CN104694978B - The processing method and processing unit of a kind of waste electrolyte - Google Patents
The processing method and processing unit of a kind of waste electrolyte Download PDFInfo
- Publication number
- CN104694978B CN104694978B CN201310653956.7A CN201310653956A CN104694978B CN 104694978 B CN104694978 B CN 104694978B CN 201310653956 A CN201310653956 A CN 201310653956A CN 104694978 B CN104694978 B CN 104694978B
- Authority
- CN
- China
- Prior art keywords
- copper
- electrolytic
- electrolytic tank
- anode
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 85
- 239000002699 waste material Substances 0.000 title claims abstract description 76
- 238000003672 processing method Methods 0.000 title abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 314
- 229910052802 copper Inorganic materials 0.000 claims abstract description 273
- 239000010949 copper Substances 0.000 claims abstract description 273
- 239000007788 liquid Substances 0.000 claims abstract description 136
- 238000000034 method Methods 0.000 claims abstract description 90
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 57
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 40
- 239000010935 stainless steel Substances 0.000 claims abstract description 40
- 238000004070 electrodeposition Methods 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims description 69
- 238000000151 deposition Methods 0.000 claims description 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002639 bone cement Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 abstract description 62
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 127
- 229910052785 arsenic Inorganic materials 0.000 description 27
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 27
- 230000008569 process Effects 0.000 description 26
- 229910052787 antimony Inorganic materials 0.000 description 25
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 25
- 229910052797 bismuth Inorganic materials 0.000 description 25
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 229910000365 copper sulfate Inorganic materials 0.000 description 15
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 15
- 239000012535 impurity Substances 0.000 description 13
- 238000007710 freezing Methods 0.000 description 12
- 230000008014 freezing Effects 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 238000007738 vacuum evaporation Methods 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides a kind of processing method of waste electrolyte, comprise the following steps：a）Waste electrolyte is handled, obtains a decopper(ing) end liquid, copper ion concentration is 35g/L~45g/L in a decopper(ing) solution；b）Using insoluble anode as anode, using stainless steel cathode as negative electrode, the decopper(ing) end liquid is handled using continuous electrodeposition method, obtains A levels copper and secondary decopper(ing) end liquid；c）Using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, the secondary decopper(ing) end liquid is handled using continuous electrodeposition method, obtains electro deposited copper, black copper plate, black copper powder and black copper mud.Present invention also offers a kind of waste electrolyte processing unit.The present invention is using a relatively low decopper(ing) end liquid of content of copper ion as raw material, using insoluble anode as anode, A level copper is produced using stainless steel cathode as negative electrode, production cost is not only reduced, reduces the waste of resource.
Description
Technical Field
The invention belongs to the technical field of copper electrolyte, and particularly relates to a treatment method and a treatment device for waste electrolyte.
Background
The electrolytic copper is copper produced by an electrolytic method, has extremely high quality and can be used for manufacturing electrical products. The general process for the electrolysis of copper is as follows: the method comprises the steps of preparing a thick plate of crude copper in advance as an anode, preparing a primary sheet of a stainless steel plate or a pure copper sheet as a cathode, preparing a mixed solution of sulfuric acid and copper sulfate as an electrolyte, and after electrifying, dissolving copper from the anode into copper ions to move to the cathode, obtaining electrons after reaching the cathode and separating out at the cathode to obtain electrolytic copper. In the copper electrolytic refining process, the components of the electrolyte are changed continuously, so that the copper ion concentration is increased continuously, the sulfuric acid concentration is reduced gradually, and impurities are accumulated continuously. In order to maintain the copper, acid content and impurity concentration in the electrolyte within specified ranges, the electrolyte must be purified and conditioned to ensure proper operation of the electrolysis process. The portion of the electrolyte that needs to be purified and conditioned is referred to as spent electrolyte.
The purification of the waste electrolyte is completed by the procedures of decoppering and impurity removal, and the currently commonly used purification procedure generally comprises the following steps: firstly, carrying out vacuum evaporation, freezing crystallization and vacuum belt filter treatment on waste electrolyte to obtain crude copper sulfate, heavy solution and crystallization mother liquor; the copper content of the crude copper sulfate is about 23 percent, and the crude copper sulfate can be directly sold; the heavy solution can be mixed with the waste electrolyte again for treatment or used for generating crude nickel sulfate; and the crystallized mother liquor can be continuously subjected to electrolytic decoppering by adopting a continuous decoppering and dearsenifying method, electrodeposited copper, black copper powder, black copper mud and the like are sequentially obtained in an electrolytic cell, and the final solution after electrolytic decoppering is used for producing nickel sulfate, and refer to fig. 1, which is a schematic diagram of a purification process flow of waste electrolyte disclosed in the prior art. When the continuous copper and arsenic removing method is adopted to carry out electrolytic copper removal on the crystallization mother liquor, an insoluble anode is generally used as an anode, and an electrolytic residual electrode is used as a cathode to carry out electrolysis, so that electrodeposited copper, black copper powder, black copper mud and the like can be obtained, wherein the purity of the electrodeposited copper can reach more than 99%, and the yield of the electrodeposited copper accounts for about half of the total yield of the electrodeposited copper, the black copper powder and the black copper mud, but the electrodeposited copper cannot be used as a product due to low purity, and can only be used for producing an anode plate by re-batching, smelting and casting, so that the production efficiency is reduced, and the production cost is increased.
Disclosure of Invention
The invention aims to provide a method and a device for treating waste electrolyte, which can prepare grade-A copper meeting the national standard of cathode copper by using primary copper removal final solution with lower copper content as a raw material, reduce the production cost and reduce the waste of resources.
The invention provides a method for treating waste electrolyte, which comprises the following steps:
a) treating the waste electrolyte to obtain a primary copper removal final solution, wherein the concentration of copper ions in the primary copper removal solution is 35-45 g/L;
b) treating the primary copper-removing final solution by using an insoluble anode as an anode and a stainless steel cathode as a cathode by adopting a continuous electrodeposition method to obtain grade A copper and secondary copper-removing final solution;
c) and (3) treating the secondary decoppering final solution by using an insoluble anode as an anode and an electrolytic residual electrode as a cathode by adopting a continuous electrodeposition method to obtain electrodeposited copper, a black copper plate, black copper powder and black copper mud.
Preferably, in the step b), the flow rate of the primary copper removal final solution is 20L/min to 28L/min; the temperature of the electrolytic deposition is 50-70 ℃; the current density of the electrolytic deposition is 180A/m2～200A/m2(ii) a The concentration of copper ions in the secondary copper removal final solution is 15 g/L-25 g/L.
Preferably, in the step b), the primary decoppering final solution is subjected to electrolytic deposition by sequentially passing through 3 or 4 electrolytic cells connected in series, wherein each electrolytic cell takes an insoluble anode as an anode and a stainless steel cathode as a cathode.
Preferably, before the step b), the method further comprises adding additives into the primary copper removal final solution, wherein the additives are bone glue and thiourea.
Preferably, the dosage of the bone glue is 20 g/t-30 g/t, and the dosage of the thiourea is 40 g/t-50 g/t.
Preferably, in the step b), the liquid inlet mode of the primary copper removal final solution is a lower inlet and an upper outlet.
Preferably, the step a) is specifically as follows:
treating the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and a primary decoppering final solution;
or,
the step a) is specifically as follows:
and sequentially carrying out vacuum evaporation, freezing crystallization and filtration treatment on the waste electrolyte to obtain copper sulfate and primary decoppering final solution.
The invention also provides a waste electrolyte treatment device, comprising:
a first decoppering device;
the liquid inlet of the second electrolytic tank is connected with the liquid outlet of the first decoppering device, and the second electrolytic tank takes an insoluble anode as an anode and a stainless steel cathode as a cathode;
and the liquid inlet of the third electrolytic tank is connected with the liquid outlet of the second electrolytic tank, and the third electrolytic tank takes an insoluble anode as an anode and takes an electrolytic residual anode as a cathode.
Preferably, the second electrolytic tank comprises:
the liquid inlet of the second electrolytic tank A is connected with the liquid outlet of the first copper removing device;
the liquid inlet of the second electrolytic tank B is connected with the liquid outlet of the second electrolytic tank A;
and the liquid inlet of the second electrolytic tank C is connected with the liquid outlet of the second electrolytic tank B.
Preferably, the electrolysis device also comprises a branch flow pipe communicated with the liquid outlet of the second C electrolysis bath.
Preferably, the liquid inlet of the second electrolytic tank A is lower than the liquid outlet; the liquid inlet of the second B electrolytic tank is lower than the liquid outlet; the liquid inlet of the second C electrolytic tank is lower than the liquid outlet.
Preferably, the second electrolytic tank comprises:
the liquid inlet of the second electrolytic tank A is connected with the liquid outlet of the first copper removing device;
the liquid inlet of the second electrolytic tank B is connected with the liquid outlet of the second electrolytic tank A;
the liquid inlet of the second electrolytic tank C is connected with the liquid outlet of the second electrolytic tank B;
and the liquid inlet of the second D electrolytic tank is connected with the liquid outlet of the second C electrolytic tank.
Preferably, the electrolysis device also comprises a branch flow pipe communicated with the liquid outlet of the second D electrolysis bath.
Preferably, the liquid inlet of the second electrolytic tank A is lower than the liquid outlet; the liquid inlet of the second B electrolytic tank is lower than the liquid outlet; the liquid inlet of the second electrolytic tank C is lower than the liquid outlet; the liquid inlet of the second D electrolytic tank is lower than the liquid outlet.
Preferably, the first decoppering device comprises a first electrolytic tank, wherein the first electrolytic tank takes an insoluble anode as an anode and a stainless steel cathode as a cathode;
or,
the first decoppering device comprises:
a vacuum evaporation device;
the freezing and crystallizing device is connected with a discharge port of the vacuum evaporation device; and
and the filtering device is connected with the discharge port of the freezing and crystallizing device.
Preferably, the electrolytic bath further comprises an additive storage tank, and a liquid outlet of the additive storage tank is communicated with a liquid inlet of the second electrolytic bath.
Compared with the prior art, the method for treating the waste electrolyte provided by the invention comprises the steps of firstly treating the waste electrolyte to obtain primary decoppering final solution, wherein the concentration of copper ions in the primary decoppering solution is 35-45 g/L; then, treating the primary copper-removing final solution by using an insoluble anode as an anode and a stainless steel cathode as a cathode by adopting a continuous electrodeposition method to obtain grade A copper and secondary copper-removing final solution; and finally, treating the secondary decoppering final solution by using an insoluble anode as an anode and an electrolytic residual electrode as a cathode by adopting a continuous electrodeposition method to obtain electrodeposited copper, a black copper plate, black copper powder and black copper mud. The method comprises the following steps of firstly, carrying out first treatment on the waste electrolyte to obtain a first copper removal final solution, wherein the first treatment can be used for producing copper sulfate and also can be used for producing A-grade copper, and the purpose of reducing the concentration of copper ions in the waste electrolyte to 35-45 g/L; then, treating the primary decoppering final solution by using an insoluble anode as an anode and a stainless steel cathode as a cathode by adopting a continuous electrodeposition method, and obtaining grade A copper which completely meets the national standard of cathode copper, has a main grade even up to 99.999 percent and has a total impurity grade of about 25ppm by using the stainless steel cathode as the cathode and adopting the continuous electrodeposition method; and then treating the secondary decoppering final solution by using an insoluble anode as an anode and an electrolytic residual electrode as a cathode by adopting a continuous electrodeposition method to obtain electrodeposited copper, a black copper plate, black copper powder and black copper mud. The method takes the primary decoppering final solution with lower copper ion content as the raw material, takes the insoluble anode as the anode and takes the stainless steel cathode as the cathode to produce the A-grade copper, thereby not only reducing the production cost and reducing the waste of resources, but also leading the obtained A-grade copper to completely meet the national standard of cathode copper, and leading the main grade to even reach 99.999 percent and leading the total impurity grade to be about 25 ppm. Experimental results show that the method provided by the invention can be used for obtaining grade-A copper meeting the national standard of cathode copper.
Drawings
FIG. 1 is a schematic view of a process for purifying a spent electrolyte disclosed in the prior art;
fig. 2 is a schematic structural view of a spent electrolyte treatment apparatus according to an embodiment of the present invention.
Detailed Description
The invention provides a method for treating waste electrolyte, which comprises the following steps:
a) treating the waste electrolyte to obtain a primary copper removal final solution, wherein the concentration of copper ions in the primary copper removal solution is 35-45 g/L;
b) treating the primary copper-removing final solution by using an insoluble anode as an anode and a stainless steel cathode as a cathode by adopting a continuous electrodeposition method to obtain grade A copper and secondary copper-removing final solution;
c) and (3) treating the secondary decoppering final solution by using an insoluble anode as an anode and an electrolytic residual electrode as a cathode by adopting a continuous electrodeposition method to obtain electrodeposited copper, a black copper plate, black copper powder and black copper mud.
In the present invention, the waste electrolyte refers to an electrolyte that needs to reduce impurities and adjust copper and acid balance, and particularly refers to a waste electrolyte obtained in a copper electrolysis process, and the present invention is not particularly limited thereto. Preferably, the concentration of copper ions in the waste electrolyte is preferably 40 g/L-60 g/L, and more preferably 42 g/L-58 g/L.
The method for the first copper removal treatment is not particularly limited, and the first copper removal treatment aims at reducing the concentration of copper ions in the waste electrolyte to obtain a copper product with higher added value because the concentration of the copper ions in the waste electrolyte is higher.
In the invention, the first copper removal treatment can be treatment of waste electrolyte to obtain copper sulfate, and the specific process is as follows:
and sequentially carrying out vacuum evaporation, freezing crystallization and filtration treatment on the waste electrolyte to obtain copper sulfate and primary decoppering final solution.
The present invention preferably sequentially performs vacuum evaporation, freezing crystallization and filtration treatment, which are well known to those skilled in the art, on the waste electrolyte to obtain crude copper sulfate and a primary decoppering final solution. The invention has no special limitation on the process parameters and the specific steps of the vacuum evaporation, the freezing crystallization and the filtration treatment, and the steps and the parameters which are commonly used by the technical personnel in the field can obtain the copper sulfate. After the treatment, the copper content in the obtained copper sulfate is preferably 20-30%; the concentration of copper ions in the final primary copper removal solution is preferably 35g/L to 45g/L, and more preferably 38g/L to 42 g/L.
In the invention, the first copper removal treatment can be to treat the waste electrolyte to obtain negative A-grade copper and a first copper removal final solution, and the specific process is as follows:
and treating the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and a primary decoppering final solution.
According to the invention, the insoluble anode is preferably used as the anode, the stainless steel cathode is preferably used as the cathode, and the electrolytic deposition method is adopted to treat the waste electrolyte to obtain grade-A copper and primary decoppering final solution. The invention has no special limit to the technological parameters and the specific steps of the electrolytic deposition method, and the A-grade copper can be obtained by electrolyzing the waste electrolyte. After the above treatment, the concentration of copper ions in the primary final copper-removing solution is preferably 35g/L to 45g/L, more preferably 38g/L to 42 g/L. In the present invention, the insoluble anode is preferably a lead anode.
In the invention, when the concentration of copper ions in the waste electrolyte is higher, such as 50 g/L-60 g/L, the waste electrolyte is preferably treated by an electrolytic deposition method to obtain grade A copper and a primary copper removal final solution; when the copper ion concentration is lower, such as 40 g/L-50 g/L, the copper ion concentration is preferably subjected to vacuum evaporation, freezing crystallization and filtration in sequence to obtain copper sulfate and a primary copper removal final solution.
And (3) after the primary copper removal final solution is obtained, treating the primary copper removal final solution by using an insoluble anode as an anode and a stainless steel cathode as a cathode by adopting a continuous electrodeposition method to obtain grade A copper and secondary copper removal final solution. The invention uses stainless steel cathode to replace electrolytic residual pole or starting pole piece, and uses primary decoppering end liquid as raw material to prepare A-grade copper by continuous electrodeposition method.
In the invention, the primary decoppering final solution is preferably subjected to electrolytic deposition by sequentially passing through 3 or 4 electrolytic cells connected in series, wherein each electrolytic cell takes an insoluble anode as an anode and a stainless steel cathode as a cathode. Specifically, when the first copper removal treatment is the electrolytic deposition method for producing the grade-A copper, the obtained first copper removal final solution preferably passes through 4 electrolytic baths connected in series in sequence for electrolytic deposition; when the first copper removing treatment is copper sulfate production, the obtained first copper removing final solution preferably passes through 3 electrolytic baths connected in series for electrolytic deposition.
In the case of performing electrodeposition in the above-mentioned electrolytic cells connected in series, the liquid flow rate, temperature, current density, etc. of each cell are the same, and the present invention will be described with reference to the first electrolytic cell as an example. When the second copper removing treatment is carried out, the flow rate of the primary copper removing final solution is preferably 20L/min to 28L/min, more preferably 21 to 25L/min; the electrolytic deposition temperature is preferably 50-70 ℃, and more preferably 60-68 ℃; the current density of the electrolytic deposition is preferably 180A/m2～200A/m2More preferably 190A/m2～198A/m2。
And (3) treating the primary decoppering final solution by using an insoluble anode as an anode and a stainless steel cathode as a cathode by using a continuous electrodeposition method to obtain grade A copper and secondary decoppering final solution, wherein the obtained grade A copper completely meets the national standard of cathode copper, the main grade can even reach 99.999%, the total impurity grade is about 25ppm, and the concentration of copper ions in the obtained secondary decoppering final solution is preferably 15 g/L-25 g/L, and more preferably 18 g/L-23 g/L.
Before the primary copper removing final solution is subjected to the secondary copper removing treatment, an additive is preferably added into the primary copper removing final solution, so that impurities such as arsenic, bismuth, antimony and the like are removed while copper is removed. The additive is preferably bone glue and thiourea, wherein the dosage of the bone glue is preferably 20 g/t-30 g/t, and more preferably 28 g/t; the dosage of the thiourea is preferably 40 g/t-50 g/t, and more preferably 45 g/t.
In the process of carrying out the second copper removal treatment on the primary copper removal final solution, the liquid inlet mode of the primary copper removal final solution is downward inlet and upward outlet, namely, the primary copper removal final solution enters from the lower part of a first electrolytic tank, flows out from the upper part after electrolysis and enters from the lower part of a second electrolytic tank, and the process is sequentially carried out, and the process is not repeated herein. A liquid inlet mode of feeding in and discharging out from the bottom is adopted, and A-grade copper with higher main product taste can be obtained.
And (3) after the secondary copper removal final solution is obtained, treating the secondary copper removal final solution by using an insoluble anode as an anode and an electrolytic residual electrode as a cathode by adopting a continuous electrodeposition method to obtain electrodeposited copper, a black copper plate, black copper powder and black copper mud. The electrolytic residual electrode refers to the residual part of anode copper electrolysis. In the present invention, the final secondary copper-removing solution is preferably subjected to electrodeposition by passing through 6 or 7 electrolytic cells connected in series, each of which has an insoluble anode as an anode and an electrolytic residual anode as a cathode. Specifically, when the primary copper removal final solution passes through 4 electrolytic cells connected in series, the secondary copper removal final solution passes through 6 electrolytic cells connected in series, wherein the first 3 electrolytic cells are used for producing electrodeposited copper, and the last 3 electrolytic cells are used for producing products such as black copper plates, black copper powder, black copper mud and the like; when the primary final copper removing solution passes through 3 electrolytic tanks connected in series, the secondary final copper removing solution passes through 7 electrolytic tanks connected in series, wherein the first 4 electrolytic tanks are used for producing electrodeposited copper, and the last 3 electrolytic tanks are used for producing products such as black copper plates, black copper powder, black copper mud and the like.
That is, in the treatment process of the waste electrolyte provided by the invention, after the waste electrolyte is subjected to a first copper removal treatment to obtain a first copper removal final solution, the waste electrolyte is preferably subjected to electrolytic deposition sequentially through 10 electrolytic baths connected in series to prepare products such as grade a copper, electrodeposited copper, black copper plates, black copper powder, black copper mud and the like. The 10 electrolytic tanks are numbered as No. 1 electrolytic tank, No. 2 electrolytic tank to No. 10 electrolytic tank in sequence, and the following two treatment methods are concretely adopted:
the first method comprises the following steps:
in the No. 1-3 tanks, insoluble anodes are used as anodes, stainless steel cathodes are used as cathodes, and A-grade copper is obtained after the electrolytic treatment of the primary decoppering final solution;
in the No. 4-10 tanks, the insoluble anode is used as the anode, the electrolytic residual anode is used as the cathode, and the No. 4-7 tanks are subjected to electrolytic treatment to obtain electrodeposited copper; and (4) carrying out electrolytic treatment in a No. 8-10 groove to obtain a black copper plate, black copper powder and black copper mud.
And the second method comprises the following steps:
in the No. 1-4 tanks, the insoluble anode is used as an anode, the stainless steel cathode is used as a cathode, and the grade-A copper is obtained after the electrolytic treatment of the primary decoppering final solution;
in the No. 5-10 tanks, the insoluble anode is used as the anode, the electrolytic residual anode is used as the cathode, and the No. 5-7 tanks are subjected to electrolytic treatment to obtain electrodeposited copper; and (4) carrying out electrolytic treatment in a No. 8-10 groove to obtain a black copper plate, black copper powder and black copper mud.
The invention has no special limitation on the technological parameters and the operation steps of using an insoluble anode as an anode and using an electrolysis residual electrode as a cathode to carry out continuous electrodeposition treatment on the secondary copper removal final solution, and the parameters and the steps known by the technical personnel in the field can obtain electrodeposited copper, black copper plates, black copper powder and black copper mud, wherein the electrodeposited copper and the black copper plates can be used for producing anode plates, and the black copper powder and the black copper mud can be sent to a material preparation workshop to be reused after treatment. Preferably, the invention preferably supplements copper ions in the process of treatment by the continuous electrodeposition method, thereby improving the arsenic removal rate.
After the third copper removing treatment, namely the second copper removing final solution passes through No. 10 electrolytic tank, the copper ion content in the obtained copper removing final solution is preferably lower than 0.5 g/L.
In the invention, for the subsequent impurity removal effect of the throw pillow, when the flow of the waste electrolyte is large and the copper content is high, the secondary copper removal final solution can be directly subjected to copper removal again to prepare grade A copper and then subjected to subsequent treatment to prepare electrodeposited copper and the like without being subjected to subsequent treatment.
In the third copper removing process, in order to achieve the aim of impurity removing by an induction method, copper removing final liquid is added into copper removing grooves No. 7, 8 and 9, and the flow rate of the copper removing final liquid is 1/9 of the inlet flow rate.
The method comprises the following steps of firstly, carrying out first treatment on the waste electrolyte to obtain a first copper removal final solution, wherein the first treatment can be used for producing copper sulfate and also can be used for producing A-grade copper, and the purpose of reducing the concentration of copper ions in the waste electrolyte to 35-45 g/L; then, treating the primary decoppering final solution by using an insoluble anode as an anode and a stainless steel cathode as a cathode by adopting a continuous electrodeposition method, and obtaining grade A copper which completely meets the national standard of cathode copper, has a main grade even up to 99.999 percent and has a total impurity grade of about 25ppm by using the stainless steel cathode as the cathode and adopting the continuous electrodeposition method; and then treating the secondary decoppering final solution by using an insoluble anode as an anode and an electrolytic residual electrode as a cathode by adopting a continuous electrodeposition method to obtain electrodeposited copper, a black copper plate, black copper powder and black copper mud. The method takes the primary decoppering final solution with lower copper ion content as the raw material, takes the insoluble anode as the anode and takes the stainless steel cathode as the cathode to produce the A-grade copper, thereby not only reducing the production cost and reducing the waste of resources, but also leading the obtained A-grade copper to completely meet the national standard of cathode copper, and leading the main grade to even reach 99.999 percent and leading the total impurity grade to be about 25 ppm. Experimental results show that the method provided by the invention can be used for obtaining grade-A copper meeting the national standard of cathode copper.
The invention also provides a waste electrolyte treatment device, comprising:
a first decoppering device;
the liquid inlet of the second electrolytic tank is connected with the liquid outlet of the first decoppering device, and the second electrolytic tank takes an insoluble anode as an anode and a stainless steel cathode as a cathode;
and the liquid inlet of the third electrolytic tank is connected with the liquid outlet of the second electrolytic tank, and the third electrolytic tank takes an insoluble anode as an anode and takes an electrolytic residual anode as a cathode.
Referring to fig. 2, fig. 2 is a schematic structural diagram of a waste electrolyte treatment device according to an embodiment of the present invention, in which 1 is a first copper removal device, 2 is a second electrolytic tank, and 3 is a third electrolytic tank.
In the invention, a first copper removing device 1 aims at carrying out first copper removing treatment on waste electrolyte, and according to different first copper removing treatment methods, the first copper removing device can be a first electrolytic tank, the first electrolytic tank takes an insoluble anode as an anode and a stainless steel cathode as a cathode, and the waste electrolyte is electrolyzed in the first electrolytic tank to obtain grade A copper and a primary copper removing final solution; the first decoppering device may also include:
a vacuum evaporation device;
the freezing and crystallizing device is connected with a discharge port of the vacuum evaporation device; and
and the filtering device is connected with the discharge port of the freezing and crystallizing device.
And the waste electrolyte is sequentially treated by a vacuum evaporation device, a freezing crystallization device and a filtering device to obtain copper sulfate and primary decoppering final solution. The present invention is not particularly limited to the specific structure of the first electrolytic cell or vacuum evaporation apparatus, the freezing and crystallization apparatus, and the filtration apparatus, and the corresponding apparatuses known to those skilled in the art may be used.
The liquid inlet of the second electrolytic tank provided by the invention is connected with the liquid outlet of the first decoppering device, and the second electrolytic tank takes an insoluble anode as an anode and a stainless steel cathode as a cathode. And feeding the primary copper removal final solution passing through the first copper removal device into a second electrolytic tank for electrolysis to obtain grade-A copper and a second copper removal final solution. In the present invention, the second electrolytic tank includes:
the liquid inlet of the second electrolytic tank A is connected with the liquid outlet of the first copper removing device;
the liquid inlet of the second electrolytic tank B is connected with the liquid outlet of the second electrolytic tank A;
and the liquid inlet of the second electrolytic tank C is connected with the liquid outlet of the second electrolytic tank B.
That is, the second electrolytic bath comprised 3 second A electrolytic bath, second B electrolytic bath and second C electrolytic bath connected in series, each electrolytic bath having an insoluble anode as an anode and a stainless steel cathode as a cathode. And electrolyzing the primary copper-removing final solution in a second A electrolytic tank, a second B electrolytic tank and a second C electrolytic tank in sequence to obtain grade A copper and secondary copper-removing final solution.
In other embodiments, the liquid inlets of the second A electrolytic cell, the second B electrolytic cell and the second C electrolytic cell are lower than the liquid outlets thereof, so that the liquid inlet mode of the liquid is that the liquid enters from the bottom and goes out from the top, thereby being more beneficial to the removal of copper ions in the waste electrolyte.
In other embodiments, the system further comprises a branch flow pipe communicated with the liquid outlet of the second C electrolytic cell, and when the flow rate of the waste electrolyte is large or the content of copper ions is high, the secondary final copper-removing liquid obtained through electrolysis in the second C electrolytic cell enters a final copper-removing liquid storage tank through the branch flow pipe or is subjected to other treatment.
In another embodiment, the second electrolytic cell may further include:
the liquid inlet of the second electrolytic tank A is connected with the liquid outlet of the first copper removing device;
the liquid inlet of the second electrolytic tank B is connected with the liquid outlet of the second electrolytic tank A;
the liquid inlet of the second electrolytic tank C is connected with the liquid outlet of the second electrolytic tank B;
and the liquid inlet of the second D electrolytic tank is connected with the liquid outlet of the second C electrolytic tank.
That is, the second electrolytic bath comprised 3 second A electrolytic bath, second B electrolytic bath, second C electrolytic bath and second D electrolytic bath connected in series, each electrolytic bath having an insoluble anode as an anode and a stainless steel cathode as a cathode. And electrolyzing the primary copper-removing final solution in a second A electrolytic tank, a second B electrolytic tank, a second C electrolytic tank and a second D electrolytic tank in sequence to obtain grade A copper and secondary copper-removing final solution.
In other embodiments, the liquid inlets of the second A electrolytic cell, the second B electrolytic cell, the second C electrolytic cell and the second D electrolytic cell are lower than the liquid outlets thereof, so that the liquid inlet mode of the liquid is that the liquid enters from the lower part and goes out from the upper part, thereby being more beneficial to removing copper ions in the waste electrolyte.
In other embodiments, the spent electrolyte treatment apparatus further comprises a branch flow pipe communicated with the liquid outlet of the second D electrolytic cell, and when the flow rate of the spent electrolyte is large or the content of copper ions is high, the secondary final copper-removing liquid obtained through electrolysis in the second D electrolytic cell enters the final copper-removing liquid storage tank through the branch flow pipe or undergoes other treatments.
In other embodiments, the waste electrolyte treatment apparatus further comprises an additive storage tank, a liquid outlet of the additive storage tank is communicated with a liquid inlet of the second electrolytic tank, and an additive can be mixed with the primary decoppering final solution through the additive storage tank and then enter the second electrolytic tank for electrolysis.
The waste electrolyte treatment device provided by the invention further comprises a third electrolytic tank, wherein a liquid inlet of the third electrolytic tank is connected with a liquid outlet of the second electrolytic tank, and the third electrolytic tank takes an insoluble anode as an anode and takes an electrolytic residual electrode as a cathode. And feeding the secondary final copper-removing solution of the second electrolytic tank into a third electrolytic tank for electrolysis to obtain electrodeposited copper, a black copper plate, black copper powder, black copper mud and final copper-removing solution.
In the present invention, the third electrolytic cell may comprise 6 electrolytic cells or 7 electrolytic cells connected in series in this order, each electrolytic cell having an insoluble anode as an anode and an electrolytic residual anode as a cathode. Specifically, when the second electrolytic cell comprises 4 electrolytic cells connected in series, the third electrolytic cell comprises 6 electrolytic cells connected in series, wherein the first 3 electrolytic cells are used for producing electrodeposited copper, and the last 3 electrolytic cells are used for producing products such as black copper plates, black copper powder, black copper mud and the like; when the second electrolytic cell comprises 3 electrolytic cells connected in series, the third electrolytic cell comprises 7 electrolytic cells connected in series, wherein the first 4 electrolytic cells are used for producing electrodeposited copper, and the last 3 electrolytic cells are used for producing products such as black copper plates, black copper powder, black copper mud and the like.
That is, in the present invention, the second electrolytic cell and the third electrolytic cell may specifically be 10 electrolytic cells connected in series, and the waste electrolyte passes through the first copper removing device and then sequentially passes through the 10 electrolytic cells connected in series for electrolytic deposition, so as to respectively prepare products such as grade a copper, electrodeposited copper, black copper plate, black copper powder, black copper mud, and the like. The 10 electrolytic cells are numbered as No. 1 electrolytic cell, No. 2 electrolytic cell to No. 10 electrolytic cell in sequence, and the electrolytic cell has the following two specific structures:
the first method comprises the following steps:
in the No. 1-3 tanks, insoluble anodes are used as anodes, stainless steel cathodes are used as cathodes, and A-grade copper is obtained after the electrolytic treatment of the primary decoppering final solution;
in the No. 4-10 tanks, the insoluble anode is used as the anode, the electrolytic residual anode is used as the cathode, and the No. 4-7 tanks are subjected to electrolytic treatment to obtain electrodeposited copper; and (4) carrying out electrolytic treatment in a No. 8-10 groove to obtain a black copper plate, black copper powder and black copper mud.
And the second method comprises the following steps:
in the No. 1-4 tanks, the insoluble anode is used as an anode, the stainless steel cathode is used as a cathode, and the grade-A copper is obtained after the electrolytic treatment of the primary decoppering final solution;
in the No. 5-10 tanks, the insoluble anode is used as the anode, the electrolytic residual anode is used as the cathode, and the No. 5-7 tanks are subjected to electrolytic treatment to obtain electrodeposited copper; and (4) carrying out electrolytic treatment in a No. 8-10 groove to obtain a black copper plate, black copper powder and black copper mud.
The working principle and the working process of the waste electrolyte treatment device provided by the invention are as follows:
carrying out primary decoppering treatment on the waste electrolyte by using a first decoppering device to obtain primary decoppering final solution;
carrying out electrolytic treatment on the primary decoppering final solution in a second electrolytic tank by taking an insoluble anode as an anode and a stainless steel cathode as a cathode to obtain grade A copper and secondary decoppering final solution;
and the secondary decoppering final solution is subjected to electrolysis treatment in a third electrolytic tank by taking an insoluble anode as an anode and taking an electrolysis residual electrode as a cathode to obtain electrodeposited copper, a black copper plate, black copper powder, black copper mud and a decoppering final solution.
The method takes the primary decoppering final solution with lower copper ion content as the raw material, takes the insoluble anode as the anode and takes the stainless steel cathode as the cathode to produce the A-grade copper, thereby not only reducing the production cost and reducing the waste of resources, but also leading the obtained A-grade copper to completely meet the national standard of cathode copper, and leading the main grade to even reach 99.999 percent and leading the total impurity grade to be about 25 ppm. Experimental results show that the method provided by the invention can be used for obtaining grade-A copper meeting the national standard of cathode copper.
In order to further illustrate the present invention, the method for treating waste electrolyte provided by the present invention is described below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
The method comprises the steps of taking waste electrolyte with copper ion concentration of 51g/L, arsenic of 5000g/L, antimony of 180g/L, bismuth of 240g/L, nickel of 15000g/L and iron of 2000g/L as raw materials, and electrolyzing the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and primary copper removal final solution, wherein in the primary copper removal final solution, the copper ion concentration is 42g/L, arsenic of 5000g/L, antimony of 180g/L, bismuth of 240g/L, nickel of 15000g/L and iron of 2000 g/L;
and (2) connecting electrolysis cells No. 1-10 in series in sequence, adopting a liquid inlet mode of bottom inlet and top outlet, wherein the electrolysis cells No. 1-3 take an insoluble lead polar plate as an anode, a stainless steel polar plate as a cathode, the electrolysis cells No. 4-10 take an insoluble lead polar plate as an anode, the area of the cathode is 800mm x 900mm, electrolysis residues are taken as a cathode for electrolysis, before electrolysis, 28g/t of bone glue and 45g/t of thiourea are added into the primary copper removal final solution, the electrolysis process parameters and results are shown in Table 1, and the Table 1 is the electrolysis parameters and results provided by the embodiment 1 of the invention. In the electrolytic process, the copper removing final solution is added into the copper removing grooves 7, 8 and 9, and the flow rate of the copper removing final solution is 1/9 of the inlet flow rate.
TABLE 1 electrolytic parameters and results provided in example 1 of the invention
In table 1, the outlet copper ion concentration is the outlet copper ion copper concentration of the No. 10 electrolytic cell, and the arsenic removal rate, the antimony removal rate and the bismuth removal rate are the removal rates of the respective substances in the final copper removal solution obtained from the No. 10 electrolytic cell.
As can be seen from Table 1, the grade A copper prepared by the method provided by the invention can meet the national standard requirement of cathode copper, and the removal rate of arsenic, antimony and bismuth is high.
Example 2
The method comprises the steps of taking waste electrolyte with copper ion concentration of 51g/L, arsenic of 5000g/L, antimony of 180g/L, bismuth of 240g/L, nickel of 15000g/L and iron of 2000g/L as raw materials, and electrolyzing the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and primary copper removal final solution, wherein in the primary copper removal final solution, the copper ion concentration is 42g/L, the arsenic is 5000g/L, the antimony is 180g/L, the bismuth is 240g/L, the nickel is 15000g/L and the iron is 2000 g/L;
and (2) connecting electrolysis cells No. 1-10 in series in sequence, adopting a liquid inlet mode of bottom inlet and top outlet, wherein the electrolysis residue is used as a cathode for electrolysis in the electrolysis cells No. 1-3 with an insoluble lead polar plate as an anode and a stainless steel polar plate as a cathode for the electrolysis cells No. 4-10 with the insoluble lead polar plate as the anode and the cathode with the area of 800mm x 900mm, adding 28g/t of bone glue and 45g/t of thiourea into the primary copper-removing final solution before electrolysis, and referring to Table 2 for electrolysis process parameters and results, wherein the Table 2 is the electrolysis parameters and results provided by the embodiment 2 of the invention. In the electrolytic process, the copper removing final solution is added into the copper removing grooves 7, 8 and 9, and the flow rate of the copper removing final solution is 1/9 of the inlet flow rate.
TABLE 2 Electrolysis parameters and results provided in example 2 of the present invention
In table 2, the outlet copper ion concentration is the outlet copper ion copper concentration of the No. 10 electrolytic cell, and the arsenic removal rate, the antimony removal rate, and the bismuth removal rate are the removal rates of the respective substances in the final copper removal solution obtained by the No. 10 electrolytic cell.
As can be seen from Table 2, the grade A copper prepared by the method provided by the invention can meet the national standard requirement of cathode copper, and the removal rate of arsenic, antimony and bismuth is high.
Example 3
The method comprises the steps of taking waste electrolyte with copper ion concentration of 51g/L, arsenic of 5000g/L, antimony of 180g/L, bismuth of 240g/L, nickel of 15000g/L and iron of 2000g/L as raw materials, and electrolyzing the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and primary copper removal final solution, wherein in the primary copper removal final solution, the copper ion concentration is 42g/L, the arsenic is 5000g/L, the antimony is 180g/L, the bismuth is 240g/L, the nickel is 15000g/L and the iron is 2000 g/L;
connecting No. 1-10 electrolytic cells in series in sequence, adopting a liquid inlet mode of feeding in and feeding out from bottom, wherein No. 1-3 electrolytic cells use an insoluble lead polar plate as an anode, a stainless steel polar plate as a cathode, No. 4-10 electrolytic cells use an insoluble lead polar plate as an anode, the area of the cathode is 800mm x 900mm, electrolysis residues are used as a cathode for electrolysis, before electrolysis, 28g/t bone glue and 45g/t thiourea are added into a primary decoppering final solution, and the parameters and results of the electrolysis process are shown in a table 3, and the table 3 is the electrolysis parameters and results provided by the embodiment of the invention. In the electrolytic process, the copper removing final solution is added into the copper removing grooves 7, 8 and 9, and the flow rate of the copper removing final solution is 1/9 of the inlet flow rate.
TABLE 3 electrolytic parameters and results provided in example 3 of the invention
In table 3, the outlet copper ion concentration is the outlet copper ion copper concentration of the No. 10 electrolytic cell, and the arsenic removal rate, the antimony removal rate and the bismuth removal rate are the removal rates of the respective substances in the final copper removal solution obtained from the No. 10 electrolytic cell.
As can be seen from Table 3, the grade A copper prepared by the method provided by the invention can meet the national standard requirement of cathode copper, and the removal rate of arsenic, antimony and bismuth is high.
Example 4
The method comprises the steps of taking waste electrolyte with copper ion concentration of 51g/L, arsenic of 5000g/L, antimony of 180g/L, bismuth of 240g/L, nickel of 15000g/L and iron of 2000g/L as raw materials, and electrolyzing the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and primary copper removal final solution, wherein in the primary copper removal final solution, the copper ion concentration is 42g/L, the arsenic is 5000g/L, the antimony is 180g/L, the bismuth is 240g/L, the nickel is 15000g/L and the iron is 2000 g/L;
and (2) connecting electrolysis cells No. 1-10 in series in sequence, adopting a liquid inlet mode of bottom inlet and top outlet, wherein the electrolysis residue is used as a cathode for electrolysis in the electrolysis cells No. 1-3 with an insoluble titanium polar plate as an anode and a stainless steel polar plate as a cathode and the electrolysis cells No. 4-10 with an insoluble lead polar plate as an anode and the area of the cathode of 800mm x 900mm, adding 28g/t bone glue and 45g/t thiourea as additives into the primary copper-removing final solution before electrolysis, and referring to Table 4 for electrolysis process parameters and results, wherein the Table 4 is the electrolysis parameters and results provided by the embodiment 4 of the invention. In the electrolytic process, the copper removing final solution is added into the copper removing grooves 7, 8 and 9, and the flow rate of the copper removing final solution is 1/9 of the inlet flow rate.
TABLE 4 electrolytic parameters and results provided in example 4 of the present invention
In table 4, the outlet copper ion concentration is the outlet copper ion copper concentration of the No. 10 electrolytic cell, and the arsenic removal rate, the antimony removal rate, and the bismuth removal rate are the removal rates of the respective substances in the final copper removal solution obtained from the No. 10 electrolytic cell.
As can be seen from Table 4, the grade A copper prepared by the method provided by the invention can meet the national standard requirement of cathode copper, and the removal rate of arsenic, antimony and bismuth is high.
In addition, the decoppering efficiency of the present example was 88%.
Example 5
The method comprises the steps of taking waste electrolyte with copper ion concentration of 51g/L, arsenic of 5000g/L, antimony of 180g/L, bismuth of 240g/L, nickel of 15000g/L and iron of 2000g/L as raw materials, and electrolyzing the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and primary copper removal final solution, wherein in the primary copper removal final solution, the copper ion concentration is 38g/L, the arsenic is 5000g/L, the antimony is 180g/L, the bismuth is 240g/L, the nickel is 15000g/L and the iron is 2000 g/L;
and (2) connecting electrolysis cells No. 1-10 in series in sequence, adopting a liquid inlet mode of bottom inlet and top outlet, wherein the electrolysis residue is used as a cathode for electrolysis in the electrolysis cells No. 1-3 with an insoluble titanium polar plate as an anode and a stainless steel polar plate as a cathode and the electrolysis cells No. 4-10 with an insoluble lead polar plate as an anode and the area of the cathode of 800mm x 900mm, adding 28g/t bone glue and 45g/t thiourea as additives into the primary copper-removing final solution before electrolysis, and referring to Table 5 for electrolysis process parameters and results, wherein the Table 5 is the electrolysis parameters and results provided by the embodiment 5 of the invention. In the electrolytic process, the copper removing final solution is added into the copper removing grooves 7, 8 and 9, and the flow rate of the copper removing final solution is 1/9 of the inlet flow rate.
TABLE 5 electrolytic parameters and results provided in example 5 of the invention
In table 5, the outlet copper ion concentration is the outlet copper ion copper concentration of the No. 10 electrolytic cell, and the arsenic removal rate, the antimony removal rate and the bismuth removal rate are the removal rates of the respective substances in the final copper removal solution obtained from the No. 10 electrolytic cell.
As can be seen from Table 5, the grade A copper prepared by the method provided by the invention can meet the national standard requirement of cathode copper, and the removal rate of arsenic, antimony and bismuth is high.
Comparative example 1
The method comprises the steps of taking waste electrolyte with copper ion concentration of 51g/L, arsenic of 5000g/L, antimony of 180g/L, bismuth of 240g/L, nickel of 15000g/L and iron of 2000g/L as raw materials, and electrolyzing the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and primary copper removal final solution, wherein in the primary copper removal final solution, the copper ion concentration is 38g/L, the arsenic is 5000g/L, the antimony is 180g/L, the bismuth is 240g/L, the nickel is 15000g/L and the iron is 2000 g/L;
and connecting No. 1-10 electrolytic cells in series in sequence, adopting a liquid inlet mode of feeding in and feeding out from bottom, wherein the No. 1-10 electrolytic cells use an insoluble lead polar plate as an anode, the area of the cathode is 800mm x 900mm, electrolysis is carried out by using an electrolysis residue as the cathode, 28g/t bone glue and 45g/t thiourea are added into the primary decoppering final solution before electrolysis, the parameters and results of the electrolysis process are shown in a table 6, and the table 6 is the electrolysis parameters and results provided by comparative example 1 of the invention. In the electrolytic process, the copper removing final solution is added into the copper removing grooves 7, 8 and 9, and the flow rate of the copper removing final solution is 1/9 of the inlet flow rate.
TABLE 6 electrolytic parameters and results provided in comparative example 1 of the present invention
| Item | |
| Current (A) | 8000 |
| Flow (L/min) | 23 |
| Import copper (g/L) | 38 |
| Export copper (g/L) | ＜0.5 |
| Arsenic removal Rate (%) | 65～75 |
| Antimony removal rate (%) | 70～80 |
| Bismuth removal rate (%) | 95～98 |
In table 5, the outlet copper ion concentration is the outlet copper ion copper concentration of the No. 10 electrolytic cell, and the arsenic removal rate, the antimony removal rate and the bismuth removal rate are the removal rates of the respective substances in the final copper removal solution obtained from the No. 10 electrolytic cell.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for treating a spent electrolyte, comprising the steps of:
a) treating the waste electrolyte by an electrolytic deposition method to obtain grade-A copper and a primary decoppering final solution, wherein the concentration of copper ions in the waste electrolyte is 50-60 g/L, and the concentration of copper ions in the primary decoppering solution is 35-45 g/L;
b) treating the primary copper-removing final solution by using an insoluble anode as an anode and a stainless steel cathode as a cathode by adopting a continuous electrodeposition method to obtain grade A copper and secondary copper-removing final solution; the liquid inlet mode of the primary copper removing final liquid is that the copper removing final liquid enters from the bottom and goes out from the top; the primary decoppering final solution sequentially passes through 3 or 4 electrolytic baths connected in series for electrolytic deposition, and each electrolytic bath takes an insoluble anode as an anode and a stainless steel cathode as a cathode; before the step b), adding additives into the primary copper removal final solution, wherein the additives are bone glue and thiourea;
c) and (3) treating the secondary decoppering final solution by using an insoluble anode as an anode and an electrolytic residual electrode as a cathode by adopting a continuous electrodeposition method to obtain electrodeposited copper, a black copper plate, black copper powder and black copper mud.
2. The treatment method according to claim 1, wherein in the step b), the flow rate of the primary decoppering final solution is 20L/min to 28L/min; the temperature of the electrolytic deposition is 50-70 ℃; the current density of the electrolytic deposition is 180A/m2～200A/m2(ii) a The concentration of copper ions in the secondary copper removal final solution is 15 g/L-25 g/L.
3. The treatment method according to claim 1, characterized in that the amount of bone glue is between 20 and 30g/t and the amount of thiourea is between 40 and 50 g/t.
4. A spent electrolyte treatment apparatus comprising:
the first copper removing device comprises a first electrolytic tank and a second electrolytic tank, wherein the first electrolytic tank is used for treating waste electrolyte with copper ion concentration of 50-60 g/L, and the copper ion concentration in the copper removing solution is 35-45 g/L;
a second electrolytic tank with a liquid inlet connected with the liquid outlet of the first copper removing device, wherein the second electrolytic tank comprises 3 or 4 electrolytic tanks connected in series for electrolytic deposition, and each electrolytic tank takes an insoluble anode as an anode and a stainless steel cathode as a cathode; the liquid inlet mode of the liquid of each electrolytic cell is that the liquid enters from the bottom and goes out from the top;
and the liquid inlet of the third electrolytic tank is connected with the liquid outlet of the second electrolytic tank, and the third electrolytic tank takes an insoluble anode as an anode and takes an electrolytic residual anode as a cathode.
5. The treatment apparatus of claim 4, wherein the second electrolytic cell comprises:
the liquid inlet of the second electrolytic tank A is connected with the liquid outlet of the first copper removing device;
the liquid inlet of the second electrolytic tank B is connected with the liquid outlet of the second electrolytic tank A;
the liquid inlet of the second electrolytic tank C is connected with the liquid outlet of the second electrolytic tank B;
the branch pipe is communicated with a liquid outlet of the second C electrolytic tank; the liquid inlet of the second electrolytic tank A is lower than the liquid outlet; the liquid inlet of the second B electrolytic tank is lower than the liquid outlet; the liquid inlet of the second C electrolytic tank is lower than the liquid outlet.
6. The treatment apparatus of claim 4, wherein the second electrolytic cell comprises:
the liquid inlet of the second electrolytic tank A is connected with the liquid outlet of the first copper removing device;
the liquid inlet of the second electrolytic tank B is connected with the liquid outlet of the second electrolytic tank A;
the liquid inlet of the second electrolytic tank C is connected with the liquid outlet of the second electrolytic tank B;
the liquid inlet of the second D electrolytic tank is connected with the liquid outlet of the second C electrolytic tank;
the branch pipe is communicated with a liquid outlet of the second D electrolytic tank; the liquid inlet of the second electrolytic tank A is lower than the liquid outlet; the liquid inlet of the second B electrolytic tank is lower than the liquid outlet; the liquid inlet of the second electrolytic tank C is lower than the liquid outlet; the liquid inlet of the second D electrolytic tank is lower than the liquid outlet.
7. The treatment apparatus according to claim 4, wherein the first electrolytic bath has an insoluble anode as an anode and a stainless steel cathode as a cathode in the first decoppering apparatus.
8. The treatment apparatus as claimed in claim 4, further comprising an additive storage tank, wherein a liquid outlet of the additive storage tank is communicated with a liquid inlet of the second electrolytic tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310653956.7A CN104694978B (en) | 2013-12-05 | 2013-12-05 | The processing method and processing unit of a kind of waste electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310653956.7A CN104694978B (en) | 2013-12-05 | 2013-12-05 | The processing method and processing unit of a kind of waste electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104694978A CN104694978A (en) | 2015-06-10 |
| CN104694978B true CN104694978B (en) | 2018-03-23 |
Family
ID=53342511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310653956.7A Active CN104694978B (en) | 2013-12-05 | 2013-12-05 | The processing method and processing unit of a kind of waste electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104694978B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420753A (en) * | 2015-12-29 | 2016-03-23 | 重庆紫光国际化工有限责任公司 | Method and device for maintaining activity of electrolyte during process of acrylonitrile electrolysis for preparing adiponitrile |
| CN106086942A (en) * | 2016-08-05 | 2016-11-09 | 江西众合装备技术有限公司 | A kind of cleaning copper electrolyte minus plate black copper mud stripping off device |
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
| CN115074784A (en) * | 2021-03-10 | 2022-09-20 | 中国科学院过程工程研究所 | Method for efficiently removing arsenic through electrolysis in refined copper electrolyte |
| CN113881967B (en) * | 2021-09-22 | 2023-03-21 | 中国恩菲工程技术有限公司 | Impurity removal method for lead electrolyte |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01159392A (en) * | 1987-12-16 | 1989-06-22 | Fujikura Ltd | Production of high purity electrolytic copper |
| JPH0222489A (en) * | 1988-07-08 | 1990-01-25 | Furukawa Electric Co Ltd:The | Method for electrolytically refining high purity copper |
| JPH02185990A (en) * | 1989-01-11 | 1990-07-20 | Dowa Mining Co Ltd | Ultrahigh purity copper and production thereof |
| JPH03260083A (en) * | 1990-03-12 | 1991-11-20 | Furukawa Electric Co Ltd:The | Production of high purity copper |
| CN1186875A (en) * | 1996-12-29 | 1998-07-08 | 中南工业大学 | Method and device for on-line control of organic additive in electrolytic deposition process of metal |
| KR20010091517A (en) * | 2000-03-16 | 2001-10-23 | 박호군 | Cementation apparatus of high purity copper |
| CN101003857A (en) * | 2006-10-31 | 2007-07-25 | 东华大学 | Method for extracting metal copper from electronical wastes |
| CN101033508A (en) * | 2007-04-16 | 2007-09-12 | 中南大学 | Method of preparing high purity copper by bacteria leaching primary sulfide ore |
| CN101049979A (en) * | 2007-05-16 | 2007-10-10 | 梅州市金雁铜业公司 | Method for extracting nickel sulfate from waste solution of copper electrolysis |
| CN101550488A (en) * | 2009-05-13 | 2009-10-07 | 中南大学 | Method of preparing high pure cathode copper by using PCB acid chlorine copper etching solution sewage |
| CN101928957A (en) * | 2010-10-04 | 2010-12-29 | 普宁市长欣五金有限公司 | Method for electrolyzing refined copper at room temperature |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | A method for recycling metal copper in waste circuit boards |
| CN102453931A (en) * | 2011-01-18 | 2012-05-16 | 嘉兴科菲冶金科技股份有限公司 | Technology for treating and purifying copper electrolyte by vortex electrolysis |
| CN102766887A (en) * | 2012-08-16 | 2012-11-07 | 张家港市江城冶化科技有限公司 | Method for manufacturing stainless steel negative plate |
| CN102776527A (en) * | 2012-07-31 | 2012-11-14 | 安徽嘉伟再生资源有限公司 | Novel clean, energy-saving and environment-friendly technology for extracting high-grade copper plate by utilizing waste containing copper |
| CN102899686A (en) * | 2011-12-19 | 2013-01-30 | 河南科技大学 | Impurity removal method for copper electrolyte |
| CN202968708U (en) * | 2012-11-28 | 2013-06-05 | 浙江和鼎铜业有限公司 | Automation copper electrolysis production line |
| CN103132101A (en) * | 2012-10-22 | 2013-06-05 | 广西有色再生金属有限公司 | Copper electrolyte decoppering method by utilizing copper electrolytic residual anodes as cathodes and device thereof |
| CN103194769A (en) * | 2013-04-22 | 2013-07-10 | 北京工业大学 | Electrolytic device and method for recovering high-purity copper from waste circuit board |
| CN103334123A (en) * | 2013-07-24 | 2013-10-02 | 阳谷祥光铜业有限公司 | Copper electrolysis system and running method |
-
2013
- 2013-12-05 CN CN201310653956.7A patent/CN104694978B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01159392A (en) * | 1987-12-16 | 1989-06-22 | Fujikura Ltd | Production of high purity electrolytic copper |
| JPH0222489A (en) * | 1988-07-08 | 1990-01-25 | Furukawa Electric Co Ltd:The | Method for electrolytically refining high purity copper |
| JPH02185990A (en) * | 1989-01-11 | 1990-07-20 | Dowa Mining Co Ltd | Ultrahigh purity copper and production thereof |
| JPH03260083A (en) * | 1990-03-12 | 1991-11-20 | Furukawa Electric Co Ltd:The | Production of high purity copper |
| CN1186875A (en) * | 1996-12-29 | 1998-07-08 | 中南工业大学 | Method and device for on-line control of organic additive in electrolytic deposition process of metal |
| KR20010091517A (en) * | 2000-03-16 | 2001-10-23 | 박호군 | Cementation apparatus of high purity copper |
| CN101003857A (en) * | 2006-10-31 | 2007-07-25 | 东华大学 | Method for extracting metal copper from electronical wastes |
| CN101033508A (en) * | 2007-04-16 | 2007-09-12 | 中南大学 | Method of preparing high purity copper by bacteria leaching primary sulfide ore |
| CN101049979A (en) * | 2007-05-16 | 2007-10-10 | 梅州市金雁铜业公司 | Method for extracting nickel sulfate from waste solution of copper electrolysis |
| CN101550488A (en) * | 2009-05-13 | 2009-10-07 | 中南大学 | Method of preparing high pure cathode copper by using PCB acid chlorine copper etching solution sewage |
| CN101928957A (en) * | 2010-10-04 | 2010-12-29 | 普宁市长欣五金有限公司 | Method for electrolyzing refined copper at room temperature |
| CN102453931A (en) * | 2011-01-18 | 2012-05-16 | 嘉兴科菲冶金科技股份有限公司 | Technology for treating and purifying copper electrolyte by vortex electrolysis |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | A method for recycling metal copper in waste circuit boards |
| CN102899686A (en) * | 2011-12-19 | 2013-01-30 | 河南科技大学 | Impurity removal method for copper electrolyte |
| CN102776527A (en) * | 2012-07-31 | 2012-11-14 | 安徽嘉伟再生资源有限公司 | Novel clean, energy-saving and environment-friendly technology for extracting high-grade copper plate by utilizing waste containing copper |
| CN102766887A (en) * | 2012-08-16 | 2012-11-07 | 张家港市江城冶化科技有限公司 | Method for manufacturing stainless steel negative plate |
| CN103132101A (en) * | 2012-10-22 | 2013-06-05 | 广西有色再生金属有限公司 | Copper electrolyte decoppering method by utilizing copper electrolytic residual anodes as cathodes and device thereof |
| CN202968708U (en) * | 2012-11-28 | 2013-06-05 | 浙江和鼎铜业有限公司 | Automation copper electrolysis production line |
| CN103194769A (en) * | 2013-04-22 | 2013-07-10 | 北京工业大学 | Electrolytic device and method for recovering high-purity copper from waste circuit board |
| CN103334123A (en) * | 2013-07-24 | 2013-10-02 | 阳谷祥光铜业有限公司 | Copper electrolysis system and running method |
Non-Patent Citations (8)
| Title |
|---|
| 二次脱铜过程中砷行为分析和工艺控制;邢卫国;《有色金属(冶炼部分)》;19990612(第03期);全文 * |
| 控制阴极电势电积法脱铜砷;陈白珍等;《中国有色金属学报》;19970630;第07卷(第02期);第40页图1 * |
| 浅析贵溪冶炼厂A级铜生产实践;聂仲文;《湿法冶金》;19990930(第03期);全文 * |
| 贵冶铜电解液净化生产实践;聂仲文;《有色冶炼》;19980520(第05期);全文 * |
| 连续脱铜电解研讨;褚仁雪;《有色冶炼》;19961228(第06期);全文 * |
| 金隆电积脱铜脱砷生产实践;吴文明;《有色冶炼》;20000830(第04期);全文 * |
| 金隆电积脱铜脱砷生产实践;吴文明;《有色冶炼》;20000830;第29卷(第04期);全文 * |
| 铜电解精炼过程杂质的溶出及脱除;肖炳瑞;《铜业工程》;20000830(第03期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104694978A (en) | 2015-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104694978B (en) | The processing method and processing unit of a kind of waste electrolyte | |
| CN109252190B (en) | Method for recovering 99.98% copper powder from etching solution and preparing 99.999% cathode copper | |
| CN101906654A (en) | Method for purifying copper electrolyte with minimal chemical reacting dose | |
| KR101659707B1 (en) | Recovering apparatus for copper from waste water containing copper and recovering method of copper thereof | |
| CN102345143A (en) | Method for separating copper, arsenic and nickel and purifying copper electrolyte | |
| CN103924267A (en) | Method for manufacturing sponge cadmium under effect of micro currents | |
| CN110938842A (en) | Copper electrolyte purification method | |
| CN210683962U (en) | Nitric acid deplating liquid recycling system | |
| CN107699918A (en) | A kind of production technology of L cysteine hydrochlorides | |
| KR101377428B1 (en) | Continuous operating method for producing ammonium persulfate | |
| CN103710732A (en) | Waste copper sulfate electrolyte purification system and method | |
| CN107429319B (en) | Method for manufacturing tungsten | |
| CN106637295A (en) | Purifying method for process of preparing electrolytic manganese metal electrolyte | |
| CN205893406U (en) | Electrodeposition clean system of copper electrolysis waste liquid | |
| CN114808031B (en) | Method for extracting copper from copper electrolysis waste liquid | |
| CN111501064A (en) | Production method of 6N copper | |
| CN102134731A (en) | Method for removing magnesium via cycle of ethanol in electrolytic manganese machining process | |
| KR101570795B1 (en) | Manufacturing method of pure nickel from fluorine containing nickel slime | |
| KR20120031445A (en) | Method for manufacturing high-purity nickel | |
| JP5993097B2 (en) | Method for producing high purity cobalt chloride | |
| CN115976577A (en) | Method for improving purification efficiency of electrolyte | |
| JP3878402B2 (en) | Metal purification method | |
| CN113774432A (en) | Continuous electrolytic refining process for high-purity copper | |
| CN218666325U (en) | Electrolytic electrodeposition collaborative production device | |
| CN118223077A (en) | A method for purifying cobalt electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |