CN105274564B - A kind of method of the recycling of electro-deposition high-concentration copper-containing cyanide bearing waste solution copper and cyanide - Google Patents
A kind of method of the recycling of electro-deposition high-concentration copper-containing cyanide bearing waste solution copper and cyanide Download PDFInfo
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- CN105274564B CN105274564B CN201410233711.3A CN201410233711A CN105274564B CN 105274564 B CN105274564 B CN 105274564B CN 201410233711 A CN201410233711 A CN 201410233711A CN 105274564 B CN105274564 B CN 105274564B
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Abstract
The invention discloses the processing methods for recycling copper and cyanide in a kind of cyanide bearing waste solution from high-concentration copper-containing simultaneously, it is characterized in that using electro-deposition method, the oxygenolysis for inhibiting cyanide in anode by adding inhibitor (such as sulphite, thiosulfate, hypophosphite), to realize the recycling of cyanide；Electro-deposition obtains copper and its alloy on cathode, realizes the recycling of Cu in waste water, zinc etc..Treated, and waste water can return to Cyanide Leaching flow, on the leaching of gold, silver without influence.This method can realize effective recycling of valuable element in the contained waste liquids containing cyanogen such as cyanide plant waste water, electroplating cyanic waste water.
Description
Technical field
The invention belongs to non-ferrous metallurgy and field of environment protection, belong to one kind from cupric cyanide bearing waste solution while recycling
The processing method of copper and cyanide.
Background technology
Gold has a very important role in fields such as national economy, finance, science and technology, in reply economic crisis, ensures
Also play key player in economic security of the country.Currently, extraction of gold by cyanidation is still the main method of golden production, it is flat by ore
Equal 5 g/t of gold content is calculated, China every year caused by cyanide wastewater up to as many as 1.4 hundred million tons.Due to cyanide plant discharge
Cyanide and other valuable elements containing severe toxicity in sewage are also made if direct emission will not only seriously affect Environmental security
At the waste of resource, it is necessary to try to handle.Currently, the main process of cyaniding sewage is broadly divided into two classes：One kind is by cyanogen
Compound Oxidative demage eliminate toxicity, metal ion formed sediment removal so that waste water is purified, compared with frequently with method have alkali
Chloridising and SO2Air method etc. is unable to synthetical recovery valuable element, and commonly used alkali using the method for purified treatment
That there is also reagent consumptions is more for chloridising, sewage residual chlorine higher the problems such as still needing to reprocessing after processing；However for gold industry
For, Cyanide in Waste Water compound is also a kind of important secondary resource, therefore relatively mostly using absorption method when handling cyaniding sewage will
Cyanide regeneration in waste water, treated, and waste water returns to use, but the copper-bearing mineral of association can be in Cyanide Leaching mistake in gold mine
It is dissolved out in journey, the cyanide complex for forming copper enters in solution, and the constantly accumulation during cyaniding solution recycles, heavier
Want be copper in leachate presence can also significantly reduce gold solution rate, increase the consumption of cyanide, make leaching efficiency
Decline.Additionally due to Some Enterprises carry gold using zinc dust precipitation technique, this to contain a large amount of zinc in sewage simultaneously, in leachate
The presence of zinc also can largely consume cyanide, increase and leach reagent cost.Therefore, recycling for cyaniding sewage is realized, just
It must select copper, the zinc in appropriate technique removal waste water.Currently, industrial most common regeneration recovery method is acidization and sulphur
Sour zinc-sulfuric acid process.Acidization, full name are acidification volatilization-alkali absorption method (AVR methods).This method is to be acidified to neutralize by sulfuric acid
Alkali is protected, so that the metal complexes cyanide such as free cyanide and copper, zinc is decomposed and generates hydrogen cyanide gas, through air stripping, lye
It absorbs and generates Cymag recycling, the formation such as copper, zinc complex precipitate containing cyanogen is removed.The treatment process is to equipment acid etching
Seriously, lye absorption tower easily blocks again, and the hydrogen cyanide of severe toxicity is generated in processing procedure, and there are serious security risks.
Zinc sulfate-sulfuric acid process is that zinc sulfate is first added into waste water, is that the metal complexes cyanide such as free cyanide and copper, zinc is converted into
Zinc cyanide precipitates, and then uses sulfuric acid treatment to zinc cyanide precipitation separation, is used with being returned after lye absorption and regeneration.Technique acid
Consume small, therefore processing cost is relatively low, however is still the technique absorbed using acidification volatilization-lye for the recycling of cyanide, because
This can not still be avoided the inherent shortcoming of acidization.It has industrially been applied, but passed using electrolysis Treatment of Cyanide-containing Wastewater
The electrolysis treatment process of system is for the purpose of destroying cyanide, and the metallic element being only capable of in recycling waste water, this is bound to cause
The waste of a large amount of cyanides, therefore it is not particularly suited for the processing of gold mine cyanide wastewater especially high cyanide containing wastewater；Electricity
Product-acidization is to be combined electrolysis with acidization, directly obtains metallic copper by electrolysis, realizes having for valuable metal element
Effect recycling, then pass through acidization recovery of cyanide.However the technique still fails fundamentally to solve acidization recovery of cyanide
Many drawbacks.Diaphragm process is aoxidized by using diaphragm cell to avoid cyanide from entering anode region, electro-deposition
Electrolyte can directly return to leaching process afterwards, realize the recycling of cyanide and fundamentally avoid lacking for acidization recycling
It falls into.But since diaphragm is expensive and service life is short, also fail to realize large-scale commercial Application.
More above-mentioned technique it is found that it is maximally efficient method to recycle valuable metal element by electro-deposition, and how
It is the key that use electrodeposition process recovery of cyanide to avoid cyanide that oxidation occurs in anode in electrodeposition process.The present invention passes through
Inhibitor electro-deposition cyanide wastewater under conditions of without diaphragm is added, has not only recycled metal, but also inhibit the anode of cyanide
Oxidation, realizes effective recycling of cyanide, fundamentally avoids the drawbacks of being acidified recovery of cyanide technique.
Invention content
For problems existing for current electrolysis process cupric cyanide wastewater, the present invention provides one kind from containing
The processing method of copper and cyanide is recycled in copper cyanide bearing waste solution simultaneously, it is characterised in that without diaphragm, by adding time Asia
Phosphate, sulphite, thiosulfate etc. inhibit electrolytic process in cyanide anode oxygenolysis, to realize to cyanogen
The recycling of compound；Electro-deposition obtains copper and copper alloy on cathode, realizes the recycling to Cu in waste water.This method, which is removed, is applied to gold
Outside the processing of Mine wastewater containing cyanogen, cyanide-containing electroplating water can be also effectively treated.
The reaction that may occur of anode is after inhibitor is added：
H2PO- 2+3OH—=HPO2- 3+2H2O+2e E0=﹣ 1.65V（1）
HPO2- 3+3OH—=PO3- 4+2H2O+2e E0=﹣ 1.05V（2）
SO2- 3+2OH—= SO2- 4+2H2O+2e E0=﹣ 0.95V（3）
S2O2- 3+6OH—= 2SO2- 3+3H2O+4e E0=﹣ 0.58V（4）
2CN—+2OH—=CNO—+H2O+2e E0=﹣ 0.97V（5）
Cu(CN)2- 3+6OH—=Cu++3CNO+3H2O+6e E0=﹣ 0.69V（6）
It is reacted in electrolytic process（5）（6）Generation can cause the loss of cyanide, research shows that in the solution not
It is reacted when cupric（5）It is difficult to occur, it can be considered that the oxidation of copper cyanogen complex ion causes cyanide consumption in solution
Main cause.Reaction（1）~（3）Standard electrode potential than reaction（6）It is more negative, it is more easy to occur in electrolytic process, to avoid
The oxidation of copper cyanogen complex ion realizes the purpose for inhibiting cyanogen root oxygenolysis recovery of cyanide.And mainly occur on cathode
The deposition of copper and the precipitation of hydrogen；Along with deposition of the copper on cathode, copper cyanogen complex ion dissociates, and releases free cyanogen
Compound improves the rate of recovery of cyanide so the concentration for carrying out free cyanide in solution with electro-deposition increases.
Embodiment 1
It is de- golden lean solution after cyanide plant zinc dust precipitation to test water sample, and ingredient is as follows：Total 12.15 g/L of CN concentration, dissociates
0.16 mg/ of CN concentration 4.61 g/L, Cu 12.88 g/L, Zn 0.58 g/L, Fe 0.46 g/L, Pb 1.74 mg/L, Au
1.40 mg/L pH value 12.4 of L, Ag.
In temperature 50 C, 150 A/m of current density2Under conditions of, hypophosphite, sulphite, thiosulfate are total
Addition be 20 g/L, each substance proportion is respectively 10 ~ 100%, 0 ~ 100%, 0 ~ 100%；After 2 ~ 8 h of electro-deposition, solution
Middle residue Cu contents are 1.12g/L, 0.47 mg/L of Zn contents, and dissociate a concentration of 8.89 g/L of CN；Copper alloy is phosphorous obtained by cathode
0.05%.Valuable metal element has obtained abundant recycling in water sample.
Water sample and clear water after electrodeposition process is respectively adopted, Cyanide Leaching experiment is carried out to certain gold mine, golden leaching rate exists
96% or more, the results showed that water sample is on leaching process without influence after processing, and institute's cyanide is recycled in water sample, therefore
The method achieve the recycling to the de- golden lean solution of cyanide plant.
Embodiment 2
Experiment water sample is high efficiency cyanide electroplating waste liquid, and ingredient is as follows：Free CN concentration 5.73 g/L, Cu 39.56
g/L。
In temperature 60 C, 50 ~ 200 A/m of current density2Under conditions of, hypophosphite, sulphite, thiosulfate
Total addition is 30 g/L, and each substance proportion is respectively 10 ~ 100%, 0 ~ 100%, 0 ~ 100%；It is molten after 2 ~ 8 h of electro-deposition
Residue Cu contents are 1.94 g/L in liquid, and dissociate a concentration of 9.27 g/L of CN；Copper phosphorous 0.04% obtained by cathode.Experimental result table
Bright this method can be applied to the recycling of valuable element and cyanide in electroplating effluent.
Embodiment 3
It is artificial preparation high concentrations of cyanide electrolyte to test water sample, and ingredient is as follows：Free CN concentration 7.4 g/L, Cu
10 g/L, pH value 13.
In temperature 60 C, 100 A/m of current density2Under conditions of, hypophosphite, sulphite, thiosulfate are total
Addition be 30 g/L, each substance proportion is respectively 10 ~ 100%, 0 ~ 100%, 0 ~ 100%；After 2 ~ 8 h of electro-deposition, solution
Middle residue Cu contents are 0.82g/L, and dissociate a concentration of 10.2 g/L of CN；Copper phosphorous 0.06% obtained by cathode, valuable metal in water sample
Element has obtained abundant recycling.Cyanide Leaching experiment is carried out using water sample after processing, golden leaching rate is 96% or more, as a result table
Bright this method can be recycled high concentrations of cyanide waste water.
Embodiment 4
It is the artificial preparation relatively low electrolyte of copper concentration to test water sample, and ingredient is as follows：Free CN concentration 3.2 g/L, Cu 5
G/L, pH value 13.
In temperature 60 C, 40 A/m of current density2Under conditions of, hypophosphite, sulphite, thiosulfate are total
Addition is 20 g/L, and each substance proportion is respectively 10 ~ 100%, 0 ~ 100%, 0 ~ 100%；After 2 ~ 8 h of electro-deposition, in solution
Remaining Cu contents are 0.34g/L, and dissociate a concentration of 4.8 g/L of CN；Copper phosphorous 0.05% obtained by cathode.Valuable metal member in water sample
Element can arrive recycling.Cyanide Leaching experiment is carried out using water sample after electrodeposition process, golden leaching rate 96% or more, is tied
Fruit shows that this method can be recycled the relatively low waste water of copper concentration.
Claims (5)
1. the processing method of copper and cyanide is recycled in a kind of cyanide bearing waste solution from cupric simultaneously, it is characterised in that inhibited by adding
Agent hypophosphite inhibits cyanide in the oxygenolysis of anode, the recycling of cyanide is realized, due to copper in electrodeposition process
The dissociation of cyanogen complex ion so that free cyanide content obviously increases in solution；Electro-deposition obtains copper and copper alloy on cathode,
Realize the recycling of copper, zinc, cyanide valuable element；
The addition of inhibitor hypophosphite is in 5~30g/L.
2. recycling the processing method of copper and cyanide in cupric cyanide bearing waste solution simultaneously according to claim 1, which is characterized in that
Cathode obtains phosphorous copper alloy, phosphorus content 0.015~0.6%.
3. recycling the processing method of copper and cyanide in cupric cyanide bearing waste solution simultaneously according to claim 1, which is characterized in that
Copper content is in 2~50g/L in handled copper-containing wastewater containing cyanogen, and free sodium cyanide concentration is 0.2~2%.
4. recycling the processing method of copper and cyanide in cupric cyanide bearing waste solution simultaneously according to claim 1, which is characterized in that
Solution ph is 9~14 in electrodeposition process, and for electrolysis temperature at 40~70 DEG C, anodic current density is 50~200A/m2。
5. recycling the processing method of copper and cyanide in cupric cyanide bearing waste solution simultaneously according to claim 1, which is characterized in that
This method can be applied to gold mine copper-containing wastewater containing cyanogen and the processing that the copper-containing wastewater containing cyanogen is electroplated.
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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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| 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 |
| 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 |
| 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 |
| 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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| DD230566A3 (en) * | 1983-05-09 | 1985-12-04 | Druckplattenwerk Berlin | METHOD FOR ELECTROLYTICALLY REMOVING COPPER AND CYANIDE FROM ALKALI AND COPPER CYANIDE-CONTAINING SOLUTIONS |
| WO2001062993A1 (en) * | 2000-02-22 | 2001-08-30 | Lakefield Oretest Pty Ltd | Process and apparatus for recovery of cyanide and metals |
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