CN214004793U - Alkaline etching waste liquid electrolysis recycling equipment - Google Patents
Alkaline etching waste liquid electrolysis recycling equipment Download PDFInfo
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- CN214004793U CN214004793U CN202021488166.XU CN202021488166U CN214004793U CN 214004793 U CN214004793 U CN 214004793U CN 202021488166 U CN202021488166 U CN 202021488166U CN 214004793 U CN214004793 U CN 214004793U
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Abstract
The utility model provides an alkaline etching waste liquid electrolysis retrieval and utilization equipment, including electrolysis regeneration tank, electrolysis positive pole, electrolysis negative pole, power, electrolysis positive pole and electrolysis negative pole are arranged in the electrolysis regeneration tank, are connected with positive pole, the negative pole of power respectively, and its characterized in that still adds the solid-liquid separation equipment who is used for carrying out solid-liquid separation to the electrolyte in the electrolysis regeneration tank, solid-liquid separation equipment with the electrolysis regeneration tank is connected to the electrolyte in the electrolysis regeneration tank is got rid of the processing of precipitate and solid impurity. The utility model discloses equipment of nature etching waste liquid electrolysis retrieval and utilization carries out solid-liquid separation to the electrolyte after alkaline etching waste liquid electrolytic treatment through setting up solid-liquid separation equipment, effectively gets rid of precipitate and solid impurity in the electrolyte for do not influence the etching quality when regeneration back electrolyte returns to the use on the etching production line.
Description
Technical Field
The utility model relates to a printed circuit board etching waste liquid's retrieval and utilization equipment especially relates to an electrolysis retrieval and utilization equipment suitable for circuit board alkaline etching waste liquid.
Background
Etching is an important step in the existing Printed Circuit Board (PCB) manufacturing process. Etching is to remove unnecessary copper on the copper-clad substrate by chemical reaction with an etching solution to form a desired circuit pattern.
The basic copper ammonium chloride etching solution (hereinafter referred to as basic etching solution) is one of the most common circuit board etching solutions at present, and the main components of the basic copper ammonium chloride etching solution are copper salt, ammonium chloride, ammonia water, optional carbonate and optional additives, wherein the carbonate is usually ammonium carbonate and/or ammonium bicarbonate. In actual production, in order to keep the components of the etching solution stable, a supplementary solution needs to be added continuously, so that the etching solution in the etching tank is inevitably increased and overflows out of the tank, and the etching solution overflowing out of the etching tank or the used etching solution is generally called etching waste solution. The alkaline etching make-up solution is generally an aqueous solution of ammonia and/or ammonium chloride and/or ammonium salt, and is referred to as an alkaline etchant in the industry when the alkaline etching make-up solution contains more than one component.
For a circuit board manufacturing plant using an alkaline etching production process, a large amount of alkaline etching waste liquid with a high copper ion concentration is required to be treated every day. At present, in addition to selling the waste liquid to an environmental protection company for treatment, some manufacturers also use electrolysis equipment to electrolyze the waste liquid in factories for copper recovery and reuse. In the prior art, the electrolytic treatment of the etching waste liquid reduces copper ions in the electrolytic waste liquid into metallic copper by performing an electrochemical reduction reaction on an electrolytic cathode.
Because the alkaline etching waste liquid contains a large amount of chloride ions, a small amount of iron is dissolved in the electrolyte because the alkaline etching waste liquid corrodes the electrolysis cathode containing iron materials in the electrolysis process, and the iron ions are easy to form solid precipitated compounds under the ammonia alkaline condition, so when the alkaline etching waste liquid is subjected to electrolytic regeneration, if the electrolysis cathode containing iron metals is adopted, the electrolyte after the electrolytic regeneration returns to an etching production line for use, and the etching quality is influenced. Therefore, in the prior art, a titanium material with better corrosion resistance in alkaline etching waste liquid is generally adopted as an electrolytic cathode, and the titanium cathode has strong corrosion resistance, so that the problem that the copper surface precipitated due to the current point discharge effect is rough and loose can be avoided, and a copper sheet with a compact structure and capable of being peeled off in a whole block can be formed on the titanium cathode; or the thin copper plate is directly adopted as the cathode for electrolysis and then collected as a whole block, and the two electrolysis cathodes are very convenient for collecting and storing the metal copper obtained by electrowinning, so that the industry prefers to adopt the titanium cathode and the thin copper plate as the electrolysis cathodes and basically does not adopt the electrolysis cathodes made of ferrous metal. This causes a problem that the material cost of the apparatus is high.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide an alkaline etching waste liquid electrolysis retrieval and utilization equipment effectively gets rid of deposit and solid impurity in the electrolyte, can not influence the etching quality because of deposit or impurity when guaranteeing the electrolyte used repeatedly after the regeneration.
In order to achieve the above purpose, the utility model adopts the following technical scheme:
the electrolytic recycling equipment for the alkaline etching waste liquid comprises an electrolytic regeneration tank, an electrolytic anode, an electrolytic cathode and a power supply, wherein the electrolytic anode and the electrolytic cathode are arranged in the electrolytic regeneration tank and are respectively connected with the anode and the cathode of the power supply.
In the utility model, the solid-liquid separation device and the electrolytic regeneration tank are connected through a pipeline provided with a pump and/or a valve.
Further, the electrolytic anode is selected from at least one of graphite, alkali-resistant metal anode, coated anode, and inert metal plated anode.
The electrolytic cathode is made of iron-containing materials, including iron and/or iron alloy and/or alloy steel and/or stainless steel.
Furthermore, the edge of the electrolytic cathode is fixedly surrounded with a plastic frame so as to facilitate the operation of stripping the electrodeposited copper.
The solid-liquid separation device is a material or a device capable of carrying out solid-liquid separation on a solid-liquid mixture. Specifically, the filter medium may be one or a combination of more than one of a filter cloth, a filter screen, a filter plate, a filter screen grid, a filter membrane, a filter paper, a plate and frame filter press, a wire-wound filter element type filter, a sand filter, a filter cloth type filter, and a rotary centrifugal dehydrator.
The inventor aims to solve the problem of high cost caused by the common copper electrolytic cathode and titanium electrolytic cathode in the existing alkaline etching waste liquid electrolytic recovery process, abandons the bias of the industry on the ferrous metal electrolytic cathode, and uses the ferrous metal electrolytic cathode. Because the iron, the iron alloy, the alloy steel and the stainless steel are cheap and easy to obtain, and the resistivity of the iron alloy is lower than that of the titanium material, if the iron-containing material is used as an electrolytic cathode used in the electrolytic process of the alkaline etching waste liquid, the material cost of electrolytic equipment can be effectively reduced, and the electrolytic electric energy can be saved. In order to solve the electrolysis negative pole of iron-containing material can be corroded in alkaline electrolyte and lead to having a small amount of iron to dissolve in electrolyte to form solid precipitate compound easily, influence the reuse's of alkaline etching waste liquid regeneration problem the utility model discloses an add solid-liquid separation equipment in the alkaline etching waste liquid electrolysis retrieval and utilization equipment, so that get rid of deposit and solid impurity in the electrolyte effectively, make even adopt iron-containing metal electrolysis negative pole, also enable to return to the use on the etching production line after the alkaline etching waste liquid electrolysis regeneration and can not influence the etching quality. Meanwhile, the inventor finds that the ferrous metal electrolytic cathode is easier to machine and polish, and if the ferrous metal is used as the electrolytic cathode after polishing and polishing the surface of the ferrous metal, the adverse effect caused by the current point discharge effect can be effectively reduced, so that the metallic copper deposited on the surface of the ferrous metal electrolytic cathode in the electrolytic process becomes compact and flat, is easy to strip, can reduce the labor intensity, and can be repeatedly polished for use.
The utility model discloses carry out following improvement, the electrolysis regeneration groove is provided with the divider, the divider is separated the electrolysis regeneration groove for electrolysis anode area and electrolysis negative pole district for electrolysis anode and electrolysis negative pole are located inside the electrolysis anode area respectively and inside the electrolysis negative pole district.
Further, the electrolytic cell partition comprises a filter cloth, a filter plate, a cation exchange membrane and a bipolar membrane.
Preferably, the electrolysis cell partition is a filter cloth. When the electrolyte contains alkaline etching waste liquid, the filter cloth can not only effectively pass positive ions, but also block oxygen in an electrolytic anode area, and the material use cost is low.
Further, when the electrolytic bath partition is arranged, the electrolytic power supply is a double-pulse power supply. When the utility model is provided with the electrolytic cell separator, the ammonium ions in the electrolytic anode area can pass along with the electric field force the electrolytic cell separator enters the electrolytic cathode area, which easily causes the precipitation of copper sludge in the electrolytic anode liquid due to the lack of ammonia. And the double-pulse power supply can reversely guide part of ammonium ions in the electrolytic catholyte back to the electrolytic anode area in the reverse-pole phase, thereby effectively avoiding the copper sludge precipitation and the waste of electric energy caused by the increase of the pressure of the electrolytic cell due to the lack of ammonia on the electrolytic anode.
Further, the electrolytic regeneration tank is provided with a liquid inlet and/or a liquid outlet and/or a stirring device, and the stirring device is a mechanical stirring device and/or a pump liquid flowing stirring device. The stirring device can effectively keep the uniformity of the electrolyte in the electrolytic regeneration tank. When the electrolytic regeneration tank is provided with the electrolytic tank separator which is divided into an electrolytic anode area and an electrolytic cathode area, the stirring device arranged in the electrolytic cathode area can also promote ammonia in the catholyte to smoothly escape so as to reduce the back corrosion of the catholyte on the metal copper precipitated on the electrolytic cathode.
The utility model discloses can further improve, alkaline etching waste liquid electrolysis retrieval and utilization equipment sets up the combination of negative pole lotion hold up tank or electrolyte hold up tank and negative pole lotion hold up tank. The electrolyte storage tank is used for temporarily storing and/or preparing the electrolyte of the electrolytic regeneration tank, and the cathode washing liquid storage tank is used for storing the cathode washing liquid for cleaning the electrolytic cathode.
More preferably, the electrolyte storage tank and/or the cathode wash storage tank are connected to the electrolytic regeneration tank by means of pipes and pumps and/or valves. When the electrolytic regeneration tank is provided with an electrolytic tank partition divided into an electrolytic anode area and an electrolytic cathode area, the electrolyte storage tank is connected with the electrolytic anode area and/or the electrolytic cathode area of the electrolytic regeneration tank through a pipeline and a pump and/or a valve, and/or the cathode washing liquid storage tank is connected with the electrolytic cathode area of the electrolytic regeneration tank through a pipeline and a pump and/or a valve.
The utility model can be further improved and is also provided with an etching regeneration liquid preparation groove. The etching regeneration liquid preparation tank is used for preparing and storing the etching regeneration liquid used on the alkaline etching production line, and the etching regeneration liquid is formed by mixing the electrolyte electrolyzed in the electrolysis regeneration tank with chemical raw materials and/or etching waste liquid.
Preferably, the etching regeneration liquid preparation tank is provided with a stirring device.
More preferably, the etching regeneration liquid preparation tank is respectively connected with the electrolytic regeneration tank and/or the alkaline etching production line through pipelines.
Further, the pipe is provided with a pump and/or a valve and/or a solid-liquid separation device and/or a flow controller. The flow controller is a variable frequency pump and/or a flow control pump valve.
Preferably, an etching waste liquid storage tank is provided for temporarily storing the etching waste liquid overflowing from the etching line.
The utility model discloses can also further do following improvement, still set up and detect the feeder. The detection batch feeder comprises a detection device, and the detection device comprises at least one of a timer, a specific gravity detector, a photoelectric colorimetric detector, an oxidation-reduction potential detector, a pH value detector, an acidimeter and a liquid level detector. The detection device is used for detecting the parameter values of the liquid in the electrolytic regeneration tank and/or the etching regeneration liquid preparation tank and/or the etching waste liquid storage tank and/or the etching production line, the detection feeder automatically adjusts the electrolytic current and/or controls the pump for adding the electrolytic replenishment liquid into the electrolytic regeneration tank according to the parameter result obtained by detecting the electrolyte in the electrolytic regeneration tank, adds the required chemical raw materials into the etching regeneration liquid preparation tank and/or adds the liquid in the etching regeneration liquid preparation tank into the electrolytic regeneration tank according to the parameter result obtained by detecting the liquid in the etching regeneration liquid preparation tank, controls the electrolytic current according to the parameter result obtained by detecting the liquid in the etching waste liquid storage tank, and controls the electrolytic current and/or controls the electrolytic current between the etching regeneration liquid preparation tank and the alkaline etching production line according to the parameter result obtained by detecting the liquid in the alkaline etching production line A flow controller. As for the detection device on the etching production line, the process parameter detector originally installed on the etching production line can be directly adopted, and the process parameter detector can also be additionally arranged.
Preferably, a cathode protection bath is provided for soaking the unused iron-containing cathode to prevent oxidation of its surface.
Further, a water-oil separator is provided. And separating oily substances in the etching waste liquid through a water-oil separator so as to ensure the normal production and use of the electrolytic regeneration system.
The utility model discloses further make following improvement, alkaline etching waste liquid electrolysis retrieval and utilization equipment still is equipped with gas pump drainage system device and/or tail gas absorption treatment tower, gas pump drainage system device is used for collecting the processing to the gas that the electrolysis in-process is escaped, the tail gas absorption treatment tower is used for absorbing electrolysis regeneration tank tail gas that escapes.
Furthermore, the tail gas absorption treatment tower can be a gas pipeline type spraying device and/or a gas absorption jet device, so that the tail gas in the production process can reach the emission standard.
Further, the tail gas absorption treatment tower is provided with a plurality of, connects gradually. When two or more tail gas absorption treatment towers are connected in series end to end for use, the tail gas absorption treatment can be more thorough.
The utility model discloses can also do following improvement, the electric conductor that electrolysis negative pole and electrolysis power negative pole are connected and/or the gas-liquid interface of electrolysis negative pole and/or the polar plate edge parcel of electrolysis negative pole have anticorrosive material to it is right to ensure to reduce under the good heat dissipation condition connect the corruption and increase of service life of the electric conductor of electrolysis negative pole and electrolysis power negative pole and/or electrolysis negative pole, and/or peel off the copper billet that goes out on the electrolysis negative pole better. The anticorrosive material is a substance with stable property in alkaline environment, and includes but is not limited to: titanium, platinum, gold, silver, plastic.
The utility model can also be improved as follows, and the electrolysis regeneration tank and/or the etching regeneration liquid preparation tank are provided with a cold-hot temperature exchanger. The temperature of the electrolyte can be effectively controlled and/or the temperature of the etching solution on the etching production line can be stabilized in a set working temperature range through the arrangement.
The utility model discloses can also further improve, electrolysis regeneration groove and etching regeneration liquid preparation groove are connected with the supplementary cistern respectively.
Compared with the prior art, the utility model, following beneficial effect has:
(1) the utility model discloses equipment of nature etching waste liquid electrolysis retrieval and utilization carries out solid-liquid separation to the electrolyte after alkaline etching waste liquid electrolytic treatment through setting up solid-liquid separation equipment, effectively gets rid of precipitate and solid impurity in the electrolyte for do not influence the etching quality when regeneration back electrolyte returns to the use on the etching production line.
(2) The utility model abandons the prejudice of the industry on the iron-containing metal electrolytic cathode, and adopts the iron-containing material as the electrolytic cathode, so that the use of noble metal can be reduced, and the manufacturing cost of equipment is saved; the iron-containing material is used as the electrolytic cathode, the surface of the electrolytic cathode plate is easy to process and polish, so that the electroanalysis copper layer can be more easily stripped, the labor intensity is reduced, in addition, the resistance of the iron-containing material is lower than that of the titanium material, and compared with the prior art that the titanium material is used as the electrolytic cathode, the electric energy can be saved.
Drawings
FIG. 1 is a schematic structural view of an alkaline etching waste liquid electrolyzing, recycling and regenerating apparatus according to embodiment 1 of the present invention;
FIG. 2 is a schematic structural view of an alkaline etching waste liquid electrolyzing, recycling and regenerating apparatus according to embodiment 2 of the present invention;
FIG. 3 is a schematic structural view of an apparatus for electrolyzing and recycling an alkaline etching waste liquid according to embodiment 3 of the present invention;
FIG. 4 is a schematic structural view of an alkaline etching waste liquid electrolyzing, recycling and regenerating apparatus according to embodiment 4 of the present invention;
FIG. 5 is a schematic structural view of an apparatus for electrolyzing and recycling an alkaline etching waste liquid according to embodiment 5 of the present invention;
FIG. 6 is a schematic structural view of an apparatus for electrolyzing and recycling an alkaline etching waste liquid according to embodiment 5 of the present invention;
reference numerals: 1-electrolytic regeneration tank; 2-an electrolytic anode; 3-an electrolytic cathode; 4-a power supply; 5-a solid-liquid separation device; 6-cell partition; 7-liquid inlet; 8-a liquid outlet; 9-a stirring device; 10-an electrolyte storage tank; 11-a cathode wash solution storage tank; 12-detecting a feeder; 13-a water-oil separator; 14-etching regeneration liquid preparation tank; 15-a flow controller; 16-gas pumping system means; 17-a tail gas absorption treatment tower; 18-a cold-hot temperature exchanger; 19-etching waste liquid storage tank; 20-a cathode protection tank; 21-a supplementary liquid tank; 22-etching production line; ^ turning to a valve; p-pump.
Detailed Description
The technical solutions of the present invention will be described in detail below with reference to specific embodiments so that those skilled in the art can better understand and implement the technical solutions.
Example 1
The electrolytic recycling equipment for the alkaline etching waste liquid shown in figure 1 comprises an electrolytic regeneration tank 1, an electrolytic anode 2, an electrolytic cathode 3, a power supply 4 and a solid-liquid separation device 5. The electrolytic anode 2 and the electrolytic cathode 3 are arranged in the electrolytic regeneration tank 1 and are respectively connected with the anode and the cathode of a power supply 4. The solid-liquid separation device 5 is used for performing solid-liquid separation on the electrolyte in the electrolytic regeneration tank 1 and is connected with the electrolytic regeneration tank 1 through a pipeline provided with a pump. The electrolytic anode 2 is graphite, and the electrolytic cathode 3 is stainless steel. The solid-liquid separation device 5 in this embodiment is a wire-wound filter element type filter.
Example 2
As shown in FIG. 2, the apparatus for electrolyzing and recycling an alkaline etching waste liquid is different from that of embodiment 1 in that it further comprises an electrolyte storage tank 10, a cathode washing liquid storage tank 11, a detection feeder 12, a,
An etching regeneration liquid preparation tank 14 and three tail gas absorption treatment towers 17. The electrolyte storage tank 10 is connected with the electrolytic regeneration tank 1 through a pipeline provided with a pump and is used for temporarily storing or blending the electrolyte in the electrolytic regeneration tank 1; the cathode washing liquid storage tank 11 is connected with the electrolytic regeneration tank 1 through a pipeline provided with a pump, and water is contained in the storage tank and used for cleaning the electrolytic cathode 3. The etching regeneration liquid preparation tank 14 and the electrolytic regeneration tank 1 are both provided with a cold-heat temperature exchanger 18, by which the temperature of the electrolyte is effectively controlled and/or the temperature of the etching liquid on the etching line 22 is stabilized in a set working temperature range. The three tail gas absorption treatment towers 17 are connected in series in sequence and are arranged above the notch of the electrolytic regeneration tank 1, wherein the first tail gas absorption treatment tower 17 is a gas pipeline type spraying device, and the second tail gas absorption treatment tower 17 and the third tail gas absorption treatment tower 17 are gas absorption jet devices. The absorption liquid of the gas pipeline type spraying device is etching regeneration liquid, and the absorption liquid groove body of the gas pipeline type spraying device for containing the absorption liquid is connected with the electrolytic regeneration groove 1 through a pipeline provided with a pump and a valve; the absorption liquid of the middle gas absorption jet device is a mixed liquid of water and alkaline etching liquid, and a groove body of the gas absorption jet device for containing the absorption liquid is connected with the etching production line 22 through a pipeline provided with a pump; the final absorption liquid of the gas absorption jet device is inorganic acid solution.
The electrolytic regeneration tank 1 is also provided with a stirring device 9, and the stirring device 9 is a pump liquid flowing type stirring device 9 in the embodiment; the detecting and feeding device 12 comprises a detecting device which is a specific gravity detector, a liquid level detector, an oxidation-reduction potential detector and a pH detector, detects the process parameter value of the electrolyte in the electrolytic regeneration tank 1 and adjusts the electrolytic current according to the detected result. In addition, in the present embodiment, the electrolytic anode 2 is a coated anode, and the electrolytic cathode 3 is iron.
Example 3
As shown in fig. 3, the difference of the apparatus for electrolyzing and recycling alkaline etching waste liquid from the embodiment 2 is that the electrolytic anode 2 is an anode plated with inert metal, and the electrolytic cathode 3 is alloy steel. The electrolytic regeneration tank 1 is provided with a liquid inlet 7 and a liquid outlet 8, an electrolytic tank separator 6, specifically a bipolar membrane, is arranged in the middle of the electrolytic regeneration tank 1 to divide the electrolytic regeneration tank 1 into an electrolytic anode 2 area and an electrolytic cathode 3 area, so that the electrolytic anode 2 and the electrolytic cathode 3 are respectively positioned in the electrolytic anode 2 area and the electrolytic cathode 3 area on both sides of the filter cloth. The electrolyte in the electrolysis anode 2 area is alkaline etching waste liquid, and the electrolyte in the electrolysis cathode 3 area is mixed liquid of the alkaline etching waste liquid, ammonia and ammonium salt. Accordingly, the power supply 4 is a double pulsed power supply.
The two solid-liquid separation devices 5 are respectively connected with the anode region and the cathode region of the electrolytic regeneration tank 1 through pipelines provided with pumps. Two replenishing liquid tanks 21 are also provided, one of which is connected to the electrolytic regeneration tank 1 through a pipe provided with a pump, and the other is connected to the etching regeneration liquid preparation tank 14 through a pipe provided with a pump. Two detection feeding devices 12 are arranged, wherein one detection feeding device 12 detects the technological parameter value of the electrolyte in the electrolytic regeneration tank 1, adjusts the electrolytic current according to the detected result and controls the pumping flow of the electrolyte supplementing liquid added to the electrolytic regeneration tank 1 by the supplementing liquid tank 21; another test batch feeder 12 pair etching
Detecting the parameter value of the liquid in the regenerated liquid preparation tank 14 and controlling the replenishing liquid tank 21 to add the required chemical raw materials into the etching regenerated liquid preparation tank 14 according to the measured result; in this embodiment, the cathode washing liquid storage tank 11 is independently arranged, and the cathode washing liquid therein is a mixed liquid of water and ammonia, alkaline etching waste liquid and alkaline etchant; the etching regeneration liquid preparation tank 14 is connected with the electrolytic regeneration tank 1 through a pipeline, and the pipeline is provided with a pump and a valve; the opening of the electrolytic regeneration tank 1 is provided with a gas pumping and exhausting system device 16 and a gas pipeline type spraying device, wherein the absorption liquid of the gas pipeline type spraying device is electrolyte, and the absorption liquid tank body containing the electrolyte is connected with an etching regeneration liquid preparation tank 14 through a pipeline; the etching regeneration liquid preparation tank 14 is provided with a cold/hot temperature exchanger 18.
Example 4
As shown in fig. 4, the difference between the apparatus for electrolyzing and recycling alkaline etching waste liquid and the embodiment 1 is that in this embodiment, the electrolysis anode 2 is an alkaline-resistant metal anode, and the electrolysis cathode 3 is an iron alloy. The electrolytic regeneration tank 1 is provided with a liquid inlet 7, a liquid outlet 8 and a mechanical stirring device 9. The electrolytic regeneration tank 1 is connected to a replenishing liquid tank 21 through a pipe provided with a pump. Three detection feeding devices 12 are arranged, wherein the first detection feeding device 12 detects the process parameter value of the electrolyte in the electrolytic regeneration tank 1 and controls the on-off of the pump of the replenishing liquid tank 21 for adding the electrolytic replenishing liquid to the electrolytic regeneration tank 1 according to the measured result.
The whole equipment is also provided with an electrolyte storage tank 10, a cathode washing liquid storage tank 11, a water-oil separator 13 and an etching regeneration liquid preparation tank 14.
Wherein, the etching regeneration liquid preparation tank 14 is connected with the liquid outlet 8 of the electrolytic regeneration tank 1 through a pipeline provided with a solid-liquid separation device 5, and is also connected with the alkaline etching production line 22 through a pipeline provided with a flow controller 15, and the flow controller 15 is a flow control pump valve. The etching regeneration liquid preparation tank 14 is provided with a stirring device 9 and is also connected with a replenishing liquid tank 21. The second detecting and feeding device 12 detects the parameter value of the liquid in the etching regeneration liquid preparation tank 14 and controls the replenishing liquid tank 21 to feed the required chemical raw materials into the etching regeneration liquid preparation tank 14 according to the measured result; the third detecting and feeding device 12 detects the parameter value of the liquid in the etching production line 22 and adjusts the flow controller 15 to feed the etching solution to the etching regeneration solution preparation tank 14 according to the detected result. The electrolyte storage tank 10, the cathode washing liquid storage tank 11 and the water-oil separator 13 are all independently arranged, and the water-oil separator 13 is used for separating oily substances in the etching waste liquid so as to ensure the normal production and use of the electrolytic regeneration system.
Example 5
As shown in fig. 5, the difference between the apparatus for electrolyzing and recycling alkaline etching waste liquid and the apparatus of embodiment 1 is that in this embodiment, the electrolysis anode 2 is an alkaline-resistant metal anode, and the electrolysis cathode 3 is an iron alloy. The electrolytic regeneration tank 1 is provided with an electrolytic tank separator 6, specifically a combination of a filter plate and a cation exchange membrane, the electrolytic regeneration tank 1 is divided into an electrolytic anode 2 area and an electrolytic cathode 3 area by the electrolytic tank separator 6, and the electrolyte in the electrolytic anode 2 area is a mixture of alkaline etching waste liquid and water
Combining the solution, wherein the electrolyte in the electrolytic cathode 3 area is a mixed solution of alkaline etching waste liquid, ammonia, ammonium salt and water; the solid-liquid separation device 5 is connected with the cathode region of the electrolytic regeneration tank 1 through a pipeline provided with a pump.
The whole equipment is also provided with two electrolyte storage tanks 10, a cathode washing liquid storage tank 11, a detection batch feeder 12, a cathode protection tank 20, two etching regeneration liquid preparation tanks 14 and an etching waste liquid storage tank 19. Wherein, the two electrolyte storage tanks 10 are respectively connected with the electrolysis anode region and the electrolysis cathode region through pipelines provided with pumping. The cathode washing liquid storage tank 11 is connected with the electrolytic cathode region through a pipeline provided with a pump and a valve, and the cathode washing liquid in the cathode washing liquid storage tank 11 is ammonia water. The cathode protection bath 20 contains an aqueous solution of a reducing agent for soaking the idle iron-containing cathode to prevent oxidation of the surface thereof. The etching waste liquid storage tank 19 is connected to the alkaline etching line 22 through a pipe. The detecting and feeding device 12 detects the parameter value of the liquid on the alkaline etching production line 22 and controls the electrolytic current according to the detected result.
Example 6
As shown in fig. 6, the difference between the apparatus for electrolyzing and recycling alkaline etching waste liquid and embodiment 1 is that in this embodiment, the electrolytic anode 2 is an alkaline-resistant metal anode, the electrolytic cathode 3 is an iron alloy, and the edge of the electrolytic cathode 3 is surrounded by an inherent plastic frame; the electrolytic regeneration tank 1 is provided with an electrolytic tank separator 6, specifically filter cloth, the electrolytic tank separator 6 divides the electrolytic regeneration tank 1 into an electrolytic anode 2 area and an electrolytic cathode 3 area, the electrolyte in the electrolytic anode 2 area is a mixed solution of alkaline etching waste liquid and water, and the electrolyte in the electrolytic cathode 3 area is a mixed solution of alkaline etching waste liquid, ammonia, ammonium salt and water. The solid-liquid separation device 5 is connected with the cathode region of the electrolytic regeneration tank 1 through a pipeline provided with a pump.
The whole equipment is also provided with an etching regeneration liquid preparation tank 14, a cathode washing liquid storage tank 11, a detection batch feeder 12, an etching waste liquid storage tank 19 and a cathode protection tank 20. The etching regeneration liquid preparation tank 14 is connected with the anode area of the electrolytic regeneration tank 1 through a pipeline provided with a pump, is connected with the alkaline etching production line 22 through a pipeline provided with a pump and a valve, and is also connected with the replenishing liquid tank 21 through a pipeline provided with a pump. The etching regeneration liquid preparation tank 14 is also provided with a stirring device 9, and the stirring device 9 adopts a mechanical stirring device 9. The etching waste liquid storage tank 19 is connected to the etching line 22 through a pipe. The cathode protection bath 20 contains an aqueous solution of a reducing agent for soaking the idle iron-containing cathode to prevent oxidation of the surface thereof. The detecting and feeding device 12 detects the parameter value of the liquid in the etching regeneration liquid preparation tank 14, controls the supplementary liquid tank 21 to add the pump of the required chemical raw material to the etching regeneration liquid preparation tank 14 according to the measured result, detects the parameter value of the liquid on the etching production line 22, controls the adding of the liquid in the etching regeneration liquid preparation tank 14 to the etching production line 22 and controls the electrolytic current according to the measured result, detects the parameter value of the liquid in the etching waste liquid storage tank 19 and controls the electrolytic current according to the measured result.
The method for electrolyzing and recycling the etching solution based on the alkaline etching waste liquid electrolyzing and recycling equipment comprises the following steps:
the electrolytic regeneration tank is filled with electrolyte, the electrolyte is started to be alkaline etching waste liquid or mixed solution of the alkaline etching waste liquid and additives, the mass concentration of copper ions of the electrolyte is equal to or lower than that of the alkaline etching waste liquid, the pH value of the alkaline etching waste liquid is 6.5-11.5, the additives are organic acid and/or reducing agent and/or ammonia and/or ammonium salt and/or alkaline etching sub-liquid and/or water, and the alkaline etching waste liquid and/or the alkaline etching waste liquid or the mixed solution of the alkaline etching waste liquid and the additives can be added into the electrolyte in the electrolytic process so as to enable the electrolytic operation to be continuously carried out. The organic acid can be used alone or in combination, and includes, but is not limited to, glycolic acid, benzoic acid, malic acid, citric acid, ascorbic acid, propionic acid, acetic acid, formic acid, lactic acid, sorbic acid, tartaric acid, lysine, glutamic acid, and salicylic acid. When organic acid is added into the alkaline etching waste liquid for electrolysis, the organic acid can be combined with free ammonia in the alkaline etching waste liquid, so that the pH value of the solution is reduced, and ammonia volatilization can be reduced. The reducing agent is a reducing substance capable of reacting with oxygen in the solution and consuming, and can be used singly or in combination of one or more, including but not limited to sulfite, thiosulfate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydrazine hydrate, oxalic acid or a salt thereof, formic acid or a salt thereof, citric acid or a salt thereof, glucose, vitamin C, tartaric acid, phosphite or hypophosphite. The reducing agent and the alkaline etching waste liquid are mixed to prepare the electrolyte, active oxygen in the electrolyte can be effectively controlled to be consumed, and the corrosion of copper precipitated from a cathode is reduced, so that the yield of electrolytic copper is improved. The ammonium salt can be used singly or in combination, and includes but is not limited to ammonium carbonate and ammonium bicarbonate. The ammonia may be ammonia gas and/or liquid ammonia and/or aqueous ammonia.
The mass concentration of the copper ions of the electrolyte is controlled to be lower than that of the alkaline etching solution, so that the attack and the return corrosion of the electrolyte to the electrolytic copper on the electrolytic cathode can be effectively reduced.
The main electrochemical reaction formula of the alkaline etching waste liquid electrolytic treatment process is as follows:
anode: h2O–e-→2H++1/2O2；
Cathode: cu2++e-→Cu+；
Cu++e-→Cu。
In the electrolytic process, along with the generation of copper metal and the breaking of the complex structure of the copper-ammonia complex, the concentrations of ammonium chloride and ammonia in the solution are higher and higher, and simultaneously, the oxygen content in the solution is gradually increased along with the generation of oxygen on the anode. Under the condition, the monovalent copper ammonia complex in the etching waste liquid can react with ammonium chloride, ammonia and oxygen dissolved in the etching waste liquid to regenerate divalent copper ammonia complex capable of reacting with the metal copper, and the metal copper obtained by electrolytic precipitation is corroded back, so that the precipitation efficiency of the metal copper on the cathode is low. The chemical reaction equation of the cupric ammine complex for corroding metallic copper is as follows:
divalent copper ammonia complex regeneration reaction: 2Cu (NH)3)2Cl+4NH4Cl+2NH3+1/2O2→
2Cu(NH)4Cl2+H2O
Back etching reaction: cu + Cu (NH)3)4Cl2→2Cu(NH3)2Cl；
And (3) total reaction: cu +2NH4Cl+2NH3+1/2O2→Cu(NH)4Cl2+H2O。
Therefore, reducing the concentration of copper ions in the electrolyte can reduce the amount of divalent copper ammonia complex that may be generated in the electrolyte, thereby improving copper extraction efficiency and protecting the electrolytic cathode of iron-containing materials.
The electrolytic regeneration tank is divided into an electrolytic anode area and an electrolytic cathode area by adopting an electrolytic tank partition, and the mass concentration of copper ions in the electrolyte of the electrolytic cathode area is lower than that of the electrolyte of the electrolytic anode area, so that oxygen generated in the electrolytic anode area can be effectively prevented from entering the electrolytic cathode area, the generation of a bivalent copper ammonia complex in the electrolytic cathode area is reduced, and the back corrosion of metal copper on the cathode is reduced, so that the electrolytic copper precipitation efficiency is improved.
When the electrolytic regeneration tank is provided with the electrolytic tank separator which is divided into an electrolytic anode area and an electrolytic cathode area, the electrolyte storage tank is used for temporarily storing the electrolyte of the electrolytic regeneration tank cathode area, and two electrolyte storage tanks with different storage objects can be arranged to be respectively used for temporarily storing the electrolyte of the electrolytic regeneration tank anode area and the electrolyte of the electrolytic regeneration tank cathode area so as to prevent the electrolytic tank separator from being subjected to overlarge pressure difference between two surfaces and shortening the service life when the electrolyte is extracted from the single-side tank area of the electrolytic regeneration tank.
Because the whole electrolytic cathode needs to be taken out of the electrolyte when the copper sheet or the copper plate is collected, a large amount of ammonia gas is usually brought out to volatilize in a workshop in the process, and the environment and the health of production personnel are seriously influenced. Therefore, before collecting the metallic copper generated on the electrolytic cathode, the electrolytic cathode is cooled, or the electrolyte in the area of the electrolytic cathode in the electrolytic regeneration tank is transferred out of the electrolytic regeneration tank, and the electrolytic cathode is cleaned in the area by adopting cathode cleaning solution, and then the electrolytic cathode is taken out of the electrolytic regeneration tank to strip and collect the metallic copper. Therefore, the ammonia gas brought by the electrolytic cathode in the copper taking process can be obviously reduced, and the pollution to the atmospheric environment is reduced. In the scheme of directly cooling the electrolytic cathode, the method can be completed by extracting part of electrolyte in the cell area where the electrolytic cathode is located in the electrolytic regeneration cell and adding cathode washing liquor in the cell area where the electrolytic cathode is located in the electrolytic regeneration cell, and can also be completed by mixing the electrolyte in the cell area where the electrolytic cathode is located in the electrolytic regeneration cell with the cathode washing liquor in the cathode washing liquor storage tank for cooling. In the scheme of transferring the electrolyte in the cell area where the electrolytic cathode is located in the electrolytic regeneration cell out of the electrolytic regeneration cell to clean the electrolytic cathode, after the cleaning of the electrolytic cathode is finished, the cathode cleaning solution can be transferred out of the electrolytic regeneration cell and injected into the electrolytic regeneration cell again, and the electrolytic operation is continued after the electrolytic cathode is installed. The used cathode washing liquid can be prepared into etching liquid and/or etching sub-liquid after supplementing required chemical raw materials according to the requirements of the etching process, and the etching liquid and/or the etching sub-liquid are reused in the etching production process.
When the etching regeneration liquid preparation tank is connected with an etching production line through a pipeline and a flow controller, the flow of the etching regeneration liquid in the pipeline enters the etching production line, and the flow control or the start and stop of the flow is carried out through the flow controller according to the specific gravity and/or the colorimetric and/or oxidation-reduction potential and/or the pH value process parameter signal value of the etching liquid on the etching production line, so as to keep the performance stability of the etching liquid on the etching production line. As for the parameter measurement of the etching solution on the etching production line, a process parameter detector originally installed on the etching production line can be directly adopted, and a process parameter detector can also be additionally arranged. In the etching process, besides the etching regeneration liquid, the etching replenishment liquid can be added to the etching production line according to the specific production process and the original etching production process method, so as to maintain the stability of the concentration of each component of the etching liquid.
The gas pumping and exhausting system device is used for collecting and treating gas escaping in the electrolysis process, and the tail gas absorption treatment tower is used for dissolving tail gas escaping from the electrolysis regeneration tank into absorption liquid in the tail gas absorption treatment tower. When two or more tail gas absorption treatment towers are connected in series end to end for use, the tail gas absorption treatment can be more thorough. The absorption liquid can be water and/or electrolyte and/or alkaline etching liquid and/or etching regeneration liquid, and also can be inorganic acid, and the absorption liquid after absorbing the tail gas can be prepared into etching liquid and/or etching sub-liquid after supplementing the required chemical raw materials and used in the etching production process.
The current of the electrolysis power supply is automatically adjusted according to the specific gravity and/or the colorimetric and/or oxidation-reduction potential and/or the pH value process parameter signal of the etching solution on the etching production line so as to balance and coordinate the work system balance of the etching section and the electrolysis section. The process parameter measurement of the etching solution on the etching production line can directly adopt the original process parameter detector on the etching production line, and can also be additionally provided with the parameter detector.
The conductor connecting the electrolytic cathode and the negative electrode of the electrolytic power supply and/or the gas-liquid interface of the electrolytic cathode and/or the edge of the polar plate of the electrolytic cathode are/is wrapped by an anticorrosive material, so that the corrosion to the conductor connecting the electrolytic cathode and the negative electrode of the electrolytic power supply and/or the electrolytic cathode is reduced under a good heat dissipation condition, the service life is prolonged, and/or a copper block electrically precipitated on the electrolytic cathode is better stripped; the anticorrosive material is a substance with stable property in alkaline environment, and includes but is not limited to: titanium, platinum, gold, silver, plastic.
The electrolyte storage tank is used for temporarily storing and/or preparing the electrolyte of the electrolytic regeneration tank, and the cathode washing liquid storage tank is used for storing the cathode washing liquid for cleaning the electrolytic cathode. The cathode washing solution can be water, a mixed solution of water and ammonia and/or alkaline etching waste liquid and/or alkaline etching sub-liquid, or an inorganic acid solution, wherein the inorganic acid includes, but is not limited to, inorganic compounds capable of ionizing in water to obtain hydrogen ions, such as hydrochloric acid, sulfuric acid, nitric acid, carbonic acid and the like. When the cathode wash is an alkaline etching waste liquid or a mixed liquid of the alkaline etching waste liquid and water and/or ammonia and/or an alkaline etchant, only the cathode wash storage tank may be provided.
When the electrolytic regeneration tank is provided with the electrolytic tank separator which is divided into an electrolytic anode area and an electrolytic cathode area, the electrolyte storage tank is used for temporarily storing the electrolyte in the electrolytic regeneration tank cathode area, and two electrolyte storage tanks with different storage objects can be arranged to be respectively used for temporarily storing the electrolyte in the electrolytic regeneration tank anode area and the electrolyte in the electrolytic regeneration tank cathode area so as to prevent the electrolytic tank separator from being subjected to overlarge pressure difference between two surfaces and shortening the service life when the electrolyte is extracted from the single-side tank area of the electrolytic regeneration tank.
The cathode protection tank is filled with aqueous solution of ammonia water and/or reducing agent and is used for soaking idle iron-containing cathodes to prevent the surfaces of the iron-containing cathodes from being oxidized; the reducing agent is one or more compounds effective in preventing oxidation of iron in water, including but not limited to sulfite, thiosulfate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydrazine hydrate, oxalic acid or its salt, formic acid or its salt, citric acid or its salt, and mixtures thereof,
Malic acid or its salt, lactic acid or its salt, glucose, vitamin C, tartaric acid, phosphite, and hypophosphite.
The above embodiments are only some of the embodiments of the present invention, but can not be taken as the limitation of the present invention, and any deformation and change based on the concept of the present invention all fall into the protection scope of the present invention, and the specific protection scope is subject to the description of the claims.
Claims (9)
1. The electrolytic recycling equipment for the alkaline etching waste liquid comprises an electrolytic regeneration tank, an electrolytic anode, an electrolytic cathode and a power supply, wherein the electrolytic anode and the electrolytic cathode are arranged in the electrolytic regeneration tank and are respectively connected with the anode and the cathode of the power supply.
2. The apparatus for the electrolytic recycling of alkaline etching waste liquid according to claim 1, wherein the solid-liquid separation device and the electrolytic regeneration tank are connected by a pipe provided with a pump and/or a valve.
3. The apparatus for recycling alkaline etching waste liquid by electrolysis according to claim 2, wherein said electrolytic anode is at least one selected from graphite, alkali-resistant metal anode, coated anode, and anode plated with inert metal.
4. The alkaline etching waste liquid electrolysis and recycling device according to claim 2, wherein the electrolysis cathode is an iron-containing material comprising iron and/or iron alloy and/or alloy steel and/or stainless steel.
5. The alkaline etching waste liquid electrolytic recycling apparatus according to any one of claims 1 to 4, characterized in that the electrolytic regeneration tank is provided with a partition dividing the electrolytic regeneration tank into an electrolytic anode region and an electrolytic cathode region such that the electrolytic anode and the electrolytic cathode are located inside the electrolytic anode region and inside the electrolytic cathode region, respectively.
6. The apparatus for recycling alkaline etching waste liquid by electrolysis according to claim 5, wherein the apparatus for recycling alkaline etching waste liquid by electrolysis is provided with a cathode washing liquid storage tank or a combination of an electrolyte storage tank and the cathode washing liquid storage tank; and the electrolyte storage tank and/or the cathode washing liquid storage tank are/is connected with the electrolytic regeneration tank through a pipeline and a pump and/or a valve.
7. The alkaline etching waste liquid electrolyzing and recycling apparatus as claimed in claim 5, further comprising an etching regeneration liquid preparing tank; the etching regeneration liquid preparation tank is respectively connected with the electrolytic regeneration tank and/or the alkaline etching production line through pipelines.
8. The apparatus for recycling alkaline etching waste liquid by electrolysis according to claim 5, further comprising a gas pumping and exhausting system device and/or a tail gas absorption and treatment tower, wherein the gas pumping and exhausting system device is used for collecting and treating gas escaping from the electrolysis process, and the tail gas absorption and treatment tower is used for absorbing tail gas escaping from the electrolytic regeneration tank.
9. The apparatus for recycling alkaline etching waste liquid by electrolysis according to claim 5, further comprising a detecting feeder, a cathode protection tank and a water-oil separator.
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| CN114855221A (en) * | 2022-04-18 | 2022-08-05 | 定颖电子(黄石)有限公司 | System and method for recovering copper-containing nitric acid waste liquid of circuit board |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114855221A (en) * | 2022-04-18 | 2022-08-05 | 定颖电子(黄石)有限公司 | System and method for recovering copper-containing nitric acid waste liquid of circuit board |
| CN114855221B (en) * | 2022-04-18 | 2023-12-01 | 超颖电子电路股份有限公司 | System and method for recovering copper-containing nitric acid waste liquid of circuit board |
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