CN111394726A - Acid etching solution recycling process - Google Patents

Acid etching solution recycling process Download PDF

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Publication number
CN111394726A
CN111394726A CN201910853156.7A CN201910853156A CN111394726A CN 111394726 A CN111394726 A CN 111394726A CN 201910853156 A CN201910853156 A CN 201910853156A CN 111394726 A CN111394726 A CN 111394726A
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China
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circulation
cathode
anode
area
etching
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CN201910853156.7A
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Chinese (zh)
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CN111394726B (en
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陈仁华
聂国勇
李建立
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Changsha Lijie Environmental Protection Technology Co ltd
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Changsha Lijie Environmental Protection Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/202—Single element halogens
    • B01D2257/2025—Chlorine

Abstract

The invention discloses a process for recycling acidic etching solution, which uses an acidic etching solution recycling system and comprises an etching line (4), an electrolytic tank (30), a circulating tank (20), a chlorine absorption and reuse tower (10), a mother liquor storage barrel (5) and a recycling solution storage barrel (6). The specific process steps are described in the specification. The process well realizes the on-line circulation and regeneration of the etching waste liquid through the arrangement of the system and the control of the process parameters of all parts in the system, has high automation degree, simple system operation and maintenance, does not influence the production in the installation and debugging, has zero emission and protects the environment.

Description

Acid etching solution recycling process
Technical Field
The invention relates to the technical field of etching, and particularly discloses a cyclic regeneration process of an acidic etching solution.
Background
Due to the higher and higher requirements on etching precision and the increasing year by year of environmental protection pressure, most PCB production enterprises select to use acidic or alkaline copper chloride etching solution to date. The main components of the acidic copper chloride etching solution are sodium chloride, HCl and copper chloride, and the main components of the alkaline copper chloride etching solution are ammonium chloride, ammonia water and copper chloride.
The acidic copper chloride etching solution has the characteristics of high etching rate, stability, easy control, regeneration and the like, and is generally applied to the current etching process of printed circuit boards. The acid etching solution can generate Cu + Cu in the process of etching the copper foil2+Reaction of → 2 CuCl. Cu in the etching solution along with the reaction2+The concentration of ions is reduced, and Cu+The concentration of ions increases and the etching capability decreases. When Cu2+After the ions are consumed to a certain extent, the etching capability of the etching solution cannot meet the production requirement and needs to be regenerated. The acidic etching solution regeneration mainly comprises a chemical regeneration method and an electrolytic regeneration method. Chemical regeneration methods such as a sodium chlorate oxidation method, a hydrogen peroxide regeneration method and the like need to add substances such as an oxidant and the like, and a part of acidic etching solution is discharged outwards finally, so that the environment is polluted, and a large amount of copper and acid are wasted. The electrolytic regeneration method is an on-line regeneration method, can realize continuous operation of etching work and etching solution regeneration in a system, namely, copper can be recovered by deposition at a cathode while the etching solution is regenerated at an anode, so that the copper increased in the etching process can be recovered, and extra income is increased for circuit board enterprises. However, the reported method for electrolytically treating the acidic copper chloride etching solution has the disadvantages that a large amount of harmful and dangerous gases such as chlorine, hydrogen and the like are separated out, the environment is polluted, and resources are wasted.
Many studies have been made on a recycling apparatus for acidic etching solution, for example: 201610646322.2 discloses a high copper content etching liquid regeneration circulation system, which comprises an etching line, a dissolution regeneration cylinder, and a filter, wherein the etching line is connected with the dissolution regeneration cylinder through a pipeline, a waste liquid lift pump is arranged on the pipeline, the dissolution regeneration cylinder is connected with the filter through a pipeline, the pipeline is provided with an etching liquid lift pump, and the filter is communicated with the etching line.
Chinese patent application publication No. CN104630825A discloses an "acidic etching solution electrolysis copper extraction device and process thereof", which can cyclically extract copper from an etching solution for multiple times and recycle the etching solution, and has high efficiency of extracting copper by multiple electrolysis and high recycling rate of the etching solution, and solves the problems of high energy consumption and low recycling rate of the prior art in the acidic etching solution electrolysis copper extraction, thereby not only improving the quality of cathode copper, but also reducing material waste and improving the recycling rate. However, the device still has large energy consumption due to practical multiple-time copper extraction by electrolysis, and the multiple-time copper extraction by electrolysis also can generate more chlorine, so that the risk of environmental pollution is increased, and along with the increase of the electrolysis times, the concentration of copper ions in subsequent electrolyte is lower and lower, the timely electrolysis power is increased, the amount of separated pure copper is very rare, and the great effort is often caused.
Disclosure of Invention
In order to solve the technical problems in the background technology, the invention provides a cyclic regeneration process of an acidic etching solution. The process well realizes the on-line circulation and regeneration of the etching waste liquid by the arrangement of the system and the control of the process parameters of all parts in the system, is directly connected with an etching line, has simple system operation and maintenance, does not influence the production in installation and debugging, has zero emission and protects the environment.
A cyclic regeneration method of an acidic etching solution uses a cyclic regeneration system of the acidic etching solution, wherein the cyclic regeneration system of the acidic etching solution comprises an etching line, an electrolytic cell, a circulation cell, a chlorine absorption and reuse tower, a mother solution storage barrel and a regenerated solution storage barrel; an anode region and a cathode region are arranged in the electrolytic cell; the circulating tank comprises a tank body, the bottom of the tank body is divided into an anode circulating area, an etching circulating area and a cathode circulating area through a partition plate, and the etching circulating area is communicated with the top of the anode circulating area; the anode area of the electrolytic cell is respectively communicated with the anode circulation area and the etching circulation area of the circulation cell; the cathode area of the electrolytic cell is communicated with the cathode circulation area; the anode area and the cathode area of the electrolytic cell, the etching circulation area and the cathode circulation area of the circulation cell are communicated with the chlorine absorption and reuse tower; the chlorine absorption and reuse tower is communicated with an anode circulation area of the circulation tank; the mother liquid storage barrel is communicated with the anode circulation area, the etching circulation area and the cathode circulation area; the regeneration liquid storage barrel is communicated with the anode circulation area and the cathode circulation area; the anode circulation area of the circulation tank is communicated with an etching line, and the etching line is communicated with the etching circulation area of the circulation tank;
the method comprises the following steps:
step 1: acid etching waste liquid after the acid etching line is etched is pumped to an anode circulating area of a circulating tank, and the anode circulating area of the circulating tank is connected with a mother liquid storage barrel; the mother solution storage barrel stores the solution discharged from the etching circulation zone;
step 2: the etching waste liquid in the anode circulation zone is pumped to an anode zone of the electrolytic cell and then overflows back to an etching circulation zone of the circulation cell, the anode circulation zone of the circulation cell is communicated with the top of the etching circulation zone, the anode circulation zone is connected with a regenerated liquid storage barrel, regenerated liquid is added to the anode circulation zone through a second specific gravity device, meanwhile, the current of the electrolytic cell is controlled by detecting the ORP value of liquid medicine in the etching circulation zone through an ORP detector, and when the liquid level is too high, the liquid medicine is automatically discharged from the etching circulation zone to a mother liquid storage barrel through a liquid level monitoring controller in the etching circulation zone; the regeneration liquid is a solution discharged from a cathode circulation area of the circulation tank;
and step 3: the etching solution in the adjusted etching circulation area is pumped back to the etching production line;
and 4, step 4: the cathode liquid in the cathode circulating area is pumped to the cathode area of the electrolytic bath and then overflows back to the cathode circulating area of the circulating bath;
and 5: the cathode circulation area is connected with a mother liquor storage barrel, and mother liquor is added to the cathode circulation area through a first specific gravity detector to complete the addition of copper ions; the cathode circulation area is connected with a regenerated liquid storage barrel, and regenerated liquid is automatically added to the cathode electrode circulation area or discharged from the cathode circulation area to the regenerated liquid storage barrel through a liquid level controller of the auxiliary tank of the cathode circulation area;
step 6: hydrochloric acid gas of the circulating tank and the electrolytic tank passes through the chlorine absorption and reuse tower to react with etching waste liquid flowing in the cathode circulating area in the chlorine absorption and reuse tower, cuprous ions are oxidized into copper ions by chlorine to be regenerated and then flow back to the anode circulating area, and Cu is obtained+→Cu2++e-。
In a preferred scheme, the specific process control parameters comprise:
controlling the chlorine ions in the etching production line to be 260-300 g/L, controlling the copper ions to be 110-155 g/L and controlling the acidity to be 1.0-3.0 mol/L;
controlling the chloride ions in an anode circulation zone of the circulation tank to be 260-300 g/L, controlling the copper ions to be 110-155 g/L, controlling the acidity to be 1.0-3.0 mol/L and controlling the specific gravity to be 1.250-1.310;
the ORP value of an etching circulation area of the circulation tank is controlled to be 300-600 mV, and the current density of the electrolytic tank 3 is correspondingly controlled to be 0-9000 mA/dm 2;
controlling the chloride ions in a cathode circulation zone of the circulation tank to be 260-300 g/L, controlling the copper ions to be 20-100 g/L, controlling the acidity to be 1.5-4 mol/L, controlling the specific gravity to be 1.190-1.240 and controlling the temperature to be 35-52 ℃;
and controlling the ORP value in the chlorine absorption and reuse tower to be 450-550 mV.
Preferably, in order to level the deposited copper on the cathode titanium plate of the electrolytic cell, a leveling agent is added into a circulating zone of the cathode of the circulating cell, wherein the leveling agent is polyethylene glycol with the mass concentration of 1-3 per mill, and the polyethylene glycol is at least one of 200-20000 in a polyethylene glycol series.
In a preferable scheme, the etching device further comprises a hydrochloric acid storage barrel, wherein the hydrochloric acid storage barrel is communicated with the etching line; when the acidity of the etching solution for etching the line is low, hydrochloric acid is automatically added into the etching solution from a hydrochloric acid storage tank.
Preferably, a cooling water pipe is arranged in the cathode circulation area, the temperature of the regenerated liquid in the cathode circulation area of the circulation tank is controlled by a temperature controller, and the temperature is controlled to be 35-52 ℃.
The electrolytic tank comprises a tank body, a cover plate covered with the tank body and a cathode plate arranged in the tank body, wherein at least one anode film frame is arranged in the tank body to form a separated anode area and a separated cathode area; the anode membrane frame comprises an ionic membrane and a frame body, an anode membrane frame overflow port is arranged at the top of the frame body, the bottom and the left and right edges of the frame body are sealed, the ionic membrane is arranged on the front side and the back side of the frame body respectively, a protective membrane is arranged on the outer side of the ionic membrane respectively, a fixed baffle is arranged on the outer side of the protective membrane respectively, and the ionic membrane, the protective membrane and the fixed baffle are sequentially fixed on the two side faces of the frame body to form a closed cavity. An anode plate is arranged in the cavity of the anode film frame. The anode area and the cathode area in the electrolytic cell are completely separated, so that the etching solution can be recycled, and the electrolytic film can be better protected from being damaged by arranging the protective film.
The preferable scheme and the establishment of a circulating system on the electrolytic cell are convenient for the cyclic regeneration and utilization of the etching solution, and specifically comprise the following steps: an anode overflow groove and a cathode overflow groove are arranged on the groove wall of the groove body; the side wall of the tank body is provided with an anode region water inlet pipe, the anode region water inlet pipe is connected with a plurality of branch pipes, each branch pipe is provided with an anode film frame water inlet pipe regulating valve, the anode film frame water inlet pipe regulating valve is connected with an anode film frame water inlet pipe, and the anode film frame water inlet pipe extends into the bottom of one side of the cathode film frame; an anode membrane frame overflow port is arranged on one side of the top of the anode membrane frame and is communicated with an anode overflow tank and an anode overflow tank interface;
the cathode overflow groove is characterized in that a cathode water inlet pipe valve is arranged at the bottom of the groove body and is communicated with a cathode region water inlet pipe, a plurality of branch cathode region circulating spray pipes are connected to the cathode region water inlet pipe, spray holes are formed in the cathode region circulating spray pipes in the direction of the groove bottom, the cathode region circulating spray pipes are communicated with a cathode region, a cathode overflow port is arranged at the top of the cathode region, and the cathode overflow port is communicated with a cathode overflow groove and a cathode overflow groove connector.
Preferably, the side wall of the top of the tank body is provided with a waste gas communication hole, and the waste gas communication hole is communicated with a waste gas pipe and a waste gas discharge connecting port.
Preferably, the bottom of the tank body is provided with a support frame for placing an anode film frame and a cathode plate.
Preferably, a plurality of anode film frames and cathode plates are alternately arranged in the tank body.
Preferably, the thickness of the protective film is 0.5-1.5 mm, and the protective film is a protective film with the pore density of 200-800 meshes.
Preferably, the cathode plate is a titanium plate.
Preferably, the ionic membrane is a heterogeneous cation exchange membrane.
In a preferred scheme, the protective film comprises strong acid resistant materials such as a polypropylene film, a polyester film and a polytetrafluoroethylene film, and can well protect the ionic membrane from being damaged.
Preferably, the fixed baffle is in a grid shape.
The anode area and the cathode area in the electrolytic cell are completely separated, and the establishment of a circulating system on the electrolytic cell is convenient for the cyclic regeneration and utilization of the etching solution, and the electrolytic film can be better protected.
The circulating tank comprises a tank body, the bottom of the tank body is divided into an anode circulating area, an etching circulating area and a cathode circulating area through a partition plate, and the etching circulating area is communicated with the top of the anode circulating area; the cathode circulating area is divided into a cathode circulating area main tank and a cathode circulating area auxiliary tank; exhaust pipes are respectively arranged at the tops of the anode circulation zone and the cathode circulation zone, and a plurality of liquid inlet pipes and liquid outlet pipes are respectively arranged on the side walls of the anode circulation zone, the etching circulation zone and the cathode circulation zone and used for circulating with external equipment; liquid level controllers are respectively arranged in the anode circulation area, the etching circulation area and the cathode circulation area, and the anode circulation area is provided with a specific gravity detector; the etching circulation zone is provided with an ORP detector, and a cooling pipe and a temperature detector are arranged in the cathode circulation zone.
Preferably, the partition plates of the anode circulation zone and the etching circulation zone are provided with a plurality of communication holes, so that when the flow rates of the whole circulation system are inconsistent, the liquid in the cathode circulation zone and the etching circulation zone can flow through the communication holes, and the liquid level is kept consistent. Further preferably, the height of the communicating hole is 150-200mm from the bottom of the groove body.
In the preferred scheme, the tops of the anode circulating area, the etching circulating area and the cathode circulating area are respectively provided with an observation window, so that the specific conditions in the circulating tank can be observed conveniently, and the observation windows are covered by glass cover plates.
Preferably, pressure relief pipes are respectively arranged on the side walls of the anode circulation area, the etching circulation area and the cathode circulation area, and are used for pressure relief when the pressure of a pipeline is overlarge.
And specific gravity sampling boxes are arranged on the anode circulation area main tank and the cathode circulation area main tank and are used for sampling.
And a cooling pipe is arranged in the cathode circulating area and used for cooling the liquid temperature in the cathode circulating area. And a temperature controller is arranged in the cathode circulating area.
The circulating tank is used as an important part in the acid etching solution circulating and regenerating system, is mainly used for connection and circulation, and can well circulate and regenerate the acid etching solution. The circulation tank is simple in structure, and stores and circulates a plurality of circulating liquids in a partitioning manner.
The chlorine absorption and reuse tower comprises a tower body, and the tower body comprises a chlorine absorption chamber and a main groove communicated with the bottom of the chlorine absorption chamber; the top of the chlorine absorption chamber is provided with a purified gas discharge port, a fog absorption filler layer is arranged inside the top of the chlorine absorption chamber, at least one layer of spray pipe is arranged below the fog absorption filler layer, at least one atomizer is arranged below the spray pipe, and a multi-surface ball layer is arranged at the lower end of the atomizer; the chlorine gas absorption device is characterized in that a chlorine gas air inlet is formed in one side of the upper end of the main groove, an overflow port is formed in the middle of the surface of the main groove, an etching liquid water inlet and outlet is formed in the lower end of the surface of the main groove, a circulating pump is arranged at the lower end of one side of the main groove, and the top of the circulating pump is communicated with a spraying pipe of the chlorine gas absorption chamber.
The electrolytic cell is characterized in that exhaust pipes are arranged on the anode area and the cathode area of the electrolytic cell and are communicated with a chlorine gas inlet of the chlorine gas absorption and recycling tower, the cathode area of the circulating cell is communicated with an etching liquid water inlet and outlet of the chlorine gas absorption and recycling tower through a pipeline, and an overflow port of the chlorine gas absorption and recycling tower is communicated with the anode area of the circulating cell through a pipeline to form reflux.
In a preferable scheme, the chlorine absorption chamber is provided with at least one observation window, so that the internal condition is convenient to observe, and the placement and the maintenance of the multi-surface ball are also convenient.
In a preferable scheme, a cooling pipeline is arranged in the main tank and communicated with an external refrigerating device, so that the temperatures of the etching solution and the chlorine gas can be reduced, and the absorption of the chlorine gas is facilitated.
Preferably, the bottom of the chlorine absorption chamber and the top of the connected main groove are provided with communication holes.
Preferably, an ORP detector is arranged in the main tank, and ORP data of the etching solution are monitored at any time.
Preferably, the absorption filter material in the mist absorption filler layer is multilayer.
The chlorine absorption and reuse tower can recycle chlorine, and can oxidize monovalent copper ions in the etching solution into divalent copper ions for cyclic regeneration.
In general, the acid etching solution recycling process provided by the invention has the following advantages:
(1) the ORP value of the electrolytic etching solution is detected and controlled in real time, the generation of chlorine is effectively controlled, monovalent copper ions are changed into divalent copper ions, the etching capacity is recovered, the production is completely returned, the closed-loop online circulation of the acidic etching solution is realized, the etching solution is recovered and reused in percentage, the purpose of zero emission is achieved, an oxidant used for production is cancelled, production materials are saved, the production cost is reduced, the emission of pollutants is greatly reduced, and the clean production is realized.
(2) The electrolytic bath with completely separated cathode area and anode area has high electrolytic efficiency and can protect the ion film.
(3) The chlorine gas recycling tower directly absorbs and utilizes chlorine gas or hydrochloric acid gas completely, and monovalent copper ions in the etching solution can be oxidized into divalent copper ions for recycling.
(4) The arrangement of the circulating tank can well circulate and regenerate the etching solution.
The process well realizes the on-line circulation and regeneration of the etching waste liquid through the arrangement of the system and the control of the process parameters of all parts in the system, has high automation degree, simple system operation and maintenance, does not influence the production in the installation and debugging, has zero emission and protects the environment.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a recycling system for acidic etching solution according to the present invention;
FIG. 2 is a schematic perspective view of an electrolytic cell according to the present invention;
FIG. 3 is a schematic perspective view of an electrolytic cell according to the present invention;
FIG. 4 is a schematic view of the internal structure of the electrolytic cell of the present invention;
FIG. 5 is a schematic side plan view (side view) of the electrolytic cell of the present invention;
FIG. 6 is a schematic view (top view) of the internal plan structure of the electrolytic cell of the present invention;
FIG. 7 is a schematic view of the overall structure of an anode membrane frame of the electrolytic cell;
FIG. 8 is a schematic view of an anode film frame of the electrolytic cell;
FIG. 9 is an enlarged view of FIG. 7 at 344;
FIG. 10 is a schematic view of the overall structure of the circulation tank according to the present invention;
FIG. 11 is a plan view of the inner structure of the circulation tank according to the present invention;
FIG. 12 is a schematic cross-sectional view of the inside A-A' of the anode circulation region inside the circulation tank according to the present invention;
FIG. 13 is a schematic cross-sectional view of the inside B-B' of the anode circulation region inside the circulation tank according to the present invention;
FIG. 14 is a schematic structural view of a chlorine absorption and recovery tower according to the present invention;
FIG. 15 is a diagram illustrating a specific control process of a recycling process of acidic etchant in an embodiment of the present invention;
in the figure: 1-a cleaning tank, 2-an anti-oxidation tank, 3-a hydrochloric acid storage barrel, 4-an etching line, 5-a mother liquid storage barrel, 6-a regenerated liquid storage barrel, 7-a waste gas absorption tower, 10-a chlorine gas absorption and reuse tower, 20-a circulation tank, 30-an electrolytic tank and 120-a chlorine gas absorption chamber; 121-a purified gas discharge port, 122-a mist absorption filler, 123-an atomizer, 124-an observation window, 125-a chlorine gas inlet, 126-an overflow port, 127-an etching solution water inlet and outlet, 128-a polyhedral ball, 129-a circulating pump, 130-a main tank, 131-a cooling pipeline, 132-an ORP detector, 133-a spray pipe, 201-a trough body of an electrolytic tank, 202-an anode overflow pipe, 203-a cathode overflow pipe, 204-a mother solution adding pipe, 205-a cathode circulating pump connecting pipe, 206-a cathode circulating pump pressure relief pipe, 207-a waste gas exhaust pipe, 207' -a second waste gas exhaust pipe, 208-a cathode area cooling pipe, 209-a regeneration liquid discharge pump connecting pipe, 210-a regeneration liquid discharge pump pressure relief pipe, 211-a regeneration liquid adding pipe, a regeneration liquid discharge pipe, 212-etching circulation pump connecting pipe, 213-etching liquid circulation pump pressure relief pipe, 214-mother liquid discharge pump connecting pipe, 215-mother liquid standby pump connecting pipe, 216-mother liquid discharge pump pressure relief pipe, 217-mother liquid standby pump pressure relief pipe, 218-regeneration liquid adding pipe, 219-mother liquid adding pipe, 220-anode circulation pump connecting pipe, 221-etching waste liquid collecting pump water inlet pipe, 222-anode circulation pump pressure relief pipe, 223-anode circulation zone liquid level controller, 224-first specific gravity sampling box, 225-ORP detector, 226-second specific gravity sampling box, 227-glass cover plate, 228-cathode circulation zone auxiliary groove liquid level controller, 229-anode circulation zone, 230-etching circulation zone, 231-cathode circulation zone, 232-cathode circulation zone auxiliary groove, 233-etching circulation area liquid level controller, 234-clapboard, 235-communication hole, 236-temperature detector, 237-cooling pipe, 238-cathode circulation area main tank, 301-anode area, 302-cathode area, 303-tank body of circulation tank, 304-cover plate, 310-anode area water inlet pipe, 311-anode film frame water inlet pipe regulating valve, 312-anode film frame water inlet pipe, 313-anode film frame, 314-anode film frame overflow port, 315-anode overflow tank, 316-anode overflow tank interface, 317-anode copper bar, 318-anode plate, 319-support frame, 320-cathode water inlet pipe valve, 321-cathode area circulation spray pipe, 322-cathode area, 323-cathode area overflow port, 324-cathode overflow tank, 325-cathode overflow tank interface, 326-cathode copper bar, 327-cathode plate, 328-cathode area seabed evacuation communication hole, 329-seabed evacuation groove, 330-cathode area seabed evacuation connecting pipe valve, 331-anode area water inlet pipe, 341-waste gas communication hole, 342-waste gas pipe, 343-waste gas discharge connecting port, 344-anode film frame overflow port schematic area, 345-frame body, 346-ionic membrane, 347-protective membrane, 348-fixed baffle, 349-titanium screw and 350 anode film frame overflow port.
Detailed Description
The invention will be further explained and explained with reference to the drawings and examples
Example 1
As shown in fig. 1, the acidic etching solution recycling system comprises an etching line 4 and an electrolytic cell 30, and is characterized by further comprising a recycling tank 20, a chlorine absorption and reuse tower 10, a mother liquor storage tank 5 and a recycling solution storage tank 6;
an anode region 301 and a cathode region 302 are arranged in the electrolytic cell 30;
the circulation tank 20 comprises a tank body, the bottom of the tank body is divided into an anode circulation area 229, an etching circulation area 230 and a cathode circulation area 231 through a partition plate, wherein the etching circulation area 230 is communicated with the top of the anode circulation area 229;
the anode area 301 of the electrolytic cell is respectively communicated with the anode circulation area 229 and the etching circulation area 230 of the circulation cell; the cathode area 302 of the electrolytic cell is communicated with the cathode circulation area 231; the anode area 301 and the cathode area 302 of the electrolytic cell, and the etching circulation area 230 and the cathode circulation area 231 of the circulation cell 20 are communicated with the chlorine absorption and reuse tower 10; the chlorine absorption and reuse tower 10 is communicated with the anode circulation area 229 of the circulation tank 20;
the mother liquid reserve tank 5 is in communication with an anode circulation zone 229, an etching circulation zone 230, and a cathode circulation zone 231;
the regeneration liquid reserve tank 6 is communicated with an anode circulation zone 229 and a cathode circulation zone 230;
the anode circulation region 229 of the circulation tank is in communication with the etch line 4 and the etch line 4 is in communication with the etch circulation region 230 of the circulation tank.
The copper obtained by the electrolysis of the electrolytic cell enters a cleaning tank 1 for cleaning and then enters an anti-oxidation tank 2 for anti-oxidation treatment.
The etching device also comprises a hydrochloric acid storage barrel 3, wherein the hydrochloric acid storage barrel 3 is communicated with the etching line 4.
The device also comprises a waste gas absorption tower 7 which is communicated with a chlorine absorption and reuse tower 10.
The specific structure of the sub-component electrolytic cell can be shown in figures 2 to 9:
at least one anode film frame 313 is arranged in the electrolytic tank 30, so that the electrolytic tank is formed into a separated anode area and a separated cathode area; the anode membrane frame 313 comprises an ion membrane 346 and a frame 345, an anode membrane frame overflow port 314 is arranged at the top of the frame 345, the bottom and the left and right edges of the frame 345 are sealed, ion membranes 346 are respectively arranged on the front side and the back side of the frame 345, protective membranes 347 are respectively arranged on the outer sides of the ion membranes 346, fixed baffles 348 are respectively arranged on the outer sides of the protective membranes 347, and the ion membranes 346, the protective membranes 347 and the fixed baffles 348 are sequentially fixed on the two side surfaces of the frame 345 to form a closed cavity; an anode plate 318 is arranged in the cavity of the anode film frame 313, a cathode plate is arranged outside the cavity of the anode film frame 313, and an electrolytic tank exhaust pipe is arranged at the top of the electrolytic tank 30.
Detailed internal structure of the cell:
an anode overflow groove 315 and a cathode overflow groove 324 are arranged on the groove wall of the electrolytic tank 30;
an anode region water inlet pipe 310 is arranged on the side wall of the electrolytic cell body 303, a plurality of branch pipes are connected to the anode region water inlet pipe 310, an anode film frame water inlet pipe regulating valve 311 is installed on each branch pipe, the anode film frame water inlet pipe regulating valve 311 is connected to an anode film frame water inlet pipe 312, and the anode film frame water inlet pipe 312 extends into the bottom of one side of an anode film frame 313; an anode membrane frame overflow port 314 is arranged on one side of the top of the anode membrane frame 313, and the anode membrane frame overflow port 314 is communicated with an anode overflow groove 315 and an anode overflow groove interface 316;
the bottom of the electrolytic cell body 303 is provided with a cathode water inlet pipe valve 320, the cathode water inlet pipe valve 320 is communicated with a cathode region water inlet pipe 331, the cathode region water inlet pipe 331 is connected with a plurality of cathode region circulating spray pipes 321, the cathode region circulating spray pipes 321 are provided with spray holes towards the direction of the cell bottom, the cathode region circulating spray pipes 321 are communicated with the cathode region 302, the top of the cathode region 302 is provided with a cathode overflow port 323, and the cathode overflow port 323 is communicated with a cathode overflow groove 324 and a cathode overflow groove interface 325.
The side wall of the top of the electrolytic cell body 303 is provided with a waste gas communication hole 341, and the waste gas communication hole 341 is communicated with a waste gas pipe 342 and a waste gas discharge connecting port 343.
A support frame 319 is arranged at the bottom of the electrolytic cell body 303.
For the subcomponent circulating slot, the specific structure can be as shown in fig. 10 to 13:
the cathode circulation zone 231 of the circulation tank 20 is divided into a cathode circulation zone main tank and a cathode circulation zone auxiliary tank 232; circulation groove exhaust pipes are respectively arranged at the tops of the anode circulation area 229 and the cathode circulation area, and a plurality of liquid inlet pipes and liquid outlet pipes are respectively arranged on the side walls of the anode circulation area 229, the etching circulation area 230 and the cathode circulation area and are used for being communicated with external equipment; liquid level controllers are respectively arranged in the anode circulation area 229, the etching circulation area 230 and the cathode circulation area, and specific gravity sampling boxes are arranged on the anode circulation area 229 and the cathode circulation area main tank; the etch cycle zone 230 is provided with an ORP detector 225, and within the cathode cycle zone is disposed a cooling tube 237 and a temperature detector 236.
The anode circulation region 229 and the etching circulation region 230 are provided with a plurality of communication holes on the partition board, so that when the flow rate of the whole circulation system is inconsistent, the liquid in the cathode circulation region and the etching circulation region can flow through the communication holes, and the liquid level is kept consistent. And the top of the anode circulating area 229, the top of the etching circulating area 230 and the top of the cathode circulating area are respectively provided with an observation window, so that the specific conditions in the circulating tank can be observed conveniently, and the observation windows are covered by glass cover plates. And pressure relief pipes are respectively arranged on the side walls of the anode circulation area 229, the etching circulation area 230 and the cathode circulation area, and are used for relieving pressure when the pressure of the circulation pump is overlarge. The circulation tank 220 further includes a specific gravity detector, a pipeline respectively disposed in the anode circulation region 229 and the cathode circulation region 231 for controlling the communication between the mother liquid storage tank 5 and the cathode circulation region 213, and a pipeline for communicating the regeneration liquid storage tank 6 with the etching circulation region 212.
For the subcomponent chlorine gas absorption and reuse tower, the specific structure can be as shown in fig. 14:
the chlorine absorption and reuse tower 10 comprises a tower body comprising a chlorine absorption chamber 120 and a main tank 130 communicated with the bottom of the chlorine absorption chamber 120; a purified gas discharge port 121 is formed in the top of the chlorine absorption chamber 120, a mist absorption filler layer (the internal substance is the mist absorption filler 122) is arranged inside the top end of the chlorine absorption chamber 120, at least one spray pipe 133 is arranged below the mist absorption filler layer, at least one atomizer 123 is arranged below the spray pipe 133, and a multi-surface spherical layer is arranged at the lower end of the atomizer 123; a chlorine gas inlet 125 is formed in one side of the upper end of the main tank 130, an overflow port 126 is formed in the middle of the surface of the main tank 130, an etching liquid inlet and outlet 127 is formed in the lower end of the surface of the main tank 130, a circulating pump 129 is formed in the lower end of one side of the main tank 310, and the top of the circulating pump 129 is communicated with the spraying pipe 133 of the chlorine gas absorption chamber 120.
The waste gas discharge connecting port 343 of the electrolytic cell, the etching circulation zone 230 and the cathode circulation zone 231 of the circulation cell are all communicated with the chlorine gas inlet 125 of the chlorine gas absorption and reuse tower through pipelines, the cathode circulation zone 231 of the circulation cell is communicated with the etching solution inlet and outlet 127 of the chlorine gas absorption and reuse tower through a pipeline, and the overflow port 126 of the chlorine gas absorption and reuse tower is communicated with the anode zone 229 of the circulation cell through a pipeline to form reflux.
Example 2
Further description of the structure and connection relationship of the acid etching solution circulation regeneration system:
the waste etching line 4 flows from the waste etching liquid collecting pump water inlet pipe 221 to the anode circulating area 229, the waste etching liquid in the anode circulating area 229 is connected to the electrolytic tank anode area water inlet pipe 310 through the anode circulating pump connecting pipe 220, (an anode circulating pump is arranged on the anode circulating pump connecting pipe 220, in order to prevent the anode circulating pump from being too high in pressure, a three-way valve is arranged on a pipeline connecting the anode circulating pump and the electrolytic tank anode area water inlet pipe 310, the three-way valve is communicated with the anode circulating pump pressure relief pipe 222 through a pipeline), and then the waste etching line flows back to the etching circulating area 230 from the electrolytic tank anode overflow pipe 202. The etching solution in the etching circulation area 230 returns to the etching line 4 through the etching circulation pump connection pipe 212, wherein the etching circulation pump is arranged on the etching circulation pump connection pipe 212, and a three-way valve is arranged on a connection pipeline between the etching circulation pump and the etching circulation line 4 in order to prevent the etching circulation pump from having too high pressure, and the three-way valve is communicated with the etching circulation pump pressure relief pipe 213 through a pipeline. The liquid level of the liquid medicine in the anode circulation area 229 is controlled by an anode circulation area liquid level controller 223, when the liquid level is lower than a set value, the liquid medicine is automatically added into the anode circulation area 229 from a mother liquid storage barrel through a mother liquid adding pipe 219, and the liquid medicine is automatically stopped after the liquid medicine is added to the set value. The liquid level of the etching circulation zone 230 is controlled by an etching circulation zone liquid level controller 233, and when the liquid level of the etching circulation zone 230 is higher than a set value, the liquid is automatically discharged to the mother liquid storage tank 5 from the mother liquid discharge pump connecting pipe 214 (the mother liquid discharge pump is arranged on the mother liquid discharge pump connecting pipe 214 to prevent the pressure of the mother liquid discharge pump from being too high, a three-way valve is arranged on a connecting pipe between the mother liquid discharge pump and the mother liquid storage tank 5, the three-way valve is communicated with a mother liquid discharge pump pressure discharge pipe 216 through a pipeline, and the discharge is automatically stopped after the liquid. The chemical solution inlet of the first weight sampling box 226 is connected to the etching waste solution which is added into the anode circulation zone 229 by the anode circulation pump, the outlet is connected to the anode circulation zone 229, the specific gravity is detected by the first specific gravity detector 226, when the specific gravity is too high, the specific gravity is reduced by adding the regeneration solution from the regeneration solution adding pipe 218 through the regeneration solution storage barrel, and the ORP detector 225 controls the current of the electrolytic cell 30 by detecting the ORP value of the chemical solution in the etching circulation zone 230. The regenerated liquid storage barrel 6 is connected with a regenerated liquid adding pipe 211, the regenerated liquid is added to a cathode circulation area main tank 231 of the circulation tank, and then the regenerated liquid is connected with a cathode area 302 of the electrolysis tank 30 through a cathode circulation pump connecting pipe 205 and pumped to the cathode area 302 of the electrolysis tank (a cathode circulation pump is arranged on the cathode circulation pump connecting pipe 205 to prevent the pressure of the cathode circulation pump from being too high, a three-way valve is arranged on a pipeline between the cathode circulation pump and the cathode area 302 and communicated with a cathode circulation pump pressure relief pipe 206 through a pipeline to relieve the cathode circulation area main tank 231), and then the regenerated liquid returns to the cathode circulation area main tank 231 through a cathode. The liquid medicine inlet of the second specific gravity sampling box 226 is connected with the liquid medicine added into the cathode circulation area main tank 231 by the cathode circulation pump, and the outlet is connected with the cathode circulation area main tank 231, so that the specific gravity is detected by the second specific gravity detector. The mother liquor adding pipe 204 is connected with the mother liquor storage barrel 5, and when the specific gravity of the liquid medicine in the cathode circulation zone main tank 231 is too low, the mother liquor is added into the cathode circulation zone main tank 231 from the mother liquor adding pipe 204. When the liquid level of the cathode circulation zone main tank 238 is too high, the liquid level of the cathode circulation zone auxiliary tank 232 overflows to the cathode circulation zone auxiliary tank 232, the liquid level of the cathode circulation zone auxiliary tank 232 is controlled by a cathode circulation zone auxiliary tank liquid level controller 228, when the liquid level of the cathode circulation zone auxiliary tank 232 is too high, a regenerated liquid discharge pump connecting pipe 209 is connected with a regenerated liquid discharge pump to be automatically pumped to the regenerated liquid storage barrel 6 (the regenerated liquid discharge pump connecting pipe 209 is provided with a regenerated liquid discharge pump, in order to prevent the pressure of the regenerated liquid discharge pump from being too high, a three-way valve is arranged on a pipeline between the regenerated liquid discharge pump and the regenerated liquid storage barrel 6 and is communicated with a regenerated liquid discharge pump pressure discharge pipe 210 through a pipeline), and the discharge of the regenerated liquid is. The temperature of the cathode region is adjusted by controlling the cooling tube 238 by the temperature detector 236, and the cooling water of the cooling tube 238 flows in from the cathode region cooling tube 208. The mother liquor backup pump connection pipe 215 and the mother liquor backup pump pressure relief pipe 217 are activated when the etching circulation pump fails.
The etching waste liquid of the circulation tank 20 is connected with an anode region water inlet pipe 310 of the electrolytic tank 30 through an anode circulation pump connecting pipe 220, the anode region water inlet pipe 310 is connected with a plurality of branch pipes, each branch pipe is provided with an anode film frame water inlet pipe adjusting valve 311, the anode film frame water inlet pipe adjusting valve 311 is connected with an anode film frame water inlet pipe 312, the anode film frame water inlet pipe 312 extends into the bottom of one side of a cathode film frame 313, the etching liquid overflows to an anode overflow tank 315 through an anode film frame overflow port 314 on the other side of the anode film frame 313, and then flows back to the circulation tank etching region circulation zone 230 from an anode overflow tank interface 316 through an anode overflow pipe 202 of the. The cathode liquor of the cathode area circulation area main tank 338 of the circulation tank 20 enters the cathode area water inlet pipe 331 from the electrolytic tank cathode water inlet pipe valve 320 through the cathode circulation pump connecting pipe 205, a plurality of branch cathode area circulation spray pipes 321 are connected on the cathode area water inlet pipe 331, a row of spray holes are formed in the cathode area circulation spray pipes 321 towards the tank bottom direction, the cathode liquor enters the cathode area 322 from the cathode area circulation spray pipes 321, overflows into the cathode overflow hole 324 from the cathode overflow hole 323, and then flows back to the cathode area circulation area main tank 238 of the circulation tank 20 through the cathode overflow groove interface 325 connecting circulation tank cathode overflow pipe 203. The hydrochloric acid gas in the electrolytic cell 30 body enters the waste gas pipe 342 from the waste gas communication hole 341, and then enters the chlorine absorption and reuse tower 10 from the waste gas discharge connection port 343 connected with the chlorine gas inlet 125.
The catholyte of the circulation tank 20 is connected with the etching solution water inlet and outlet 127 of the chlorine absorption and reuse tower 10 through the cathode circulation connecting pipe 205 and enters the main tank 130, then the catholyte containing high-concentration monovalent copper ions enters the chlorine absorption chamber 120 through the atomizer 123 through the circulation pump 129, then the catholyte returns to the main tank 130 from the bottom of the chlorine absorption chamber 120 and the communication hole of the main tank 130 through the polyhedral ball 128, then the regenerant adding pipe 218 of the circulation tank 20 is connected with the overflow port 126 of the main tank 130 and returns to the anode circulation zone 229 of the circulation tank 20, the main tank 130 is provided with the ORP detector 132 for adding the catholyte in time, the chlorine generated by the electrolysis tank 30 and the hydrochloric acid gas of the circulation tank 20 enter the main tank 130 of the chlorine absorption and reuse tower 10 through the waste gas discharge connecting port 343 and the waste gas exhaust pipes 207 and 207', and then the catholyte enters the chlorine absorption chamber 120 and the chlorinated catholyte in the chlorine absorption chamber 120 and the cathode solution on the polyhedral ball 128 after atomization through the bottom of the chlorine absorption chamber 120 and the communication Cuprous reacts to generate copper chloride, absorption of chlorine is completed, the residual waste gas is filtered by the mist absorption filler 122 and enters the waste gas absorption tower 7 from the purified gas discharge port 121, the waste gas is absorbed by sodium hydroxide and is discharged after neutralization, the purified gas discharge port 121 is provided with a chlorine detector, and the chlorine detector gives an alarm to indicate that the chlorine in the chlorine absorption and reuse tower 2 does not fully react with the catholyte, and at the moment, the operation of the device is stopped and the device is overhauled to prevent the chlorine from leaking to generate adverse results. The temperature of the catholyte in the main tank 130 is reduced through the cooling pipe 131, and the temperature of the catholyte in the main tank 130 is kept below the normal temperature, which is more beneficial to the absorption of chlorine.
Example 3
A specific control process of the cyclic regeneration process of the acidic etching solution is shown in FIG. 15, and mainly comprises the following steps:
step 1: the waste acidic etching solution after etching of the acidic etching line 4 is pumped to an anode circulation area 229 of the circulation tank 20, and the anode circulation area 229 of the circulation tank is connected with the mother solution storage tank 5.
Step 2: the etching waste liquid in the anode circulation area 229 is pumped to the anode area 301 of the electrolytic cell 30 and then overflows back to the etching circulation area 230 of the circulation cell 20, the anode circulation area 229 of the circulation cell 20 is communicated with the top of the etching circulation area 230, the anode circulation area 229 is connected with the regeneration liquid storage barrel 6, the regeneration liquid is added to the anode circulation area 229 through the second specific gravity device 226, meanwhile, the ORP detector 225 detects the ORP value of the liquid medicine in the etching circulation area 230 to control the current of the electrolytic cell 30, and when the liquid level is too high, the liquid medicine is automatically discharged from the etching circulation area 230 to the mother liquid storage barrel 5 through the etching circulation area liquid level monitoring controller 233.
And step 3: the etching solution in the adjusted etching circulation area 230 is pumped back to the etching line 4.
And 4, step 4: the catholyte in the cathode circulation zone 231 is pumped to the cathode zone 302 of the electrolytic cell 30 and then overflows back into the cathode zone 231 of the circulation cell.
And 5: the cathode circulation zone 231 is connected with the mother liquor storage barrel 5, and the mother liquor is added to the cathode circulation zone 231 through the first specific gravity detector 224 to complete the addition of copper ions. The cathode circulation zone 231 is connected with the regeneration liquid storage barrel 6, and the regeneration liquid is automatically added to the cathode electrode circulation zone 231 through the cathode circulation zone secondary tank liquid level controller 228 or discharged from the cathode circulation zone 231 to the regeneration liquid storage barrel 6.
Step 6: hydrochloric acid gas in the circulating tank 20 and the electrolytic tank 30 passes through the chlorine absorption and reuse tower 10 and reacts with the etching waste liquid flowing in the cathode circulating area 231 in the chlorine absorption and reuse tower 10, cuprous ions are oxidized into copper ions by chlorine to be regenerated, and Cu ions are regenerated+→Cu2++e-。
And 7: in order to level the copper deposited on the cathode titanium plate of the electrolytic bath 30, 1 to 3 per mill of polyethylene glycol as a leveling agent can be added into the cathode circulation zone 231 of the circulation bath 20, wherein the polyethylene glycol is at least one of 200 to 20000 in the polyethylene glycol series.
And 8: when the acidity of the etching solution of the etching line 4 is low, hydrochloric acid is automatically added to the etching solution from the hydrochloric acid storage tank 3.
And step 9: the cathode circulation zone 231 is provided with a cooling water pipe, the temperature of the regenerated liquid in the cathode circulation zone 231 of the circulation tank 20 is controlled by a temperature controller 236, and the temperature is controlled to be 35-52 ℃.
Step 10: after a certain period of electrolysis, the cathode titanium plate attached with the copper foil is taken out from the electrolytic bath 30 by a hoisting device and is put into the cleaning tank 1 to wash away residual acid liquid medicine on the surface of the copper, then the cathode copper plate is moved into the oxidation resisting tank 2, antioxidant solution in the oxidation resisting tank is used for carrying out oxidation resistance treatment on the surface of the cathode copper plate, the oxidation resisting layer is attached to the surface of the cathode copper plate, finally, the cathode copper plate attached with the oxidation resisting layer is moved out, the copper is detached from the cathode plate, filtered and dried, and then packaged and put in storage.
The working principle is as follows:
excess in acidic etching waste liquidCopper can also be recovered by cathodic reduction electrochemical methods, Cu2+Ions are first reduced to Cu+Ion, Cu+The ions are then electrodeposited as metallic copper. The ion membrane electrolytic regeneration method is an on-line regeneration method, and can realize continuous operation of etching work and etching solution regeneration in a circulating system, namely, copper can be recovered by cathodic electrodeposition while the etching solution is regenerated by an anode, so that the copper added in the etching engineering can be recovered. The electrolytic regeneration process of the acidic copper chloride etching solution involves the following reactions:
at the anode: cu+→Cu2++e-
At the cathode: cu2++e-→Cu+······Cu++e-→Cu
The ion membrane electrolysis method is characterized in that the anode of an electrolytic tank 30 can be a graphite plate or a titanium anode plate, the cathode is a titanium plate, an anode liquid and a cathode liquid are separated by an ion membrane, the anode is an etching mother liquid needing regeneration, the cathode is an etching waste liquid with copper ions of 20-100 g/L and acidity of 1.5-4 mol/L, the electrolytic tank 30 is formed by connecting a plurality of unit electrolytic tanks in series, the unit electrolytic tank 30 is formed by one or a plurality of anode mold frames, the acidic etching waste liquid enters an electrolytic anode circulation area 301 through an anode circulation area 229 of a circulation tank 20, an etching circulation area 230 of an overflow circulation tank 20, the concentration of slotted copper ions of a cathode circulation area 231 of the circulation tank 20 is adjusted to be 20-100 g/L, the normal circulation is completed through the cathode of the electrolytic tank 30 and the anode circulation area 231 of the overflow circulation tank 20, the cathode titanium plate of a cathode in the electrolysis process generates metal copper, the copper can be stripped after a certain time, the remaining waste water becomes a regeneration liquid, the concentration of the copper ions of the regeneration liquid is gradually reduced due to electrolysis, the acidity is increased, the specific gravity of the copper ions are automatically added through an automatic regenerator, the ORP ion concentration controller is increased, the copper ion concentration of the regeneration liquid is controlled by adding a corresponding ORP ion controller, the ORP ion controller is controlled by adding a specific gravity of 9000-600 mV controller, and a specific gravity controller is controlled2. When ORP is low, the automatic ORP detection controller automatically adjusts current to ensure that the waste etching solution liquidThe Cu + ions in the solution are converted into Cu again through anodic oxidation2+The ions recover their etching ability, and the ORP detector automatically reduces the current to prevent the generation of chlorine when the ORP is higher.
The process control parameters for the various components are preferably as follows:
controlling the chlorine ions in the etching production line to be 260-300 g/L, controlling the copper ions to be 110-155 g/L and controlling the acidity to be 1.0-3.0 mol/L;
the chloride ions in an anode circulation area 229 of the circulation tank are controlled to be 260-300 g/L, the copper ions are controlled to be 110-155 g/L, the acidity is controlled to be 1.0-3.0 mol/L, and the specific gravity is controlled to be 1.250-1.310;
the ORP value of an etching circulation zone 230 of the circulation tank is controlled to be 300-600 mV, and the current density of the electrolytic tank 3 is correspondingly controlled to be 0-9000 mA/dm 2;
the chlorine ion in the cathode circulation zone 231 of the circulation tank is controlled to be 260-300 g/L, the copper ion is controlled to be 20-100 g/L, the acidity is controlled to be 1.5-4 mol/L, the specific gravity is controlled to be 1.190-1.240, and the temperature is 35-52 ℃.
And controlling the ORP value in the chlorine absorption and reuse tower to be 450-550 mV.
The PH value in the waste gas absorption tower is controlled to be more than 8.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. A method for recycling acidic etching solution is characterized in that an acidic etching solution recycling system is used, and the acidic etching solution recycling system comprises an etching line (4), an electrolytic cell (30), a circulating cell (20), a chlorine absorption and reuse tower (10), a mother solution storage barrel (5) and a recycling solution storage barrel (6); an anode region (301) and a cathode region (302) are arranged in the electrolytic tank (30); the circulating tank (20) comprises a tank body, the bottom of the tank body is divided into an anode circulating area (229), an etching circulating area (230) and a cathode circulating area (231) through a partition plate, wherein the etching circulating area (230) is communicated with the top of the anode circulating area (229); the anode area (301) of the electrolytic cell is respectively communicated with the anode circulation area (229) and the etching circulation area (230) of the circulation cell; the cathode area (302) of the electrolytic cell is communicated with the cathode circulation area (231); the anode area (301) and the cathode area (302) of the electrolytic cell, the etching circulation area (230) and the cathode circulation area (231) of the circulation cell (20) are communicated with the chlorine absorption and reuse tower (10); the chlorine absorption and reuse tower (10) is communicated with an anode circulation area (229) of the circulation tank (20); the mother liquor storage barrel (5) is communicated with an anode circulation zone (229), an etching circulation zone (230) and a cathode circulation zone (231); the regeneration liquid storage barrel (6) is communicated with the anode circulation area (229) and the cathode circulation area (230); the anode circulation area (229) of the circulation tank is communicated with an etching line (4), and the etching line (4) is communicated with the etching circulation area (230) of the circulation tank;
the method comprises the following steps:
step 1: acid etching waste liquid after the acid etching line is etched is pumped to an anode circulation area (229) of a circulation tank (20), and the anode circulation area (229) of the circulation tank is connected with a mother liquid storage barrel (5);
step 2: the etching waste liquid in the anode circulation area (229) is pumped to an anode area (301) of the electrolytic cell (30) and then overflows back to an etching circulation area (230) of the circulation cell (20), the anode circulation area (229) of the circulation cell (20) is communicated with the top of the etching circulation area (230), the anode circulation area (229) is connected with a regeneration liquid storage barrel (6), regeneration liquid is added to the anode circulation area (229) through a second specific gravity device (226), meanwhile, the ORP value of the liquid medicine in the etching circulation area (230) is detected through an ORP detector (225) to control the current of the electrolytic cell (30), and when the liquid level is overhigh, the liquid medicine is automatically discharged from the etching circulation area (230) to a mother liquid storage barrel (5) through an etching circulation area liquid level monitoring controller (233);
and step 3: the etching solution in the adjusted etching circulation area (230) is pumped back to the etching production line (4);
and 4, step 4: the cathode liquor in the cathode circulation area (231) is pumped to the cathode area (302) of the electrolytic bath (30) and then overflows back to the cathode circulation area (231) of the circulation bath;
and 5: the cathode circulation area (231) is connected with a mother liquor storage barrel (5), and mother liquor is added into the cathode circulation area (231) through a first specific gravity detector (224) to complete the addition of copper ions; the cathode circulation area (231) is connected with a regeneration liquid storage barrel (6), and regeneration liquid is automatically added to the cathode circulation area (231) through a cathode circulation area auxiliary tank liquid level controller (228) or discharged from the cathode circulation area (231) to the regeneration liquid storage barrel (6);
step 6: hydrochloric acid gas of the circulating tank (20) and the electrolytic tank (30) passes through the chlorine absorption and reuse tower (10) and reacts with etching waste liquid flowing in the cathode circulating area (231) in the chlorine absorption and reuse tower (10), cuprous ions are oxidized into copper ions by chlorine and then are regenerated and then flow back to the anode circulating area (229), and Cu is obtained+→Cu2++e-。
2. The method for recycling acidic etching solution as claimed in claim 1, wherein the specific process control parameters include:
controlling the chlorine ions in the etching production line to be 260-300 g/L, controlling the copper ions to be 110-155 g/L and controlling the acidity to be 1.0-3.0 mol/L;
controlling the chloride ions in an anode circulation zone of the circulation tank to be 260-300 g/L, controlling the copper ions to be 110-155 g/L, controlling the acidity to be 1.0-3.0 mol/L and controlling the specific gravity to be 1.250-1.310;
the ORP value of an etching circulation area of the circulation tank is controlled to be 300-600 mV, and the current density of the electrolytic tank 3 is correspondingly controlled to be 0-9000 mA/dm 2;
controlling the chloride ions in a cathode circulation zone of the circulation tank to be 260-300 g/L, controlling the copper ions to be 20-100 g/L, controlling the acidity to be 1.5-4 mol/L, controlling the specific gravity to be 1.190-1.240 and controlling the temperature to be 35-52 ℃;
and controlling the ORP value in the chlorine absorption and reuse tower to be 450-550 mV.
3. The method for recycling acidic etching solution as claimed in claim 1, wherein a leveling agent is added to the cathode circulation zone (231) of the circulation tank (20) for leveling the copper deposit on the cathode titanium plate of the electrolytic tank (30), wherein the leveling agent is polyethylene glycol with a mass concentration of 1 to 3 per mill, and the polyethylene glycol is at least one of the polyethylene glycol series of 200 to 20000.
4. The method for recycling acidic etching solution according to claim 1, further comprising a hydrochloric acid storage tank (3), wherein the hydrochloric acid storage tank (3) is communicated with the etching line (8); when the acidity of the etching solution of the etching line (4) is low, hydrochloric acid is automatically added into the etching solution from the hydrochloric acid storage barrel (3).
5. The method for recycling acidic etching solution as claimed in claim 1, wherein the cathode circulation zone (231) is provided with a cooling water pipe, and the temperature of the recycling solution in the cathode circulation zone (231) of the circulation tank (20) is controlled by a temperature controller (236) and is controlled within 35-52 ℃.
6. The system for recycling acidic etching solution as claimed in claim 1, wherein at least one anode film frame (313) is arranged in the electrolytic bath (30) to form the electrolytic bath into an anode region and a cathode region which are separated; the anode membrane frame (313) comprises an ion membrane (346) and a frame body (345), an anode membrane frame overflow port (314) is formed in the top of the frame body (345), the bottom and the left and right edges of the frame body (345) are sealed, ion membranes (346) are respectively arranged on the front side and the rear side of the frame body (345), protective membranes (347) are respectively arranged on the outer sides of the ion membranes (346), fixed baffle plates (348) are respectively arranged on the outer sides of the protective membranes (347), and the ion membranes (346), the protective membranes (347) and the fixed baffle plates (348) are sequentially fixed on the two side faces of the frame body (345) to form a closed cavity; an anode plate (318) is arranged in the cavity of the anode film frame (313), a cathode plate is arranged outside the cavity of the anode film frame (313), and an electrolytic tank exhaust pipe is arranged at the top of the electrolytic tank (30).
7. The acid etching solution circulation regeneration system as claimed in claim 6, wherein the electrolytic tank (30) is provided with an anode overflow tank (315) and a cathode overflow tank (324) on the tank wall;
an anode region water inlet pipe (310) is arranged on the side wall of the electrolytic cell body (303), the anode region water inlet pipe (310) is connected with a plurality of branch pipes, each branch pipe is provided with an anode film frame water inlet pipe adjusting valve (311), the anode film frame water inlet pipe adjusting valve (311) is connected with an anode film frame water inlet pipe (312), and the anode film frame water inlet pipe (312) extends into the bottom of one side of the anode film frame (313); an anode membrane frame overflow port (314) is formed in one side of the top of the anode membrane frame (313), and the anode membrane frame overflow port (314) is communicated with an anode overflow groove (315) and an anode overflow groove interface (316);
the electrolytic cell is characterized in that a cathode water inlet pipe valve (320) is arranged at the bottom of the electrolytic cell body (303), the cathode water inlet pipe valve (320) is communicated with a cathode region water inlet pipe (331), a plurality of cathode region circulating spray pipes (321) are connected onto the cathode region water inlet pipe (331), spray holes are formed in the cathode region circulating spray pipes (321) towards the direction of the cell bottom, the cathode region circulating spray pipes (321) are communicated with a cathode region (302), a cathode overflow port (323) is arranged at the top of the cathode region (302), and the cathode overflow port (323) is communicated with a cathode overflow groove (324) and a cathode overflow groove interface (325).
8. The acid etching solution circulation and regeneration system as claimed in claim 1, wherein the cathode circulation zone (231) of the circulation tank (20) is further divided into a cathode circulation zone main tank and a cathode circulation zone auxiliary tank (232); circulation groove exhaust pipes are respectively arranged at the tops of the anode circulation zone (229) and the cathode circulation zone, and a plurality of liquid inlet pipes and liquid outlet pipes are respectively arranged on the side walls of the anode circulation zone (229), the etching circulation zone (230) and the cathode circulation zone and are used for being communicated with external equipment; liquid level controllers are respectively arranged in the anode circulating area (229), the etching circulating area (230) and the cathode circulating area, and a specific gravity sampling box is arranged on the main tank of the anode circulating area (229) and the main tank of the cathode circulating area; the etching circulation zone (230) is provided with an ORP detector (225), and a cooling pipe (237) and a temperature detector (236) are arranged in the cathode circulation zone.
9. The system for recycling the acidic etching solution as claimed in claim 1, wherein the chlorine absorption and reuse tower (10) comprises a tower body, and the tower body comprises a chlorine absorption chamber (120) and a main tank (130) communicated with the bottom of the chlorine absorption chamber (120); a purified gas discharge port (121) is formed in the top of the chlorine absorption chamber (120), a mist absorption filler layer is arranged inside the top end of the chlorine absorption chamber (120), at least one layer of spray pipe (133) is arranged below the mist absorption filler layer, at least one atomizer (123) is arranged below the spray pipe (133), and a multi-surface ball layer is arranged at the lower end of the atomizer (123); a chlorine gas inlet (125) is formed in one side of the upper end of the main groove (130), an overflow port (126) is formed in the middle of the surface of the main groove (130), an etching liquid inlet and outlet (127) is formed in the lower end of the surface of the main groove (130), a circulating pump (129) is arranged at the lower end of one side of the main groove (130), and the top of the circulating pump (129) is communicated with a spraying pipe (133) of the chlorine gas absorption chamber (120).
10. The system for recycling acidic etching solution as claimed in claim 9, wherein the exhaust gas discharge connection port (343) of the electrolytic cell, the etching circulation zone (230) of the circulation cell and the cathode circulation zone (231) are all communicated with the chlorine gas inlet (125) of the chlorine gas absorption and reuse tower through pipes, the cathode circulation zone (231) of the circulation cell is communicated with the etching solution inlet and outlet port (127) of the chlorine gas absorption and reuse tower through pipes, and the overflow port (126) of the chlorine gas absorption and reuse tower is communicated with the anode zone (229) of the circulation cell through pipes to form reflux.
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Cited By (6)

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CN111733444A (en) * 2020-08-05 2020-10-02 上海毅蓝电子科技有限公司 Stainless steel etching solution cyclic regeneration system and method of ferric trichloride
CN114774989A (en) * 2022-04-01 2022-07-22 安徽中科冉图环保科技有限公司 Chlorine absorption cylinder for electrolytic treatment of acidic etching solution
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CN114772624A (en) * 2022-05-12 2022-07-22 西安益维普泰环保股份有限公司 Method for producing high-purity aluminum chloride
CN115449849A (en) * 2022-08-31 2022-12-09 长沙利洁环保科技有限公司 Micro-etching liquid on-line electrolysis copper extraction cyclic regeneration process
CN115449849B (en) * 2022-08-31 2023-06-02 长沙利洁环保科技有限公司 Microetching solution on-line electrolytic copper extraction cyclic regeneration process

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