CN105970249B - The electrodeposition cleaning system and its purification method of waste solution of copper electrolysis - Google Patents
The electrodeposition cleaning system and its purification method of waste solution of copper electrolysis Download PDFInfo
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- CN105970249B CN105970249B CN201610541005.4A CN201610541005A CN105970249B CN 105970249 B CN105970249 B CN 105970249B CN 201610541005 A CN201610541005 A CN 201610541005A CN 105970249 B CN105970249 B CN 105970249B
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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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
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Abstract
The invention discloses a kind of electrodeposition cleaning system of waste solution of copper electrolysis, and it includes head tank and N number of Winning cell being sequentially arranged, and the liquid outlet of head tank leads to each Winning cell by pipeline connection, 1st, 2 ... ..., the material liquid outlet of 1 Winning cell of i ... ..., N respectively leads to the 2nd, 3 ... ..., i+1, ..., N number of Winning cell, the material liquid outlet of n-th Winning cell leads to the 1st Winning cell and electric effusion recovery system, natural numbers of the wherein i between 2~N 1, N >=6.The invention also discloses a kind of purification method of the electrodeposition cleaning system of waste solution of copper electrolysis as described above, compared with prior art, Winning cell in cleaning system of the present invention is the series-parallel connection feeding structure being combined using series, parallel, the cleaning system is not only easy to use, and solve thes problems, such as that the block electrodeposition black copper of prior art can not directly apply to fire refining recovery process.
Description
Technical field
The present invention relates to the technical field of smelting of copper, and in particular to the electrodeposition cleaning system of a kind of waste solution of copper electrolysis and its net
Change method.
Background technology
In the prior art, copper mine enterprise is usually that the blister copper being prepared is used into electro deposition fine copper, but actual
In production, with copper electrolytically generated arsenic ion, antimony ion and bismuth ion can synchronously occur for the impurity such as arsenic, antimony, bismuth in blister copper, this
A little ionic impurities can form the flocculent substance of solubility very little in copper electrolyte and be adhered to the table of negative electrode and cathode copper
Face, greatly reduce the quality of the cathode copper of generation.To solve the above problems, enterprise uses electrodeposition method to waste solution of copper electrolysis more
(copper electrolyte i.e. containing certain impurity concentration) carries out purified treatment, specifically, the cupric electrolysis after separating out copper sulphate will be crystallized
Waste liquid is poured into Winning cell, and Winning cell is using stereotype as anode, and starting sheet or anode scrap are as negative electrode, the so work in direct current
Under, the copper ion in waste solution of copper electrolysis gradually will separate out to form black copper plate in negative electrode, and the impurity such as arsenic, antimony and bismuth will sink
Product forms decopper(ing) mud in the bottom land of Winning cell, so can reach the purpose of purifying copper electrolyte, wherein caused black copper and de-
Copper sludge can deliver to recovery process to reclaim valuable metal.
At present, the method for purified treatment waste solution of copper electrolysis is divided into interruption electrodeposition method and continuous electrodeposition method：It is interrupted at electrodeposition method
The technological process for managing waste solution of copper electrolysis as shown in Figure 1, crystallizes the waste solution of copper electrolysis after separating out copper sulphate and flowed into simultaneously by head tank 1
Join electrolytic deposition output cathodic metal black copper in the Winning cell 2 of arrangement, the electric effusion then flowed out from Winning cell 2 is in parallel to be flowed into
Lower tank 3, then extract electric effusion from Lower tank 3 with acid-proof pump 4 and carry out circulation electrodeposition to head tank 1, to improve electrolysis waste solution
Clean-up effect；As shown in Figure 2, electrolysis waste solution flows through head tank 1 for the technological process of continuous electrodeposition method processing waste solution of copper electrolysis
Enter electrolytic deposition in the Winning cell 2 of arranged in series, output cathodic metal black copper, then flowed out from last Winning cell 2
Electric effusion flows into Lower tank 3 with use to be discharged, and the purification of logical electrolyte can also be realized so by way of continuous electrolysis
Processing.In general, the copper concentration of the waste solution of copper electrolysis flowed into Winning cell 2 is 45~50g/l, by repeatedly circulating electrodeposition most
Outflow Winning cell, the copper concentration for the electrolytic liquid that can enter next procedure are 6~10g/l eventually.
It is in bulk that the product black copper obtained using interruption electrodeposition method and continuous electrode method electrodeposition waste solution of copper electrolysis, which is, these
Block black copper is only applicable to traditional hydrometallurgy to reclaim copper metal, but for " double sudden strains of a muscle " Copper making technique, due to
Flash converting furnace can only handle granular material, so as to cause the smelting of melting down of these block black copper to have certain difficulty, therefore
How the effective utilization of the electrodeposition product of waste solution of copper electrolysis is ensured, this is the problem of enterprise is being studied always.
The content of the invention
The primary and foremost purpose of the present invention is to provide a kind of electrodeposition purification system of waste solution of copper electrolysis simple in construction, using effect is good
System.
To achieve the above object, the technical solution adopted by the present invention is：A kind of electrodeposition cleaning system of waste solution of copper electrolysis, its
It is characterised by：Including N number of Winning cell being sequentially arranged, the waste solution of copper electrolysis after crystallization precipitation copper sulphate is led to by pipeline connection
Each Winning cell, the the 1st, 2 ... ..., i ... ..., the material liquid outlet of N-1 Winning cell respectively lead to the 2nd, 3 ... ..., i+
1 ... ..., N number of Winning cell, the material liquid outlet of n-th Winning cell leads to the 1st Winning cell and electric effusion recovery system, wherein i are
Natural number between 2~N-1, N >=6.
It is using beneficial effect caused by above-mentioned technical proposal：Compared with prior art, purification system of the present invention
Winning cell in system is the series-parallel connection feeding structure being combined using series, parallel, when specifically used, the feed liquid of n-th Winning cell
The electric effusion part for exporting the low copper concentration of discharge is drained into electric effusion recovery system, and some can introduce first electricity
It in product groove, can so increase total liquid inlet volume of each Winning cell, reduce local copper concentration deviation, and can reduces expects in each Winning cell
The initial copper concentration of liquid, so as to slow down speed of separating out of the copper ion on negative electrode, so it is possible to prevente effectively from the production of block black copper
Raw, cleaning system disclosed by the invention is not only easy to use, and the block electrodeposition black copper for efficiently solving prior art can not
Directly apply to the problem of double fire dodged in Copper making technique refine recovery process.
Another object of the present invention is to provide a kind of the net of electrodeposition cleaning system of waste solution of copper electrolysis as described above
Change method, its step are as follows：The waste solution of copper electrolysis crystallized after separating out copper sulphate is passed through in N number of Winning cell, the the 1st, 2 ... ...,
Electric effusion in i ... ..., N-1 Winning cells each leads into the 2nd, 3 ... ..., i+1 ... ..., N number of Winning cell, n-th Winning cell
Electric effusion be passed through whole liquid bath, the electric effusion of whole liquid bath is passed through the 1st Winning cell and feed liquid recovery system, from n-th Winning cell
The copper ion concentration of the electric effusion of discharge is controlled in the range of 0.1~2g/L.
Brief description of the drawings
Fig. 1,2 are two kinds of prior art purification process charts；
Fig. 3 is the cleaning system structure chart of the present invention.
Embodiment
A kind of electrodeposition cleaning system of waste solution of copper electrolysis, as shown in figure 3, it includes N number of Winning cell 20 being sequentially arranged, knot
The waste solution of copper electrolysis that partial crystallization goes out after copper sulphate leads to each Winning cell 20, the the 1st, 2 ... ..., i ... ..., N-1 by pipeline connection
The material liquid outlet of individual Winning cell 20 respectively leads to the 2nd, 3 ... ..., i+1 ... ..., N number of Winning cell 20, n-th Winning cell 20b's
Material liquid outlet leads to the 1st Winning cell 20a and electric effusion recovery system, natural numbers of the wherein i between 2~N-1, N >=6.Root
Factually test summary to show, arrange that the Winning cell 20 of 6 and more than 6 can ensure that the copper electrolyte that electrodeposition obtains under normal circumstances
Removing impurities disclosure satisfy that the reuse requirement of postorder, and it is in powder that black copper caused by final electrodeposition scrapes off from minus plate
Shape；Preferably, the total number N of Winning cell 20 value is the natural number between 7~11.Compared with prior art, institute of the present invention
Winning cell 20 in the cleaning system stated is the series-parallel connection feeding structure being combined using series, parallel, when specifically used, by N
An electric effusion part for the low copper concentration of the material liquid outlet discharge of individual Winning cell 20 is introduced into first Winning cell 20a, remaining
Then directly outer drain into carries out processing recycling in electric effusion recovery system, can so increase total liquid inlet volume of each Winning cell 20,
And can reduces the initial copper concentration in each Winning cell 20, so as to slow down speed of separating out of the copper ion on negative electrode, can so have
Effect avoids the generation of block black copper, in addition, entering the 2nd ... ..., electrolyte in N-1 Winning cell 20 can by 2 or
The electrodeposition removing impurities processing of the Winning cell 20 of more than 2, can also so avoid influenceing because the single removing impurities efficiency of Winning cell 20 is low
The removing impurities effect of electrolyte.Cleaning system disclosed by the invention is not only easy to use, and efficiently solves the block of prior art
Shape electrodeposition black copper can not directly apply to the problem of double fire dodged in Copper making technique refine recovery process.
As further preferred scheme, as shown in figure 3, the cleaning system includes head tank 10, crystallization separates out sulfuric acid
Waste solution of copper electrolysis after copper leads to each Winning cell 20 by head tank 10.
Specifically, as shown in figure 3, the cleaning system includes whole liquid bath 30, the inlet 31 of whole liquid bath 30 connects n-th
Winning cell 20b material liquid outlet, the liquid outlet 32 of whole liquid bath 30 lead to the 1st Winning cell 20a and electric effusion recovery system.So
Whole liquid bath 30 can be first passed through from the electric effusion of n-th Winning cell 20b discharges to be stored, it is then reasonable further according to actual conditions
Distribute the whereabouts of electric effusion therein.
Further, as shown in figure 3, the liquid outlet 32 of whole liquid bath 30 leads on the 1st Winning cell 20a pipeline is disposed with
The delivery pump 40 of electric effusion is conveyed, the 1st Winning cell 20a can be reliably passed through with the part electric effusion ensured in whole liquid bath 30
In.
In addition, the invention also discloses the purification method of the electrodeposition cleaning system of waste solution of copper electrolysis as described above, its step
It is as follows：The waste solution of copper electrolysis crystallized after separating out copper sulphate is passed through in N number of Winning cell 2010, the the 1st, 2 ... ..., i ... ..., N-1
Electric effusion in individual Winning cell 20 each leads into the 2nd, 3 ... ..., i+1 ... ..., N number of Winning cell 20, n-th Winning cell 20b's
Electric effusion is passed through the 1st Winning cell 20a and feed liquid recovery system, dense from the copper ion of the electric effusion of n-th Winning cell 20b discharges
Degree control is in the range of 0.1~2g/L.During actual use, the parameter such as size of current by controlling electrodeposition reaction is i.e. adjustable
The electrodeposition response intensity of Winning cell 20, and then the copper ion concentration in adjustment control electric effusion, and applicant passes through verification experimental verification
It was found that when the waste solution of copper electrolysis separated out using electrodeposition cleaning system disclosed by the invention to crystallization after copper sulphate carries out electrodeposition, will
The copper ion concentration of the electric effusion of n-th Winning cell 20b discharges is controlled in the range of 0.1~2g/L, so may insure electricity
Black copper caused by product is scraped off from minus plate in powdered, so as to meet requirement of the pyrometallurgical smelting to material.
Further, with reference to shown in Fig. 3, head tank 10 is passed through the copper after the crystallized precipitation copper sulphate of each Winning cell 20
The liquid measure of electrolysis waste solution is equal, and by being additionally passed through the electric effusion of low copper concentration to the 1st Winning cell 20a, so may be used
Copper concentration in each Winning cell 20 is reduced with regulation, so as to slow down speed of separating out of the copper ion on negative electrode, meanwhile, Ge Ge electricity
Product groove 20 enters that flow quantity is controllable, specifically can be controlled the copper concentration in each Winning cell 20 in 1-10g/ using above-mentioned liquid inlet volume
L, the copper concentration of purification method processing crystalline mother solution (i.e. crystallization separates out the waste solution of copper electrolysis after copper sulphate) of the prior art
The scope of application only has 20-40g/L, and by comparison, it is applicable to locate using electrodeposition cleaning system disclosed by the invention and method
The crystalline mother solution that copper concentration is 20-70g/L is managed, it is applied widely.
Claims (7)
- A kind of 1. electrodeposition cleaning system of waste solution of copper electrolysis, it is characterised in that：Including N number of Winning cell (20) being sequentially arranged, knot The waste solution of copper electrolysis that partial crystallization goes out after copper sulphate leads to each Winning cell (20), the the 1st, 2 ... ..., i ... ..., N- by pipeline connection The material liquid outlet of 1 Winning cell (20) respectively leads to the 2nd, 3 ... ..., i+1 ... ..., N number of Winning cell (20), n-th Winning cell The material liquid outlet of (20b) leads to the 1st Winning cell (20a) and electric effusion recovery system, natures of the wherein i between 2~N-1 Number, N >=6.
- A kind of 2. electrodeposition cleaning system of waste solution of copper electrolysis according to claim 1, it is characterised in that：The cleaning system Including head tank (10), the waste solution of copper electrolysis after crystallization precipitation copper sulphate leads to each Winning cell (20) by head tank (10).
- A kind of 3. electrodeposition cleaning system of waste solution of copper electrolysis according to claim 1, it is characterised in that：The cleaning system Including whole liquid bath (30), the material liquid outlet of inlet (31) the connection n-th Winning cell (20b) of whole liquid bath (30), whole liquid bath (30) liquid outlet (32) leads to the 1st Winning cell (20a) and electric effusion recovery system.
- A kind of 4. electrodeposition cleaning system of waste solution of copper electrolysis according to claim 2, it is characterised in that：Winning cell (20) Total number N value is the natural number between 7~11.
- A kind of 5. electrodeposition cleaning system of waste solution of copper electrolysis according to claim 3, it is characterised in that：Whole liquid bath (30) Liquid outlet (32) leads on the pipeline of the 1st Winning cell (20a) delivery pump (40) for being disposed with conveying electric effusion.
- 6. a kind of purification method of the electrodeposition cleaning system of the waste solution of copper electrolysis as described in claim any one of 3-5, its step is such as Under：The waste solution of copper electrolysis crystallized after separating out copper sulphate is passed through in N number of Winning cell (10), the the 1st, 2 ... ..., i ... ..., N-1 Electric effusion in Winning cell (20) each leads into the 2nd, 3 ... ..., i+1 ... ..., N number of Winning cell (20), n-th Winning cell The electric effusion of (20b) is passed through whole liquid bath (30), and the material liquid outlet of whole liquid bath (30) leads to the 1st Winning cell (20a) and feed liquid is returned Receipts system, the flow that the electric effusion in whole liquid bath (30) is passed through the 1st Winning cell (20a) is 0.1~5m3/ h, from n-th electrodeposition The copper ion concentration of the electric effusion of groove (20b) discharge is controlled in the range of 0.1~2g/L.
- 7. the electrodeposition cleaning system of waste solution of copper electrolysis according to claim 6, it is characterised in that：Head tank (10) is passed through respectively The liquid inlet volume of individual Winning cell (10) is 0.1~1m3/h。
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| CN201610541005.4A CN105970249B (en) | 2016-07-11 | 2016-07-11 | The electrodeposition cleaning system and its purification method of waste solution of copper electrolysis |
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| CN201610541005.4A CN105970249B (en) | 2016-07-11 | 2016-07-11 | The electrodeposition cleaning system and its purification method of waste solution of copper electrolysis |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009167451A (en) * | 2008-01-15 | 2009-07-30 | Sumitomo Metal Mining Co Ltd | Method for electrolytically extracting copper |
| CN102010036A (en) * | 2010-12-04 | 2011-04-13 | 金川集团有限公司 | Treatment method of waste silver electrolyte |
| CN104630824A (en) * | 2015-01-20 | 2015-05-20 | 铜陵有色金属集团股份有限公司金冠铜业分公司 | Purification process of copper electrolysis waste liquid |
| CN104894607A (en) * | 2015-05-22 | 2015-09-09 | 铜陵有色设计研究院 | Method for purifying waste copper sulfate electrolyte |
| CN205893406U (en) * | 2016-07-11 | 2017-01-18 | 铜陵有色金属集团股份有限公司金冠铜业分公司 | Electrodeposition clean system of copper electrolysis waste liquid |
-
2016
- 2016-07-11 CN CN201610541005.4A patent/CN105970249B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009167451A (en) * | 2008-01-15 | 2009-07-30 | Sumitomo Metal Mining Co Ltd | Method for electrolytically extracting copper |
| CN102010036A (en) * | 2010-12-04 | 2011-04-13 | 金川集团有限公司 | Treatment method of waste silver electrolyte |
| CN104630824A (en) * | 2015-01-20 | 2015-05-20 | 铜陵有色金属集团股份有限公司金冠铜业分公司 | Purification process of copper electrolysis waste liquid |
| CN104894607A (en) * | 2015-05-22 | 2015-09-09 | 铜陵有色设计研究院 | Method for purifying waste copper sulfate electrolyte |
| CN205893406U (en) * | 2016-07-11 | 2017-01-18 | 铜陵有色金属集团股份有限公司金冠铜业分公司 | Electrodeposition clean system of copper electrolysis waste liquid |
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Effective date of registration: 20190410 Address after: 244100 West Building of Changjiang West Road Nonferrous Courtyard, Tongling City, Anhui Province Patentee after: Tongling Nonferrous Metals Group Co., Ltd. Address before: 244100 Jinguan Copper Branch of Tongling Nonferrous Circular Economy Industrial Park, Anhui Province Patentee before: JINGUAN COPPER INDUSTRY BRANCH OF TONGLING NONFERROUS METALS GROUP HOLDING CO., LTD. |