CN106350677A - Method for extracting copper-containing cyanided waste liquid by solvent to recycle copper - Google Patents
Method for extracting copper-containing cyanided waste liquid by solvent to recycle copper Download PDFInfo
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- CN106350677A CN106350677A CN201510414954.1A CN201510414954A CN106350677A CN 106350677 A CN106350677 A CN 106350677A CN 201510414954 A CN201510414954 A CN 201510414954A CN 106350677 A CN106350677 A CN 106350677A
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- copper
- cyanide
- cyaniding
- cupric
- solvent extraction
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for extracting copper-containing cyanided waste liquid by a solvent to recycle copper. The method is characterized in that quaternary ammonium salt is used as an extracting agent, and a sodium chloride solution is used as a back washing agent; by extraction and back washing, enrichment of the copper in waste water is realized, and the treatment volume of the waste water is reduced; the copper can be recycled from high-concentration copper-containing back washing liquid in various ways; the method does not have the extraction effect on cyanides existing in a free state, so that an extracting solution can be directly returned to a cyanidation leaching procedure to recycle the cyanides.
Description
Technical field
The invention belongs to Non-ferrous Metallurgy and field of environment protection, belong to the processing method of low concentration cupric cyanide wastewater.
Background technology
At present, Cyanide Leaching is the main method of golden production, and will occupy critical role for a long time；However as the progressively increasing of exploitation dynamics, high-quality gold mineral product resource tends to exhausted, and developing low-grade association gold mineral product has become the development trend of many gold manufacturing enterprises；All sliming cyanidation carbon slurry therapy extracting gold has the characteristics that process is simple, low production cost, the golden response rate are high, is currently popular both at home and abroad golden production technique, and the strong adaptability to Ore for this technique, is suitable for processing association type gold mine.
Copper-bearing mineral is extremely common associated mineral in gold mine, and in cyanidation-leaching process, copper mineral can dissolve, and forms copper cyano complex and is present in leachate, and constantly accumulates with the recycling of leachate.Even if the average gold content of Ore is pressed 5g/t and calculated, the annual cyaniding waste liquid producing of China also can reach more than 1.4 hundred million tons；Due to the presence of copper in waste liquid, if direct return the leaching velocity consuming and substantially reducing gold increasing cyanide using meeting, before reuse, therefore must go to the impact of copper removal.Processing method more common at present is chlorination and sulfur dioxide air method, said method is all waste liquid to be carried out with decyanation process so that copper is removed with sedimentary form, although this technique achieves the recycling of water resource, but do not enable the recovery of valuable element and cyanide, and also there is the problems such as reagent cost is high, and after process, chlorine residue is higher in the chlorination being most frequently with.Acidifying volatilization-soda liquor absorption technique (avr method) makes the decomposition of Cyanide in Waste Water compound generate hydrogen cyanide gas by acidifying neutralization protection alkali, realizes the recovery of cyanide through alkali liquor absorption, valuable metal element forms cyaniding complex precipitate simultaneously；Big due to processing the water yield, the method acid consumption is high, the corrosion resistance of equipment is also required that higher；There is serious potential safety hazard in the hydrogen cyanide gas producing severe toxicity in processing procedure；Handling process is longer cause cyanide the response rate relatively low.Zinc sulfate-sulfuric acid process is also to be commercially used for processing one of method of cyanide wastewater；The method makes free cyanide and metal cyanogen complex ion be converted into precipitation by adding zinc sulfate in waste water, then carries out sulfuric acid treatment, alkali liquor absorption recovery of cyanide to detached precipitation, and after process, zinc sulfate returns and uses.Because this method reduces treating capacity thus acid consumption is less, but to the recovery of cyanide still using the method for acidifying-alkali liquor absorption, the problem of equipment acid etching and complex process still suffers from.Electrolysis is applied to cyanide-containing electroplating water, but the method cannot recovery of cyanide, can only metallic element in recycle-water, be therefore only suitable for processing the electroplating wastewater of the high cyanogen of high-copper；When processing low concentration wastewater because power consumption is higher, therefore do not possess price advantage.
For gold mine produces, the optimum recovery mode of Cyanide in Waste Water compound is that direct return uses, and the copper containing in water will affect the Cyanide Leaching of gold；Because the required process water yield is larger, all there is many unfavorable factors when processing low concentration copper-containing wastewater in above-mentioned processing method, the technique therefore developing quick decopper(ing) a kind of cupric cyanide wastewater from low concentration just seems particularly necessary.The present invention is directed to the problem that the existing handling process of low concentration gold mine waste water exists, achieve the removal of Cu in waste water by solvent-extracted method, the method no affects on the content of free cyanide in waste water, and raffinate can directly return Cyanide Leaching operation it is achieved that the recycling of cyanide；Load organic phases can obtain high-concentration copper-containing stripping workshop after back extraction, recoverable metal copper after electrolysis, and electrolysis tail washings can continue on for back extraction organic faciess.
Content of the invention
Process the problem that low concentration cupric cyanide wastewater exists for current, the invention provides a kind of method using quaternary ammonium salt solvent extracting-back extraction-electro-deposition achieves the recovery of copper and cyanide, it is characterized in that: the copper cyanogen complex ion in eliminating water is removed using quaternary ammonium salt solvent extraction, raffinate returns and leaches operation, golden leaching is had no adverse effects, realizes the recycling of cyanide；The method recovery of cyanide process is simple, flow process are short, the response rate is high, low production cost, safe operation.Load organic phases obtain high concentration strip liquor after nitrate solution back extraction, electrodeposited after obtain metallic copper it is achieved that the recovery of Cu in waste water；After electrolysis, solution can continue on for back extraction, has saved cost.
Effluent of cuprous cyanide reaction principle in extraction is:
cu(cn)2-3(l)+2r4n
+(o) = 2r4n·cu(cn)3(o)
cu(cn)3-4(l)+3r4n+(o)
= 3r4n·cu(cn)4(o)
To be extracted dose when approaching to saturation, using high concentration sodium chloride solution back extraction, its reaction principle is as follows:
2r4n·cu(cn)3(o) +2cl-(l)
= cu(cn)2-3(l)+ 2r4ncl (o)
3r4n·cu(cn)4(o) +3cl-(l)
= cu(cn)3-4(l)+ 3r4ncl (o).
Specific embodiment
Embodiment 1
Experiment water sample is the artificial cupric cyanide-contained solution prepared, and its copper content is 1g/l, and free cyanide concentration is 12.6 for 0.2%, ph value.
Extractant proportioning is aliquat336 8g, sec-octyl alcohol 20ml, sulfonated kerosene 25ml, extracts o/a=1, and in raffinate, copper content is less than 0.01g/l, and free cyaniding concentration is constant；Through multiple extraction until extractant reaches saturation, using sodium chloride 10%, Cyanogran. 0.1% solution back extraction, back extraction o/a=2, strip liquor copper content is 14.8g/l, and back extraction ratio reaches 87%, strip liquor obtains metallic copper after electrolysis, and after electrolysis, solution continues on for back extraction and harmful effect does not occur.
Cyanide Leaching experiment is carried out using raffinate to certain gold mine sample, the leaching rate of gold reaches more than 97%, contrasted the Cyanide Leaching experiment newly joined, after showing extraction processing, water sample has no adverse effects to leaching process, the method achieves the recovery of cyanide.
Embodiment 2
Experiment water sample produces waste water for certain gold mining enterprises, and its copper content is 2.14g/l, and free cyanide concentration is 13.2 for 0.3%, ph value.
Extractant proportioning is aliquat336 100g, sec-octyl alcohol 100ml, sulfonated kerosene 300ml, extracts o/a=1, and in raffinate, copper content is less than 0.01g/l, and free cyaniding concentration is constant；After extractant reaches saturation, using sodium chloride 15%, Cyanogran. 0.1% solution back extraction, back extraction o/a=3, strip liquor copper content is 25.2g/l.Strip liquor obtains metallic copper after electrolysis, and after electrolysis, solution continues on for back extraction and harmful effect does not occur.
Cyanide Leaching experiment is carried out using raffinate to certain gold mine, the leaching rate of gold reaches more than 97%, the method achieves the recovery of cyanide.
Embodiment 3
Experiment water sample produces waste water for certain gold mining enterprises, and its copper content is 0.79g/l, and free cyanide concentration is 12.4 for 0.14%, ph value.
Extractant proportioning is aliquat336 150g, sec-octyl alcohol 150ml, sulfonated kerosene 350ml, extracts o/a=3, and in raffinate, copper content is less than 0.01g/l, and free cyaniding concentration is constant；After extractant reaches saturation, using sodium chloride 10%, solution back extraction, back extraction o/a=2, strip liquor copper content is 15.2g/l.Strip liquor obtains metallic copper after electrolysis, and after electrolysis, solution continues on for back extraction and harmful effect does not occur.
Cyanide Leaching experiment is carried out using raffinate to certain gold mine, the leaching rate of gold reaches more than 97%, the method achieves the recovery of cyanide.
Claims (5)
1. it is characterised in that being extractant using quaternary ammonium salt, villaumite type Arquad may be directly applied to extract a kind of method of solvent extraction cupric cyaniding devil liquor recovery copper without pre-treatment.
2. it is characterised in that back washing agent adopts nitrate solution, its main component is the method for solvent extraction cupric cyaniding devil liquor recovery copper according to claim 1: sodium chloride 2% ~ 15%, Cyanogran. < 0.7%；Ph value is 9 ~ 14.
3. solvent extraction cupric cyaniding devil liquor recovery copper according to claim 1 method it is characterised in that in low concentration cupric cyaniding waste liquid copper content be 0.02 ~ 7g/l.
4. solvent extraction cupric cyaniding devil liquor recovery copper according to claim 1 method it is characterised in that in strip liquor copper concentration be 9 ~ 30g/l.
5. the method for solvent extraction cupric cyaniding devil liquor recovery copper according to claim 1 is it is characterised in that raffinate can be directly used for Cyanide Leaching.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510414954.1A CN106350677A (en) | 2015-07-16 | 2015-07-16 | Method for extracting copper-containing cyanided waste liquid by solvent to recycle copper |
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| CN201510414954.1A CN106350677A (en) | 2015-07-16 | 2015-07-16 | Method for extracting copper-containing cyanided waste liquid by solvent to recycle copper |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821472A (en) * | 2018-07-04 | 2018-11-16 | 中国矿业大学 | Metal top cradle and wastewater recycling method in precipitating-gas floatation process recycling Cyanide Wastewater of Gold Mine |
| CN110565120A (en) * | 2019-10-18 | 2019-12-13 | 东北大学 | Method for removing and recovering copper from copper-containing iron liquid |
Citations (4)
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| CN85103707A (en) * | 1985-05-13 | 1986-07-02 | 华东化工学院 | The comprehensive technological process of extracting gold and silver, copper from gold mine |
| CN1263165A (en) * | 1999-03-18 | 2000-08-16 | 莱州市黄金冶炼厂 | Gold-extracting process by using reusable cyanide gold-leaching lean solution |
| CN1263166A (en) * | 1999-03-18 | 2000-08-16 | 莱州市黄金冶炼厂 | Treatment method of reusable cyanide gold-leaching lean solution |
| CN101619391A (en) * | 2009-08-10 | 2010-01-06 | 暨南大学 | Method for separating and extracting gold from cyanide gold-leaching barren solution |
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2015
- 2015-07-16 CN CN201510414954.1A patent/CN106350677A/en active Pending
Patent Citations (4)
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| CN85103707A (en) * | 1985-05-13 | 1986-07-02 | 华东化工学院 | The comprehensive technological process of extracting gold and silver, copper from gold mine |
| CN1263165A (en) * | 1999-03-18 | 2000-08-16 | 莱州市黄金冶炼厂 | Gold-extracting process by using reusable cyanide gold-leaching lean solution |
| CN1263166A (en) * | 1999-03-18 | 2000-08-16 | 莱州市黄金冶炼厂 | Treatment method of reusable cyanide gold-leaching lean solution |
| CN101619391A (en) * | 2009-08-10 | 2010-01-06 | 暨南大学 | Method for separating and extracting gold from cyanide gold-leaching barren solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821472A (en) * | 2018-07-04 | 2018-11-16 | 中国矿业大学 | Metal top cradle and wastewater recycling method in precipitating-gas floatation process recycling Cyanide Wastewater of Gold Mine |
| CN110565120A (en) * | 2019-10-18 | 2019-12-13 | 东北大学 | Method for removing and recovering copper from copper-containing iron liquid |
| CN110565120B (en) * | 2019-10-18 | 2021-09-07 | 东北大学 | Method for removing and recovering copper from copper-containing iron liquid |
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