CN117403282A - Electro-deposition purification system and method for copper electrolysis waste liquid - Google Patents
Electro-deposition purification system and method for copper electrolysis waste liquid Download PDFInfo
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- CN117403282A CN117403282A CN202311337530.0A CN202311337530A CN117403282A CN 117403282 A CN117403282 A CN 117403282A CN 202311337530 A CN202311337530 A CN 202311337530A CN 117403282 A CN117403282 A CN 117403282A
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- decoppering
- tank
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- copper
- liquid
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- 239000007788 liquid Substances 0.000 title claims abstract description 112
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 98
- 239000010949 copper Substances 0.000 title claims abstract description 98
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 71
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000000746 purification Methods 0.000 title claims abstract description 22
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 14
- 229910001431 copper ion Inorganic materials 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000011550 stock solution Substances 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000001698 pyrogenic effect Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 11
- 230000008901 benefit Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 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
- 238000007670 refining Methods 0.000 description 2
- 241000530268 Lycaena heteronea Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052969 tetrahedrite Inorganic materials 0.000 description 1
Classifications
-
- 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
- C25C7/06—Operating or servicing
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to an electro-deposition purification system and method for copper electrolysis waste liquid, comprising a titanium-based lead dioxide anode plate, a copper anode scrap, a two-stage decoppering electro-deposition tank, a two-stage decoppering raw liquid tank, a two-stage decoppering circulating tank, a two-stage decoppering overhead tank and a two-stage decoppering post-liquid tank; the two-stage decoppering electrodeposition tanks comprise a plurality of parallel connection, the electrolytic waste liquid is connected to each two-stage decoppering electrodeposition tank through a pipeline, and the liquid outlet of each two-stage decoppering electrodeposition tank is connected with a two-stage decoppering post-liquid tank and a two-stage decoppering circulation tank through pipelines; the copper electrolysis waste liquid after copper sulfate is crystallized and separated out is led to each two-stage copper removal electrodeposition tank through the two-stage copper removal overhead tank; the liquid inlet of the two-section decoppering circulation tank is connected with the liquid outlet of the two-section decoppering electrodeposition tank, and the liquid outlet is connected with the two-section decoppering overhead tank. The invention adds the two-section decoppering circulation tank and the two-section decoppering heater, and returns part of the electrodeposited liquid from the new heating to the two-section decoppering overhead tank, thereby effectively reducing the concentration of the mother liquid, leading the electrodeposited black copper powder to be effectively utilized by a pyrogenic process.
Description
Technical Field
The invention relates to the technical field of electro-deposition purification systems of copper electrolysis waste liquid, in particular to an electro-deposition purification system and method of copper electrolysis waste liquid.
Background
Copper ore refers to a general term of available copper-containing natural mineral aggregate, copper ore is generally an aggregate formed by sulfide or oxide of copper and other minerals, and comprises natural copper, chalcopyrite, chalcocite, tetrahedrite, blue copper ore and the like, copper ore mined from copper ore is beneficiated into copper concentrate with higher copper content, high-quality refined copper can be obtained after pyrometallurgy and electrolytic refining, in the electrolytic refining process, the impurity content in electrolyte can gradually rise along with the lengthening of electrolytic time, and finally the quality of the refined copper is influenced, so that the electrolyte is required to be purified, redundant impurities are removed, and the purity of the electrolyte is ensured. The main current treatment process is to take a copper starting sheet or a residual electrode as a cathode to carry out electrodeposition on the electrolyte, and remove impurities in the electrolyte while obtaining black copper.
Disclosure of Invention
The invention provides an electro-deposition purification system for copper electrolysis waste liquid, which can at least solve one of the technical problems.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an electro-deposition purification system of copper electrolysis waste liquid comprises a titanium-based lead dioxide anode plate, a copper anode scrap, pump equipment and a control system,
a second-stage decoppering electrodeposition tank, a second-stage decoppering raw liquid tank, a second-stage decoppering circulation tank, a second-stage decoppering overhead tank and a second-stage decoppering post liquid tank;
the two-stage decoppering electrodeposition tanks comprise a plurality of parallel connection, the electrolytic waste liquid is connected to each two-stage decoppering electrodeposition tank through a pipeline, and the liquid outlet of each two-stage decoppering electrodeposition tank is connected with a two-stage decoppering post-liquid tank and a two-stage decoppering circulation tank through pipelines;
the copper electrolysis waste liquid after the copper sulfate is crystallized and separated out is led to each two-stage copper removal electrodeposition tank through the two-stage copper removal overhead tank;
the liquid inlet of the two-section decoppering circulating tank is connected with the liquid outlet of the two-section decoppering electrodeposition tank, and the liquid outlet is connected with the two-section decoppering overhead tank.
Further, a pipeline leading to the two-stage decoppering stock solution tank to the two-stage decoppering overhead tank is provided with a two-stage decoppering stock solution pump for conveying copper electrolysis waste liquid.
Further, a pipeline leading to the two-stage copper removal overhead tank from the two-stage copper removal circulating tank is provided with a two-stage copper removal circulating pump for conveying the electrodeposited liquid.
Further, a pipeline leading to the two-section decoppering circulation tank is provided with two-section decoppering heaters.
Further, a pipeline leading the liquid tank after the second-stage copper removal to the nickel removal procedure is provided with a liquid pump after the second-stage copper removal for conveying the liquid after the electrodeposition.
On the other hand, the invention also discloses an electro-deposition purification method of the copper electrolysis waste liquid, which adopts the electro-deposition purification system of the copper electrolysis waste liquid and comprises the following steps of,
the mother liquor in the secondary decoppering stock solution tank is firstly sent to a secondary decoppering overhead tank, copper ions in the secondary overhead tank are diluted by a dilution solution and then flow to a secondary decoppering electrodeposition tank, the secondary decoppering electrodeposition tank takes a titanium-based lead dioxide anode plate, copper residues as cathodes, impurities such as arsenic, tellurium and bismuth and redundant copper can separate black copper on the copper residues under the action of current, the copper ions in the liquid after the electrodeposition are reduced to 0.5g/L to 1g/L, the copper ions respectively flow to a secondary decoppering circulation tank and a secondary decoppering liquid tank, the liquid after the electrodeposition in the secondary decoppering circulation tank is heated to more than 55 ℃ by a secondary decoppering heater and is sent to the secondary decoppering overhead tank again, and the liquid after the electrodeposition in the secondary decoppering liquid tank is sent to a decoppering process and returns to a furnace for remelting after the black copper powder is treated.
Further, the copper electrolysis waste liquid is diluted to 8g/L by the dilution liquid in the two-stage overhead tank.
Further, the temperature of the two-stage electrolytic copper removal is 55-70 ℃.
Further, the current intensity of the two-stage electrolytic copper removal is 250-300A/m 2 。
Further, the copper ions in the liquid after electrodeposition are reduced to 0.5g/L to 1g/L.
According to the technical scheme, the electro-deposition purification system for the copper electrolysis waste liquid has the following beneficial effects:
the system discloses an electro-deposition purifying system for copper electrolysis waste liquid, which comprises: the device comprises a titanium-based lead dioxide anode plate, a copper anode scrap, a two-stage decoppering electrodeposition tank, a two-stage decoppering heater, a two-stage decoppering raw liquid tank, a two-stage decoppering circulation tank, a two-stage decoppering overhead tank, a two-stage decoppering post-liquid tank and pump equipment. The invention discloses a process method of electro-deposition clean liquid, which is used for removing impurities such as arsenic, tellurium, bismuth and the like and redundant copper generated in the copper electrolysis process. The main process of the electro-deposition cleaning solution is as follows: the titanium-based lead dioxide anode plate is used as an anode, the copper residue is used as a cathode, and impurities such as arsenic, tellurium, bismuth and the like and redundant copper are separated out on the copper residue under the action of current so as to remove the impurities in the electrolyte. Compared with the prior art, the system is added with the two-section decoppering circulating tank and the two-section decoppering heater, and part of the electrodeposited liquid is returned to the two-section decoppering overhead tank from new heating, so that the concentration of the mother liquid is effectively reduced, the electrodeposited black copper powder is obtained, and the black copper powder is effectively utilized by a pyrogenic process.
Drawings
FIG. 1 is a schematic flow diagram of the apparatus connection diagram of the copper electrowinning liquid cleaning system and the process method of copper electrowinning liquid cleaning of the present invention;
symbol description: the first pump is a two-section decoppering raw liquid pump, the second pump is a two-section decoppering circulating pump, and the third pump is a two-section decoppering post-liquid pump.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention.
As shown in fig. 1, the electro-deposition purification system for copper electrolysis waste liquid according to this embodiment includes:
the device comprises a titanium-based lead dioxide anode plate, a copper anode scrap, a two-stage decoppering electrodeposition tank, a two-stage decoppering heater, a two-stage decoppering raw liquid tank, a two-stage decoppering circulation tank, a two-stage decoppering overhead tank, a two-stage decoppering post-liquid tank and pump equipment.
The pump equipment comprises a two-section decoppering raw liquid pump, a two-section decoppering circulating pump and a two-section decoppering post-liquid pump;
in the copper electro-deposition clean liquid system, the outlet of the secondary copper removal raw liquid tank is communicated with the inlet of the secondary copper removal raw liquid pump, the outlet of the secondary copper removal raw liquid pump is communicated with the inlet of the secondary copper removal overhead tank, the overflow port of the secondary copper removal overhead tank is communicated with the inlet of the secondary copper removal circulating tank, the outlet of the secondary copper removal overhead tank is communicated with the secondary copper removal electro-deposition tank, the anode plate of titanium-based lead dioxide and the copper residual electrode are placed in the secondary copper removal electro-deposition tank at intervals, the overflow port of the secondary copper removal electro-deposition tank is respectively communicated with the inlet of the secondary copper removal circulating tank and the inlet of the secondary copper removal liquid tank, the outlet of the secondary copper removal circulating tank is communicated with the inlet of the secondary copper removal circulating pump, the outlet of the secondary copper removal circulating pump is communicated with the inlet of the secondary copper removal heater, the outlet of the secondary copper removal heater is communicated with the inlet of the secondary copper removal overhead tank, the electrolyte is circulated in the circulation, the outlet of the secondary copper removal liquid tank is communicated with the secondary copper removal liquid pump, and the electro-deposition liquid is transferred out; the invention uses the circulating pump and the heater to reheat part of the electrodeposited liquid and send the part of the electrodeposited liquid back to the overhead tank, and uses the electrodeposited liquid to reduce the concentration of copper ions in the waste electrolyte, so that the concentration of copper ions is maintained at a lower level, and the invention is beneficial to the precipitation and removal of impurity electrodeposited.
A process method of copper electro-deposition clean liquid comprises the following steps:
the mother liquor in the secondary decoppering stock solution tank is firstly sent to a secondary decoppering overhead tank, in the secondary decoppering overhead tank, copper ions are diluted to 8g/L by the dilution liquor in the secondary decoppering overhead tank, the advantage of 8g/L is that the concentration of copper ions in the waste electrolyte is reduced by utilizing the electrolyte after electrodeposition, so that the concentration of copper ions is kept at a lower level, the concentration is favorable for precipitation and removal of impurity electrodeposits, and then the solution flows to the secondary decoppering electrodeposition tank, the secondary decoppering electrodeposition tank is provided with a titanium-based lead dioxide anode plate and a copper residue cathode, under the action of current, impurities such as arsenic, tellurium, bismuth and the like and redundant copper can precipitate black copper on the copper residue, the copper ions in the electrolyte after electrodeposition are reduced to 0.5g/L to 1g/L, the benefits of 0.5 g/L-1 g/L are that the nickel sulfate byproduct contains less copper elements, waste is avoided (only the price of nickel is calculated when the nickel sulfate product is sold), the electrodeposited liquid is changed into electrodeposited liquid which flows into a two-section decoppering circulating groove and a two-section decoppering liquid groove respectively, the electrodeposited liquid in the two-section decoppering circulating groove is heated to more than 55 ℃ by a two-section decoppering heater and is sent to the two-section decoppering high-level groove again, the advantage of 55 ℃ is that the temperature is improved, the diffusion speed of ions in the mother liquid is improved, the precipitation of impurities is facilitated, the electrodeposited liquid in the two-section decoppering liquid groove is sent to the nickel removal process, and black copper is treated and returned to the furnace for remelting.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An electro-deposition purification system for copper electrolysis waste liquid comprises a titanium-based lead dioxide anode plate, a copper anode scrap and pump equipment, and is characterized by further comprising,
a second-stage decoppering electrodeposition tank, a second-stage decoppering raw liquid tank, a second-stage decoppering circulation tank, a second-stage decoppering overhead tank and a second-stage decoppering post liquid tank;
the two-stage decoppering electrodeposition tanks comprise a plurality of parallel connection, the electrolytic waste liquid is connected to each two-stage decoppering electrodeposition tank through a pipeline, and the liquid outlet of each two-stage decoppering electrodeposition tank is connected with a two-stage decoppering post-liquid tank and a two-stage decoppering circulation tank through pipelines;
the copper electrolysis waste liquid after the copper sulfate is crystallized and separated out is led to each two-stage copper removal electrodeposition tank through the two-stage copper removal overhead tank;
the liquid inlet of the two-section decoppering circulating tank is connected with the liquid outlet of the two-section decoppering electrodeposition tank, and the liquid outlet is connected with the two-section decoppering overhead tank.
2. The electro-deposition purification system of copper electrolysis waste liquid according to claim 1, wherein: the pipeline of the two-stage decoppering raw liquid tank, which is communicated with the two-stage decoppering overhead tank, is provided with a two-stage decoppering raw liquid pump for conveying copper electrolysis waste liquid.
3. The electro-deposition purification system of copper electrolysis waste liquid according to claim 1, wherein: the pipeline of the two-section decoppering circulation tank, which is led into the two-section decoppering overhead tank, is provided with a two-section decoppering circulation pump for conveying the electrodeposited liquid.
4. The electro-deposition purification system of copper electrolysis waste liquid according to claim 1, wherein: and a pipeline leading to the two-section decoppering circulation tank to the two-section decoppering overhead tank is provided with a two-section decoppering heater.
5. The electro-deposition purification system of copper electrolysis waste liquid according to claim 1, wherein: the pipeline of the liquid tank after the second-stage decoppering, which is communicated with the nickel removal process, is provided with a liquid pump after the second-stage decoppering for conveying the liquid after the electro-deposition.
6. An electro-deposition purification method for copper electrolysis waste liquid, which adopts the electro-deposition purification system for copper electrolysis waste liquid according to any one of claims 1-5, and is characterized in that: comprises the steps of,
the mother liquor in the secondary decoppering stock solution tank is firstly sent to a secondary decoppering overhead tank, copper ions in the secondary overhead tank are diluted by a dilution solution and then flow to a secondary decoppering electrodeposition tank, the secondary decoppering electrodeposition tank takes a titanium-based lead dioxide anode plate, copper residues as cathodes, impurities such as arsenic, tellurium and bismuth and redundant copper can separate black copper on the copper residues under the action of current, the copper ions in the liquid after the electrodeposition are reduced to 0.5g/L to 1g/L, the copper ions respectively flow to a secondary decoppering circulation tank and a secondary decoppering liquid tank, the liquid after the electrodeposition in the secondary decoppering circulation tank is heated to more than 55 ℃ by a secondary decoppering heater and is sent to the secondary decoppering overhead tank again, and the liquid after the electrodeposition in the secondary decoppering liquid tank is sent to a decoppering process and returns to a furnace for remelting after the black copper powder is treated.
7. The method for electro-deposition purification of copper electrolysis waste liquid according to claim 6, wherein:
the copper electrolysis waste liquid is diluted to 8g/L by the dilution liquid in the two-stage overhead tank.
8. The method for electro-deposition purification of copper electrolysis waste liquid according to claim 6, wherein:
the temperature of the secondary electrolytic copper deposition and removal is 55-70 ℃.
9. The method for electro-deposition purification of copper electrolysis waste liquid according to claim 6, wherein:
the current intensity of the two-stage electro-deposition decoppering is 250-300A/m 2 。
10. The method for electro-deposition purification of copper electrolysis waste liquid according to claim 6, wherein: the copper ions in the liquid after electrodeposition are reduced to 0.5 g/L-1 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202311337530.0A CN117403282A (en) | 2023-10-13 | 2023-10-13 | Electro-deposition purification system and method for copper electrolysis waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311337530.0A CN117403282A (en) | 2023-10-13 | 2023-10-13 | Electro-deposition purification system and method for copper electrolysis waste liquid |
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| Publication Number | Publication Date |
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| CN117403282A true CN117403282A (en) | 2024-01-16 |
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| CN202311337530.0A Pending CN117403282A (en) | 2023-10-13 | 2023-10-13 | Electro-deposition purification system and method for copper electrolysis waste liquid |
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| Country | Link |
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| CN (1) | CN117403282A (en) |
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