CN106048659A - Spent solution treatment method of silver electrolyte - Google Patents
Spent solution treatment method of silver electrolyte Download PDFInfo
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- CN106048659A CN106048659A CN201610683844.XA CN201610683844A CN106048659A CN 106048659 A CN106048659 A CN 106048659A CN 201610683844 A CN201610683844 A CN 201610683844A CN 106048659 A CN106048659 A CN 106048659A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- 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
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Abstract
The invention discloses a spent solution treatment method of a silver electrolyte. A silver electrolyte spent solution, as a silver electro-deposition liquid, is fed into a whirl-flow electro-deposition system to perform primary electro-deposition; and then metal copper is added to a low-silver liquid to replace crude silver powder; a desilverized solution, as a copper electro-deposition mother liquid, is fed into the whirl-flow electro-deposition system to perform secondary electro-deposition; and finally, a part of a low-copper liquid is fed back to a sliver liquid preparing system, while the rest part of the low-copper liquid is sent to an environmental protection workshop for treatment. The spent solution treatment method of the silver electrolyte is simple in processes, convenient to carry out and low in cost, can be used for directly recycling valuable metal, such as silver, copper and the like, in a high-effective, low-cost and high-recovery-rate manner.
Description
Technical field
The present invention relates to non-ferrous metal hydrometallurgy resource comprehensive utilization technology, particularly to liquid after a kind of silver electrolyte
Processing method.
Background technology
Electrorefining of silver process belongs to the electrochemistry dedoping step of silver, in the process, high than silver-colored electropositive in alloy sheets
Metal impurities there is not electrochemical dissolution, become the earth of positive pole and be removed；Electrolyte is entered than silver-colored electronegative metal impurities
In, thus reach the purpose that refines silver.Copper is one of principal metal impurities in thick alloy, and usual content is also the highest, its mark
Collimator electrode electromotive force more silver-colored negative much, in the electrorefining processes of silver, the copper in alloy sheets will be oxidized into ion and quilt
It is enriched in electrolyte.Although copper ion has enhancing electrolyte conductivity, minimizing concentration polarization, changes during electrorefining of silver
The effects such as kind electricity argentum powder crystal structure (being become bulky grain spicule from spongy body), but when electrolyte copper ion concentration exceedes necessarily
After scope, part will be discharged precipitations at negative electrode together with silver, the quality of reduction electrolytic silver powder；Therefore, copper ion concentration is worked as
Need extraction section electrolyte to carry out purified treatment after exceeding certain limit, supplement corresponding new liquid.The most traditional silver electrolyte
Purified treatment is mainly by 3 kinds of methods: one is displacement method, displaces the silver in waste electrolyte with copper sheet or copper anode scrap, and copper displaces
Argentum powder send a point silver stove, the electrolyte after displacement send waste water processing station to reclaim other impurity；Two is the Sal sedimentation method, uses sodium chloride
Aqueous solution makes the silver in silver electrolyte waste liquid be precipitated as AgCl, AgCl to be replaced as raw Ag powder through pulp ferrum and return at point silver stove
Reason, the waste liquid after heavy silver send waste water processing station to process；Three is crystallization-decomposition method, utilizes the decomposition temperature of nitric acid and other base metal
Degree difference is isolated, and controls that uniform temperature makes that base metal nitrate is decomposed into oxide and silver nitrate does not decomposes, and then heats
Water makes silver nitrate dissolve, and base metal oxide is water insoluble, can reuse through solid-liquid separation silver nitrate solution, base metal oxygen
Compound send pyrogenic process system to process.Above-mentioned traditional electrolyte purifies technique and there is long flow path, trivial operations, defect that cost is high.
Summary of the invention
It is an object of the invention to provide a kind of technique be simple and convenient to operate, liquid process side after the silver electrolyte of low cost
Method, it is achieved in silver electrolytic liquid, efficient, low cost, the high-recovery of the valuable metal such as silver, copper directly reclaim.
For realizing object above, after a kind of silver electrolyte of the present invention, the operating procedure of liquid processing method is as follows:
(1) silver electrolytic liquid is entered eddy flow electrodeposition system as silver electric effusion and carry out electrodeposition, No. 1 standard argentum powder of output for the first time
With low silvering solution；
(2) the low silvering solution obtained in step (1) addition metallic copper being displaced raw Ag powder, the argentum powder that copper displaces returns smelter
Sequence, it is thus achieved that desilverization liquid；
(3) desilverization liquid step (2) obtained carries out second time electrodeposition, output as copper electrodeposition mother solution entrance eddy flow electrodeposition system
Standard cathode copper and low copper liquid；
(4) low copper liquid part step (3) obtained returns silver liquid making system, and remaining low copper liquid send environmental protection workshop to process.
The low copper liquid that described step (3) obtains enters back into third time eddy flow electrodeposition output blister copper powder and decopper(ing) liquid, output
Blister copper powder is used for replacing silver operation, and a decopper(ing) liquid part returns silver liquid making system, and remaining decopper(ing) liquid send environmental protection workshop to process.
Described a part of decopper(ing) liquid returns in silver liquid making system, and the ratio of decopper(ing) liquid shared by this partial amt is 10-100%.
In described eddy flow electrodeposition third time electrolytic deposition process, the flow velocity of low copper liquid is 0.5-8m/s, electric current density 500 ~ 1100
A/m2, electrolyte circulating load is 600 ~ 1500 L/h, and the electrodeposition time is 1 ~ 5 h；In described decopper(ing) liquid, silver content is 10-500
Ppm, copper content is 0.1-5 g/L.
In step (1) described silver electrolytic liquid, the content of silver is 50 ~ 200 g/L, and copper content is 10 ~ 60 g/L；Described
In electrolytic deposition process, the flow velocity of silver electric effusion is 0.5-8m/s, electric current density 300 ~ 800 A/m2, electrolyte circulating load is 300
~ 900 L/h, the electrodeposition time is 1 ~ 5 h；In described low silvering solution, the content of silver is 1-30 g/L, and copper content is 10-60 g/L.
Metallic copper described in step (2) is copper billet, copper wire or copper powder, and copper content is 10-60g/L, and displacement temperature is 30-95
DEG C, time swap 0.1-3 h；In described desilverization liquid, the content of silver is 10-500 ppm.
In step (3) described eddy flow electrodeposition second time electrolytic deposition process, the flow velocity of desilverization liquid is 0.5-8m/s, and electrolyte circulates
Amount is 600 ~ 1500 L/h, electric current density 400 ~ 1000 A/m2, the electrodeposition time is 1 ~ 5 h,；In described low copper liquid, silver content is
10-500 ppm, copper content is 1-10 g/L.
After above-mentioned silver electrolyte, liquid processing method has techniques below feature and a beneficial effect:
1, directly being reclaimed silver and copper from open circuit silver electrolyte by the method for electrolysis, the response rate of silver and copper respectively reaches 99%
Being standard argentum powder with silver products more than 98%, and 80%, the copper of 70% is standard cathode copper, and the blister copper powder of output can be used for replacing
Silver operation.
2, use the method for eddy flow electrodeposition can reduce the yield of raw Ag powder, improve the production capacity of ANODE SLIME TREATMENT operation, can be by
The copper content delivering to the process of environmental protection workshop is reduced to 500 below mg/L by 10-100 g/L, and can reduce by 50% environmental protection treatment water
Amount, reduces Ag electrolyte cost.
3, the new technology of a kind of Processing Ag electrolytic liquid is proposed first, can directly reclaim open circuit silver electrolyte liquid in silver and
Copper, it is to avoid valuable metal iterative cycles operation in big system, improves smelting production capacity, it is achieved silver-colored electrolytic liquid low
Cost, efficiently process.
After a kind of silver electrolyte of the present invention, liquid processing method uses advanced electrodeposition process, is come by strengthening electric effusion flowing
Eliminate the concentration polarization that electrolytic deposition process produces, reduce foreign ion and separate out at negative electrode, improve the electrolytic deposition process selectivity to metal,
Can valuable metal silver major part in silver electrolytic liquid directly be reclaimed with the form of standard argentum powder, valuable metal copper is with standard cathode
The form of copper and blister copper powder directly reclaims, and after decopper(ing), liquid can return to Ag electrolyte system, it is achieved that silver electrolytic liquid has valency gold
The low-cost high-efficiency belonged to directly reclaims, and reduces environmental protection treatment and Ag electrolyte cost.
Detailed description of the invention
Below in conjunction with detailed description of the invention, liquid processing method after one silver electrolyte of the present invention is described in further detail.
After a kind of silver electrolyte of the present invention, the process route of liquid processing method is that peracid high ferro electrodeposition lean solution is used eddy flow
Electrodeposition carries out one section and carries silver and two-stage nitration carries copper, and period uses the replacing process degree of depth desilverization, the final low one-tenth realizing silver electrolytic liquid
Present treatment and high-valued recovery.Concrete operations and process conditions are as follows:
(1) one section of desilverization technique of eddy flow electrodeposition: electric current density 300 ~ 800 A/m2, electrolyte circulating load is 300 ~ 900 L/h, electricity
The long-pending time is 1 ~ 5 h, and product is standard argentum powder；
(2) replacing process: add copper powder 1-50 kg, carries out displacement silver-colored under conditions of 60-95 DEG C, time swap 0.1-3 h,
Output raw Ag powder；
(3) one section of decopper(ing) technique of eddy flow electrodeposition: electric current density 400 ~ 1000 A/m2, electrolyte circulating load is 600 ~ 1500 L/h,
The electrodeposition time is 1 ~ 5 h, and product is standard cathode copper.
(4) eddy flow electrodeposition two-stage nitration decopper(ing) technique: electric current density 500 ~ 1100 A/m2, electrolyte circulating load is 600 ~ 1500
L/h, the electrodeposition time is 1 ~ 5 h, and product is blister copper powder and decopper(ing) liquid.Finally, the decopper(ing) liquid of the 10-90% obtained is returned silver electricity
Solving, a small amount of decopper(ing) liquid is delivered to environmental protection workshop and is processed.
Embodiment 1
By argentiferous 100g/L during electrorefining of silver, silver-colored electrolytic liquid 50L of the open circuit of cupric 30g/L is entered with the flow velocity of 3m/s
Row for the first time eddy flow electrodeposition, output standard argentum powder and low silvering solution, in its low silvering solution, silver content is 7g/L, and copper content is 30g/L；
Subsequently, add a small amount of copper powder under conditions of 75 DEG C, carry out displacement silver, it is thus achieved that raw Ag powder and desilverization liquid, the silver in its desilverization liquid
Content is 4 mg/L, and copper content is 36 g/L；Again, desilverization liquid is carried out second time eddy flow electrodeposition, output criteria tough cathode and
Low copper liquid, in its low copper liquid, copper content is 4g/L；Finally, the low copper liquid of obtain 70% is returned silver electrolysis, the low copper liquid of 30%
Deliver to environmental protection workshop process.
Embodiment 2
By argentiferous during electrorefining of silver 120 g/L, silver-colored electrolytic liquid 50 L of the open circuit of cupric 35 g/L, with 3.3 m/s
Flow velocity carry out for the first time eddy flow electrodeposition, output standard argentum powder and low silvering solution, in its low silvering solution, silver content is 8 g/L, and copper contains
Amount is 35g/L；Subsequently, add a small amount of copper powder under conditions of 80 DEG C, carry out displacement silver, it is thus achieved that raw Ag powder and desilverization liquid, its
Silver content in desilverization liquid is 4 mg/L, and copper content is 40 g/L；Again, desilverization liquid is carried out second time with the flow velocity of 1.5m/s
Eddy flow electrodeposition, output criteria tough cathode and low copper liquid, in its low copper liquid, copper content is 4 g/L；Thereafter, by decopper(ing) liquid with 2 m/s
Flow velocity carry out third time eddy flow electrodeposition, output blister copper and decopper(ing) liquid, in its decopper(ing) liquid, copper content is 50 mg/L；Finally, will obtain
The low copper liquid of 90% obtained returns silver electrolysis, and the low copper liquid of 10% is delivered to environmental protection workshop and processed.
Embodiment 3
By argentiferous during electrorefining of silver 90 g/L, silver-colored electrolytic liquid 50 L of the open circuit of cupric 25 g/L, with 3.5 m/s'
Flow velocity carries out for the first time eddy flow electrodeposition, and output standard argentum powder and low silvering solution, in its low silvering solution, silver content is 5 g/L, copper content
It is 25 g/L；Subsequently, adding a small amount of copper powder and carry out displacement silver under conditions of 80 DEG C, it is thus achieved that raw Ag powder and desilverization liquid, it takes off
Silver content in silvering solution is 4 mg/L, and copper content is 28 g/L；Again, with the flow velocity of 2 m/s, desilverization liquid is carried out second time to revolve
Stream electrodeposition, output criteria tough cathode and low copper liquid, in its low copper liquid, copper content is 3 g/L；Thereafter, by decopper(ing) liquid with 3 m/s'
Flow velocity carries out third time eddy flow electrodeposition, and output blister copper and decopper(ing) liquid, in its decopper(ing) liquid, copper content is 40 mg/L；Finally, will obtain
85% decopper(ing) liquid return silver electrolysis, the decopper(ing) liquid of 15% deliver to environmental protection workshop process.
Contrast three above embodiment, the comprehensive technical indexes of embodiment 2 is best, is most preferred embodiment.
It should be pointed out that, the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, exist
Without departing from the principles of the invention, it is also possible to improved according to the above description or modify, all these improvement or modification
All should fall in the protection domain of the claims in the present invention.
Claims (7)
1. a liquid processing method after silver electrolyte, is characterized in that operating as follows:
(1) silver electrolytic liquid is entered eddy flow electrodeposition system as silver electric effusion and carry out electrodeposition, No. 1 standard argentum powder of output for the first time
With low silvering solution；
(2) the low silvering solution obtained in step (1) addition metallic copper being displaced raw Ag powder, the argentum powder that copper displaces returns smelter
Sequence, it is thus achieved that desilverization liquid；
(3) desilverization liquid step (2) obtained carries out second time electrodeposition, output as copper electrodeposition mother solution entrance eddy flow electrodeposition system
Standard cathode copper and low copper liquid；
(4) low copper liquid part step (3) obtained returns silver liquid making system, and remaining low copper liquid send environmental protection workshop to process.
2. liquid processing method after silver electrolyte as claimed in claim 1, is characterized in that: the low copper liquid that described step (3) obtains is again
Entering third time eddy flow electrodeposition output blister copper powder and decopper(ing) liquid, the blister copper powder of output is used for replacing silver operation, a decopper(ing) liquid part
Returning silver liquid making system, remaining decopper(ing) liquid send environmental protection workshop to process.
3. liquid processing method after silver electrolyte as claimed in claim 1 or 2, is characterized in that: described a part of decopper(ing) liquid returns silver
In liquid making system, the ratio of decopper(ing) liquid shared by this partial amt is 10-100%.
4. liquid processing method after silver electrolyte as claimed in claim 1 or 2, is characterized in that: described eddy flow electrodeposition third time electricity
During Ji, the flow velocity of low copper liquid is 0.5-8m/s, electric current density 500 ~ 1100 A/m2, electrolyte circulating load is 600 ~ 1500
L/h, the electrodeposition time is 1 ~ 5 h；In described decopper(ing) liquid, silver content is 10-500 ppm, and copper content is 0.1-5 g/L.
5. liquid processing method after silver electrolyte as claimed in claim 1, is characterized in that: silver in step (1) described silver electrolytic liquid
Content be 50 ~ 200 g/L, copper content is 10 ~ 60 g/L；In described first time electrolytic deposition process, the flow velocity of silver electric effusion is 0.5-
8m/s, electric current density 300 ~ 800 A/m2, electrolyte circulating load is 300 ~ 900 L/h, and the electrodeposition time is 1 ~ 5 h；Described low silver
In liquid, the content of silver is 1-30 g/L, and copper content is 10-60 g/L.
6. as claimed in claim 1 liquid processing method after silver electrolyte, is characterized in that: the metallic copper described in step (2) be copper billet,
Copper wire or copper powder, copper content is 10-60g/L, and displacement temperature is 30-95 DEG C, time swap 0.1-3 h；Silver in described desilverization liquid
Content be 10-500 ppm.
7. liquid processing method after silver electrolyte as claimed in claim 1, is characterized in that: step (3) described eddy flow electrodeposition second time
In electrolytic deposition process, the flow velocity of desilverization liquid is 0.5-8m/s, and electrolyte circulating load is 600 ~ 1500 L/h, electric current density 400 ~ 1000
A/m2, the electrodeposition time is 1 ~ 5 h,；In described low copper liquid, silver content is 10-500 ppm, and copper content is 1-10 g/L.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779607A (en) * | 2017-11-01 | 2018-03-09 | 紫金铜业有限公司 | A kind of method of the high arsenic smoke dust low cost dearsenification of Copper making |
| CN109097794A (en) * | 2018-09-13 | 2018-12-28 | 紫金矿业集团股份有限公司 | The method of silver electrolyte open circuit processing |
| CN110923751A (en) * | 2019-11-28 | 2020-03-27 | 广东先导稀材股份有限公司 | Method for recovering indium from solution after indium electrolysis |
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
| WO2021129205A1 (en) * | 2019-12-25 | 2021-07-01 | 北京工业大学 | Method for coordinated treatment of slag from pyrolysis of and smoke from smelting scrap circuit board |
| CN117222761A (en) * | 2023-07-27 | 2023-12-12 | 青美邦新能源材料有限公司 | Method for extracting metal from saprolite type laterite-nickel ore |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779607A (en) * | 2017-11-01 | 2018-03-09 | 紫金铜业有限公司 | A kind of method of the high arsenic smoke dust low cost dearsenification of Copper making |
| CN107779607B (en) * | 2017-11-01 | 2019-06-28 | 紫金铜业有限公司 | A kind of method of the high arsenic smoke dust low cost dearsenification of Copper making |
| CN109097794A (en) * | 2018-09-13 | 2018-12-28 | 紫金矿业集团股份有限公司 | The method of silver electrolyte open circuit processing |
| CN110923751A (en) * | 2019-11-28 | 2020-03-27 | 广东先导稀材股份有限公司 | Method for recovering indium from solution after indium electrolysis |
| WO2021129205A1 (en) * | 2019-12-25 | 2021-07-01 | 北京工业大学 | Method for coordinated treatment of slag from pyrolysis of and smoke from smelting scrap circuit board |
| US11692238B2 (en) | 2019-12-25 | 2023-07-04 | Beijing University Of Technology | Method for disposal of waste printed circuit board thermal cracking slag and smelting soot |
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
| CN117222761A (en) * | 2023-07-27 | 2023-12-12 | 青美邦新能源材料有限公司 | Method for extracting metal from saprolite type laterite-nickel ore |
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