CN108866572A - A kind of iron displacement copper electrolysis cells - Google Patents
A kind of iron displacement copper electrolysis cells Download PDFInfo
- Publication number
- CN108866572A CN108866572A CN201810994575.8A CN201810994575A CN108866572A CN 108866572 A CN108866572 A CN 108866572A CN 201810994575 A CN201810994575 A CN 201810994575A CN 108866572 A CN108866572 A CN 108866572A
- Authority
- CN
- China
- Prior art keywords
- major trough
- trough body
- copper
- electrolysis cells
- iron
- 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.)
- Pending
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- 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
-
- 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
- C25C7/02—Electrodes; Connections thereof
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of iron displacement copper electrolysis cells that metallic copper is extracted from acidic etching waste liquid.Electrolyte bath alternately places anode titanium frame and tough cathode/titanium sheet, and scrap iron is placed in anode titanium frame, and anode titanium frame connects DC power anode, and tough cathode/titanium sheet connects DC power cathode.Acidic etching waste liquid is pumped into from iron displacement copper electrolysis cells bottom feed pipe, and under DC electric field effect, anode titanium frame iron plate dissolution, copper is precipitated in cathode copper sheet/titanium sheet.Acidic etching waste liquid after electrolysis is back to external feeding device circulating collection through built-in overflow launder and flows back again electrolytic cell.After acidic etching waste liquid copper ion concentration is reduced to a certain concentration, it is pumped into external memory through iron displacement copper electrolysis cells bottom evacuated tube, then External electrolytic slot electrolytic recovery by-product is pumped by external memory.The present invention is the electrolytic cell for being specifically applied to extra electric field induction iron displacement process for copper and recycling the copper in acidic etching waste liquid, being capable of copper in high efficiente callback acidic etching waste liquid.
Description
Technical field
The present invention relates to from the field of liquid waste recycling non-ferrous metal, more particularly a kind of electrolytic method that passes through is from acid
Property etching waste liquor in recycle metallic copper device.
Background technique
Need to consume a large amount of acidic etching liquid, resulting acid etching in printed circuit board (PCB) etching process
Univalent copper ion concentration is high in waste liquid, and the circuit board enterprise of most of production high-precision multilayer circuit boards can select etching waste liquor
The company for being sold to special disposal waste liquid goes to handle.Therefore, the acidic etching waste liquid amount to be processed of these recycling companies is huge.
In existing technology, the method for metallic copper being recycled from acidic etching waste liquid is mainly iron displacement process for copper.Iron
Displacement process for copper principle is to utilize the reproducibility of iron higher than copper, is added in iron displacement acidic etching liquid in oxytropism etching waste liquor
Copper.But it is the reproducibility iron powder or iron plate of large specific surface area that this method, which requires the iron being added in waste liquid, and replaces reaction
Directly occur on the surface of iron, reaction rate is slow and generates copper sponge and is wrapped in iron surface, thus leads to that iron consumption is big, copper produces
Product purity only has 70% or so, added value of product not high.The part prior art also uses ionic membrane that electrolysis method is isolated, but this
Method treatment scale is smaller, and anode is easy to produce chlorine and causes secondary pollution, and ionic membrane is expensive, and large-scale application is not
Enough economy.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the present invention provides a kind of principles based on electrolysis, can
On a large scale, the copper ion in acidic etching waste liquid is efficiently reduced to the device of metallic copper, to solve the deficiency of prior art.
The content of technical solution of the present invention is as follows：
A kind of iron displacement copper electrolysis cells, including major trough body, anode and cathode, the bottom of major trough body further include feed pipe and row
Blank pipe, feed pipe one end are located inside major trough body, the external connection of one end and iron displacement copper electrolysis cells, and evacuated tube one end is located at master
Inside groove body, the external connection of one end and iron displacement copper electrolysis cells；Anode is located at the inner space of the electrolytic cell, and additional straight
The anode of galvanic electricity field is connected, and cathode is located at the inner space of the electrolytic cell, is connected with the cathode of applying direct current electric field；Anode is
Titanium frame is also placed with scrap iron in titanium frame, and titanium frame is open-topped plate frame structure, and titanium frame further includes inactive, conductive material, inertia
Conductive material is located at the top open part of titanium frame；The material of cathode is copper sheet or titanium sheet.
The beneficial effect of above scheme is：
When electrolysis, using the strong reducing property of iron, the copper ion in original waste liquid is replaced into metallic copper on cathode plate
It is precipitated, improves the added value of recycling copper products, and since iron material is inside titanium frame, so that the copper generated will not be covered on entirely
On portion's iron material, the rate of recovery of copper in whole process is further increased, also avoids consuming excessively for iron material, improves reaction speed
Rate.Cathode material appropriate is selected further according to copper ion concentration, metallic copper is further displaced from waste liquid, improves its recycling effect
Rate.And iron displacement copper reaction speed is fast, and Faradaic current is high-efficient, and treatment scale is big, can be realized inexpensive large-scale application.
Further, titanium frame replaces placement in the inside of major trough body with cathode；This structure, which can be improved, to be entirely electrolysed
The reaction rate of journey, while waste liquid being enabled to come into full contact with raw material iron.
Further, major trough body also has spray head, and spray head connect with one end that feed pipe is located inside major trough body, realizes
Control the effect of feed liquor rate.
Further, major trough body further includes overflow launder, and overflow launder is located at the junction at the top of major trough body side surface and major trough body；
Overflow launder also has the overflow hole for being connected to overflow launder and major trough body；Overflow launder is used for the acid etching that circulation and stress overflows
Liquid realizes that acidic etching waste liquid recycles between iron displacement copper electrolysis cells and external feeding device in iron displacement copper electrolysis cells, outside
Portion's feeding device is arranged heat exchanger and absorbs the heat that electrolytic process generates, and cyclic process guarantees that copper ion concentration is equal in electrolytic cell
It is even.
Further, spray head is to be flexibly connected with feed inlet, and the bottom surface angle of spray head and major trough body is 45 ° -75 °；Spray head
Acidic etching waste liquid is sprayed between titanium frame and cathode, on the one hand spray head plays acidic etching waste liquid in circulation stirring electrolytic cell and makees
With the copper for being on the other hand electrolysed generation on removal cathode plate pierces, and prevents electric pole short circuit.
Further, titanium frame opening width is 50mm-80mm, and the framework of titanium frame has latticed or Process knot
Structure, this structure enable acidic etching waste liquid and iron ion to pass freely through, and guarantee electricity between cathode and anode titanium frame
Current density is uniform.
Further, iron displacement copper electrolysis cells also have a waste gas absorption slot, waste gas absorption slot position side at the top of major trough body,
It is connected to major trough body inside.
Further, major trough body further includes internal support rib, external reinforcing hoop, support plate, electrode fixing structure and use
In the cover board of sealing iron displacement copper electrolysis cells；Internal support rib is looped around inside the major trough body, is fenestral fabric；It is external
Reinforced Hoop is ring structure, tightly around in the exterior lateral sides of major trough body；Support plate is located at the folder of major trough body inner bottom surface and side
At angle；Electrode fixing structure is connect with titanium frame and cathode, is connected outside major trough body and with major trough；For sealing iron displacement
The cover board of copper electrolysis cells is located at the top of major trough body；These structures strengthen the intensity of note groove body, avoid in electrolytic process
Major trough body is caused to deform due to fever.
Further, iron displacement copper electrolysis cells also have acid resistance water pump, and the acid resistance water pump is in feed pipe or row
Blank pipe is located at one end inside major trough body, for accelerating major trough body feed liquor or the out rate of liquid.
Detailed description of the invention
Fig. 1 is the planing surface figure of the one of preferred embodiment lateral plan of the present invention；
Fig. 2 is the structural schematic diagram of the one of preferred embodiment of anode titanium frame of the invention.
In figure：1, major trough body；2, electrode；3, internal support rib；4, top side external reinforcing hoop；5, waste gas absorption slot supports
Plate；6, electrode fixing structure；7, cover board；8, feed pipe；9, spray head；10, overflow launder；11, overflow hole；12, evacuated tube；13, it gives up
Aspiration slot；14, inner support panels；15, bottom side external reinforcing hoop；21, titanium frame；22, it is covered with the copper sheet of titanium layer；23, latticed
Framework.
Specific embodiment
Below in conjunction with attached drawing of the invention, technical scheme in the embodiment of the invention is clearly and completely described.
Embodiments described below is only that a part of the embodiment of the present invention is based on scheme disclosed in this invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
In conjunction with Fig. 2 anode titanium mount structure, as shown in Figure 1, having electrode 2 inside major trough body 1, electrode 2 includes having grid
The anode titanium frame and tough cathode/titanium sheet of shape；Internal support rib 3 is located on the inner wall of major trough body 1,4 He of top side external reinforcing hoop
Bottom side external reinforcing hoop 15 is located on 1 outer wall of major trough body；Waste gas absorption slot support plate 5 and inner support panels 14 are located at master
The outer wall upper end of groove body 1 and bottom；Electrode fixing structure 6 is located at 1 top of major trough body, is above stamped cover board 7；Feed pipe 8 is located at master
1 bottom of groove body, connect with spray head 9；Overflow launder 10 is located at the upper end of major trough body 1, has overflow hole 11；Evacuated tube 12 is located at major trough
1 bottom of body；Waste gas absorption slot 13 is set in the top exterior walls of major trough body 1, with 1 inside connection of major trough body.
When work, acidic etching waste liquid is sufficiently sprayed onto the anode titanium frame and cathode of electrode 2 by spray head 9 from feed pipe 8
On copper sheet, anode titanium frame and cathode copper sheet are alternately placed；When waste liquid reaches certain liquid level, electrode 2 loads DC electric field and starts
Electrolysis, since a large amount of heat can be generated in electrolytic process, so increasing internal support rib 3, top side external reinforcing hoop 4, bottom
Side external reinforcing hoop 15, waste gas absorption slot support plate 5, inner support panels 14 are to reinforce the intensity of electrolytic cell 1；When the liquid level of waste liquid
When more than specified altitude assignment, acidic etching waste liquid enters overflow launder 10 through overflow hole 11, overflows back external feeding device heat exchange cooling,
It is pumped into iron displacement copper electrolysis cells and is recycled through feed pipe 8 by acid resistance water pump again；Cover board 7 seals electrolytic cell, and electrolysis generates
Exhaust gas by waste gas recovery slot 13 be absorbed into exhaust gas processing device processing；When electrolysis, copper ion is precipitated in cathode and useless
Concentration in liquid reduces, and when its concentration is lower than 40g/L, stops electrolysis, waste liquid in iron displacement copper electrolysis cells is pumped into outside and is deposited
Storage device, then it is pumped into electrolytic recovery by-product in External electrolytic slot, the copper ion in acidic etching waste liquid can be recycled all.
It for the ordinary skill in the art, without departing from the principles and spirit of the present invention can be right
These technical solutions carry out a variety of change, modification, replacement and modification, are in protection scope of the present invention.
Claims (8)
1. a kind of iron displacement copper electrolysis cells, including major trough body, anode and cathode, the bottom of the major trough body further include feed pipe and
Evacuated tube, described feed pipe one end are located inside major trough body, and the external connection of one end and electrolytic cell, described evacuated tube one end is located at
Inside major trough body, the external connection of one end and electrolytic cell；The anode is located at the inner space of the electrolytic cell, with external dc
The anode of electric field is connected, and the cathode is located at the inner space of the electrolytic cell, is connected with the cathode of applying direct current electric field；It is special
Sign is：The anode is titanium frame, and scrap iron is also placed in the titanium frame, and the titanium frame is open-topped plate frame structure, institute
Stating titanium frame further includes inactive, conductive material, and the inactive, conductive material is located at the top open part of titanium frame；The material of the cathode
For copper sheet or titanium sheet.
2. iron displacement copper electrolysis cells according to claim 1, it is characterised in that：The titanium frame and the cathode are in major trough body
It alternately places inside.
3. iron displacement copper electrolysis cells according to claim 1, it is characterised in that：There are spray head, the spray head in the major trough body
The one end being located inside major trough body with the feed pipe is connect.
4. iron displacement copper electrolysis cells according to claim 1, it is characterised in that：The major trough body further includes overflow launder, described
Overflow launder is located at the junction at the top of major trough body side surface and major trough body；The overflow launder is equipped with for being connected to overflow launder and major trough body
Overflow hole.
5. iron displacement copper electrolysis cells according to claim 1, it is characterised in that：The spray head and the feed inlet are that activity connects
It connects, the bottom surface angle of the spray head and the major trough body is 45 ° -75 °.
6. iron displacement copper electrolysis cells according to claim 1, it is characterised in that：The titanium frame opening width is 50mm-80mm,
The framework of the titanium frame has latticed or Process structure.
7. iron displacement copper electrolysis cells according to claim 1, it is characterised in that：It further include waste gas absorption slot, the exhaust gas is inhaled
Slot position is received at the top of major trough body, the waste gas absorption slot is connected to inside the major trough body by overflow launder.
8. according to claim 1 to any one of 7 iron displacement copper electrolysis cells, it is characterised in that：The major trough body further includes interior
Portion's support rib, external reinforcing hoop, support plate, electrode fixing structure and the cover board for sealing iron displacement copper electrolysis cells；It is described
Internal support rib is looped around inside the major trough body, is fenestral fabric；The external reinforcing hoop be ring structure, tightly around
On the outside of the major trough body side surface；The support plate is located at the angle of the major trough body inner bottom surface and side；The electricity
Pole fixed structure is connect with the titanium frame and the cathode, is connected outside major trough body and with major trough；It is described to be used to seal
The cover board of iron displacement copper electrolysis cells is located at the top of major trough body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810994575.8A CN108866572A (en) | 2018-08-27 | 2018-08-27 | A kind of iron displacement copper electrolysis cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810994575.8A CN108866572A (en) | 2018-08-27 | 2018-08-27 | A kind of iron displacement copper electrolysis cells |
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| Publication Number | Publication Date |
|---|---|
| CN108866572A true CN108866572A (en) | 2018-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810994575.8A Pending CN108866572A (en) | 2018-08-27 | 2018-08-27 | A kind of iron displacement copper electrolysis cells |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628747A (en) * | 2019-01-16 | 2019-04-16 | 成都虹华环保科技股份有限公司 | A kind of device and method using aluminium displacement copper |
| CN109852996A (en) * | 2019-04-12 | 2019-06-07 | 深圳市泓达环境科技有限公司 | A kind of electro-deposition recycling copper device and the copper recycling producing line using it |
| CN109851003A (en) * | 2019-03-14 | 2019-06-07 | 湖南富栊新材料股份有限公司 | A kind of method of comprehensive utilization of copper-containing wastewater |
| CN110565120A (en) * | 2019-10-18 | 2019-12-13 | 东北大学 | Method for removing and recovering copper from copper-containing iron liquid |
| CN117448826A (en) * | 2023-10-30 | 2024-01-26 | 天水华洋电子科技股份有限公司 | Recycling process of etching solution of integrated circuit lead frame |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5573872A (en) * | 1978-11-22 | 1980-06-03 | Kernforschungsanlage Juelich | Etching of surface comprising coppur or coppur alloy |
| CN101348916A (en) * | 2007-07-19 | 2009-01-21 | 住友金属矿山株式会社 | Electrolytic oxidation method of etching waste liquor |
| CN205420566U (en) * | 2016-04-05 | 2016-08-03 | 陕西金泰氯碱化工有限公司 | Ionic exchange membrane electrolyser |
| CN106884185A (en) * | 2017-03-28 | 2017-06-23 | 苏碧云 | The technique and system and device of copper in a kind of recovery acidic etching liquid |
-
2018
- 2018-08-27 CN CN201810994575.8A patent/CN108866572A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5573872A (en) * | 1978-11-22 | 1980-06-03 | Kernforschungsanlage Juelich | Etching of surface comprising coppur or coppur alloy |
| CN101348916A (en) * | 2007-07-19 | 2009-01-21 | 住友金属矿山株式会社 | Electrolytic oxidation method of etching waste liquor |
| CN205420566U (en) * | 2016-04-05 | 2016-08-03 | 陕西金泰氯碱化工有限公司 | Ionic exchange membrane electrolyser |
| CN106884185A (en) * | 2017-03-28 | 2017-06-23 | 苏碧云 | The technique and system and device of copper in a kind of recovery acidic etching liquid |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628747A (en) * | 2019-01-16 | 2019-04-16 | 成都虹华环保科技股份有限公司 | A kind of device and method using aluminium displacement copper |
| CN109851003A (en) * | 2019-03-14 | 2019-06-07 | 湖南富栊新材料股份有限公司 | A kind of method of comprehensive utilization of copper-containing wastewater |
| CN109852996A (en) * | 2019-04-12 | 2019-06-07 | 深圳市泓达环境科技有限公司 | A kind of electro-deposition recycling copper device and the copper recycling producing line using it |
| CN109852996B (en) * | 2019-04-12 | 2024-02-23 | 株洲稷维环保有限公司 | Electrodeposition copper recovery device and copper recovery production line using same |
| CN110565120A (en) * | 2019-10-18 | 2019-12-13 | 东北大学 | Method for removing and recovering copper from copper-containing iron liquid |
| CN110565120B (en) * | 2019-10-18 | 2021-09-07 | 东北大学 | Method for removing and recovering copper from copper-containing iron liquid |
| CN117448826A (en) * | 2023-10-30 | 2024-01-26 | 天水华洋电子科技股份有限公司 | Recycling process of etching solution of integrated circuit lead frame |
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| PB01 | Publication | ||
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Application publication date: 20181123 |