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CN111394729A - Electrolytic device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof - Google Patents

Electrolytic device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof Download PDF

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Publication number
CN111394729A
CN111394729A CN202010339532.3A CN202010339532A CN111394729A CN 111394729 A CN111394729 A CN 111394729A CN 202010339532 A CN202010339532 A CN 202010339532A CN 111394729 A CN111394729 A CN 111394729A
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cathode
anode
plate
frame
tank
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CN202010339532.3A
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CN111394729B (en
Inventor
王红华
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Jiangsu Diyi Environmental Protection Technology Co ltd
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Jiangsu Diyi Environmental Protection Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F1/00Etching metallic material by chemical means
    • C23F1/46Regeneration of etching compositions
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04Diaphragms; Spacing elements
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06Operating or servicing
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The electrolysis device comprises a press and an electrolysis unit; the press machine is provided with a pressing space, and an electrolysis unit is arranged in the pressing space; the electrolysis unit comprises an anode plate, an anode frame, an ion exchange layer, a cathode frame and a cathode plate; the press machine can sequentially compress the anode plate, the anode frame, the ion exchange layer, the cathode frame and the cathode plate to form a closed anode chamber and a closed cathode chamber. The anode plate, the anode frame, the ion exchange layer, the cathode frame and the cathode plate of the electrolysis unit are sequentially pressed by the electrolysis device through the press machine to form the closed anode chamber and the closed cathode chamber, so that gas generated by the electrolysis reaction of the electrolysis device can not be released, the generated corrosive gas is prevented from corroding equipment, and the quality of the operation environment is improved.

Description

Electrolytic device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof
Technical Field
The invention relates to the technical field of electrolytic units for electrolytic treatment of electrolyte, in particular to an electrolytic device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof.
Background
Most of the existing electrolytic treatment devices for treating waste liquid are in an open state, and when the waste liquid is treated by electrolysis, generated gas is often released into the air, and some gas is corrosive gas, so that the volatilization of the corrosive gas reduces the quality of the air in the operation environment on the one hand, and on the other hand, the long-term volatilization of the corrosive gas can corrode equipment and some harmful gas can pollute the environment. Therefore, it is necessary to develop a closed electrolytic processing device.
Disclosure of Invention
In order to solve the problem that the volatile gas in the conventional electrolytic treatment device has adverse effect in the electrolytic process, the invention designs an electrolytic unit structure, and develops an electrolytic device of an electrolytic unit with a sealed anode chamber and a sealed cathode chamber, wherein the gas generated by the electrolytic unit cannot be released in the electrolytic process.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electrolysis device comprises a press and an electrolysis unit;
the press machine is provided with a pressing space, and an electrolysis unit is arranged in the pressing space;
the electrolysis unit comprises an anode plate, an anode frame, an ion exchange layer, a cathode frame and a cathode plate;
the press machine can sequentially compress the anode plate, the anode frame, the ion exchange layer, the cathode frame and the cathode plate to form a closed anode chamber and a closed cathode chamber.
Preferably, the press machine comprises an abutting part, a moving part and a driving part;
a pressing space is arranged between the abutting part and the driving part;
the moving part is arranged in the pressing space;
the driving part drives the moving part to move along the pressing space, and a plurality of electrolysis units are pressed between the abutting part and the moving part in rows.
Preferably, a plurality of the electrolysis units are arranged in rows in the pressing space;
an anode frame is arranged between the abutting part and the anode plate, and an anode frame is arranged between the moving part and the anode plate.
Or
A cathode frame is arranged between the abutting part and the cathode plate, and a cathode frame is arranged between the moving part and the cathode plate
Or alternatively
The abutting part abuts against the anode plate or the cathode plate, and the moving part abuts against the anode plate or the cathode plate;
preferably, the two sides of the anode plate are provided with anode frames;
cathode frames are arranged at two sides of the cathode plate;
every two adjacent electrolysis units share the same anode plate or cathode plate.
Preferably, the anode frame and the cathode frame are both of a square structure;
the press can sequentially compress the anode plate, the anode frame, the ion exchange layer, the cathode frame and the cathode plate, so that the anode plate, the anode frame and the ion exchange layer form an anode chamber, and the ion exchange layer, the cathode frame and the cathode plate form a cathode chamber.
Preferably, one side of the anode frame is provided with an anolyte inlet, and the other side of the anode frame is provided with an anolyte outlet;
one side of the cathode frame is provided with a cathode liquid inlet, and the other side of the cathode frame is provided with a cathode liquid outlet;
the anolyte inlet and the anolyte outlet are communicated with the anode chamber;
the catholyte inlet and catholyte outlet are both in communication with the cathode chamber.
Preferably, the electrolysis device further comprises a transfusion pipeline;
the liquid conveying pipeline comprises an anolyte liquid inlet main pipe, an anolyte liquid outlet main pipe, a catholyte liquid inlet main pipe and a catholyte liquid outlet main pipe;
the anolyte liquid inlet header pipe is communicated with an anolyte inlet;
one end of the anolyte liquid inlet main pipe is provided with an anolyte liquid inlet valve, and the other end of the anolyte liquid inlet main pipe is provided with an anolyte emptying valve;
the anolyte outlet main pipe is communicated with the anolyte outlet;
the catholyte liquid inlet header pipe is communicated with the catholyte inlet;
one end of the cathode liquid inlet header pipe is provided with a cathode liquid inlet valve, and the other end of the cathode liquid inlet header pipe is provided with a cathode emptying valve;
the catholyte outlet main pipe is communicated with the catholyte outlet.
Preferably, the electrolysis device further comprises an anode conductive copper bar, the anode conductive copper bar is arranged at the top of the anode plate, one end of the anode conductive copper bar extends outwards to form a first connecting rod, the other end of the anode conductive copper bar extends outwards to form a second connecting rod, and the second connecting rod is provided with a cathode insulating head.
Preferably, the electrolysis device further comprises a cathode conductive copper bar, the cathode conductive copper bar is arranged at the top of the cathode plate, one end of the cathode conductive copper bar extends outwards to form a third connecting rod, the other end of the cathode conductive copper bar extends outwards to form a fourth connecting rod, and the fourth connecting rod is provided with an anode insulating head.
The first connecting rod and the fourth connecting rod are positioned on the same side, and the second connecting rod and the third connecting rod are positioned on the same side.
Preferably, the electrolysis device further comprises a power supply assembly;
the power supply assembly comprises a rectifier, an anode conductive part and a cathode conductive part;
the first connecting rod is connected with the anode conductive part;
the third connecting rod is connected with the cathode conductive part;
the anode conductive part is electrically connected with the rectifier, and the cathode conductive part is electrically connected with the rectifier.
Preferably, the anode conductive part is an anode connecting copper bar or an anode conductive wire;
the cathode conductive part is a cathode connecting copper bar or a cathode conductive wire.
Preferably, the anode conductive part is an anode connecting copper bar, and the cathode conductive part is a cathode connecting copper bar;
the first connecting rod and the anode insulating head are at the same height, and the third connecting rod and the cathode insulating head are at the same height;
the first connecting rod and the anode insulating head are both connected with the anode connecting copper bar;
and the third connecting rod and the cathode insulating head are connected with the cathode connecting copper bar.
A printed board acid etching waste liquid regeneration and copper recovery device comprises the electrolysis device;
the ion exchange layer is an ion membrane or a diaphragm cloth;
preferably, the ion exchange layer is a cation membrane;
the electrolytic device is used for electrolytically treating the printed board acid etching waste liquid.
Preferably, the printed board acid etching waste liquid regeneration and copper recovery equipment further comprises a waste liquid collecting storage tank, a cathode circulating tank, an anode circulating tank, a mixing tank, a vacuum recovery device, a vacuum treatment device and a waste gas purification tower;
the waste liquid collecting and storing tank is used for storing the acidic etching waste liquid of the printed board;
the waste liquid collecting and storing tank is communicated with the cathode circulating tank;
the cathode circulating tank is in circulating communication with the cathode chamber, and the cathode circulating tank is provided with a specific gravity measuring instrument;
the mixing tank is provided with a hydrometer, an acidity meter and a redox value measuring meter;
the mixing tank is communicated with the anode chamber;
the anode chamber is communicated with the anode circulating tank;
discharging the regenerated acidic etching solution of the printed board subjected to electrolytic treatment by using an anode circulating tank;
the waste liquid collecting storage tank, the cathode circulating tank, the anode circulating tank and the mixing tank are communicated with the vacuum recovery device to collect waste gas;
the vacuum recovery device is used for recovering chlorine and hydrogen chloride gas; the vacuum recovery device is communicated with the vacuum treatment device, and the vacuum treatment device is used for further treating chlorine and hydrogen chloride gas which are not completely recovered by the vacuum recovery device;
the waste gas purification tower is communicated with the vacuum treatment device and is used for purifying waste gas discharged by the vacuum treatment device so as to ensure standard discharge.
Preferably, the vacuum recovery device is simultaneously communicated with the cathode circulation tank and the mixing tank, the cathode circulation tank pumps the electrolyzed printed board acid etching waste liquid, namely cathode liquid, into the vacuum recovery device, the vacuum recovery device recovers chlorine and hydrogen chloride gas by using the printed board acid etching waste liquid, and the reacted cathode liquid flows into the mixing tank;
the waste liquid collecting storage tank is communicated with the mixing tank, and the waste liquid collecting storage tank adds the printed board acid etching waste liquid into the mixing tank so as to stabilize the copper content of the solution in the regeneration and recovery process.
The anode plate, the anode frame, the ion exchange layer, the cathode frame and the cathode plate of the electrolysis unit are sequentially pressed by the electrolysis device through the press machine to form the closed anode chamber and the closed cathode chamber, so that gas generated by the electrolysis reaction of the electrolysis device can not be released, the corrosion of harmful gas to equipment and the pollution to the environment are avoided, and the quality of the operation environment is improved.
Drawings
FIG. 1 is a front view of an embodiment of an electrolyzer;
FIG. 2 is a rear view of the electrolyzer;
FIG. 3 is a schematic view of the structure of an electrolysis apparatus;
FIG. 4 is an enlarged view of the location designated A in FIG. 1;
FIG. 5 is an enlarged view of the location indicated by B in FIG. 1;
FIG. 6 is a schematic view of the structure of an electrolysis cell;
FIG. 7 is a cross-sectional view taken at the location indicated by C-C in FIG. 6;
FIG. 8 is an exploded view of an electrolysis cell;
FIG. 9 is an exploded view from another angle of the electrolysis cell;
FIG. 10 is a schematic structural view of an anode frame;
FIG. 11 is a schematic structural view of a cathode frame;
FIG. 12 is a schematic view of an apparatus for recycling acidic waste etching solution of printed boards and recovering copper.
Description of reference numerals:
100-an electrolysis device; 1-a press, 11-a butting part, 12-a driving part, 13-a moving part, 14-a pressing space and 15-a driving rod; 2-electrolysis unit, 21-anode plate, 21 a-anode conductive copper bar, 211-first connecting rod, 212-second connecting rod, 213-cathode insulating head, 22-anode frame, 221-anolyte inlet, 222-anolyte outlet, 23-cathode frame, 231-catholyte inlet, 232-catholyte outlet, 24-cathode plate, 24 a-cathode conductive copper bar, 241-third connecting rod, 242-fourth connecting rod, 243-anode insulating head, 25-ion exchange layer, 26-anode chamber and 27-cathode chamber; 3-transfusion pipeline, 31-anode liquid outlet main pipe, 32-cathode liquid inlet main pipe, 321-anode liquid inlet valve, 322-anode emptying valve, 33-cathode liquid outlet main pipe, 34-anode liquid inlet main pipe, 341-cathode liquid inlet valve and 342-cathode emptying valve; 4-power supply assembly, 41-cathode conductive part, 42-anode conductive part, 43-rectifier; 5-a waste liquid collecting and storing tank; 6-cathode circulation tank; 7-a mixing tank; 8-an anode circulation tank; 9-etching production line; 10-vacuum recovery device; 20-a vacuum treatment device; 30-a waste gas purification tower; 200-equipment for regenerating acid etching waste liquid of printed boards and recovering copper.
Detailed Description
The embodiments of the invention will be described in detail below with reference to the drawings, but the invention can be implemented in many different ways as defined and covered by the claims.
Referring to fig. 1 to 3 and 6 to 7, the electrolysis apparatus 100 includes a press 1 and an electrolysis unit 2. Wherein, the press machine 1 is provided with a pressing space 14, an electrolysis unit 2 is arranged in the pressing space 14, and the electrolysis unit 2 comprises an anode plate 21, an anode frame 22, an ion exchange layer 25, a cathode frame 23 and a cathode plate 24. The press 1 can press the anode plate 21, the anode frame 22, the ion exchange layer 25, the cathode frame 23 and the cathode plate 24 in sequence to form a closed anode chamber 26 and a closed cathode chamber 27. In this way, the electrolyzer 100 presses the anode plate 21, the anode frame 22, the ion exchange layer 25, the cathode frame 23 and the cathode plate 24 of the electrolyzer 2 in sequence by the press 1 to form the closed anode chamber 26 and cathode chamber 27, so that the gas generated by the electrolysis reaction of the electrolyzer 100 is not released, the corrosion of the equipment by the generated corrosive gas and the influence of harmful gas on the environment are avoided, and the quality of the working environment is improved.
The number of the electrolytic cells 2 provided in the holding space 14 may be one or more. In this embodiment, the electrolytic treatment efficiency of the electrolytic apparatus 100 can be increased by pressing a plurality of electrolytic cells 2 in a row in the pressing space 14.
Referring to fig. 1 to 3, the press machine 1 may be an electric press machine or a manual press machine, and when the press machine 1 is an electric press machine, the press machine 1 includes a butting part 11, a moving part 13 and a driving part 12, and the driving part 12 may be an existing driving structure. A pressing space 14 is arranged between the abutting part 11 and the driving part 12, the moving part 13 is arranged in the pressing space 14, the driving part 12 drives the moving part 13 to move along the pressing space 14 by acting on the driving rod 15, and the plurality of electrolysis units 2 in the pressing space 14 are pressed between the abutting part 11 and the moving part 13 in a row.
The two ends of the plurality of electrolysis units 2 arranged in rows in the pressing space 14 are provided with the anode plates 21 or the cathode plates 24, when the abutting part 11 abuts against the anode plates 21 or the cathode plates 24 and the moving part 13 abuts against the anode plates 21 or the cathode plates 24, only one side surface of the anode plates 21 or the cathode plates 24 can be contacted with the electrolytic liquid for electrolytic reaction.
The two ends of the plurality of electrolysis units 2 arranged in a row in the holding space 14 may be the anode frame 22 or the cathode frame 23, in this case, the abutting portion 11 abuts against the anode frame 22 or the cathode frame 23 between the anode plate 21 or the cathode plate 24, and the moving portion 13 abuts against the anode frame 22 or the cathode frame 23 between the anode plate 21 or the cathode plate 24.
Preferably, referring to fig. 3-5, in the present embodiment, the number of the electrolysis units 2 disposed in the pressing space 14 is odd (e.g. 7 or 9), and the anode frames 22 are disposed between the anode plate 21 and the abutting portion 11, and between the anode plate 21 and the moving portion 13. The method has the highest regeneration efficiency of the liquid medicine, and simultaneously, the recovery of copper cannot be influenced.
The electrolysis device 100 adopts the arrangement, the anode frames 22 arranged at the two ends avoid the direct contact of the anode plate 21 and the abutting part 11 or the moving part 13, the abutting part 11 and the moving part 13 act on the electrolysis unit 2 through the anode frame 22 because the matching performance of the anode frame 22 and the anode plate 21 and the anode frame 22 and the cathode plate 24 on the contact surface is good, the pressing tightness among the anode plate 21, the anode frame 22, the ion exchange layer 25, the cathode frame 23 and the cathode plate 24 of the electrolysis unit 2 can be improved, and the sealing performance of the electrolysis unit 2 is improved. More importantly, the two sides of the anode plate 21 or the cathode plate 24 at the two ends are subjected to electrolytic reaction, so that the electrolytic treatment efficiency is accelerated, and potential safety hazards possibly generated by the heating surfaces of the anode plate 21 or the cathode plate 24 are eliminated.
Referring to fig. 1-2, when a plurality of electrolysis units 2 are disposed in the holding space 14, the anode plate 21 has an anode frame 22 on both sides thereof, the cathode plate 24 has a cathode frame 23 on both sides thereof, and the adjacent electrolysis units 2 share the same anode plate 21 or cathode plate 24. The electrolytic apparatus 100 with such an arrangement can simplify the structure, improve the utilization rate of the anode plate 21 or the cathode plate 24, and accelerate the electrolytic treatment efficiency.
Referring to fig. 6-11, for the electrolysis unit 2, the anode plate 21 and the cathode plate 24 are both plate-shaped structures, the anode plate 21 and the cathode plate 24 are made of conductive materials, in this embodiment, the anode plate 21 and the cathode plate 24 are made of titanium materials, and the surface of the anode plate 21 is coated with a platinum group metal active coating. The cross sections of the anode frame 22 and the cathode frame 23 are in a shape of a square, the anode frame 22 and the cathode frame 23 are in a shape of a square as a whole, and the anode plate 21 and the anode frame 22, and the cathode plate 24 and the cathode frame 23 can be in an integral structure or in a separate structure. The electrolysis unit 2 is of a frame type pressing electrolysis bath structure as a whole, and the ion exchange layer 25 is arranged between the anode frame 22 and the cathode frame 23 at intervals and can be made of materials such as an anion exchange membrane, a cation exchange membrane or diaphragm cloth.
In the electrolytic cell 2, the anode plate 21, the anode frame 22 and the ion exchange layer 25 form an anode chamber 26, and the ion exchange layer 25, the cathode frame 23 and the cathode plate 24 can form a cathode chamber 27 in a pressed state. Under energized conditions, when ion exchange layer 25 is a cation exchange membrane, cations in anode chamber 26 can pass through ion exchange layer 25 into cathode chamber 27, undergo an oxidation reaction on anode plate 21, and undergo a reduction reaction on cathode plate 24.
Specifically, referring to fig. 3-4 and fig. 8-11, for convenience of power supply, the anode plate 21 and the cathode plate 24 are provided with an anode conductive copper bar 21a on top of the anode plate 21, and a cathode conductive copper bar 24a on top of the cathode plate 24, and the anode conductive copper bar 21a and the cathode conductive copper bar 24a may be fixed by screws or welding.
One end of the anode conductive copper bar 21a extends outwards to form a first connecting bar 211, the other end of the anode conductive copper bar 21a extends outwards to form a second connecting bar 212, the second connecting bar 212 is provided with a cathode insulating head 213, and the cathode insulating head 213 can be formed by wrapping insulating glue on the end side of the second connecting bar 212 or sleeving a plastic head on the second connecting bar 212. One end of the cathode conductive copper bar 24a extends outwards to form a third connecting bar 241, the other end of the cathode conductive copper bar 24a extends outwards to form a fourth connecting bar 242, the fourth connecting bar 242 is provided with an anode insulating head 243, and the anode insulating head 243 can be formed by wrapping insulating glue on the end side of the fourth connecting bar 242 or sleeving a plastic head on the fourth connecting bar 242. The first connection bar 211 and the third connection bar 241 are electrically connected to the power supply assembly 4, and when the power supply assembly 4 is powered on, the first connection bar 211 and the third connection bar 241 respectively conduct electricity to the anode plate 21 and the cathode plate 24.
With reference to fig. 3-4 and fig. 8-11, the first connecting rod 211 and the second connecting rod 212 are disposed on opposite sides of the anode plate 21, the third connecting rod 241 and the fourth connecting rod 242 are disposed on opposite sides of the cathode plate 24, the first connecting rod 211 and the fourth connecting rod 242 are disposed on the same side, and the second connecting rod 212 and the third connecting rod 241 are disposed on the same side, so as to be electrically connected to the power supply assembly 4.
Referring to fig. 1-5, the power supply assembly 4 includes a rectifier 43, an anode conductive portion 42 and a cathode conductive portion 41, and the anode conductive portion 42 and the cathode conductive portion 41 may be made of a wiring material such as a copper bar or a wire. The anode conductive part 42 is electrically connected to the rectifier 43, and the cathode conductive part 41 is electrically connected to the rectifier 43.
When the anode conductive part 42 is an anode conductive wire and the cathode conductive part 41 is a cathode conductive wire, the anode conductive part 42 is electrically connected to the first connection bar 211, and the cathode conductive part 41 is electrically connected to the third connection bar 241.
When the anode conductive part 42 adopts an anode connection copper strip, and the cathode conductive part 41 adopts a cathode connection copper strip, the first connecting rod 211 and the anode insulating head 243 are both connected with the anode conductive part 42, the third connecting rod 241 and the cathode insulating head 213 are both connected with the cathode conductive part 41, the connection between the first connecting rod 211 and the anode conductive part 42, and the connection between the third connecting rod 241 and the cathode conductive part 41 can be realized by lapping or screw fixation, the connection between the anode insulating head 243 and the anode conductive part 42, and the connection between the cathode insulating head 213 and the cathode conductive part 41 actually only use the anode conductive part 42 and the cathode conductive part 41 as a supporting function, and the direct lapping is placed on the anode conductive part 42 and the cathode conductive part 41. And the first connection bar 211 and the anode insulating head 243 are located at the same height, and the third connection bar 241 and the cathode insulating head 213 are located at the same height. Thus, the anode conductive part 42 and the cathode conductive part 41 are made of copper strips and arranged not only to facilitate the energization to the anode plate 21 and the cathode plate 24 but also to stabilize the electrolytic unit 2 to some extent.
With respect to the specific structure of feeding electrolytic liquid to the anode chamber 26 and the cathode chamber 27, as shown in fig. 8 to 11, an anolyte inlet 221 is provided on one side of the anode frame 22, an anolyte outlet 222 is provided on the other side of the anode frame 22, and both the anolyte inlet 221 and the anolyte outlet 222 communicate with the anode chamber 26. One side of the cathode frame 23 is provided with a catholyte inlet 231, the other side of the cathode frame 23 is provided with a catholyte outlet 232, and the catholyte inlet 231 and the catholyte outlet 232 are both communicated with the cathode chamber 27. Specifically, the anolyte inlet 221 is disposed at the bottom of the anode chamber 26, the anolyte outlet 222 is disposed at the top of the anode chamber 26, the catholyte inlet 231 is disposed at the bottom of the cathode chamber 27, and the catholyte outlet 232 is disposed at the top of the cathode chamber 27, so that the electrolyte can sufficiently flow in the anode chamber 26 and the cathode chamber 27, which is beneficial to the electrolytic reaction. The input electrolytic liquid can be various, such as tin sulfate solution, sodium chloride solution, industrial waste liquid (including PCB etching waste liquid) and other electrolytic liquids.
When the electrolytic liquid is a tin sulfate solution, the anode plate 21 is a tin plate or a titanium plate coated with an active coating, the ion exchange layer 25 is a cationic membrane, and the cathode plate 24 is a titanium plate, so that stannous sulfate is produced.
When the electrolytic solution is a sodium chloride solution, the anode plate 21 is a titanium plate coated with an active coating, the ion exchange layer 25 is an ion membrane, and the cathode plate 24 is a titanium plate, thereby producing sodium chlorate, sodium hydroxide, and hydrochloric acid.
As shown in fig. 1 to 3 and fig. 8 to 11, the liquid feeding pipe 3 includes an anolyte liquid outlet header pipe 31, an anolyte liquid feeding header pipe 34, a catholyte liquid outlet header pipe 33, and a catholyte liquid feeding header pipe 32. The anolyte inlet manifold 34 is communicated with the anolyte inlet 221, the anolyte outlet manifold 31 is communicated with the anolyte outlet 222, and electrolytic liquid is input and output to the anolyte chamber 26 through the anolyte inlet manifold 34 and the anolyte outlet manifold 31; the catholyte inlet manifold 32 is communicated with the catholyte inlet 231, the catholyte outlet manifold 33 is communicated with the catholyte outlet 232, and electrolytic liquid is input and output to the cathode chamber 27 through the catholyte inlet manifold 32 and the catholyte outlet manifold 33. In order to improve the reaction efficiency of the electrolytic liquid in the anode chamber 26 and the cathode chamber 27, the anolyte inlet 221 is communicated with the bottom of the anode chamber 26, and the anolyte outlet 222 is communicated with the top of the anode chamber 26; catholyte inlet 231 communicates with the bottom of cathode chamber 27 and catholyte outlet 232 communicates with the top of cathode chamber 27.
In addition, one end of the anolyte liquid inlet main pipe 34 is provided with an anolyte liquid inlet valve 341, and the other end is provided with an anolyte emptying valve 342, wherein the anolyte liquid inlet valve 341 is opened and the anolyte emptying valve 342 is closed when liquid is fed; one end of the cathode liquid inlet main pipe 32 is provided with a cathode liquid inlet valve 321, the other end is provided with a cathode emptying valve 322, and during liquid inlet, the cathode liquid inlet valve 321 is opened, and the cathode emptying valve 322 is closed. When the treatment of the electrolytic liquid in the electrolytic cell 2 is completed, or when the electrolytic liquid in the electrolytic cell 2 needs to be discharged under other conditions (such as the removal and installation of the cathode plate 24), the anode liquid inlet valve 341 is closed, the anode exhaust valve 342 is opened, and the electrolytic liquid in the anode chamber 22 is exhausted; the cathode feed valve 321 is closed, and the cathode exhaust valve 322 is opened to exhaust the electrolytic liquid in the catholyte 23.
An example of a specific application of the electrolysis apparatus 100 is listed below.
With the annual growth rate of the electronic industry in China exceeding 20%, the development of Printed Circuit Boards (PCBs) and related industries is driven, and China becomes the biggest PCB production center in the world. The etching process is an essential step in the present PCB manufacturing process, and in the PCB production process, the acidic and alkaline etching processes are usually used to produce the circuit boards, and these enterprises generate a large amount of copper-containing etching waste liquid every year.
Wherein the acidic etching solution comprises hydrochloric acid + sodium chlorate, hydrochloric acid + hydrogen peroxide, hydrochloric acid + ammonium chloride and the like, and the main component of the acidic etching waste solution is CuCl2,HCl,NaClO3,NH4Cl or NaCl, etc. There are three main methods for treating acidic etching solutions: displacement method, dilution and neutralization extraction method and sulfuric acid extractive distillation method, but the displacement method discharges a large amount of salt and Cl2The wastewater of (2) can pollute the environment and cannot be regenerated; dilution neutralization extraction also produces large amounts of waste waterThe problems of large equipment investment, low utilization rate of liquid medicine and the like exist; the sulfuric acid extractive distillation method needs to add a large amount of sulfuric acid to replace CuCl into copper sulfate, and the copper sulfate belongs to chemical products, so that special chemical production qualification is needed, and circuit board production enterprises do not have production qualification.
In order to solve the problems of the prior art in processing the acidic etching solution, the electrolytic device 100 can be used for preparing the printed board acidic etching waste solution regeneration and copper recovery equipment 200 to process the printed board acidic etching waste solution, the printed board acidic etching waste solution regeneration and copper recovery equipment 200 can recover copper and convert the printed board acidic etching waste solution into the printed board regenerated acidic etching solution, the printed board regenerated acidic etching solution can be used for producing Printed Circuit Boards (PCBs), the generated chlorine can be recycled, and the waste gas reaches the standard and is discharged.
Specifically, referring to fig. 1 and 12, in fig. 12, a single line flow direction indicates a liquid flow direction, a double line indicates a gas flow direction, and the printed board acid etching waste liquid recycling and copper recovering apparatus 200 includes an electrolysis device 100, a waste liquid collecting tank 5, a cathode circulation tank 6, an anode circulation tank 8, a mixing tank 7, a vacuum recovering device 10, a vacuum processing device 20, and an exhaust gas purifying tower 30. The waste liquid collecting and storing tank 5 is communicated with a cathode circulating tank 6 and a mixing tank 7 of the electrolysis device 100 through pipelines, the cathode circulating tank 6 is communicated with a cathode chamber 27 in a circulating manner, the cathode circulating tank 6 conveys the printed board acidic etching waste liquid to the cathode chamber 27 through a cathode liquid inlet 231, on-off is controlled by arranging a control valve (not shown), some printed board acidic etching waste liquid is conveyed through a pump (shown by a triangular mark in fig. 12), and the cathode chamber 27 conveys the printed board acidic etching waste liquid after reaction back to the cathode circulating tank 6 through a cathode liquid outlet 232.
The cathode circulation tank 6 is also communicated with the vacuum recovery device 10, the cathode circulation tank 6 inputs the printed board acid etching waste liquid after reaction into the vacuum recovery device 10 to recover gas, the vacuum recovery device 10 is communicated with the mixing tank 7, the printed board acid etching waste liquid is input into the mixing tank 7 after recovery treatment, the mixing tank 7 is communicated with the anode chamber 26, the mixing tank 7 inputs the printed board acid etching waste liquid into the anode chamber 26 through an anolyte inlet 221, the anode chamber 26 is communicated with the anode circulation tank 8 through an anolyte outlet 222, the printed board acid etching waste liquid generates normal printed board regeneration acid etching liquid after electrolytic reaction in the anode chamber 26, the printed board acid etching liquid is input into the anode circulation tank 8 by the anode circulation tank 8, the printed board regeneration acid etching liquid is input into the etching production line 9 by the anode circulation tank 8, the etching production line 9 generates printed board acid etching waste liquid by using the printed board regeneration acid etching liquid for etching reaction, and the printed board acidic etching waste liquid is discharged into a waste liquid collecting tank 5.
In addition, the waste liquid collecting storage tank 5, the cathode circulation tank 6, the anode circulation tank 8 and the mixing tank 7 are respectively communicated with the vacuum recovery device 10, the vacuum recovery device 10 recovers waste gases such as chlorine gas and hydrogen chloride gas in the waste liquid collecting storage tank 5, the cathode circulation tank 6, the anode circulation tank 8 and the mixing tank 7, the vacuum recovery device 10 recovers and recycles the chlorine gas and the hydrogen chloride gas, the waste gas treated by the vacuum recovery device 10 flows into the vacuum treatment device 20 for treatment, the waste gas treated by the vacuum treatment device 20 enters the waste gas purification tower 30 for treatment, and then the waste gas is discharged after reaching the standard.
More specifically, in the process of treating the printed board acidic etching waste liquid, the ion exchange layer 25 of the electrolysis device 100 is selected to be a cation exchange membrane, cations in the printed board acidic etching waste liquid in the anode chamber 26 can enter the cathode chamber 27 through the ion exchange layer 25, and cations in the printed board acidic etching waste liquid in the cathode chamber 27 cannot enter the anode chamber 26 through the ion exchange layer 25. In cathode chamber 27, the reactions carried out on cathode plate 24 are: cu2++2e→Cu;Cu2++e→Cu+;Cu++ e → Cu; in the anode chamber 26, the reactions performed on the anode plate 21 are: cu+-e→Cu2+. Thus, copper ions in the waste printed board acid etching solution are separated from the cathode plate 24 after the electrolytic reaction, when a large amount of copper is separated from the cathode plate 24, before the copper on the cathode plate 24 is removed, the waste printed board acid etching solution in the anode chamber 26 and the cathode chamber 27 is discharged from the anolyte drain pipe 36 and the catholyte drain pipe 33, respectively, and then the driving part 12 of the press 1 drives the moving part 13 to reversely drive, so that the cathode plate is drivenThe copper on the cathode plate 24 is removed and replaced with a new cathode plate 24.
The cathode circulation tank 6 conveys the printed board acid etching waste liquid to the cathode chamber 27, and the waste liquid is continuously circulated, the specific gravity of the catholyte is in the range of 1.1-1.3g/ml, after the electrolytic reaction of the cathode chamber 27, the specific gravity of the catholyte is reduced due to the precipitation of copper, and at the moment, the printed board acid etching waste liquid in the waste liquid collecting and storing tank 5 is conveyed to the mixing tank 7 to adjust the specific gravity of the catholyte in the range of 1.1-1.3g/ml, so as to ensure the stability of the copper concentration of the catholyte.
In the mixing tank 7, the specific gravity, acidity and redox value of the printed board acid etching waste liquid in the mixing tank 7 are measured by a specific gravity meter, an acidity meter and a redox value measuring meter, the specific gravity of the printed board acid etching waste liquid in the mixing tank 7 is controlled within the range of 1.2-1.3g/ml, the acidity is controlled within the range of 1.5-2.5N, and the redox value is controlled within the range of 300 plus 600mv, and then the printed board acid etching waste liquid is transported to the anode chamber 26 by the mixing tank 7.
Because copper is separated out through electrolytic reaction in the cathode chamber 27, copper ions in the printed board acidic etching waste liquid are reduced, the specific gravity of the printed board acidic etching waste liquid flowing into the cathode circulation tank 6 is reduced, the printed board acidic etching waste liquid in the cathode circulation tank 6 flows into the mixing tank 7 after waste gas is recovered by the vacuum recovery device 10, finally the printed board acidic etching waste liquid flows into the anode circulation tank 8, the printed board regenerated acidic etching liquid in the anode circulation tank 8 flows into the etching production line 9 for etching reaction, in order to ensure the stability of the copper content in the printed board regenerated acidic etching liquid, the adverse influence on the etching reaction caused by too low copper content in the printed board regenerated acidic etching liquid is avoided, the waste liquid collecting and storing tank 5 is also communicated with the mixing tank 7, the printed board acidic etching waste liquid flows into the mixing tank 7 from the waste liquid collecting and storing tank 5, the copper content in the printed board acidic etching waste liquid flowing into the mixing tank 7 from the waste liquid, can be mixed with the printed board acid etching waste liquid flowing into the mixing tank 7 by the vacuum recovery device 10, finally stabilize the copper content in the printed board regenerated acid etching liquid, and ensure that the printed board regenerated acid etching liquid stably performs etching reaction in the etching production line 9.
Printed board acidThe waste etching solution is electrolyzed in the anode chamber 26, and part of Cu in the waste etching solution is printed in the anode chamber 26+、Cu2+Will pass through ion exchange layer 25 into cathode chamber 27.
Electrolytic reaction of the printed board acidic etching waste liquid in the cathode chamber 27 to separate out copper, and electrolytic reaction of Cu in the anode chamber 26+、Cu2+The copper ion concentration in the printed board acidic etching waste liquid can be obviously reduced by the electrolytic reaction of the ion exchange layer 25 entering the cathode chamber 27 again, the printed board acidic etching waste liquid flows through the anode chamber 26 and is converted into the printed board regenerated acidic etching liquid, the printed board acidic etching liquid is conveyed to the anode circulating tank 8 by the anode chamber 26, and the printed board acidic etching liquid is conveyed to the etching production line 9 by the anode circulating tank 8.
The waste liquid is collected storage tank 5, the negative pole circulation groove 6, waste gas in positive pole circulation groove 8 and the mixing tank 7 gets into vacuum recovery unit 10, vacuum recovery unit 10 still communicates with negative pole circulation groove 6 and mixing tank 7 simultaneously, negative pole circulation groove 6 is to vacuum recovery unit 10 suction printing board acid etching waste liquid, printing board acid etching waste liquid reacts with chlorine and hydrogen chloride gas body in the waste gas in the vacuum recovery unit 10 and recycles, chlorine can the oxidation waste liquid, the acidity that can improve the waste liquid after the hydrogen chloride gas body dissolves in the waste liquid, the two can make the waste liquid reach preliminary regeneration's effect, printing board acid etching waste liquid after the reaction flows into mixing tank 7. Vacuum recovery unit 10 sends into vacuum processing apparatus 20 with waste gas, and vacuum processing apparatus 20 can be multi-stage processing apparatus, through letting in liquid caustic soda in toward vacuum processing apparatus 20, lets the chlorine reaction in liquid caustic soda and the waste gas, and generates sodium hypochlorite solution to carry waste gas purification tower 30 after will handling, use 5% liquid caustic soda at waste gas purification tower 30 and purify, behind waste gas purification tower 30 purification treatment, make waste gas discharge to reach standard.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.

Claims (15)

1. An electrolysis device is characterized by comprising a press and an electrolysis unit;
the press machine is provided with a pressing space, and an electrolysis unit is arranged in the pressing space;
the electrolysis unit comprises an anode plate, an anode frame, an ion exchange layer, a cathode frame and a cathode plate;
the press machine can sequentially compress the anode plate, the anode frame, the ion exchange layer, the cathode frame and the cathode plate to form a closed anode chamber and a closed cathode chamber.
2. The electrolysis device according to claim 1, wherein the press comprises an abutting portion, a moving portion and a driving portion;
a pressing space is arranged between the abutting part and the driving part;
the moving part is arranged in the pressing space;
the driving part drives the moving part to move along the pressing space, and a plurality of electrolysis units are pressed between the abutting part and the moving part in rows.
3. The electrolysis device according to claim 2, wherein a plurality of said electrolysis cells are arranged in a row in said holding space;
an anode frame is arranged between the abutting part and the anode plate, and an anode frame is arranged between the moving part and the anode plate; or
A cathode frame is arranged between the abutting part and the cathode plate, and a cathode frame is arranged between the moving part and the cathode plate; or
The abutting part abuts against the anode plate or the cathode plate, and the moving part abuts against the anode plate or the cathode plate.
4. The electrolysis device according to claim 3, wherein the anode plate is flanked by anode frames;
cathode frames are arranged on two sides of the cathode plate;
every two adjacent electrolysis units share the same anode plate or cathode plate.
5. The electrolysis device according to any one of claims 1 to 4, wherein the anode frame and the cathode frame are both of a meander configuration;
the press machine can sequentially compress the anode plate, the anode frame, the ion exchange layer, the cathode frame and the cathode plate, so that the anode plate, the anode frame and the ion exchange layer form an anode chamber, and the ion exchange layer, the cathode frame and the cathode plate form a cathode chamber.
6. The electrolysis device according to claim 5, wherein one side of the anode frame is provided with an anolyte inlet, and the other side of the anode frame is provided with an anolyte outlet;
one side of the cathode frame is provided with a cathode liquid inlet, and the other side of the cathode frame is provided with a cathode liquid outlet;
the anolyte inlet and the anolyte outlet are communicated with the anode chamber;
the catholyte inlet and catholyte outlet are both in communication with the cathode chamber.
7. The electrolyzing apparatus of claim 6 further comprising an infusion tube;
the liquid conveying pipeline comprises an anolyte liquid inlet main pipe, an anolyte liquid outlet main pipe, a catholyte liquid inlet main pipe and a catholyte liquid outlet main pipe;
the anolyte liquid inlet header pipe is communicated with an anolyte inlet;
one end of the anolyte liquid inlet header pipe is provided with an anolyte liquid inlet valve, and the other end of the anolyte liquid inlet header pipe is provided with an anolyte emptying valve;
the anolyte liquid outlet main pipe is communicated with an anolyte outlet;
the catholyte liquid inlet header pipe is communicated with the catholyte inlet;
one end of the catholyte inlet header pipe is provided with a catholyte inlet valve, and the other end of the catholyte inlet header pipe is provided with a catholyte emptying valve;
the cathode liquid outlet header pipe is communicated with the cathode liquid outlet.
8. The electrolysis device according to claim 5, further comprising an anode conductive copper bar disposed on top of the anode plate, wherein one end of the anode conductive copper bar extends outward to form a first connecting rod, and the other end of the anode conductive copper bar extends outward to form a second connecting rod, and the second connecting rod is provided with a cathode insulation head.
9. The electrolysis device according to claim 8, further comprising a cathode conductive copper bar, wherein the cathode conductive copper bar is arranged on the top of the cathode plate, one end of the cathode conductive copper bar extends outwards to form a third connecting rod, the other end of the cathode conductive copper bar extends outwards to form a fourth connecting rod, and the fourth connecting rod is provided with an anode insulating head;
the first connecting rod and the fourth connecting rod are located on the same side, and the second connecting rod and the third connecting rod are located on the same side.
10. The electrolysis device of claim 9, further comprising a power supply assembly;
the power supply assembly comprises a rectifier, an anode conductive part and a cathode conductive part;
the first connecting rod is connected with the anode conductive part;
the third connecting rod is connected with the cathode conductive part;
the anode conductive part is electrically connected with the rectifier, and the cathode conductive part is electrically connected with the rectifier.
11. The electrolysis device of claim 10, wherein the anode conductive portion is an anode connecting copper bar or an anode conductive wire;
the cathode conductive part is a cathode connecting copper bar or a cathode conductive wire.
12. The electrolyzer of claim 11 wherein the anode conductive portion is an anode connecting copper bar and the cathode conductive portion is a cathode connecting copper bar;
the first connecting rod and the anode insulating head are at the same height, and the third connecting rod and the cathode insulating head are at the same height;
the first connecting rod and the anode insulating head are both connected with the anode connecting copper bar;
and the third connecting rod and the cathode insulating head are connected with the cathode connecting copper bar.
13. An apparatus for regenerating printed board acid etching waste liquid and recovering copper, characterized by comprising the electrolysis apparatus according to any one of claims 1 to 12;
the ion exchange layer is an ionic membrane or diaphragm cloth;
the electrolytic device is used for electrolytic treatment of the printed board acid etching waste liquid.
14. The apparatus for recycling printed board acid etching waste liquid and copper according to claim 13, further comprising a waste liquid collecting storage tank, a cathode circulation tank, an anode circulation tank, a mixing tank, a vacuum recycling device, a vacuum processing device and a waste gas purifying tower;
the waste liquid collecting and storing tank is used for storing the printed board acid etching waste liquid;
the waste liquid collecting storage tank is communicated with the cathode circulating tank;
the cathode circulating tank is communicated with the cathode chamber in a circulating manner, and a specific gravity measuring instrument is installed on the cathode circulating tank;
the cathode circulating tank is also communicated with the mixing tank;
the mixing tank is provided with a hydrometer, an acidity meter and a redox value measuring meter;
the mixing tank is communicated with the anode chamber;
the anode chamber is communicated with the anode circulating tank;
the anode circulating tank discharges the regenerated acidic etching solution of the printed board after electrolytic treatment;
the waste liquid collecting storage tank, the cathode circulating tank, the anode circulating tank and the mixing tank are communicated with the vacuum recovery device to collect waste gas;
the vacuum recovery device is used for recovering chlorine and hydrogen chloride gas; the vacuum recovery device is communicated with the vacuum treatment device, and the vacuum treatment device is used for further treating chlorine and hydrogen chloride gas which are not completely recovered by the vacuum recovery device;
the waste gas purification tower is communicated with the vacuum treatment device and is used for purifying waste gas discharged by the vacuum treatment device so as to ensure that the waste gas is discharged up to the standard.
15. The apparatus for recycling printed board acid etching waste liquid and recovering copper according to claim 14, wherein the vacuum recovery device is simultaneously communicated with a cathode circulation tank and a mixing tank, the cathode circulation tank pumps the printed board acid etching waste liquid after electrolytic treatment into the vacuum recovery device, the vacuum recovery device recovers chlorine gas and hydrogen chloride gas by using the printed board acid etching waste liquid, and the solution after reaction flows into the mixing tank;
the waste liquid collecting and storing tank is communicated with the mixing tank, and the waste liquid collecting and storing tank adds the printed board acid etching waste liquid into the mixing tank so as to stabilize the copper content of the solution in the regeneration and recovery process.
CN202010339532.3A 2020-04-26 2020-04-26 Electrolysis device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof Active CN111394729B (en)

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