S
2O2-3+6OH
—=2SO2-3+3H
2O+4eE
0=﹣0.58V（4）
2CN
—+2OH
—=CNO
—+H
2O+2eE
0=﹣0.97V（5）
Cu(CN)2-3+6OH
—=Cu
++3CNO+3H
2O+6eE
0=﹣0.69V（6）
The generation of reacting (5) (6) in electrolytic process can cause the loss of prussiate, research show in the solution not cupric time reaction (5) be difficult to occur, therefore can think that the oxidation of copper cyanogen complexing ion is the major cause causing cyanide consumption in solution.The standard potential of reaction (1) ~ (3) is more negative than reaction (6), more easily occurs, thus avoid the oxidation of copper cyanogen complexing ion in electrolytic process, achieves the object suppressing cyanogen root oxygenolysis recovery of cyanide.And the main generation deposition of copper and the precipitation of hydrogen on negative electrode; Along with the deposition of copper on negative electrode, copper cyanogen complexing ion dissociates, and discharges free cyanide, thus along with galvanic deposit carry out free cyanide in solution concentration increase, improve the rate of recovery of prussiate.
Embodiment 1
Experiment water sample is degold lean solution after cyanide plant zinc dust precipitation, and its composition is as follows: total CN concentration 12.15g/L, free CN concentration 4.61g/L, Cu12.88g/L, Zn0.58g/L, Fe0.46g/L, Pb1.74mg/L, Au0.16mg/L, Ag1.40mg/LpH value 12.4.
At temperature 50 C, current density 150A/m
2condition under, the total add-on of hypophosphite, sulphite, thiosulphate is 20g/L, and each material proportion is respectively 10 ~ 100%, 0 ~ 100%, 0 ~ 100%; After galvanic deposit 2 ~ 8h, remaining Cu content in solution is 1.12g/L, Zn content 0.47mg/L, and free CN concentration is 8.89g/L; Negative electrode gained copper alloy phosphorous 0.05%.In water sample, valuable metal element obtains abundant recovery.
After adopting electrodeposition process respectively, water sample and clear water carry out Cyanide Leaching experiment to certain gold mine, the leaching yield of gold is all more than 96%, result shows to process rear water sample to leaching process without impact, in water sample, institute's prussiate obtains recycling, therefore the method achieves the recovery to cyanide plant degold lean solution.
Embodiment 2
Experiment water sample is high-level efficiency cyanide electroplating waste liquid, and its composition is as follows: free CN concentration 5.73g/L, Cu39.56g/L.
At temperature 60 C, current density 50 ~ 200A/m
2condition under, the total add-on of hypophosphite, sulphite, thiosulphate is 30g/L, and each material proportion is respectively 10 ~ 100%, 0 ~ 100%, 0 ~ 100%; After galvanic deposit 2 ~ 8h, remaining Cu content in solution is 1.94g/L, and free CN concentration is 9.27g/L; Negative electrode gained copper phosphorous 0.04%.Experimental result shows that the method can be applied to the recovery of valuable element and prussiate in electroplating effluent.
Embodiment 3
Experiment water sample is artificial preparation high concentrations of cyanide electrolytic solution, and its composition is as follows: free CN concentration 7.4g/L, Cu10g/L, pH value 13.
At temperature 60 C, current density 100A/m
2condition under, the total add-on of hypophosphite, sulphite, thiosulphate is 30g/L, and each material proportion is respectively 10 ~ 100%, 0 ~ 100%, 0 ~ 100%; After galvanic deposit 2 ~ 8h, remaining Cu content in solution is 0.82g/L, and free CN concentration is 10.2g/L; Negative electrode gained copper phosphorous 0.06%, in water sample, valuable metal element obtains abundant recovery.After adopting process, water sample carries out Cyanide Leaching experiment, and the leaching yield of gold is more than 96%, and result shows that the method can recycle high concentrations of cyanide waste water.
Embodiment 4
Experiment water sample is the lower electrolytic solution of artificial preparation copper concentration, and its composition is as follows: free CN concentration 3.2g/L, Cu5g/L, pH value 13.
At temperature 60 C, current density 40A/m
2condition under, the total add-on of hypophosphite, sulphite, thiosulphate is 20g/L, and each material proportion is respectively 10 ~ 100%, 0 ~ 100%, 0 ~ 100%; After galvanic deposit 2 ~ 8h, remaining Cu content in solution is 0.34g/L, and free CN concentration is 4.8g/L; Negative electrode gained copper phosphorous 0.05%.In water sample, valuable metal element can arrive recovery.After adopting electrodeposition process, water sample carries out Cyanide Leaching experiment, and the leaching yield of gold is all more than 96%, and result shows that the method can recycle the lower waste water of copper concentration.
Claims (6)
1. one kind is reclaimed the treatment process of copper and prussiate from cupric cyanide bearing waste solution simultaneously, it is characterized in that by adding inhibitor (as sulphite, thiosulphate, hypophosphite etc.), suppress prussiate in the oxygenolysis of anode, achieve the recovery of prussiate, because dissociating of copper cyanogen complexing ion in electrodeposition process makes free cyanide content in solution obviously increase; Negative electrode substrates obtains Copper and its alloy, achieves the recovery of the valuable elements such as copper, zinc, prussiate.
2. reclaim the treatment process of copper and prussiate according to claim 1 in cupric cyanide bearing waste solution simultaneously, it is characterized in that, the total add-on of inhibitor is at 5 ~ 30g/L, and wherein ortho phosphorous acid salts contg is 10 ~ 100%, sulphite is 0 ~ 100%, and thiosulphate is 0 ~ 100%.
3. reclaim the treatment process of copper and prussiate according to claim 1 in cupric cyanide bearing waste solution, it is characterized in that, negative electrode obtains phosphorous copper alloy, its phosphorus content 0.015 ~ 0.6% simultaneously.
4. reclaim the treatment process of copper and prussiate according to claim 1 in cupric cyanide bearing waste solution simultaneously, it is characterized in that, handled containing copper content in cyanogen copper-containing wastewater at 2 ~ 50g/L, free sodium cyanide concentration is 0.2 ~ 2%.
5. reclaim the treatment process of copper and prussiate according to claim 1 in cupric cyanide bearing waste solution, it is characterized in that, in electrodeposition process, solution ph is 9 ~ 14, and electrolysis temperature is at 40 ~ 70 DEG C, and anodic current density is 50 ~ 200A/m simultaneously
2.
6. reclaim the treatment process of copper and prussiate according to claim 1 in cupric cyanide bearing waste solution simultaneously, it is characterized in that, the method can be applicable to gold mine containing cyanogen copper-containing wastewater and the plating process containing cyanogen copper-containing wastewater.
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| CN201410233711.3A CN105274564B (en) | 2014-05-30 | 2014-05-30 | A kind of method of the recycling of electro-deposition high-concentration copper-containing cyanide bearing waste solution copper and cyanide |
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| CN201410233711.3A CN105274564B (en) | 2014-05-30 | 2014-05-30 | A kind of method of the recycling of electro-deposition high-concentration copper-containing cyanide bearing waste solution copper and cyanide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108754535A (en) * | 2018-07-06 | 2018-11-06 | 拉萨品志工贸有限公司 | A kind of cupric tailing solution of leaching gold electro deposited copper new recovering technology |
| CN109097792A (en) * | 2018-10-29 | 2018-12-28 | 东北大学 | A kind of electrolysis unit from low concentration cupric cyanide barren solution recycling copper and cyanide |
| CN109881023A (en) * | 2019-01-30 | 2019-06-14 | 东北大学 | A method of the protection electro-deposition of lean solution containing cyanogen recycles |
| CN109881022A (en) * | 2019-01-30 | 2019-06-14 | 东北大学 | A method of the whole process green circulatory of lean solution containing cyanogen utilizes |
| CN112863613A (en) * | 2021-01-25 | 2021-05-28 | 山东黄金矿业科技有限公司选冶实验室分公司 | Method for determining extreme value of dosage of copper salt for treating cyanide-containing wastewater by copper salt precipitation method |
Citations (2)
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|---|---|---|---|---|
| DD230566A3 (en) * | 1983-05-09 | 1985-12-04 | Druckplattenwerk Berlin | METHOD FOR ELECTROLYTICALLY REMOVING COPPER AND CYANIDE FROM ALKALI AND COPPER CYANIDE-CONTAINING SOLUTIONS |
| US20030089619A1 (en) * | 2000-02-22 | 2003-05-15 | Sunil Jayasekera | Process and apparatus for recovery of cyanide and metals |
-
2014
- 2014-05-30 CN CN201410233711.3A patent/CN105274564B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD230566A3 (en) * | 1983-05-09 | 1985-12-04 | Druckplattenwerk Berlin | METHOD FOR ELECTROLYTICALLY REMOVING COPPER AND CYANIDE FROM ALKALI AND COPPER CYANIDE-CONTAINING SOLUTIONS |
| US20030089619A1 (en) * | 2000-02-22 | 2003-05-15 | Sunil Jayasekera | Process and apparatus for recovery of cyanide and metals |
Non-Patent Citations (1)
| Title |
|---|
| 王庆生等: "用电解法从富集氰化废液中回收铜的研究", 《环境科学研究》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108754535A (en) * | 2018-07-06 | 2018-11-06 | 拉萨品志工贸有限公司 | A kind of cupric tailing solution of leaching gold electro deposited copper new recovering technology |
| CN109097792A (en) * | 2018-10-29 | 2018-12-28 | 东北大学 | A kind of electrolysis unit from low concentration cupric cyanide barren solution recycling copper and cyanide |
| CN109881023A (en) * | 2019-01-30 | 2019-06-14 | 东北大学 | A method of the protection electro-deposition of lean solution containing cyanogen recycles |
| CN109881022A (en) * | 2019-01-30 | 2019-06-14 | 东北大学 | A method of the whole process green circulatory of lean solution containing cyanogen utilizes |
| CN112863613A (en) * | 2021-01-25 | 2021-05-28 | 山东黄金矿业科技有限公司选冶实验室分公司 | Method for determining extreme value of dosage of copper salt for treating cyanide-containing wastewater by copper salt precipitation method |
| CN112863613B (en) * | 2021-01-25 | 2022-07-29 | 山东黄金矿业科技有限公司选冶实验室分公司 | Method for determining extreme value of dosage of copper salt for treating cyanide-containing wastewater by copper salt precipitation method |
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| CN105274564B (en) | 2018-09-18 |
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Granted publication date: 20180918 |