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WO2023217253A1 - 一种递进式电解回用酸性蚀刻废液的方法及其装置 - Google Patents

一种递进式电解回用酸性蚀刻废液的方法及其装置 Download PDF

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Publication number
WO2023217253A1
WO2023217253A1 PCT/CN2023/093720 CN2023093720W WO2023217253A1 WO 2023217253 A1 WO2023217253 A1 WO 2023217253A1 CN 2023093720 W CN2023093720 W CN 2023093720W WO 2023217253 A1 WO2023217253 A1 WO 2023217253A1
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Prior art keywords
tank
electrolytic
cathode
electrolytic tank
area
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PCT/CN2023/093720
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English (en)
French (fr)
Inventor
叶涛
叶旖婷
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Individual
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Priority to CN202380040101.9A priority Critical patent/CN119278295A/zh
Publication of WO2023217253A1 publication Critical patent/WO2023217253A1/zh
Priority to US18/944,020 priority patent/US20250066947A1/en
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/12—Etching of semiconducting materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • C25F7/02—Regeneration of process liquids

Definitions

  • the invention belongs to the technical field of circuit board etching waste liquid recovery and recycling, and specifically relates to a progressive electrolytic method and device for recycling acidic etching waste liquid.
  • the etching method using acidic etching solution spray processing is an important step. It uses acidic etching solution to chemically corrode the unnecessary copper on the copper-clad foil substrate. method to remove it to form the required circuit pattern.
  • Current acid etching solutions mainly use copper chloride and/or ferric chloride as copper etching agents.
  • the main components of existing acid etching solutions in the industry are copper chloride and hydrochloric acid, and may contain ferric chloride and/or ammonium chloride and/or sodium chloride.
  • the copper etching agent is reduced and loses its etching ability. Specifically, copper chloride is reduced to cuprous chloride, and/or ferric chloride is reduced to ferrous chloride.
  • oxidants, hydrochloric acid and/or ferric chloride and optional additives need to be added to the etching solution so that cuprous chloride and ferrous chloride can be oxidized and regenerated into cupric chloride and ferric chloride and continue to participate. Etching also causes the volume of etching liquid to continuously increase and overflow out of the tank. Additives in etching solutions are often used to improve etching performance.
  • ferric chloride is both a copper etching agent and an additive that can increase the same ion effect. Since acidic etching solutions containing ferric chloride copper etching agents can effectively reduce the pool effect during the etching process, the industry prefers to use acidic iron-containing etching solutions in pursuit of high-quality and efficient products.
  • the etching liquid that overflows out of the tank is called etching waste liquid
  • the solution in the etching tank is called etching working liquid
  • the solutions containing hydrochloric acid and/or oxidants and/or additives added during the etching process are collectively called etching.
  • Sub liquid The copper ion concentration of most acidic etching waste liquids is 70-200g/L, and the total iron content of ferric chloride and ferrous chloride in iron-containing acidic etching waste liquids can be as high as 200g/L.
  • Circuit board production factories produce a large amount of acidic etching waste liquid from the etching process every day.
  • This method uses an electrolytic cell separated by an anode tank area and a cathode tank area, and adds the acidic etching waste liquid into the anode tank area for direct electrolysis.
  • the loss of chloride ions in the etching waste liquid is relatively large, and more oxidants need to be added to the etching working fluid to maintain the etching operation, which leads to an increase in the etching waste liquid.
  • the solution of adding acidic etching waste liquid to electrolysis in the cathode tank area can effectively reduce or even avoid it.
  • Adding oxidant to the etching working fluid during the reuse-free etching process solves the problem of waste liquid increase.
  • copper etching agent in the acidic etching waste liquid, it is very corrosive to metal copper.
  • the acidic etching waste liquid containing iron is particularly aggressive to metal copper. Therefore, when acidic etching waste liquid is added to the cathode tank area, the introduced copper etching agent will etch back the copper electrolyzed by the cathode.
  • circuit board manufacturers in the industry are looking forward to the launch of a new process that can solve the shortcomings of the current acid etching waste electrolytic recovery and recycling process.
  • the first object of the present invention is to provide a progressive electrolytic method for recycling acidic etching waste liquid of circuit boards, so that circuit board production enterprises can safely recover copper from the acidic etching waste liquid while reducing the electrolytic copper extraction process. It can prevent the etching back of the metal copper electrolyzed on the cathode and avoid the introduction of new impurities, reducing electrolysis energy consumption. It helps to redeploy the waste liquid after recovering copper into a regenerated etching sub-liquid to improve the recycling rate of the waste liquid. , which not only significantly reduces production costs but also reduces environmental pollution.
  • the second object of the present invention is to provide a device for progressive electrolysis and recycling of acidic etching waste liquid for circuit boards.
  • a progressive electrolytic method for recycling circuit board acid etching waste liquid which mainly includes the following steps:
  • Step 1 Use at least one electrolytic tank A.
  • the inside of the electrolytic tank A is divided into an anode tank area and a cathode tank area using electrolytic tank dividers; during electrolysis operation, the anode tank area and the cathode tank area of the electrolytic tank A are respectively
  • An electrolytic anode and an electrolytic cathode are provided to perform electrolysis operations on the anolyte and catholyte of electrolytic tank A respectively; the catholyte of electrolytic tank A contains acidic etching waste liquid;
  • Step 2 Use at least one electrolytic tank B for progressive electrolysis to extract copper.
  • the electrolytic tank B is divided into an anode tank area and a cathode tank area; during electrolysis operation, the anode tank area and cathode tank area of the electrolytic tank B are An electrolytic anode and an electrolytic cathode are respectively provided in the electrolytic tank B, and electrolysis operations are performed on the anolyte and catholyte of electrolytic tank B respectively, so that an electrochemical reaction in which copper ions are reduced to metallic copper occurs on the electrolytic cathode of electrolytic tank B; so
  • the catholyte of electrolytic tank B includes the catholyte of electrolytic tank A after electrolysis treatment or a mixture thereof and acidic etching waste liquid;
  • Step 3 When the metallic copper deposited on the electrolytic cathode of electrolytic tank B due to electrochemical reaction reaches the preset electrolysis target amount, take out the electrolytic cathode of electrolytic tank B from electrolytic tank B.
  • the anolyte of electrolytic tank A includes at least one of etching working fluid, etching waste liquid, and the catholyte of electrolytic tank B after electrolysis treatment.
  • the anolyte of electrolytic tank B includes at least one of the catholyte of electrolytic tank B, etching working fluid, and etching waste liquid after electrolysis treatment.
  • chlorine gas is electrolytically precipitated on the electrolytic anode of electrolytic cell A and the electrolytic anode of electrolytic cell B and/or an electrochemical reaction occurs in which low-valence metal ions in the electrolyte are oxidized into high-valence ions. .
  • the reduction reaction of metal ions mainly occurs on the electrolytic cathode of electrolytic tank A, causing the concentration of the copper etching agent in the catholyte to decrease.
  • the electrochemical reaction of copper ions being reduced to metallic copper occurs on the electrolytic cathode of electrolytic tank B. reaction.
  • corresponding electrolytic solutions are continuously added to each tank area during operation.
  • the catholyte of electrolytic tank B after electrolytic treatment can be oxidized in the anode tank area of electrolytic tank A and/or the anode tank area of electrolytic tank B, and/or can be electrolyzed and escaped using the electrolytic tank.
  • the chlorine gas is oxidized and then recycled directly or after preparation as a regenerated etching sub-liquid.
  • the above preparation can also be changed to prepare in advance at least one of the anolyte and catholyte of electrolytic tank A and the anolyte and catholyte of electrolytic tank B, which can also achieve the purpose of the present invention.
  • the electrolytic cell separator of the electrolytic cell A can effectively cause the anolyte to undergo an oxidation reaction and the catholyte to undergo a reduction reaction of reducing the price of high-valence metal ions.
  • anion exchange membrane, bipolar membrane, and reverse osmosis are selected. At least one of the membranes.
  • the electrolytic tank B can be an electrolytic tank divided into an anode tank area and a cathode tank area in any structural form.
  • the electrolytic tank separators of the electrolytic tank B can be anion exchange membranes, bipolar membranes, and reverse osmosis membranes. at least one of them.
  • the present invention can make the following improvements: detect the redox potential of the catholyte in the cathode tank area of electrolytic tank A to monitor the electrolysis process and the concentration of high-valence metal ions in the solution, so that the catholyte of electrolytic tank A can
  • the reaction of reducing the concentration of the copper etching agent mainly occurs, and the electrochemical reaction of electrolyzing copper does not occur or rarely occurs.
  • the present invention can further make the following improvements: according to the redox potential value of the cathode electrolyte in the cathode tank area of electrolytic tank A, the output current of the electrolytic power supply of electrolytic tank A is adjusted or started and shut down according to the process requirements, and/or to The cathode tank area of electrolytic tank A is added with a solution containing acidic etching waste liquid to maintain the concentration of copper etching agent in the cathode electrolyte, so that little or even no metal copper is precipitated on the electrolytic cathode, and the main function is to The electrochemical reduction reaction reduces the copper-etching agent CuCl 2 or the concentration of CuCl 2 and FeCl 3 in the catholyte of electrolytic tank A or even eliminates its copper-etching ability.
  • the redox potential value of the catholyte of the electrolytic cell A is controlled at 200-580 mv, that is, the ORP value of the externally injected waste liquid is used to control the control point range at 200-580 mv. between 580mv. More preferably, the redox potential value of the catholyte of the electrolytic tank A is controlled to 300 to 499 mv. In order to obtain a better progressive copper extraction effect of eliminating copper-etching agents, the ORP value of the catholyte of electrolytic tank A is controlled at 350 to 470 mv.
  • the present invention can make the following improvements: add at least one electrolytic tank C arranged behind the electrolytic tank B.
  • the electrolytic tank C is divided into an anode tank area and a cathode tank area; the anode tank area of the electrolytic tank C during electrolysis operation
  • An electrolytic anode and an electrolytic cathode are respectively provided in the and cathode tank areas, and the anolyte and catholyte are respectively subjected to electrolysis operations
  • the anolyte of the electrolytic tank C includes an acidic etching working fluid, an electrolytic tank after electrolysis treatment
  • the catholyte of electrolytic tank C includes electrolysis treatment.
  • the catholyte of electrolytic tank B may further include the catholyte of electrolytic tank A and/or the etching waste liquid.
  • the anolyte of electrolytic tank A includes at least one of the catholyte of electrolytic tank B after electrolysis treatment, the catholyte of electrolytic tank C after electrolysis treatment, etching working liquid, and etching waste liquid.
  • the anolyte of electrolytic tank B includes at least one of the catholyte of electrolytic tank B after electrolysis treatment, the catholyte of electrolytic tank C after electrolysis treatment, etching working fluid, and etching waste liquid. kind.
  • an electrochemical reaction occurs on the electrolytic cathode of the electrolytic tank C, in which copper ions are reduced to metallic copper, and then copper is further extracted through progressive electrolysis.
  • the electrolytically treated catholyte of electrolytic tank B and/or the electrolytically treated catholyte of electrolytic tank C can be in the anode tank area of electrolytic tank A, the anode tank area of electrolytic tank B, and the anode tank area of electrolytic tank C.
  • One or more of them are oxidized and/or chlorine gas is used for oxidation, and then directly or after preparation, it is recycled as a regenerated etching sub-liquid.
  • the above preparation can also be changed to the anolyte and catholyte of electrolytic tank A and electrolytic tank B.
  • the object of the present invention can also be achieved by preparing at least one of the anolyte and catholyte, and the anolyte and catholyte of electrolytic tank C in advance.
  • the electrolytic tank C can be an electrolytic tank divided into an anode tank area and a cathode tank area in any structural form.
  • the electrolytic tank separator of the electrolytic tank C can be at least one of an anion exchange membrane, a bipolar membrane, and a reverse osmosis membrane.
  • electrolytic tank A since the anolyte of electrolytic tank A, the anolyte of electrolytic tank B, and the anolyte of electrolytic tank C all contain chloride ions, so electrolytic tank A
  • the electrochemical reaction in which chloride ions are oxidized into chlorine gas occurs on the electrolytic anode of electrolytic tank B, the electrolytic anode of electrolytic tank C, and the electrolytic anode of electrolytic tank B.
  • the generated chlorine gas has strong oxidizing properties and can oxidize low-valence metal ions in the anolyte of electrolytic tank A, the anolyte of electrolytic tank B, and the anolyte of electrolytic tank C, thereby achieving the oxidation of the copper etching agent. regeneration.
  • a reaction-reduction electrochemical reaction occurs on the electrolytic cathode of electrolytic tank A, causing the copper-etching agent in the cathode electrolyte to undergo a reduction reaction to form cuprous chloride and/or ferrous chloride, causing it to lose its copper-etching ability.
  • the catholyte of electrolytic tank A that has lost or reduced its ability to corrode copper is added to the cathode tank area of electrolytic tank B as part or all of its catholyte for electrolysis, so that copper is electrolytically precipitated on the electrolytic cathode of electrolytic tank B.
  • Metal When an electrolytic tank C is added, the electrolyzed catholyte of electrolytic tank B is added to the cathode tank area of electrolytic tank C as part or all of the catholyte of electrolytic tank C for further advancement to the next level. Electrolytic extraction of copper.
  • the present invention uses a method of progressive electrolysis of copper, so that the metallic copper electrolytically deposited on the electrolytic cathode of electrolytic tank B and the electrolytic cathode of electrolytic tank C is generated in an environment with a low copper etching agent concentration, which can effectively Reduce the chemical reaction of the catholyte to etch back the metal copper deposited during the electrolysis recycling process, so that the metal copper layer deposited by electrolysis is smoother and denser.
  • the process of the invention solves the process shortcoming of the loose copper layer in the electrolysis of the existing acidic etching waste liquid recovery technology, and at the same time helps to achieve 100% recovery and recycling of the etching waste liquid.
  • the electrolytic anode in the present invention uses a material whose shape and properties are stable in the electrolyte. Specifically, materials whose surface is gold and/or platinum and/or an alloy containing at least one of the above metals, titanium-based coating insoluble anodes can be used , at least one type of conductive graphite, preferably a titanium-based coating insoluble anode.
  • the material of the electrolytic cathode of the electrolytic cell A is gold and/or platinum and/or titanium and/or an alloy containing at least one of the above metals and/or conductive graphite, preferably titanium.
  • the electrolytic cathode of the electrolytic tank B and the electrolytic cathode of the electrolytic tank C can be made of gold and/or platinum and/or titanium and/or copper and/or an alloy containing at least one of the above metals and/or stainless steel, Copper metal is preferred.
  • electrolytic tank A The main chemical reactions occurring in each tank area of electrolytic tank A, electrolytic tank B, and electrolytic tank C are as follows:
  • the present invention can make the following improvements: control the copper ion concentration of the electrolytic cathode of electrolytic tank B and the catholyte of electrolytic tank C to not be lower than 5g/L.
  • the inventor has found through many experiments that when the copper ion concentration of the catholyte is maintained at no less than 5g/L, more hydrogen electrolysis side reactions can be avoided.
  • the present invention can make the following improvements: the electrolyzed catholyte from terminal electrolytic tank B or the electrolyzed catholyte from terminal electrolytic tank C is oxidized and regenerated according to process requirements and/or hydrochloric acid and additives are added To reformulate the regenerated etching sub-liquid so that the concentration of cuprous ions and/or ferrous ions in the regenerated etching sub-liquid meets the minimum requirements of the process, and will not affect the etching performance when it is returned to the etching production line for use.
  • the present invention can be improved as follows: a cathode cloth filter bag is used to cover the electrolytic cathode of at least one electrolytic cell at the end to collect sponge copper produced during the copper electrolysis process.
  • the present invention can make the following improvements: detect the parameter value of at least one electrolyte in the present invention, and use the data measured on site as a basis to control the electrolytic power supply of electrolytic tank A and/or the electrolytic power supply and/or electrolysis of electrolytic tank B.
  • the output current of the electrolytic power supply of tank C can be turned on and off, and/or the addition of various materials can be controlled.
  • the chlorine gas generated in the anode tank area of the electrolytic tank A and/or the anode tank area of the electrolytic tank B and/or the anode tank area of the electrolytic tank C is safely controlled and relatively completely utilized, and/or the solution reaction is carried out according to the Process requirements are carried out.
  • the detected parameter values include but are not limited to any one or more of acidity value, specific gravity value, redox potential value, photoelectric colorimetric value, liquid level, temperature, flow rate, and harmful gas concentration.
  • the present invention can be improved as follows: the anolyte of electrolytic tank A and/or the anolyte of electrolytic tank B and/or the anolyte of electrolytic tank C in an electrolytic tank provided with an electrolytic separator are combined with the etching process on the etching production line.
  • the working fluid is circulated and mixed, so that the etching working fluid on the etching production line can be replenished with copper etching agent online. That is, the low-valent copper ions or low-valent iron ions in the etching working fluid can use the electrochemical reaction of the anode of the electrolytic cell to obtain the regenerated copper etching agent copper chloride or ferric chloride, and continue to participate in the etching reaction.
  • the etching tank is connected to the anode tank area of at least one electrolytic tank through a pipeline, so that the etching working fluid circulates in each anode tank area and serves as the anolyte of electrolytic tank A and electrolytic tank B after electrolytic oxidation.
  • At least one of the anolyte and the anolyte of electrolytic tank C is directly returned to the etching tank to be used as the etching working fluid for the new copper etching agent, which can effectively reduce or even eliminate the need to add input from outside the etching system in the traditional production process. oxidant, helping to reduce production costs.
  • the present invention can be further improved as follows: adding a circulating mixing and exchange tank for etching working fluid and anolyte between the etching production line and the anode tank area of at least one electrolytic tank, and controlling the redox potential value of the mixed solution to be higher than that of the etching solution.
  • the redox potential value of the working fluid Preferably, a circulating mixing exchange tank with a larger total volume is used to efficiently utilize the electrolysis equipment to prepare more copper etching agent in advance as a response to rapid addition during the etching reaction.
  • the present invention can be further improved as follows: temperature adjustment and control of the solution prepared to enter the etching production line to avoid affecting the stability of the etching rate due to changes in the temperature of the etching working fluid when the mixed solution is added to the etching production line.
  • the present invention can further make the following improvements: remove oil and solid impurities before the etching working fluid enters the electrolytic bath.
  • the present invention can be further improved as follows: when the etching waste liquid contains iron ions, the etching waste liquid is added to the cathode tank area of electrolytic tank B and/or electrolytic tank C according to process requirements.
  • the feeding port is close to the separator, and the Fe 3+ ions in the etching waste liquid are used to react with the CuCl copper sludge to react the insoluble cuprous chloride sludge to generate copper chloride, thereby avoiding clogging of the separator and affecting the electrolysis operation.
  • a device for progressive electrolysis to recycle acidic etching waste liquid of circuit boards which mainly includes:
  • the inside of the electrolytic tank A is divided into an anode tank area and a cathode tank area using electrolytic tank dividers.
  • the inside of the electrolytic tank B is divided into an anode tank area and a cathode area.
  • Cell area; a redox potentiometer is installed in the cathode cell area of electrolytic cell A, and the cathode cell of electrolytic cell A The area is connected to the cathode tank area of electrolytic tank B through a liquid flow pipeline.
  • the solution that has undergone electrolysis reaction in the cathode tank area of electrolytic tank A is added to the cathode tank area of electrolytic tank B for progressive electrolysis to extract copper; electrolytic tank A An electrolytic anode and an electrolytic cathode are respectively provided in the anode tank area and the cathode tank area of electrolytic tank A, and the electrolytic anode and electrolytic cathode are respectively connected to the positive and negative electrodes of the electrolytic power supply of electrolytic tank A; the anode tank of electrolytic tank B
  • the electrolytic anode and electrolytic cathode of electrolytic tank B are respectively provided in the electrolytic tank area and the cathode tank area of electrolytic tank B.
  • the electrolytic anode and electrolytic cathode are respectively connected to the positive and negative electrodes of the electrolytic power supply of electrolytic tank B.
  • the anode tank area of electrolytic tank A and the cathode tank area of electrolytic tank A are respectively filled with anolyte and catholyte
  • the anode tank area of electrolytic tank B and the cathode tank area of electrolytic tank B are respectively filled with anolyte and catholyte.
  • the anolyte of electrolytic tank A includes at least one of etching working fluid, etching waste liquid, and the catholyte of electrolytic tank B after electrolysis treatment, and the electrolytic tank A
  • the catholyte contains acidic etching waste liquid
  • the anolyte of electrolytic tank B contains at least one of the catholyte of electrolytic tank B, etching working fluid, and etching waste liquid after electrolysis treatment, and the electrolytic
  • the catholyte of tank B includes the catholyte of electrolytic tank A that has undergone electrolysis treatment or a mixed solution with the acidic etching waste liquid.
  • the electrolytic cell separator of electrolytic cell A is selected from at least one of anion exchange membrane, bipolar membrane, and reverse osmosis membrane.
  • the electrolytic tank B can be an electrolytic tank divided into an anode tank area and a cathode tank area in any structural form. Specifically, it can be divided into structural forms with electrolytic separators and without electrolytic separators. When the anode tank area and the cathode tank area of the electrolytic tank B are separated by electrolytic tank separators, the electrolytic tank separators of the electrolytic tank B are selected from at least one of anion exchange membrane, bipolar membrane and reverse osmosis membrane. A sort of.
  • the present invention can make the following improvements: according to the value measured by the redox potentiometer in the cathode tank area of the electrolytic tank A, the output current of the electrolytic power supply A is adjusted or shut down according to the process requirements, and/or the output current of the electrolytic power supply A is supplied to the cathode of the electrolytic tank A.
  • the tank area is controlled to add a solution containing acidic etching waste liquid.
  • the present invention can make the following improvements: add at least one electrolytic tank C arranged after the electrolytic tank B.
  • the electrolytic tank C is divided into an anode tank area and a cathode tank area; the cathode tank area of the electrolytic tank B and the electrolytic tank C
  • the cathode tank area is connected through a liquid flow pipeline, and the electrolyzed solution in the cathode tank area of electrolytic tank B is added to the cathode tank area of electrolytic tank C; the anode tank area of electrolytic tank C and the cathode tank area of electrolytic tank C
  • the anolyte of electrolytic tank C includes at least one of the etching working fluid, the catholyte of electrolytic tank B after electrolysis treatment, the catholyte of electrolytic tank C after electrolysis treatment, or in On this basis, it further includes etching waste liquid; the catholyte of electrolytic tank C includes the catholyte of electrolytic tank B after electrolysis treatment, or on this basis, it further includes the catholyte of electrolytic tank A and/or etching. Waste liquid.
  • the anolyte of electrolytic tank A includes at least one of the catholyte of electrolytic tank B after electrolysis treatment, the catholyte of electrolytic tank C after electrolysis treatment, etching working liquid, and etching waste liquid.
  • the anolyte of electrolytic tank B includes at least one of the catholyte B of electrolytic tank B after electrolysis treatment, the catholyte of electrolytic tank C after electrolysis treatment, etching working liquid, and etching waste liquid. kind.
  • the electrolytic tank C can be an electrolytic tank divided into an anode tank area and a cathode tank area in any structural form. Specifically, it can be divided into structural forms with electrolytic separators and without electrolytic separators.
  • the electrolytic tank separators of electrolytic tank C can be selected from anion exchange membranes, bipolar membranes, and reverse osmosis membranes. of at least one.
  • the electrolytic anode in the present invention uses a material whose shape and properties are stable in the electrolyte. Specifically, materials whose surface is gold and/or platinum and/or an alloy containing at least one of the above metals, titanium-based coating insoluble anodes can be used , at least one type of conductive graphite, preferably a titanium-based coating insoluble anode.
  • the material of the electrolytic cathode of the electrolytic cell A is gold and/or platinum and/or titanium and/or an alloy containing at least one of the above metals and/or conductive graphite, preferably titanium.
  • the electrolytic cathode of the electrolytic tank B and the electrolytic cathode of the electrolytic tank C can be made of gold and/or platinum and/or titanium and/or copper and/or an alloy containing at least one of the above metals and/or stainless steel, preferably Copper metal.
  • the present invention can be improved as follows: a cathode cloth filter bag is used to cover the electrolytic cathode of at least one electrolytic cell at the end to collect sponge copper produced during the copper electrolysis process.
  • the present invention can be improved as follows: add a sensor and an automatic detection and feeding controller, and use at least one sensor to detect the anolyte and catholyte of electrolytic tank A, the anolyte and catholyte of electrolytic tank B, and the electrolytic tank C. Detect at least one of the anolyte and catholyte, and transmit the data measured on site to the automatic detection and feeding controller for processing to control the size of the output current of at least one electrolytic power supply and/or various materials additional investment.
  • the senor is at least one selected from the group consisting of an acidometer, a hydrometer, a redox potentiometer, a photoelectric colorimeter, a liquid level meter, a thermometer, a flow meter, and a chlorine gas detector.
  • the present invention can be improved as follows: add a circulating mixing exchange tank, and provide an anode tank area of electrolytic tank A and/or an anode tank area of electrolytic tank B and/or an anode tank area of electrolytic tank C in the electrolytic separator electrolytic tank.
  • the circulating mixing exchange tank is connected with a circulation pipeline, and the circulating mixing exchange tank is connected with the etching production line as a circulating pipeline, so that the anolyte and the etching working fluid are mixed in the circulating mixing exchange tank, and the etching working fluid on the etching production line can be mixed.
  • a larger volume circulating mixing exchange tank is used to control the redox potential of the solution in the tank to be higher than that of the etching working fluid, so that the copper etching agent concentration of the solution in the tank is much higher than that of the etching working fluid, thereby efficiently utilizing the electrolytic equipment .
  • the present invention can be improved as follows: adding a hot and cold temperature exchanger to adjust and control the temperature of the solution prepared to enter the etching production line.
  • the present invention can be improved as follows: adding a temporary storage tank for temporarily storing various solutions and/or being used as a chemical reaction preparation tank for the solution.
  • the present invention can be improved as follows: an exhaust gas treatment tank is added to treat the exhaust gas precipitated from each electrolytic tank and each temporary storage tank during the working process.
  • the present invention can be improved as follows: add a stirrer, whose structures include an impeller type stirrer and a circulating liquid flow pump tube stirrer, which are used to stir and mix the solutions in the electrolytic tank and the temporary storage tank.
  • the present invention can be improved as follows: adding an overflow buffer tank to solve the problem of solution flow depending on the liquid level between the tanks.
  • the present invention can make the following improvements: add a sealed tank cover with a vent and a feeding port for the electrolytic tank to collect the electrolyzed chlorine or oxygen for safe production use.
  • the present invention can make the following improvements: adding a movable tank cover in the cathode tank area of the electrolytic tank, so that the acidic waste gas can be conveniently collected and processed and the cathode can be easily extracted to recover metallic copper.
  • the present invention can be improved as follows: a gas-liquid mixer is added, and its structure can be a vacuum jet gas-liquid mixer or a spray-type gas-liquid mixer for mixing gas and liquid.
  • the present invention can be improved as follows: add a filter, perform solid-liquid separation on the treated solution or remove impurities from organic matter.
  • the present invention can be improved as follows: add an etching waste liquid feeding pipe in the cathode tank area of electrolytic tank B and/or electrolytic tank C.
  • the feeding pipe is installed close to the separator so that the Fe 3+ ions in the iron-containing etching waste liquid react with the cuprous chloride adhering to the separator and generate copper chloride that is dissolved in the catholyte to avoid Separator blocked plug.
  • Addition can be controlled according to time interval or tank pressure.
  • the present invention has the following beneficial effects:
  • the present invention solves the problem that the copper blocks electrolyzed in the existing process of recycling acidic etching waste liquid of circuit boards are loose and easily broken.
  • the present invention can realize 100% recycling of acidic etching waste liquid of circuit boards through electrolysis, greatly reducing production costs and reducing environmental pollution.
  • the process of the present invention can eliminate the need to add external oxidants from the acid etching system in recycling production, thereby reducing production costs.
  • the process of the present invention can take advantage of the acidic iron-containing etching process, which can not only improve the etching efficiency but also improve the etching quality.
  • Figure 1 is a progressive electrolysis device for recycling acidic etching waste liquid of circuit boards according to Embodiment 1 of the present invention
  • Figure 2 is a progressive electrolysis device for recycling acidic etching waste liquid of circuit boards according to Embodiment 2 of the present invention
  • Figure 2.1 is an enlarged view of 2-E of Figure 2;
  • Figure 2.2 is an enlarged view of 2-F in Figure 2;
  • Figure 2.3 is an enlarged view of 2-G in Figure 2;
  • Figure 2.4 is an enlarged view of 2-H in Figure 2;
  • Figure 3 is a progressive electrolysis device for recycling acidic etching waste liquid of circuit boards according to Embodiment 3 of the present invention
  • Figure 3.1 is an enlarged view of 3-E in Figure 3;
  • Figure 3.2 is an enlarged view of 3-F in Figure 3;
  • Figure 3.3 is an enlarged view of 3-G in Figure 3;
  • Figure 3.4 is an enlarged view of 3-H in Figure 3;
  • Figure 3.5 is a 3-K enlarged view of Figure 3;
  • Figure 4 is a progressive electrolysis device for recycling acidic etching waste liquid of circuit boards according to Embodiment 4 of the present invention
  • Figure 4.1 is an enlarged view of 4-E of Figure 4.
  • Figure 4.2 is an enlarged view of 4-F in Figure 4.
  • Figure 4.3 is an enlarged view of 4-G in Figure 4.
  • Figure 4.4 is an enlarged view of 4-H in Figure 4.
  • Figure 5 is a progressive electrolysis device for recycling acidic etching waste liquid of circuit boards according to Embodiment 8 of the present invention.
  • Figure 5.1 is an enlarged view of 5-E of Figure 5;
  • Figure 5.2 is an enlarged view of 5-F in Figure 5;
  • Figure 5.3 is an enlarged view of 5-G in Figure 5;
  • Figure 5.4 is an enlarged view of 5-H in Figure 5;
  • Figure 5.5 is a 5-K enlarged view of Figure 5;
  • Figure 6 is a photo of metallic copper recovered using the solution of the present invention.
  • Figure 7 is a photo of metallic copper obtained by using existing technology to add etching waste liquid to the cathode tank area for direct electrolysis.
  • the electrolytic tank, temporary storage tank, exhaust gas treatment tank, overflow buffer tank, vacuum jet gas-liquid mixer, spray gas-liquid mixer, agitator, and water-oil separator used in the following examples are all from Guangdongzhou. Products manufactured by Foshan Yegao Environmental Protection Equipment Manufacturing Co., Ltd. Solid-liquid separation filters, electrolytic cell separation membranes, sensors, PLC controllers, valves, pumps, and chemical raw materials are all commercially available products. In addition to the above list, skills Those skilled in the art can also choose other products with similar performance to the above-mentioned products listed in the present invention based on routine selection, all of which can achieve the purpose of the present invention.
  • Figure 1 shows a basic embodiment 1 of a progressive electrolytic method for recycling circuit board acid etching waste liquid and its device, which includes an electrolytic tank A 1, an electrolytic tank B 2, and a cathode tank of the electrolytic tank A.
  • the separator 3 of electrolytic tank A is a reverse osmosis membrane
  • the separator 4 of electrolytic tank B is an anion exchange membrane
  • the anode material of electrolytic cell A is platinum metal, and the cathode material is conductive graphite plate.
  • the anode material of electrolytic cell B is titanium-based coated electrode, and the cathode material is stainless steel.
  • the sensors 101 and 102 are redox potentiometers, and the sensor 103 is a hydrometer (measuring the concentration of metal ions in the solution).
  • the vacuum jet gas-liquid mixer 71 is used to absorb and guide the chlorine gas electrolyzed and escaped from the anode tank area of the electrolytic tank A and the electrolytic tank B to the temporary storage tank 28 for oxidation and regeneration reaction to prepare the regeneration etching device. Liquid 252.
  • the sensor 101 liquid level gauge is installed in the anode tank area of the electrolytic tank A, and the pump 133-1 is controlled to throw the etching waste liquid into the anode tank area of the electrolytic tank A.
  • the redox potential controller 7 is installed in the cathode tank area of the electrolytic tank A to control the pump 133-2 according to the process to add the acidic etching waste liquid 251 in the temporary storage tank 23 to the cathode tank area of the electrolytic tank A.
  • the overflow liquid 268 from the cathode tank area of the electrolytic tank A that has undergone electrolysis treatment is directed to the temporary storage tank 25 for temporary storage, and its copper ion concentration is the same as the original waste liquid.
  • the electrolytic tank B 2 is a progressive electrolytic electrolytic tank for extracting copper. Its function is that the anode tank area of the electrolytic tank B oxidizes the electrolyte and produces chlorine, while the cathode performs electrolytic precipitation of copper.
  • the anolyte of electrolytic tank B is the catholyte 256 overflowing from the electrolytic tank B 2 that has undergone copper recovery treatment. An oxidation reaction is performed in the anode tank area of electrolytic tank B to generate a regenerated etching subliquid 252 .
  • a sensor 103 is installed in the cathode tank area of electrolytic tank B to control the overflow liquid 268 in the cathode tank area of electrolytic tank A in the temporary storage tank 25. Throw it into the cathode tank area of electrolytic tank B 2 as a progressive electrolytic copper treatment.
  • the catholyte 256 overflowing from the electrolytic tank B 2 that has been treated for copper recovery is partially pumped to the temporary storage tank 28 by the pump 133-4, and is used with chlorine gas to prepare an oxidation reaction of the regenerated etching sub-liquid, so that the temporary storage
  • the cuprous chloride and ferrous chloride in the solution in the tank 28 undergo an oxidation reaction under the control of the sensor 104 ORP meter to generate a copper etching agent of cupric chloride and ferric chloride.
  • the standard requirements for regenerating the etching subliquid are met, it is pumped to the temporary storage tank 26 for temporary storage by the pump 133-7.
  • the regenerated etching sub-liquid 252 with a low copper ion concentration that meets the process requirements after the oxidation treatment can be prepared.
  • the main components of the acidic etching waste liquid in this embodiment are: hydrochloric acid, copper chloride, ferric chloride, ferrous chloride, sodium chloride, ammonium chloride and water.
  • the acidity is 1.2mol/L
  • the copper ion concentration is 120g/L
  • the total iron ion concentration is 100g/L.
  • Its oxidation-reduction potential value ORP value is 610mv.
  • the sensor 103 in B monitors the overflow liquid 268 of the cathode tank area of electrolytic tank A in the temporary storage tank 25 through the pump 133-3 to the cathode tank area of electrolytic tank B and controls the cathode tank area of electrolytic tank B in the process.
  • the copper ion concentration of the catholyte is the concentration of the catholyte.
  • the anodes of electrolytic tank A and the anode of electrolytic tank B respectively perform electrochemical oxidation reactions on the acidic etching waste liquid 251 and the overflowing catholyte 256 of electrolytic tank B that has been treated for recycling copper.
  • the anodes of electrolytic tank A and electrolytic tank B Chlorine gas escaping from the tank area
  • the ejector 71 mixes gas and liquid to oxidize the solution in the temporary storage tank 28 to generate a regenerated etching sub-liquid 252;
  • the cathode electrolyte in the electrolytic tank A performs a reduction reaction to eliminate the copper etching agent, and the cathode in the electrolytic tank B electro-precipitates metallic copper 253.
  • the anode of electrolytic tank B is used to oxidize the catholyte 256 overflowing from electrolytic tank B that has been processed for copper recovery to prepare a regenerated etching sub-liquid.
  • the parameter values of the regenerated etching sub-liquid are acidity 4.0M/L, copper ion concentration 60g/L, iron ion concentration 100g/L, and ORP value 650mv.
  • FIG. 2 shows Embodiment 2 of a progressive electrolysis method for recycling circuit board acid etching waste liquid and its device, which includes an electrolytic tank A 1 and two electrolytic tanks B 2-1 and 2-2 , cathode tank area redox potential controller 7 of electrolytic tank A, separator 3 of electrolytic tank A, separators 4-1 and 4-2 of electrolytic tank B, electrolytic power supply 5 of electrolytic tank A, electrolytic power supply 6 of electrolytic tank B -1 and 6-2, temporary storage tank 23 ⁇ 28, overflow buffer tank 51 ⁇ 56, water and oil separator 96, sensor 101 ⁇ 112, automatic detection feeding controller 131, valve 132-1 ⁇ 132-23, pump Pu 133-1 ⁇ 133-23, cathode tank area etching waste liquid feed pipe 134, acidic etching waste liquid 251, regenerated etching sub-liquid 252, recycled metal copper 253, overflowing catholyte from electrolytic tank B that has been treated for copper recycling 256.
  • the electrolytic tank A separator 3 is an anion exchange membrane.
  • the separator 4-1 of electrolytic tank B is a bipolar membrane, and the separator 4-2 is a reverse osmosis membrane.
  • the anode material of the electrolytic cell A is a titanium-based coating insoluble anode, and the cathode material is titanium metal.
  • the anode material of the electrolytic tank B 2-1 is a titanium-based coating insoluble anode, and the cathode material is a metal copper sheet; the anode material of the electrolytic tank B 2-2 is conductive graphite, and the cathode material is a metal copper sheet.
  • the sensors 101 and 109 are hydrometers
  • the sensor 102 is an acidometer
  • the sensors 103, 106 and 111 are redox potentiometers (i.e. ORP meters)
  • the sensors 104 and 107 are thermometers
  • the sensors 105, 108 and 112 are liquid levels.
  • the sensor 110 is a photoelectric colorimeter.
  • the on-site data of all sensors are sent to the automatic detection and feeding controller 131 for processing and the entire device is controlled according to the program.
  • Sensors 101, 102, 103, and 104 are installed in the circuit board etching production line 257.
  • the sensor 102 acidometer controls the pump 133-1 to add the regenerated etching subliquid 252 as the etching working fluid as the acid. degree control; the sensor 101 hydrometer controls the valve to add 288 clean water to control the proportion of the etching working fluid; the sensor 103 ORP meter controls the speed of the variable frequency pump 133-4 to control the oxidation-reduction potential of the etching working fluid at 540mv according to the process; the sensor 104 thermometer makes the etching The temperature of the working fluid is controlled at 50°C. Therefore, the etching line 257 of the circuit board is controlled to maintain the acidity of the etching working fluid at 0.9mol/L, the specific gravity at 1.34g/ml, and the ORP at 530mv to stabilize the etching performance.
  • the etching waste liquid overflowing from the circuit board etching production line 257 first flows into the water-oil separator 96 for separation of the organic matter of the ink and film residue, and then flows into the liquid flow buffer tank 51, and is then pumped through the pump 133-3 to the temporary storage tank 24 used as a circulating mixing and exchange tank.
  • the oxidation regeneration etching liquid 260 in the temporary storage tank 24 is full, it is controlled by the sensor 105 liquid level meter to start the pump 133-7 to remove part of the temporary storage tank 24.
  • the solution is pumped to the temporary storage tank 25 for temporary storage.
  • the described circulating mixing exchange tank that is, the temporary storage tank 24, is connected with the circuit board etching line 257 as a circulating liquid flow pipeline, and is connected with the anode tank area of the electrolytic tank B 2-1 and 2-2 as a circulating liquid flow pipeline.
  • the solution in the mixing exchange tank is the oxidation regeneration etching solution 260 .
  • the oxidation-reduction potential value of the oxidation regeneration etching liquid 260 in the temporary storage tank 24 is transmitted to the automatic detection and feeding controller 131 for processing through the sensor 107 ORP meter, and the working currents of the electrolytic power supplies 6-1 and 6-2 are adjusted and controlled. , so that the oxidation-reduction potential value range of the oxidation regeneration etching solution 260 is controlled at 750 to 800 mv.
  • the redox potential controller 7 controls the pump 133-10 to add the etching waste liquid 251 in the temporary storage tank 25 to the cathode tank area of the electrolytic tank A, and the overflow liquid 268 after electrolysis treatment is pumped 133-10. 9 is pumped to the temporary storage slot 26 for temporary storage.
  • the copper ion concentration of the solution in the temporary storage tank 26 is still about 140g/L.
  • the anode of electrolytic tank A is specially used to generate chlorine gas to oxidize the cathode overflow liquid 256 of electrolytic tank B 2-1 and 2-2 to prepare regeneration etching sub-liquid 252.
  • the electrolytic tanks B 2-1 and 2-2 are a progressive electrolytic electrolytic tank for extracting copper. Its function is to electrolyze the cathode to extract copper, and the anode to oxidize the oxidation regeneration etching solution 260 to maintain the etching process.
  • the sensor 109 hydrometer and the sensor 110 photoelectric colorimeter control the pumps 133-13 and 133-14 respectively to add the overflow liquid 268 from the cathode tank area of the electrolytic tank A in the temporary storage tank 26 to the electrolytic tank B 2-1 and 2 -2 in the cathode tank area to achieve progressive electrolysis of copper.
  • the copper ion concentration control setting value in the catholyte of electrolytic cells B 2-1 and 2-2 is 40g/L
  • the cathodes of electrolytic cells B 2-1 and 2-2 are electrolytically precipitated copper metal 253.
  • the overflowing catholyte 256 from the electrolytic tanks B 2-1 and 2-2 that have been treated for copper recovery is pumped to the temporary storage tank 27, and then the pump 133 is controlled by the sensor 111 ORP meter and the sensor 112 liquid level meter. -19
  • the chlorine gas is pumped into the temporary storage tank 28 through the spray tower to perform an oxidation reaction on the catholyte 256 overflowing from the electrolytic tank B that has been treated for copper recovery, so that the cuprous chloride and ferrous chloride in the solution are oxidized. It becomes copper chloride and ferric chloride copper etching agent to produce a regeneration etching sub-liquid with low copper ion concentration that meets the process requirements.
  • etching waste liquid feeding pipes 296 and 297 in the cathode tank area of electrolytic tanks B 2-1 and 2-2 are used to add etching waste liquid to react and remove the chlorination on the separators 4-1 and 4-2 of electrolytic tank B. Cuprous copper mud to avoid copper mud clogging of separators.
  • the main components of the acidic iron-containing etching waste liquid in this embodiment are: aqueous solutions of hydrochloric acid, copper chloride, sodium chloride, ammonium chloride, ferric chloride and ferrous chloride.
  • the acidity is 0.9mol/L
  • the copper ion concentration is 140g/L
  • the total iron ion concentration is 20g/L.
  • the main steps of a progressive electrolysis device for recycling acidic etching waste liquid of circuit boards are as follows.
  • the anode tank area of electrolytic tank A is used for the electrolysis of chlorine gas; electrolytic tank B
  • the sensor 109 hydrometer in 2-1 monitors the overflow liquid 268 in the cathode tank area of electrolytic tank A in the temporary storage tank 26 and is thrown to the cathode tank area of electrolytic tank B 2-1 through the pump 133-14.
  • the sensor 110 photoelectric colorimeter controls the pump 133-13 to add the solution in the temporary storage tank 26 to the cathode tank area of the electrolytic tank B, so that the cathodes in the electrolytic tank B 2-1 and 2-2 are electrolytically coated with copper;
  • the anodes of electrolytic tanks B 2-1 and 2-2 perform an electrochemical oxidation reaction on the oxidation regeneration etching solution 260, so that the circuit board etching production line 257 maintains etching production by controlling the rotational speed and delivery volume of the pump 133-4; at the same time, the electrolytic tank
  • the chlorine gas escaping from the anode tank area of A is absorbed by the spray gas-liquid mixer 76 and the processor prepares the overflowing catholyte 256 of the electrolytic tank B that has been treated for copper recycling to regenerate the etching sub-liquid 252.
  • the working parameter indicators of the prepared regeneration etching sub-liquid 252 are acidity 4.5M/L, copper ion concentration 40g/L, and iron ion concentration 20g/L.
  • Embodiment 3 of a progressive electrolytic device for recycling circuit board acidic etching waste liquid includes electrolytic tank A 1, electrolytic tank B 2-1 and 2-2, and electrolytic tank C 8 .
  • An oxidation-reduction potential controller 7 is installed in the cathode tank area of electrolytic tank A.
  • the electrolytic tank A separator 3 provided in the electrolytic tank A is a bipolar membrane.
  • the electrolytic tank B separator 4-1 of electrolytic tank B is an anion exchange membrane, and 4-22 is an anion exchange membrane.
  • the electrolytic tank C separator 9 of the electrolytic tank C is an anion exchange membrane.
  • electrolytic power supply 5 for electrolytic tank A
  • two electrolytic power supplies 6-1 and 6-2 for electrolytic tank B for electrolytic tank B
  • electrolytic power supply 10 for electrolytic tank C temporary storage tanks 23-31
  • overflow buffer tanks 51-56 Vacuum jet gas-liquid mixer 71, spray gas-liquid mixer 76, circulating liquid flow mixer 81 ⁇ 86, sensor, 110 ⁇ 112, automatic detection feeding controller 131, acidic etching waste liquid 251, regenerated etching sub-liquid 252 , Recycle metallic copper 253, overflow catholyte of electrolytic tank B3 ⁇ 4 that has been treated for copper recovery 256, circuit board etching production line 257, valves 132-1 ⁇ 132-19, pumps 133-1 ⁇ 133-20, hydrogen Sodium oxide solution 267, exhaust gas treatment tank 281, overflow liquid from the cathode tank area of electrolytic tank A 268, clean water 288, movable tank covers 289 ⁇ 291.
  • the anode material of electrolytic cell A is an insoluble anode with a gold-plated surface, and the cathode is platinum metal.
  • the anode material of the electrolytic cell B 2-1 is conductive graphite, and the cathode is a titanium plate.
  • the anode material of electrolytic cell B 2-2 is a titanium-based coating insoluble anode, and the cathode is a titanium plate.
  • the anode material of electrolytic cell C 8 is a titanium-based coated insoluble anode, and the cathode material is copper sheet.
  • the circuit board etching production line 257 is connected with each anode tank area of electrolytic cells A and B by liquid flow pipelines.
  • the sensor 101 acidometer controls the addition of the pump 133-1 to regenerate the etching liquid 252
  • the sensor 102 hydrometer controls the addition of clean water 288, and the sensor 103 redox potentiometer controls the adjustment of the output current of each electrolytic power supply or shutdown.
  • the concentration of copper etching agent in the etching working fluid reaches the process setting value, all electrolytic power supplies will be shut down.
  • the sensor 104 temperature controller controls the temperature of the etching working fluid to 50°C. Through the above control of multiple acidity, specific gravity, redox potential, and temperature parameters, the etching working fluid can still maintain its etching performance during the continuous etching production process.
  • the overflow buffer tank 51 is provided with an output pump pipeline with a solid-liquid separation filter 97.
  • the organic oil residue floating on the etching working fluid is separated by filtration and the etching waste liquid is directed to the temporary storage tank 25.
  • the overflowing acid etching waste liquid 251 is stored in the middle.
  • the circulating mixing exchange tank is not provided.
  • pumps 133-4 to 133-6 are directly used to pump the etching working fluid to the anode tank areas of electrolytic tank A and electrolytic tank B, and then the etching working liquid is pumped to the anode tank area of electrolytic tank A and electrolytic tank B.
  • the respective anode tank area overflow ports flow back to the circuit board etching production line 257.
  • multiple electrolytic power supplies are started or adjusted to respond, so that the etching working fluid is oxidized and the copper etching agent is regenerated.
  • the redox potential controller 7 is installed in the cathode tank area of the electrolytic tank A, and is set to 200mv according to the process to control the amount of etching waste liquid 251 in the temporary storage tank 25 to the cathode tank area of the electrolytic tank A. All the ferric iron ions in the catholyte are changed into divalent iron ions, and at the same time, the cathode electrolytically precipitates copper metal as little as possible.
  • the treated overflow liquid 268 from the cathode tank area of electrolytic tank A is pumped by the pump 133-7 to the temporary storage tank 26 for temporary storage, and the copper ion concentration of the solution is reduced to 98g/L.
  • the electrolytic tank B adopts a progressive electrolytic copper extraction process compared to the electrolytic tank A, while the electrolytic tank C adopts a further progressive electrolytic copper extraction process.
  • Hydrometers namely sensors 105 and 106, are respectively installed in the cathode tank area of electrolytic tank B.
  • a sensor 107 ORP meter is installed in the anode tank area of electrolytic tank C, and a sensor 108 hydrometer is installed in the cathode tank area of electrolytic tank C.
  • the detection data of the above multiple sensors are sent to the automatic detection and feeding controller 131 for processing, and the overflow liquid 268 of the cathode tank area of the electrolytic tank A in the temporary storage tank 26 is controlled to be added to the cathode tank area of the electrolytic tank B, so that the electrolysis
  • the concentration of each component in the electrolyte in each cathode tank area of tank B is controlled during the copper electrolysis process, and the cathode overflow liquid of electrolytic tank B is pumped to the temporary storage tank 27 by pumps 133-11 and 133-12 for temporary storage. .
  • the copper ion concentration of the solution in the temporary storage tank 27 is set and controlled at 60g/L.
  • the automatic detection feeding controller 131 controls the pump 133-13 to pour the solution 256 into the cathode tank area of the electrolytic tank C.
  • the sensor 108 hydrometer controls the copper ion concentration of the catholyte in the electrolytic tank C to be 5g/L.
  • sponge copper will be produced and collected by the cathode cloth filter bag 294.
  • its catholyte overflows into the overflow buffer tank 56 and is pumped to the temporary storage tank 30 for temporary storage through the pump 133-18.
  • the temporary storage tank 31 is used as a chlorine oxidation reaction tank, with a vacuum jet gas-liquid mixer 71 installed on the top of the tank and a sensor 109 liquid level gauge installed in the tank. During the process, the chlorine gas escaped from the anode tank area of each electrolytic tank is directed to the temporary storage tank 31 to react with the solution in the tank.
  • the sensor 109 liquid level meter controls the pump 133-19 to put the solution in the temporary storage tank 31, and the sensor 107 ORP meter controls the pump 133-20 to put the solution in the temporary storage tank 31 into the anode tank area of the electrolytic tank C, so that the electrolytic tank C's catholyte can oxidize cuprous chloride and ferrous chloride into copper etching agents after electrolytically removing copper to meet some of the standard requirements for regenerating the etching sub-liquid.
  • the temporary storage tank 28 is used for preparing regenerated etching liquid. After the solution is put into the temporary storage tank 29, hydrochloric acid, ferric chloride, and ammonium chloride are put in, and the liquid flow circulation stirrer 84 is started to prepare the regeneration etching sub-liquid 252. After passing the manual inspection, the prepared regeneration etching sub-liquid 252 is pumped to the temporary storage tank 23 for temporary storage.
  • the exhaust gas treatment tank 281 is used to absorb the acidic exhaust gas S escaping from each tank for environmental protection treatment.
  • the redox potential value of the etching working fluid is controlled at 580mv.
  • the main components of the acidic iron-containing etching waste liquid in this embodiment are: aqueous solutions of hydrochloric acid, copper chloride, ammonium chloride and ferric chloride.
  • the acidity is 1.6mol/L
  • the copper ion concentration is 100g/L
  • the total iron ion concentration is 140g/L.
  • the operation steps of a progressive electrolysis device for recycling circuit board acidic etching waste liquid are as follows.
  • etching working liquid to the anode tank area of electrolytic tank A and add etching waste liquid 251 to the cathode tank area.
  • An oxidation-reduction potential controller 7 is installed in the cathode tank area of electrolytic tank A to control during the electrolysis process.
  • the amount of electricity added by the etching waste liquid 251 to the cathode tank area of the electrolytic tank A is controlled to have an ORP value of the catholyte of 200 mv.
  • each electrolytic tank can perform electrolysis operation.
  • the etching working fluid in the etching production line 257 is used to circulate between the anode tank areas of electrolytic tanks A and B, so that each electrolytic tank can The anode performs an electrochemical reaction of oxidation and regeneration of the etching working fluid.
  • Electrolyzers A and B The chlorine gas precipitated from the anode tank area is directed to the temporary storage tank 31 for oxidizing the electrolyte overflowing from the cathode tank area of electrolytic tank C that has been treated to recover copper.
  • Metal is electrolytically precipitated from the cathodes of electrolytic tank B and electrolytic tank C. Copper 253.
  • the acidic exhaust gas S escaped from each tank is directed to the exhaust gas treatment tank 281 for environmental protection treatment.
  • the process flow of the entire equipment system is automatically controlled by the automatic detection and feeding controller 131 according to the program, and the regenerated etching sub-liquid in the temporary storage tank 23 is put into the etching line for recycling.
  • FIG. 4 shows Embodiment 4 of a progressive electrolysis method for recycling circuit board acid etching waste liquid and its device, which includes an electrolytic tank A 1 and two electrolytic tanks B 2-1 and 2-2 , the redox potential controller 7 of the cathode tank area of electrolytic tank A, the separator 3 of electrolytic tank A, the separators 4-1 and 4-2 of electrolytic tank B, the electrolysis power supply 5 of electrolytic tank A, and the electrolysis of the two electrolytic tanks B Power supplies 6-1 and 6-2, temporary storage tanks 23 ⁇ 28, overflow buffer tanks 51 ⁇ 56, water and oil separators 96, sensors 101 ⁇ 112, automatic detection feeding controller 131, valves 132-1 ⁇ 132-20 , Pump 1331 ⁇ 133-20, Acidic etching waste liquid 251, Regenerated etching sub-liquid 252, Recycled metal copper 253, Overflowing catholyte from electrolytic tank B that has been treated for copper recycling 256, Circuit board etching production line 257, Oxidation regeneration Etching liquid 260 and overflow liquid 2
  • the electrolytic tank A separator 3 is an anion exchange membrane.
  • the separator 4-1 of the electrolytic tank B is a bipolar membrane, and the separator 4-2 is a reverse osmosis membrane.
  • the anode material of the electrolytic cell A is a titanium-based coating insoluble anode, and the cathode material is titanium metal.
  • the anode material of the electrolytic tank B 2-1 is a titanium-based coating insoluble anode, and the cathode material is a metal copper sheet; the anode material of the electrolytic tank B 2-2 is conductive graphite, and the cathode material is a metal copper sheet.
  • the sensor 101 is an acidometer
  • the sensors 102, 106, and 111 are redox potentiometers or ORP meters
  • the sensors 103 and 107 are thermometers
  • the sensors 104 and 109 are hydrometers
  • the sensors 105 and 112 are liquid level meters
  • the sensor 110 It is a photoelectric colorimeter. All sensor field detection data are transmitted It is processed by the automatic detection and feeding controller 131 and controls the operation of the entire device according to the program.
  • the circuit board etching production line 257 is equipped with sensors 101 to 103, in which the sensor 101 acidity meter controls the valve to add external acidic ferric chloride solution for acidity control of the etching working fluid; the sensor 102 ORP meter controls the variable frequency pump 133-4 The rotation speed controls the oxidation-reduction potential of the etching working fluid to 510 mv according to the process; the sensor 103 thermometer controls the temperature of the etching working fluid to 50°C. Among them, the specific gravity of the etching working fluid is detected and controlled by the sensor 104 hydrometer installed in the circulating mixing exchange tank.
  • the control pump 133-1 When the specific gravity of the solution in the circulating mixing exchange tank increases due to copper corrosion, the control pump 133-1 will temporarily store The solution in tank 23 is pumped into the circulating mixing exchange tank to reduce the copper ion concentration in the solution. Therefore, the circuit board etching production line 257 uses the above control to maintain the acidity of the etching working fluid at 1 mol/L, the specific gravity at 1.33 g/ml, and the ORP at 510mv to stabilize the etching performance.
  • the etching waste liquid overflowing from the circuit board etching production line 257 first flows into the water-oil separator 96 for separation of the organic matter of the ink and film residue, and then flows into the liquid flow buffer tank 51, and is then pumped through the pump 133-3 to the temporary storage tank 24 used as a circulating mixing exchange tank.
  • the oxidation regeneration etching liquid 260 in the temporary storage tank 24 is full, it is controlled by the sensor 105 liquid level meter to start the pump 133-7 to remove part of the temporary storage tank 24.
  • the solution is pumped to the temporary storage tank 25 for temporary storage.
  • the said circulating mixing exchange tank that is, the temporary storage tank 24 is connected to the circuit board etching production line 257 as a circulating liquid flow pipeline, and is connected to the anode tank area of the electrolytic tank A and the electrolytic tank B as a circulating liquid flow pipeline.
  • the temporary storage tank 24 The redox potential value of the oxidation regeneration etching liquid 260 is transmitted to the automatic detection and feeding controller 131 for processing through the sensor 107 ORP meter, and the working current of the two electrolytic power supplies B is adjusted and controlled to circulate the mixed exchange tank solution 260.
  • the redox potential value range is controlled at 750 ⁇ 800mv.
  • the regenerated etching subliquid in the temporary storage tank 23 is not thrown into the etching line but directly into the circulating mixing exchange tank, which can Quickly balance the copper ion concentration of the etching working fluid, and quickly oxidize and regenerate the remaining Fe 2+ ferrous ions in the etching sub-liquid, making the ORP value of the etching working fluid more stable.
  • the redox potential controller 7 controls the pump 133-11 according to the process setting value to add the etching waste liquid 251 in the temporary storage tank 25 to the cathode tank area of the electrolytic tank A, and the overflow liquid 268 after electrolysis treatment It is pumped by the pump 133-10 to the temporary storage tank 26 for temporary storage.
  • the electrolysis operation since metallic copper is not electrolytically precipitated from the cathode of electrolytic tank A, the copper ion concentration of the solution in the temporary storage tank 26 is still 120g/L.
  • the anode of electrolytic tank A is used to oxidize the etching working fluid.
  • the electrolytic tank B is an electrolytic tank that is a progressive electrolytic copper extraction electrolytic tank of the electrolytic tank A.
  • the cathode is used for electrolytic extraction of copper
  • the anode is used for oxidation of the oxidation regeneration etching solution 260 to maintain the etching process.
  • the sensor 109 hydrometer and the sensor 110 photoelectric colorimeter control the pumps 133-12 and 133-13 respectively to add the overflow liquid 268 from the cathode tank area of electrolytic tank A in the temporary storage tank 26 to the cathode tanks of the two electrolytic tanks B.
  • the copper ion concentration control setting value in the catholyte of electrolytic tank B is 30g/L
  • the cathode in electrolytic tank B electrolytically precipitates copper metal 253.
  • the catholyte 256 that has been treated for copper recovery and overflows from the electrolytic tank B is pumped to the temporary storage tank 27 through the pumps 133-15 and 133-17, and then is measured by the sensor 111 ORP meter and the sensor 112 liquid level meter.
  • the pump 133-18 is controlled to pump the chlorine gas escaping into the temporary storage tank 28 through the spray tower to suck the chlorine gas escaping from the anode electrolyte of the electrolytic tank to oxidize the catholyte 256 overflowing from the electrolytic tank B that has been treated to recover copper, so that Part of the cuprous chloride and ferrous chloride in the solution are oxidized to form copper chloride and ferric chloride copper etching agents to prepare a regenerated etching sub-liquid with a low copper ion concentration. There is still a certain amount of ferrous iron ions that have not been oxidized by the chlorine gas in the regeneration etching sub-liquid.
  • the main components of the acidic iron-containing etching waste liquid in this embodiment are: aqueous solutions of hydrochloric acid, copper chloride, sodium chloride, ammonium chloride, ferric chloride and ferrous chloride.
  • the acidity is 1mol/L
  • the copper ion concentration is 120g/L
  • the total iron ion concentration is 120g/L.
  • the main steps of a progressive electrolysis device for recycling acidic etching waste liquid of circuit boards are as follows.
  • etching working liquid to the anode tank area of electrolytic tank A and add etching waste liquid 251 to the cathode tank area as the starting electrolyte, wherein the redox potential installed in the cathode tank area of electrolytic tank A Controller 7, during the electrolysis operation, sets the setting value of the redox potential controller 7 to 470mV to control the amount of etching waste liquid 251 added to the cathode tank area of electrolytic tank A, and no metallic copper is generated on the cathode. , only the reaction of eliminating the copper etching agent occurs, and the anode tank area of electrolytic tank A is used for the oxidation reaction of the etching working fluid.
  • the redox potential controller 7 monitors the etching waste liquid 251 and throws it into the cathode tank area of the electrolytic tank A, and the electrolytic tank B 2
  • the sensor 109 hydrometer in -1 monitors the overflow liquid 268 in the cathode tank area of electrolytic tank A in the temporary storage tank 26 and is thrown into the cathode tank area of electrolytic tank B through the pump 133-13.
  • the sensor 110 photoelectric colorimeter in the electrolytic tank B 2-2 controls the pump 133-12 to add the temporary storage tank 26 solution to the cathode tank area of the electrolytic tank B, so that the cathodes in the electrolytic tank B are electrolyzed with copper;
  • the anode of electrolytic tank B performs an electrochemical oxidation reaction on the oxidation regeneration etching solution 260, so that the etching production line 257 maintains etching production by controlling the rotational speed of the pump 133-4; at the same time, the anode tank area of each electrolytic tank escapes A small amount of chlorine gas is absorbed into the processor through the spray gas-liquid mixer 76 to prepare the regenerated etching subliquid 252 for the catholyte 256 overflowing from the electrolytic tank B that has been processed for copper recovery.
  • the working parameter indicators of the prepared regeneration etching sub-liquid 252 are acidity 6M/L, copper ion concentration 30g/L, and iron ion concentration 120g/L.
  • the main components of the acidic etching waste liquid in this embodiment are: hydrochloric acid, copper chloride and water.
  • the acidity is 3.2mol/L and the copper ion concentration is 120g/L.
  • Its oxidation-reduction potential value ORP value is 500mv.
  • electrolytic tank A is thrown into the cathode tank area of electrolytic tank B and technically controls the copper ion concentration of the catholyte.
  • the anodes of electrolytic tank A and the anode of electrolytic tank B respectively perform electrochemical oxidation reactions on the acidic etching waste liquid 251 and the overflowing catholyte 256 of electrolytic tank B that has been treated for recycling copper.
  • the anodes of electrolytic tank A and electrolytic tank B The chlorine gas escaping from the tank area is mixed with gas and liquid through the ejector 71 to oxidize the solution in the temporary storage tank 28 to generate a regenerated etching sub-liquid 252; the cathode electrolyte of the electrolytic tank A undergoes a reduction reaction to eliminate the copper etching agent, and the cathode of the electrolytic tank B Electrodeposition of metallic copper 253.
  • the anode of electrolytic tank B is used to oxidize the catholyte 256 overflowing from electrolytic tank B that has been processed for copper recovery to prepare a regenerated etching sub-liquid.
  • the parameter values of the regenerated etching sub-liquid are acidity 4.0M/L, copper ion concentration 60g/L, and ORP value 520mv.
  • the main components of the acidic etching waste liquid in this embodiment are: hydrochloric acid, copper chloride, ammonium chloride and water.
  • the acidity is 2.5mol/L and the copper ion concentration is 120g/L.
  • Its oxidation-reduction potential value ORP value is 520mv.
  • etching working liquid to the anode tank area of electrolytic tank A and add acidic etching waste liquid 251 to the cathode tank area.
  • An oxidation-reduction potential controller 7 is installed in the cathode tank area to control the etching waste liquid during the electrolysis process.
  • 251 is added to the cathode tank area of electrolytic tank A, and the ORP value of the catholyte is controlled to be 350mv.
  • the etching working fluid to the anode tank area of the two electrolytic tanks B, and add the overflow liquid 268 from the cathode tank area of electrolytic tank A in the temporary storage tank 26 to the cathode tank area of the electrolytic tank B, and use sensors 105 respectively.
  • the 106 hydrometer controls the amount of overflow liquid 268 from the cathode tank area of electrolytic tank A to each cathode tank area of electrolytic tank B during the process.
  • the etching working fluid in the etching production line 257 circulates between the anode tank areas of electrolytic tanks A and B, causing each electrolytic anode to perform an electrochemical reaction of oxidizing and regenerating the etching working fluid.
  • the chlorine gas precipitated from the anode tank areas of electrolytic tanks A and B is directed to the temporary storage tank 31 for oxidizing the overflowing electrolyte from the cathode tank area of electrolytic tank C that has been treated to recover copper.
  • the acidic exhaust gas S escaped from each tank is directed to the exhaust gas treatment tank 281 for environmental protection treatment.
  • the process flow of the entire equipment system is automatically controlled by the automatic detection and feeding controller 131 according to the program, and the regenerated etching sub-liquid in the temporary storage tank 23 is put into the etching line for recycling.
  • the main components of the acidic etching waste liquid in this embodiment are: hydrochloric acid, copper chloride, sodium chloride and water.
  • the acidity is 2.7mol/L, and the copper ion concentration is 110g/L.
  • Its oxidation-reduction potential value ORP value is 480mv.
  • the redox potential controller 7 monitors the etching waste liquid 251 and throws it into the cathode tank of the electrolytic tank A. area, the sensor 109 hydrometer in the electrolytic tank B 2-1 monitors the overflow liquid 268 of the cathode tank area of the electrolytic tank A in the temporary storage tank 26 and is thrown to the cathode tank area of the electrolytic tank B through the pump 133-13.
  • the electrolytic tank B 2- The sensor 110 photoelectric colorimeter in 2 controls the pump 133-12 to add the temporary storage tank 26 solution to the cathode tank area of the electrolytic tank B, so that the cathodes in the electrolytic tank B are electrolyzed with copper; the anode of the electrolytic tank B
  • the oxidation regeneration etching liquid 260 is subjected to an electrochemical oxidation reaction, so that the etching production line 257 maintains the etching production by controlling the rotational speed of the pump 133-4; at the same time, a small amount of chlorine escaped from the anode tank area of each electrolytic tank is sprayed
  • the gas-liquid mixer 76 absorbs the overflowing catholyte 256 from the electrolytic tank B that has been processed for copper recycling to prepare a regenerated etching sub-liquid 252.
  • the working parameters of the prepared regeneration etching sub-liquid 252 are acidity 5.2M/L and copper ion concentration 30g/L.
  • Figure 5 shows an embodiment 8 of a progressive electrolysis method for recycling circuit board acidic etching waste liquid and its device, which includes two electrolytic tanks A 1-1 and 1-2, and two electrolytic tanks B 2-1 and 2-2, the redox potential controller 7-1 is installed in the cathode tank area of electrolytic tank A 1-1, and the redox potential controller 7-2 is installed in the cathode tank area of electrolytic tank A 1-2.
  • the two electrolytic tank A separators 3-1 and 3-2 are both anion exchange membranes.
  • the separators 4-1 and 4-2 of electrolytic tank B are both anion exchange membranes.
  • the anode materials of the two electrolytic cells A 1-1 and 1-2 are titanium-based coated insoluble anodes, and the cathode materials are titanium metal.
  • the anode materials of the electrolytic cells B 2-1 and 2-2 are titanium-based coated insoluble anodes; the electrolytic cells
  • the cathode materials of B 2-1 and 2-2 are both metal copper sheets.
  • the sensors 101, 111, 112 and 113 are all hydrometers, the sensors 102 and 114 are acidimeters, the sensors 103, 106, 109 and 111 are redox potentiometers (i.e. ORP meters), and the sensors 104 and 107 are thermometers. Sensors 105, 108, 110 and 116 are liquid level gauges. The on-site data of all sensors are sent to the automatic detection and feeding controller 131 for processing and the entire device is controlled according to the program.
  • Sensors 101, 102, 103, and 104 are installed in the circuit board etching production line 257.
  • the sensor 101 hydrometer controls the pump 133-1 and adds the regenerated etching liquid 252 to control the chlorine salt concentration of the etching working fluid;
  • the sensor 102 The acidometer controls the valve 132-2 to add hydrochloric acid 283 to control the acidity of the etching working fluid;
  • the sensor 103 ORP meter controls the speed of the variable frequency pump 133-4 to control the oxidation-reduction potential of the etching working fluid at 530mv according to the process;
  • the sensor 104 thermometer makes the etching working fluid
  • the temperature is controlled at 50°C. Therefore, the etching line 257 of the circuit board is controlled to maintain the acidity of the etching working fluid at 0.9mol/L, the specific gravity at 1.35g/ml, and the ORP at 530mv to stabilize the etching performance.
  • the etching waste liquid overflowed from the circuit board etching production line 257 first flows into the water-oil separator 96 for separation of the organic matter of the ink and film residue, and then flows into the liquid flow buffer tank 51, and is then pumped through the pump for circulation.
  • the temporary storage tank 24 used in the mixing exchange tank when the oxidation regeneration etching liquid 260 in the temporary storage tank 24 is full, it is controlled by the sensor 105 liquid level meter to start the pump 133-7 to pump part of the solution in the temporary storage tank 24. Temporarily store in temporary storage slot 25.
  • electrolytic tank A 1-2 is used to prepare the 256 solution that has taken copper from electrolytic tank B and then electrolytically oxidize and regenerate the etching sub-liquid.
  • the described circulating mixing exchange tank that is, the temporary storage tank 24, is connected to the circuit board etching line 257 as a pipeline for circulating liquid flow, and is respectively connected to the anode tank areas of electrolytic tank A 1-1, electrolytic tank B 2-1 and 2-2.
  • the circulating liquid flow pipeline is connected, and the solution in the circulating mixing exchange tank is the oxidation regeneration etching liquid 260.
  • the oxidation-reduction potential value of the oxidation regeneration etching liquid 260 in the temporary storage tank 24 is transmitted to the automatic detection feeding controller 131 for processing through the sensor 106 ORP meter, and the electrolytic power supply 5-1 and the electrolytic power supply 6-1 and 6- are respectively The working current of 2 is adjusted and controlled to control the oxidation-reduction potential value range of the oxidation regeneration etching liquid 260 at 750-850 mv.
  • the redox potential controllers 7-1 and 7-2 respectively control the pumps 133-14 and 133-13 to add the etching waste liquid 251 in the temporary storage tank 25 to the cathode tank areas of the two electrolytic tanks A, After electrolysis treatment The overflow liquid 268 is pumped to the temporary storage tank 26 for temporary storage.
  • the copper ion concentration of the solution in the temporary storage tank 26 is still about 140g/L.
  • the electrolytic tanks B 2-1 and 2-2 are a progressive electrolytic electrolytic tank for extracting copper. Its function is to electrolyze the cathode to extract copper, and the anode to oxidize the oxidation regeneration etching solution 260 to maintain the etching process.
  • Sensors 111 and 112 hydrometers control pumps 133-18 and 133-17 respectively to add the overflow liquid 268 from the cathode tank area of the two electrolytic tanks A in the temporary storage tank 26 to the cathodes of electrolytic tanks B 2-1 and 2-2. In the tank area, copper is extracted by progressive electrolysis.
  • the copper ion concentration control setting value in the catholyte of electrolytic cells B 2-1 and 2-2 was both 40g/L, and copper metal 253 was electrolytically precipitated from the cathodes of electrolytic cells B 2-1 and 2-2.
  • the catholyte 256 overflowing from the electrolytic tanks B 2-1 and 2-2 that have been treated for copper recovery is pumped to the temporary storage tank 27, and then the pump 113 is controlled by the sensor 113 hydrometer and the sensor 114 acidometer. -23 pumps the solution in the tank 27 to the temporary storage tank 28 for preparation.
  • the impeller stirrer 92 is turned on, and hydrochloric acid 283, ammonium chloride 285, and ferric hydroxide 297 are put into the tank 28 to prepare the solution of the electrolytic tank A 1-2. Anolyte.
  • etching waste liquid feeding pipes 296 and 297 in the cathode tank area of electrolytic tanks B 2-1 and 2-2 are used to add etching waste liquid to react and remove the chlorination on the separators 4-1 and 4-2 of electrolytic tank B. Cuprous copper mud to avoid copper mud clogging of separators.
  • the exhaust gas treatment tank 281 uses a spray tower to introduce exhaust gas for treatment.
  • the main components of the acidic iron-containing etching waste liquid in this embodiment are: aqueous solutions of hydrochloric acid, copper chloride, sodium chloride, ammonium chloride, ferric chloride and ferrous chloride.
  • the acidity is 0.9mol/L
  • the copper ion concentration is 140g/L
  • the total iron ion concentration is 30g/L.
  • the main steps of a progressive electrolysis device for recycling acidic etching waste liquid of circuit boards are as follows.
  • etching working fluid to the anode tank area of electrolytic tank A 1-1 and add etching waste liquid 251 to the cathode tank area as the starting electrolyte, and mix the anolyte of electrolytic tank A 1-1 with the circulation
  • the exchange tank solution can circulate and flow, and the etching sub-liquid (tank 28 solution) that needs to be regenerated and oxidized is added to the anode tank area of electrolytic tank A 1-2.
  • the sensor 101 liquid level meter is installed in the anode tank area of electrolytic tank A 1-1
  • the sensor 109 ORP meter is installed in the anode tank area of electrolytic tank A 1-2
  • the redox potential control devices are respectively installed in the cathode tank areas of the two electrolytic tanks A. Devices 7-1 and 7-2.
  • the electrolytic power supplies 5-1 and 5-2 of the two electrolytic tanks A and the electrolytic power supplies 6-1 and 6-2 of the two electrolytic tanks B so that the two electrolytic tanks A and the two electrolytic tanks B can perform electrolysis operations.
  • the setting values of the redox potential controllers 7-1 and 7-2 are both set to 480mV to control the acidic iron-containing etching waste liquid 251 to be thrown into the cathode tank areas of the two electrolytic tanks A, and the two cathodes and the upper No metallic copper is generated, only the reaction of eliminating the copper etching agent occurs.
  • the anodes of the two electrolytic tanks A carry out oxidation reactions on the anolyte respectively; the sensor 111 hydrometer in the electrolytic tank B 2-1 monitors the electrolytic tank A in the temporary storage tank 26 The overflow liquid 268 in the cathode tank area is thrown into the cathode tank area of the electrolytic tank B 2-1 through the pump 133-18.
  • the sensor 112 hydrometer in the electrolytic tank B 2-2 controls the pump 133-17 and adds it to the temporary storage tank 26.
  • the solution is poured into the two cathode tank areas of electrolytic tank B, so that the cathodes in electrolytic tank B 2-1 and 2-2 are electrolyzed with copper; the anodes of electrolytic tank B 2-1 and 2-2 regenerate the etching solution for oxidation 260 performs an electrochemical oxidation reaction, so that the circuit board etching production line 257 maintains etching production by controlling the rotation speed of the pump 174; during the electrolysis process, a metering pump is used to control and add a small amount of etching waste liquid 251 to the electrolysis according to time.
  • a metering pump is used to control and add a small amount of etching waste liquid 251 to the electrolysis according to time.
  • the pump 133-24 is controlled to put the solution in the tank 28 into the anode tank area of the electrolytic tank A 1-2, and a regenerated etching sub-liquid that meets the process requirements is obtained through electrochemical oxidation for etching. Production recycling.

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Abstract

本发明公开了一种递进式电解回用酸性蚀刻废液的方法及其装置，其采用至少一个电解槽A，其内有阳极槽区和阴极槽区；电解作业时分别设置有电解阳极和电解阴极；电解槽A的阴极电解液包含酸性蚀刻废液；采用至少一个电解槽B，其内分有阳极槽区和阴极槽区；电解作业时分别设置有电解阳极和电解阴极，令电解槽B的电解阴极上发生铜离子被还原为金属铜的电化学反应；电解槽B的阴极电解液包含经过电解处理后的电解槽A的阴极电解液或者其与酸性蚀刻废液的混合液。本发明使线路板生产企业在对酸性蚀刻废液进行铜的安全回收的同时，减少电解取铜过程中对阴极上所电析金属铜的返蚀并避免引入新的杂质，降低电解能耗。

Description

一种递进式电解回用酸性蚀刻废液的方法及其装置 技术领域
本发明属于线路板蚀刻废液回收和循环再用的工艺技术领域，具体涉及一种递进式电解回用酸性蚀刻废液的方法及其装置。
背景技术
现有的印刷线路板生产制作过程中，其中采用酸性蚀刻液喷淋加工的蚀刻方式是重要的一步工序，它是将覆铜箔基板上所不需要的铜使用酸性蚀刻液进行化学反应腐蚀的方法作去除，使其形成所需要的电路图形。目前的酸性蚀刻液主要以氯化铜和/或氯化铁作为蚀铜剂。业界现有的酸性蚀刻液的主要成分为氯化铜和盐酸，以及可能含有的氯化铁和/或氯化铵和/或氯化钠。
蚀刻过程中，金属铜被腐蚀的同时蚀铜剂被还原而失去蚀刻能力，具体为氯化铜被还原为氯化亚铜，和/或氯化铁被还原为氯化亚铁。为了维持蚀刻生产，需要向蚀刻液中补充氧化剂、盐酸和/或氯化铁以及可选的添加剂，使氯化亚铜和氯化亚铁得以氧化再生成为氯化铜和氯化铁并继续参与蚀刻，也因此导致蚀刻液的体积不断增大而溢出槽外。蚀刻液中的添加剂通常用于改善蚀刻性能。其中有一类用于增加氯离子的同离子效应的添加剂，常见的有三氯化铁、二氯化铁、氯化铵、氯化钠、氯酸钠。三氯化铁既是蚀铜剂，也是能增加同离子效应的添加剂。由于含有氯化铁蚀铜剂的酸性蚀刻液能有效减少蚀刻过程中的水池效应，所以业界在追求产品高质高效下偏好使用酸性含铁蚀刻液。
业内将溢出槽外的蚀刻液称为蚀刻废液，将蚀刻槽内的溶液称为蚀刻工作液，而将蚀刻过程中加投补充的含有盐酸和/或氧化剂和/或添加剂的溶液统称为蚀刻子液。大部分酸性蚀刻废液的铜离子浓度为70～200g/L，含铁的酸性蚀刻废液中氯化铁和氯化亚铁的总铁含量可高达200g/L。
线路板生产工厂每天都在蚀刻工序上产出大量的酸性蚀刻废液。现有技术中有采用电解槽对酸性蚀刻废液进行直接电解取铜的方案，其采用分隔有阳极槽区和阴极槽区的电解槽并将酸性蚀刻废液加入阳极槽区中直接进行电解。但此方案中蚀刻废液的氯离子损失较大，且需要向蚀刻工作液加投较多氧化剂来维持蚀刻作业，并因此导致蚀刻废液增量。
而采用将酸性蚀刻废液改为加入阴极槽区中电解的方案能有效减少甚至避 免回用蚀刻过程中往蚀刻工作液加投氧化剂，使废液增量问题得到解决。但由于酸性蚀刻废液中仍存有大量蚀铜剂，其对金属铜的腐蚀性非常强，其中含铁的酸性蚀刻废液对金属铜的攻击性尤为突出。因此，向阴极槽区加入酸性蚀刻废液时，所引入的蚀铜剂会对阴极电析的铜作返蚀。如此不仅耗费大量的电能，还会导致所电析出来的铜层因被腐蚀变得疏松粗糙，在从阴极上取铜块容易断碎而跌落在电解槽中影响生产。业界为了克服上述电解回收工艺缺点，采用向阴极电解液中投入电镀铜光亮剂使所电析出来的金属铜块改善得较为平整密致。但这种方法实际上是向蚀刻废液中加投了新的杂质，令电解回收工艺无法实现将蚀刻废液作100％循环回用。
因此，业内线路板生产企业期盼着有一种能解决目前酸性蚀刻废液电解回收循环再用工艺缺点的新工艺推出。
发明内容
本发明的第一个目的在于提供一种递进式电解回用线路板酸性蚀刻废液的方法，使线路板生产企业在对酸性蚀刻废液进行铜的安全回收的同时，减少电解取铜过程中对阴极上所电析金属铜的返蚀并避免引入新的杂质，降低电解能耗，有助于将回收铜后的废液重新调配成为再生蚀刻子液以提高废液回用率，这样，既大幅降低生产成本又能减少环境污染。
本发明的第二个目的在于提供一种递进式电解回用线路板酸性蚀刻废液的装置。
本发明的第一个目的可以采用以下的技术方案来实现：
一种递进式电解回用线路板酸性蚀刻废液的方法，其主要包括以下步骤：
步骤一：采用至少一个电解槽A，所述的电解槽A内部采用电解槽分隔物分隔有阳极槽区和阴极槽区；电解作业时所述电解槽A的阳极槽区和阴极槽区中分别设置有电解阳极和电解阴极，分别对电解槽A的阳极电解液和阴极电解液进行电解作业；所述的电解槽A的阴极电解液包含酸性蚀刻废液；
步骤二：采用至少一个电解槽B作递进式电解取铜，所述的电解槽B内分有阳极槽区和阴极槽区；电解作业时所述的电解槽B阳极槽区和阴极槽区中分别设置有电解阳极和电解阴极，分别对电解槽B阳极电解液和阴极电解液进行电解作业，令所述电解槽B的电解阴极上发生铜离子被还原为金属铜的电化学反应；所 述电解槽B的阴极电解液包含经过电解处理后的电解槽A的阴极电解液或者其与酸性蚀刻废液的混合液；
步骤三：所述电解槽B的电解阴极上因电化学反应沉积的金属铜达到预先设定的电析目标量时，将所述电解槽B的电解阴极从电解槽B取出。
所述电解槽A的阳极电解液包含蚀刻工作液、蚀刻废液、经过电解处理后电解槽B的阴极电解液中的至少一种。所述电解槽B的阳极电解液包含经过电解处理后的电解槽B的阴极电解液、蚀刻工作液、蚀刻废液中的至少一种。
本发明的电解作业过程中，所述电解槽A的电解阳极和所述电解槽B的电解阳极上电析出氯气和/或发生电解液中低价态金属离子氧化为高价态离子的电化学反应。所述电解槽A的电解阴极上主要发生金属离子的还原反应使得其阴极电解液中的蚀铜剂浓度下降，所述电解槽B的电解阴极上则发生铜离子被还原为金属铜的电化学反应。为维持电解的持续进行，作业时不断向各槽区加投补充相应的电解溶液。
经过电解处理后的电解槽B的阴极电解液可在所述电解槽A的阳极槽区和/或所述电解槽B的阳极槽区中作氧化，和/或使用电解槽所电析逸出的氯气进行氧化，然后直接或经调配后作为再生蚀刻子液循环再用。上述的调配也可以改为对电解槽A的阳极电解液和阴极电解液、及电解槽B的阳极电解液和阴极电解液中的至少一种进行提前调配，同样可以实现本发明的目的。
所述电解槽A的电解槽分隔物能够有效地使所述的阳极电解液作氧化反应和使阴极电解液作高价态金属离子降价的还原反应，具体选用阴离子交换膜、双极膜、反渗透膜中的至少一种。
所述的电解槽B可以是采用任意结构形式分有阳极槽区和阴极槽区的电解槽。而当所述电解槽B的阳极槽区和阴极槽区为采用电解槽分隔物进行槽区分隔时，所述电解槽B的电解槽分隔物可选用阴离子交换膜、双极膜、反渗透膜中的至少一种。
本发明可以作以下改进：对电解槽A的阴极槽区中阴极电解液的氧化还原电位进行检测，以监测电解进程及溶液中的高价态金属离子浓度，使所述电解槽A的阴极电解液主要发生蚀铜剂浓度降低的反应，不发生或者少发生电析铜的电化学反应。
本发明可以进一步作以下改进：根据电解槽A的阴极槽区中阴极电解液的氧化还原电位数值按工艺要求对电解槽A的电解电源的输出电流大小作调整或者启动关停，和/或向电解槽A的阴极槽区加投补充包含酸性蚀刻废液的溶液，以保持其阴极电解液中蚀铜剂的浓度令其电解阴极上少电析出金属铜甚至不电析出金属铜，而主要作电化学还原反应使电解槽A的阴极电解液中的蚀铜剂CuCl2，或者CuCl2和FeCl3浓度降低甚至消除其蚀铜能力。
优选地，电解过程中将所述的电解槽A的阴极电解液的氧化还原电位数值控制在200～580mv，即采取其外投废液的氧化还原电位值ORP值投控点范围控制在200～580mv之间。更优选地，将所述电解槽A的阴极电解液的氧化还原电位数值控制在300～499mv。为获得更好的消除蚀铜剂的递进式取铜效果，将所述电解槽A的阴极电解液的ORP值控制在350～470mv。
本发明可以作以下改进：增设排序在电解槽B后的至少一个电解槽C，所述的电解槽C内分有阳极槽区和阴极槽区；电解作业时所述电解槽C的阳极槽区和阴极槽区中分别设置有电解阳极和电解阴极，分别对其阳极电解液和阴极电解液进行电解作业；所述电解槽C的阳极电解液包含酸性蚀刻工作液、经过电解处理后的电解槽B的阴极电解液、经过电解处理后的电解槽C的阴极电解液中的至少一种，或者在此基础上进一步包含蚀刻废液；所述电解槽C的阴极电解液包含经过电解处理后的电解槽B的阴极电解液，或者在此基础上进一步包含电解槽A的阴极电解液和/或蚀刻废液。此时，所述电解槽A的阳极电解液包含经过电解处理后的电解槽B的阴极电解液、经过电解处理后的电解槽C的阴极电解液、蚀刻工作液、蚀刻废液中的至少一种；所述的电解槽B的阳极电解液包含经过电解处理后的电解槽B的阴极电解液、经过电解处理后的电解槽C的阴极电解液、蚀刻工作液、蚀刻废液中的至少一种。
本发明在采用电解槽C的电解作业过程中，电解槽C的电解阴极上发生铜离子被还原为金属铜的电化学反应再进一步作递进式的电解取铜。经过电解处理的电解槽B的阴极电解液和/或经过电解处理的电解槽C的阴极电解液可在电解槽A的阳极槽区、电解槽B的阳极槽区、电解槽C的阳极槽区中的一种或一种以上作氧化和/或使用氯气进行氧化，然后直接或经调配后作为再生蚀刻子液循环再用。上述的调配也可以改为对电解槽A的阳极电解液和阴极电解液、电解槽B 的阳极电解液和阴极电解液、电解槽C的阳极电解液和阴极电解液中的至少一种进行提前调配，同样可以实现本发明的目的。
所述的电解槽C可以是采用任意结构形式分有阳极槽区和阴极槽区的电解槽。而当所述的电解槽C为采用电解槽分隔物进行槽区分隔时，所述电解槽C的电解槽分隔物可选用阴离子交换膜、双极膜、反渗透膜中的至少一种。
本发明的整套递进式电解装置在电解过程中，由于所述电解槽A的阳极电解液、电解槽B的阳极电解液、电解槽C的阳极电解液中均含有氯离子，所以电解槽A的电解阳极、电解槽B的电解阳极、电解槽C的电解阳极上均有发生氯离子被氧化为氯气的电化学反应。所生成的氯气具有强氧化性，能够将电解槽A的阳极电解液、电解槽B的阳极电解液和电解槽C的阳极电解液中的低价态金属离子作氧化，实现蚀铜剂的氧化再生。同时，电解槽A的电解阴极上发生反应还原电化学反应，令其阴极电解液中的蚀铜剂作还原反应生成为氯化亚铜和/或氯化亚铁使其失去蚀铜能力。随后将已失去或减少蚀铜能力的电解槽A的阴极电解液加入到电解槽B的阴极槽区中作为其阴极电解液的部分或全部进行电解，使电解槽B的电解阴极上电析出铜金属。当增设有电解槽C时，经电解的电解槽B的阴极电解液被加投到电解槽C的阴极槽区中作为电解槽C的阴极电解液的部分或全部进行下一级进一步的递进式电解取铜。
本发明通过递进式电解析铜的方法，令所述电解槽B的电解阴极和电解槽C的电解阴极上电析出的金属铜在蚀铜剂浓度较低的环境中生成，如此能有效地减少电解回收过程中阴极电解液对所电析出来的金属铜进行返蚀的化学反应，从而使电析出来的金属铜层较为平整密致。本发明工艺解决了现有电解回收酸性蚀刻废液技术中所电析铜层疏松的工艺缺点，同时有助于实现将蚀刻废液作100％回收循环回用。
本发明中的电解阳极采用在电解液中其形状及性质为稳定的材料，具体可采用表面为金和/或铂和/或包含上述至少一种金属的合金的材料、钛基涂层不溶性阳极、导电石墨中的至少一种，优选为钛基涂层不溶性阳极。所述电解槽A的电解阴极的材料采用金和/或铂和/或钛和/或包含上述至少一种金属的合金和/或导电石墨，优选为钛材。所述电解槽B的电解阴极和电解槽C的电解阴极的材料可采用金和/或铂和/或钛和/或铜和/或包含上述至少一种金属的合金和/或不锈钢， 优选为铜金属。
电解槽A、电解槽B、电解槽C中各槽区内发生的主要化学反应如下所示：
(1)各阳极槽区
2CuCl+Cl2→2CuCl2；
2FeCl2+Cl2→2FeCl3(当蚀刻液中含有铁离子时)。
(2)电解槽A的阴极槽区
(当蚀刻液中含有铁离子时)。
(3)电解槽B的阴极槽区和电解槽C的阴极槽区
本发明可以作以下改进：控制所述电解槽B的电解阴极和电解槽C的阴极电解液的铜离子浓度不低于5g/L。经发明人多次实验发现，将阴极电解液的铜离子浓度保持在不低于5g/L时，能避免发生较多的电析氢副反应。
本发明可以作以下改进：对来自末端电解槽B的经电解后的阴极电解液或者来自末端电解槽C的经电解后的阴极电解液按工艺要求进行氧化再生处理和/或加投盐酸、添加剂来重新配制为再生蚀刻子液，使再生蚀刻子液中的亚铜离子和/或亚铁离子的浓度符合工艺最低要求，在回投到蚀刻生产线中使用时不会影响蚀刻性能。
本发明可以作以下改进：采用阴极布滤袋套装着末端至少一个电解槽的电解阴极，以收集电析铜过程中产生的海绵铜。
本发明可以作以下改进：对本发明中至少一种电解液的参数值进行检测，并以现场测得的数据作为依据控制电解槽A的电解电源和/或电解槽B的电解电源和/或电解槽C的电解电源的输出电流大小和/或开启关停，和/或控制各种物料的加投。使所述电解槽A的阳极槽区和/或电解槽B的阳极槽区和/或电解槽C的阳极槽区中产生的氯气得到安全控制和较完全的利用，和/或使溶液反应按工艺要求进行。所检测的参数值包括但不限于酸度值、比重值、氧化还原电位值、光电比色值、液位、温度、流量、有害气体浓度中的任意一种或以上。
本发明可以作以下改进：将设有电解分隔物电解槽中的电解槽A的阳极电解液和/或电解槽B的阳极电解液和/或电解槽C的阳极电解液与蚀刻生产线上的蚀刻工作液循环混和，令蚀刻生产线上的蚀刻工作液能进行在线补充蚀铜剂。即蚀刻工作液中的低价铜离子或低价铁离子能利用电解槽阳极的电化学反应得到再生蚀铜剂氯化铜或氯化铁，并继续参与蚀刻反应使用。本发明采取蚀刻槽与至少一个电解槽的阳极槽区通过管道作连接，使蚀刻工作液在各阳极槽区中作循环流动，作为电解氧化后的电解槽A的阳极电解液、电解槽B的阳极电解液和电解槽C的阳极电解液中的至少一种直接回流到蚀刻槽中作为新生蚀铜剂的蚀刻工作液使用，能有效减少甚至免去传统生产过程中需要从蚀刻系统外面加投的氧化剂，有助于降低生产成本。
本发明可以进一步作以下改进：在蚀刻生产线和至少一个电解槽的阳极槽区之间增设蚀刻工作液和阳极电解液的循环混和交换槽，并控制混和后的溶液其氧化还原电位值高于蚀刻工作液的氧化还原电位值。优选地，采用总容积较大的循环混和交换槽，以高效利用电解设备预先制备更多的蚀铜剂作为蚀刻反应中迅速加投的响应。
本发明可以进一步作以下改进：对准备进入蚀刻生产线的溶液进行温度调整控制，以避免混和后的溶液加投入蚀刻生产线时因蚀刻工作液的温度发生变化而影响到蚀刻速率的稳定性。
本发明可以进一步作以下改进，对蚀刻工作液进入电解槽之前作除油和固体杂质处理。
本发明可以进一步作以下改进：当蚀刻废液中含有铁离子时，对电解槽B和/或电解槽C的阴极槽区按工艺要求加投蚀刻废液。优选地，其投料口靠近分隔物，利用蚀刻废液中的Fe3+离子与CuCl铜泥反应，使不溶性氯化亚铜泥反应生成氯化铜，避免分隔物堵塞影响电解作业。
本发明的第二个目的可以采用以下的技术方案来实现：
一种递进式电解回用线路板酸性蚀刻废液的装置，其主要包括：
使用至少一个电解槽A和至少一个电解槽B，所述的电解槽A内部采用电解槽分隔物作分隔有阳极槽区和阴极槽区，所述的电解槽B内部划分有阳极槽区和阴极槽区；电解槽A的阴极槽区中安装有氧化还原电位计，电解槽A的阴极槽 区与电解槽B的阴极槽区通过液流管道连接将电解槽A的阴极槽区中经过电解反应的溶液加投到电解槽B的阴极槽区中作递进式电解取铜；电解槽A的阳极槽区和电解槽A的阴极槽区中分别设置有电解阳极和电解阴极，所述的电解阳极和电解阴极分别与电解槽A的电解电源的正极和负极连接；电解槽B的阳极槽区和电解槽B的阴极槽区中分别设置有电解槽B的电解阳极和电解阴极，所述的电解阳极和电解阴极分别与电解槽B的电解电源的正极和负极连接。
电解过程中，电解槽A的阳极槽区和电解槽A的阴极槽区中分别装有阳极电解液和阴极电解液，电解槽B的阳极槽区和电解槽B的阴极槽区中分别装有阳极电解液和阴极电解液；所述电解槽A的阳极电解液包含蚀刻工作液、蚀刻废液、经过电解处理后的电解槽B的阴极电解液中的至少一种，所述的电解槽A的阴极电解液包含酸性蚀刻废液；所述的电解槽B的阳极电解液包含经过电解处理后的电解槽B的阴极电解液、蚀刻工作液、蚀刻废液中的至少一种，所述电解槽B的阴极电解液包含经过电解处理后的电解槽A的阴极电解液或者其与酸性蚀刻废液的混合液。
所述电解槽A的电解槽分隔物选用阴离子交换膜、双极膜、反渗透膜中的至少一种。
所述的电解槽B可以是采用任意结构形式分有阳极槽区和阴极槽区的电解槽，具体分有带电解分隔物和不带电解分隔物的结构形式。而当所述电解槽B的阳极槽区和阴极槽区为采用电解槽分隔物进行分隔时，所述电解槽B的电解槽分隔物选用阴离子交换膜、双极膜、反渗透膜中的至少一种。
本发明可以作以下改进：根据电解槽A的阴极槽区中氧化还原电位计测得的数值按工艺要求对电解电源A的输出电流大小作调整或者关停，和/或向电解槽A的阴极槽区控制加投补充包含酸性蚀刻废液的溶液。
本发明可以作以下改进：增设排序在电解槽B后的至少一个电解槽C，所述的电解槽C中分有阳极槽区和阴极槽区；电解槽B的阴极槽区与电解槽C的阴极槽区通过液流管道连接将电解槽B的阴极槽区中经电解处理后的溶液加投到电解槽C的阴极槽区中；电解槽C的阳极槽区和电解槽C的阴极槽区中分别设置有电解阳极和电解阴极，电解阳极和电解阴极分别与电解电源C的正极和负极连接；电解过程中，电解槽C的阳极槽区和阴极槽区中分别装有阳极电解液和阴极电解 液；所述的电解槽C的阳极电解液包含蚀刻工作液、经过电解处理后的电解槽B的阴极电解液、经过电解处理后的电解槽C的阴极电解液中的至少一种，或者在此基础上进一步包含蚀刻废液；所述电解槽C的阴极电解液包含经过电解处理后的电解槽B的阴极电解液，或者在此基础上进一步包含电解槽A的阴极电解液和/或蚀刻废液。此时，所述电解槽A的阳极电解液包含经过电解处理后的电解槽B的阴极电解液、经过电解处理后的电解槽C的阴极电解液、蚀刻工作液、蚀刻废液中的至少一种；所述电解槽B的阳极电解液包含经过电解处理后的电解槽B的阴极电解液B、经过电解处理后的电解槽C的阴极电解液、蚀刻工作液、蚀刻废液中的至少一种。
所述的电解槽C可以是采用任意结构形式分有阳极槽区和阴极槽区的电解槽，具体分有带电解分隔物和不带电解分隔物的结构形式。而当所述电解槽C的阳极槽区和电解槽C的阴极槽区为采用电解槽分隔物进行分隔时，电解槽C的电解槽分隔物选用阴离子交换膜、双极膜、反渗透膜中的至少一种。
本发明中的电解阳极采用在电解液中其形状及性质为稳定的材料，具体可采用表面为金和/或铂和/或包含上述至少一种金属的合金的材料、钛基涂层不溶性阳极、导电石墨中的至少一种，优选为钛基涂层不溶性阳极。所述电解槽A的电解阴极的材料采用金和/或铂和/或钛和/或包含上述至少一种金属的合金和/或导电石墨，优选为钛材。所述电解槽B的电解阴极和电解槽C的电解阴极的材料可采用金和/或铂和/或钛和/或铜和/或包含上述至少一种金属的合金和/或不锈钢，优选为铜金属。
本发明可以作以下改进：采用阴极布滤袋套装着末端至少一个电解槽的电解阴极，以收集电析铜过程中产生的海绵铜。
本发明可以作以下改进：增设传感器和自动检测投料控制器，采用至少一个传感器对电解槽A的阳极电解液和阴极电解液、及电解槽B的阳极电解液和阴极电解液、及电解槽C的阳极电解液和阴极电解液中的至少一种进行检测，并将现场测得的数据传送到自动检测投料控制器中处理，以控制至少一个电解电源的输出电流的大小和/或各种物料的加投。
优选地，所述的传感器为是选自酸度计、比重计、氧化还原电位计、光电比色计、液位计、温度计、流量计、氯气检测仪中的至少一种。
本发明可以作以下改进：增设循环混和交换槽，设有电解分隔物电解槽中的电解槽A的阳极槽区和/或电解槽B的阳极槽区和/或电解槽C的阳极槽区与循环混和交换槽作循环管道连接，所述的循环混和交换槽与蚀刻生产线作循环管道连接，使阳极电解液和蚀刻工作液在循环混和交换槽中得到混和，对蚀刻生产线上的蚀刻工作液能进行实时在线补充蚀铜剂。
优选地，采用较大容积的循环混和交换槽，对槽内溶液作高于蚀刻工作液的氧化还原电位值控制，使槽内溶液的蚀铜剂浓度远高于蚀刻工作液高效地利用电解设备。
本发明可以作以下改进：增设冷热温度交换器，对准备进入蚀刻生产线的溶液进行温度调整控制。
本发明可以作以下改进：增设暂存槽，用于暂存各种溶液和/或作为溶液的化学反应配制槽使用。
本发明可以作以下改进：增设尾气处理槽，用于处理各电解槽和各暂存槽在工作过程中所析出的尾气。
本发明可以作以下改进：增设搅拌器，其结构分别有叶轮式搅拌器、循环液流式泵管搅拌器，用于对电解槽、暂存槽中的溶液进行搅拌混和。
本发明可以作以下改进：增设溢流缓冲槽，以解决各槽间液位高低的溶液流动问题。
本发明可以作以下改进：增设电解槽带排气孔和投料口的密闭槽盖，以收集所电析出的氯气或氧气作安全生产利用。
本发明可以作以下改进：增设电解槽阴极槽区活动式槽盖，使酸性废气能方便收集处理和方便提取阴极回收金属铜。
本发明可以作以下改进：增设气液混合器，其结构可以是真空射流气液混合器，也可以是喷淋式气液混合器用于对气体和液体的混合处理。
本发明可以作以下改进：增设过滤器，对所处理的溶液进行固液分离或对有机物的除杂处理。
本发明可以作以下改进：增设电解槽B和/或电解槽C的阴极槽区蚀刻废液投料管。优选地，将投料管安装靠近于分隔物，使含铁蚀刻废液中的Fe3+离子与粘附在分隔物上的氯化亚铜反应并生成氯化铜溶于阴极电解液中，避免分隔物堵 塞。可根据时间间隔或槽压作控制加投。
与现有技术相比，本发明具有以下有益效果：
1.本发明解决了现有的电解回收线路板酸性蚀刻废液工艺中所电析的铜块疏松易断碎的工艺难题。
2.本发明能实现线路板酸性蚀刻废液电解回收100％的循环利用，大幅度降低生产成本和减少环境污染。
3.本发明的工艺在循环回用整个过程中因没有加投新的物质，回用再生蚀刻子液对蚀刻生产质量和效率没有影响。
4.本发明工艺能在循环回用生产中实现不再需要从酸性蚀刻体系外加投外来氧化剂，使生产成本降低。
5.采用含铁的酸性蚀刻液时，本发明工艺能发挥酸性含铁蚀刻工艺优势，既能提高蚀刻效率又能提升蚀刻质量。
附图说明：
以下通过附图对本发明工艺进一步说明。
图1为本发明实施例1一种递进式电解回用线路板酸性蚀刻废液的装置；
图2为本发明实施例2一种递进式电解回用线路板酸性蚀刻废液的装置；
图2.1为图2的2-E放大图；
图2.2为图2的2-F放大图；
图2.3为图2的2-G放大图；
图2.4为图2的2-H放大图；
图3为本发明实施例3一种递进式电解回用线路板酸性蚀刻废液的装置；
图3.1为图3的3-E放大图；
图3.2为图3的3-F放大图；
图3.3为图3的3-G放大图；
图3.4为图3的3-H放大图；
图3.5为图3的3-K放大图；
图4为本发明实施例4一种递进式电解回用线路板酸性蚀刻废液的装置；
图4.1为图4的4-E放大图；
图4.2为图4的4-F放大图；
图4.3为图4的4-G放大图；
图4.4为图4的4-H放大图；
图5为本发明实施例8一种递进式电解回用线路板酸性蚀刻废液的装置；
图5.1为图5的5-E放大图；
图5.2为图5的5-F放大图；
图5.3为图5的5-G放大图；
图5.4为图5的5-H放大图；
图5.5为图5的5-K放大图；
图6为采用本发明方案回收获得的金属铜相片；
图7为采用现有技术将蚀刻废液加入阴极槽区直接电解方案所获得的金属铜相片。
1-电解槽A、2-电解槽B、3-电解槽A分隔物、4-电解槽B分隔物、5-电解槽
A的电解电源、6电解槽B的电解电源、7-电解槽A的阴极槽区的氧化还原电位控制器、8-电解槽C、9-电解槽C分隔物、10-电解槽C的电解电源、23～50-暂存槽、51～70-溢流缓冲槽、71～75-真空射流气液混合器、76～80-喷淋式气液混合器、81～90-循环液流搅拌混合器、91-固体投料机、92～95-叶轮搅拌器、96-水油分离器、97～100-固液分离过滤器、101～130-传感器、131-自动检测投料控制器、132-阀门、133-泵浦、134-阴极槽区蚀刻废液投料管、251-酸性含铁蚀刻废液、252-再生蚀刻子液、253-电解回收金属铜、256-已作回收铜处理的电解槽B溢出的阴极电解液、257～259-线路板蚀刻生产线、260-氧化再生蚀刻液、261～266-冷热温度交换器、267-氢氧化钠溶液、268-电解槽A的阴极槽区的溢出液、269～280-电解槽带排气孔和投料口密封槽盖、281～282-尾气处理槽、283-盐酸、284-氯化铁、285-氯化铵、286-氯化钠、287-酸性尾气、288-清水、289～293-活动式槽盖、294～295-阴极布滤袋、296-氯化亚铁、297-氢氧化铁、298-氢氧化亚铁。
具体实施方式
以下述实施例中所使用的电解槽、暂存槽、尾气处理槽、溢流缓冲槽、真空射流气液混合器、喷淋式气液混合器、搅拌器、水油分离器均为广东省佛山市业高环保设备制造有限公司制造的产品。固液分离过滤器、电解槽分隔膜、传感器、PLC控制器、阀门、泵浦、化工原料均为市售商品。除上述列举之外，本领 域技术人员根据常规选择，也可以选择其它具有与本发明列举的上述产品中而具有相似性能的产品，均可以实现本发明的目的。
实施例1
如图1所示为一种递进式电解回用线路板酸性蚀刻废液的方法及其装置的基础实施例1，其包括有电解槽A 1、电解槽B 2、电解槽A的阴极槽区氧化还原电位控制器7、电解槽A分隔物3、电解槽B分隔物4、电解槽A的电解电源5、电解槽B的电解电源6、暂存槽23～28、真空射流气液混合器71、传感器101～103、阀门132-1～132-7、泵浦133-1～133-7、酸性蚀刻废液251、再生蚀刻子液252、回收金属铜253、已作回收铜处理的电解槽B溢出的阴极电解液256、电解槽A阴极槽区的溢出液268。
所述的电解槽A分隔物3为反渗透膜，所述电解槽B分隔物4为阴离子交换膜。
所述的电解槽A的阳极材料为铂金属，阴极材料为导电石墨板。
所述的电解槽B的阳极材料为钛基涂层电极，阴极材料为不锈钢。
所述的传感器101和102为氧化还原电位计，传感器103为比重计(测量溶液中的金属离子浓度)。
所述的真空射流气液混合器71用于吸取并引流电解槽A和电解槽B的阳极槽区所电析逸出的氯气到暂存槽28中作氧化再生反应配制所述的再生蚀刻子液252。
所述的电解槽A的阳极槽区安装传感器101液位计，控制泵浦133-1将蚀刻废液投向电解槽A的阳极槽区。电解槽A的阴极槽区内安装有氧化还原电位控制器7以按工艺控制泵浦133-2将暂存槽23中酸性蚀刻废液251向电解槽A的阴极槽区作加投。经过电解处理的电解槽A的阴极槽区的溢出液268被引流到暂存槽25中暂存，其铜离子浓度与原废液相同。
所述的电解槽B 2是一递进式电解取铜的电解槽，其功能是电解槽B的阳极槽区对电解液作氧化处理和产出氯气而阴极作电析取铜。其电解槽B的阳极电解液为所述的已作回收铜处理的电解槽B 2溢出的阴极电解液256，在电解槽B的阳极槽区中作氧化反应生成再生蚀刻子液252。电解槽B的阴极槽区安装传感器103比重计控制将暂存槽25中电解槽A阴极槽区的溢出液268加 投到电解槽B 2的阴极槽区作为递进式电解析铜处理。
所述的已作回收铜处理的电解槽B 2溢出的阴极电解液256部分地被泵浦133-4抽送到暂存槽28中，跟氯气作配制再生蚀刻子液的氧化反应，使暂存槽28中溶液的氯化亚铜、氯化亚铁在传感器104ORP计的控制下进行氧化反应生成为氯化铜和氯化铁的蚀铜剂。当符合再生蚀刻子液的标准要求后通过泵浦133-7泵送到暂存槽26中暂储。
通过对传感器102和104氧化还原电位计的设定值调节，能够调制出经氧化处理后符合工艺要求的低铜离子浓度的再生蚀刻子液252。
本实施例的酸性蚀刻废液主要成分为：盐酸、氯化铜、氯化铁、氯化亚铁、氯化钠、氯化铵和水。其中酸度为1.2mol/L，铜离子浓度为120g/L，总铁离子浓度100g/L。其氧化还原电位值ORP值为610mv。
本实施例的具体步骤如下。
1.向电解槽A的阳极槽区和阴极槽区加投酸性蚀刻废液251作为起始的电解液，电解作业过程中控制酸性蚀刻废液251向电解槽A的阴极槽区的加投量，使蚀刻废液中的二价铜离子和三价铁离子进行电化学的还原反应，所述的阴极槽区因满液溢流到暂存槽25中。
2.向电解槽B的阴极槽区加投暂存槽25中的电解槽A阴极槽区的溢出液268，向其阳极槽区加投暂存槽27中已作回收铜处理的电解槽B溢出的阴极电解液256。
3.人工操作接通电解电源5和电解电源6使电解槽A和电解槽B进行电解作业；电解过程中，电解槽A的阳极槽区电解产出氯气；氧化还原电位控制器7设置控制氧化还原电位为580mV，监控酸性蚀刻废液251投向电解槽A的阴极槽区，使其中的阴极电解液中的蚀铜剂浓度降低且控制电解槽A的电解阴极上没有电析出金属铜；电解槽B中传感器103比重计监控暂存槽25中的电解槽A阴极槽区的溢出液268通过泵浦133-3投向电解槽B的阴极槽区并在工艺上控制电解槽B的阴极槽区中的阴极电解液的铜离子浓度。电解槽A的阳极和电解槽B的阳极分别对酸性蚀刻废液251和已作回收铜处理的电解槽B溢出的阴极电解液256进行电化学氧化反应，同时电解槽A和电解槽B的阳极槽区所逸出氯气 通过射流器71作气液混合来氧化暂存槽28中的溶液生成再生蚀刻子液252；电解槽A的阴极电解液作还原反应消除蚀铜剂，电解槽B的阴极电析出金属铜253。电解槽B的阳极用来氧化已作回收铜处理的电解槽B溢出的阴极电解液256作再生蚀刻子液的配制。
4.再生蚀刻子液的参数值为酸度4.0M/L，铜离子浓度为60g/L，铁离子浓度为100g/L，ORP值为650mv。
以上是通过使用图1中的装置和按照上述的工艺步骤，能实现一种递进式电解回用线路板酸性蚀刻废液的循环回用工艺。
实施例2
如图2所示为一种递进式电解回用线路板酸性蚀刻废液的方法及其装置的实施例2，其包括有电解槽A 1、两个电解槽B 2-1和2-2、电解槽A的阴极槽区氧化还原电位控制器7、电解槽A分隔物3、电解槽B分隔物4-1和4-2、电解槽A的电解电源5、电解槽B的电解电源6-1和6-2、暂存槽23～28、溢流缓冲槽51～56、水油分离器96、传感器101～112、自动检测投料控制器131、阀门132-1～132-23、泵浦133-1～133-23、阴极槽区蚀刻废液投料管134、酸性蚀刻废液251、再生蚀刻子液252、回收金属铜253、已作回收铜处理的电解槽B溢出的阴极电解液256、线路板蚀刻生产线257、氧化再生蚀刻液260、电解槽A阴极槽区的溢出液268。
所述的电解槽A分隔物3为阴离子交换膜。电解槽B分隔物4-1为双极膜，分隔物4-2为反渗透膜。
所述的电解槽A的阳极材料为钛基涂层不溶性阳极，阴极材料为钛金属。
所述的电解槽B 2-1的阳极材料为钛基涂层不溶性阳极，阴极材料为金属铜片；电解槽B 2-2的阳极材料为导电石墨，阴极材料为金属铜片。
所述的传感器101和109为比重计，传感器102为酸度计，传感器103、106和111为氧化还原电位计(即ORP计)，传感器104和107为温度计，传感器105、108和112为液位计，传感器110为光电比色计。所有传感器的现场数据均传送到自动检测投料控制器131处理并按程序控制整套装置工作运转。
所述的线路板蚀刻生产线257里安装有传感器101、102、103、104，其中传感器102酸度计控制泵浦133-1加投再生蚀刻子液252作蚀刻工作液作酸 度控制；传感器101比重计控制阀门加投清水288以控制蚀刻工作液的比重；传感器103ORP计控制变频泵浦133-4转速使蚀刻工作液氧化还原电位按工艺控于540mv；传感器104温度计使蚀刻工作液的温度控为50℃。所以使线路板蚀刻线257通过以上控投使蚀刻工作液维持其酸度为0.9mol/L、比重为1.34g/ml、ORP为530mv来稳定蚀刻性能。
所述的线路板蚀刻生产线257溢出的蚀刻废液先流入所述的水油分离器96作油墨和菲林渣的有机物分离后流入到液流缓冲槽51中，后通过泵浦133-3泵送到作为循环混和交换槽使用的暂存槽24中，当暂存槽24中氧化再生蚀刻液260在液满后受传感器105液位计控制启动泵浦133-7将暂存槽24中的部分溶液泵送到暂存槽25中暂存。
所述的循环混和交换槽即暂存槽24分别与线路板蚀刻线257作循环液流的管道连接，与电解槽B 2-1和2-2的阳极槽区作循环液流管道连接，循环混和交换槽中的溶液即为氧化再生蚀刻液260。暂存槽24中的氧化再生蚀刻液260的氧化还原电位值是通过传感器107ORP计将现场参数传送到自动检测投料控制器131处理并对电解电源6-1和6-2的工作电流作调节控制，使氧化再生蚀刻液260的氧化还原电位数值范围受控在750～800mv。
所述的氧化还原电位控制器7控制泵浦133-10将暂存槽25中蚀刻废液251向电解槽A的阴极槽区作加投，经过电解处理后的溢出液268被泵浦133-9抽送到暂存槽26中暂存。电解作业时因阴极A没有电析出金属铜，故暂存槽26中溶液的铜离子浓度仍为约140g/L。电解槽A的阳极是专用产生氯气来氧化电解槽B 2-1和2-2的阴极溢出液256以配制再生蚀刻子液252。
所述的电解槽B 2-1和2-2是一递进式电解取铜的电解槽，其功能是阴极作电解取铜，阳极作氧化所述的氧化再生蚀刻液260来维持蚀刻进行。传感器109比重计和传感器110光电比色计分别控制泵浦133-13和133-14将暂存槽26中电解槽A的阴极槽区的溢出液268加投到电解槽B 2-1和2-2的阴极槽区中以实现递进式电解取铜。过程中电解槽B 2-1和2-2的阴极电解液中铜离子浓度控制设定值为40g/L，电解槽B 2-1和2-2的阴极均电析出铜金属253。
所述的已作回收铜处理的电解槽B 2-1和2-2溢出的阴极电解液256被泵送到暂存槽27中，再由传感器111ORP计和传感器112液位计控制泵浦133-19 抽送到暂存槽28中通过喷淋塔抽吸氯气对已作回收铜处理的电解槽B溢出的阴极电解液256作氧化反应，使其溶液中的氯化亚铜、氯化亚铁氧化生成为氯化铜和氯化铁蚀铜剂，制得符合工艺要求的低铜离子浓度的再生蚀刻子液。
所述的电解槽B 2-1和2-2的阴极槽区蚀刻废液投料管296和297用于加投蚀刻废液反应去除电解槽B分隔物4-1和4-2上面的氯化亚铜铜泥，避免分隔物发生铜泥堵塞。
本实施例的酸性含铁蚀刻废液主要成分为：盐酸、氯化铜、氯化钠、氯化铵、氯化铁和氯化亚铁的水溶液。其中酸度为0.9mol/L，铜离子浓度为140g/L，总铁离子浓度为20g/L。
一种递进式电解回用线路板酸性蚀刻废液的装置其主要使用步骤如下。
1.向电解槽A的阳极槽区加投蚀刻工作液和阴极槽区中加投蚀刻废液251作为起始的电解液，其中所述的阳极槽区安装传感器101液位计，所述的电解槽A的阴极槽区中安装的氧化还原电位控制器7。
2.向电解槽B 2-1和2-2的阴极槽区加投暂存槽26中的溶液，其电解槽B的阳极槽区的电解液与作为循环混合交换槽的暂存槽24中溶液作循环流动。
3.接通电解电源5、两个电解电源B 6-1和6-2使电解槽A和两个电解槽B进行电解作业；过程中将氧化还原电位控制器7设定值设为499mV以控制酸性蚀刻废液251投向电解槽A的阴极槽区，其阴极上无金属铜生成，仅发生消除蚀铜剂的反应，电解槽A的阳极槽区用于作电析氯气反应；电解槽B 2-1中传感器109比重计监控暂存槽26中电解槽A阴极槽区的溢出液268通过泵浦133-14投向电解槽B 2-1的阴极槽区，电解槽B 2-2中的传感器110光电比色计控制泵浦133-13加投暂存槽26内溶液到电解槽B的阴极槽区中，使电解槽B 2-1和2-2中的阴极均电析上铜；电解槽B 2-1和2-2的阳极对氧化再生蚀刻液260进行电化学氧化反应，使线路板蚀刻生产线257通过控制泵浦133-4的转速投送量来维持蚀刻生产；同时电解槽A的阳极槽区所逸出氯气通过喷淋式气液混合器76吸收处理器对已作回收铜处理的电解槽B溢出的阴极电解液256进行配制再生蚀刻子液252，电解槽A的阴极电解液作还原 反应消除蚀铜剂；电解过程中，采用计量泵浦133-11和133-12分别按时间控制加投小量蚀刻废液251到电解槽B 2-1和2-2的阴极槽中，以去除分隔物上的氯化亚铜。
4.对回配的所述的再生蚀刻子液252的工作参数指标为酸度4.5M/L，铜离子浓度为40g/L，铁离子浓度为20g/L。
以上是通过使用示意图2中的装置和按照上述的工艺步骤，能实现一种递进式电解回用的线路板酸性含铁蚀刻废液的100％循环回用工艺。
实施例3
如图3所示为一种递进式电解回用线路板酸性蚀刻废液的装置的实施例3，其包括有电解槽A 1，电解槽B 2-1和2-2、电解槽C 8。电解槽A的阴极槽区安装氧化还原电位控制器7。电解槽A设有的电解槽A分隔物3为双极膜。电解槽B的电解槽B分隔物4-1为阴离子交换膜，4-22为阴离子交换膜。电解槽C的电解槽C分隔物9为阴离子交换膜。还包括有电解槽A的电解电源5，两个电解槽B的电解电源6-1和6-2，电解槽C的电解电源10，暂存槽23～31，溢流缓冲槽51～56，真空射流气液混合器71，喷淋式气液混合器76，循环液流搅拌器81～86，传感器,110～112，自动检测投料控制器131，酸性蚀刻废液251，再生蚀刻子液252，回收金属铜253，已作回收铜处理的电解槽B3～4的溢出阴极电解液256,线路板蚀刻生产线257,阀门132-1～132-19,泵浦133-1～133-20,氢氧化钠溶液267,尾气处理槽281，电解槽A的阴极槽区溢出液268，清水288，活动式槽盖289～291。
所述的电解槽A的阳极材料为表面镀金的不溶性阳极，阴极为铂金属。所述的电解槽B 2-1的阳极材料为导电石墨，阴极为钛板。电解槽B 2-2的阳极材料为钛基涂层不溶性阳极，阴极为钛板。电解槽C 8的阳极材料为钛基涂层不溶性阳极，阴极材料为铜片。
所述的线路板蚀刻生产线257与电解槽A和B的各阳极槽区作液流管道连接，线路板蚀刻生产线257上安装有四种传感器，分别是传感器101酸度计、传感器102比重计、传感器103氧化还原电位计和传感器104温度计。传感器101酸度计控制泵浦133-1加投再生蚀刻子液252，传感器102比重计控制加投清水288，传感器103氧化还原电位计控制调整各电解电源的输出电流大小或关停的 工作状态，当蚀刻工作液中的蚀铜剂浓度达到工艺设定值时，则关停所有的电解电源。传感器104温控计以控制蚀刻工作液温度控为50℃。通过以上对多个的酸度、比重、氧化还原电位、温度参数控制使蚀刻工作液在不断的蚀刻生产过程仍能维持其蚀刻性能。
所述的溢流缓冲槽51中设有一条带固液分离过滤器97的输出泵浦管道，将漂浮在蚀刻工作液上的有机油渣利用过滤分离后将蚀刻废液引流到暂存槽25中装储溢出的酸性蚀刻废液251。本实施例不设所述的循环混和交换槽，蚀刻工作时直接采用泵浦133-4至133-6将蚀刻工作液分别泵送到电解槽A和电解槽B的阳极槽区中，再由各自的阳极槽区溢流口流回到线路板蚀刻生产线257中。在传感器103ORP计的控制下使多个电解电源作启动或调节响应，令蚀刻工作液得到氧化再生蚀铜剂。
所述的电解槽A的阴极槽区内安装有氧化还原电位控制器7，按工艺设置为200mv以控制暂存槽25中蚀刻废液251向电解槽A的阴极槽区的加投量并使其阴极电解液中的三价铁离子全部变为二价铁离子，同时又使其阴极尽量少电析出金属铜。经过处理的电解槽A的阴极槽区的溢出液268被泵浦133-7抽送到暂存槽26中暂存，其溶液的铜离子浓度降为98g/L。
所述的电解槽B是对电解槽A采用递进式电解取铜的工艺，而电解槽C是采用进一步的递进式电解取铜的工艺方式。电解槽B的阴极槽区里分别安装有比重计，即传感器105和106。电解槽C中的阳极槽区中安装有传感器107ORP计，电解槽C的阴极槽区安装传感器108比重计。将以上多个传感器的检测数据送至自动检测投料控制器131中处理，控制暂存槽26的电解槽A的阴极槽区的溢出液268向电解槽B的阴极槽区作加投，使电解槽B各阴极槽区的电解液中各成分浓度在电析铜过程中得到控制，且电解槽B的阴极溢出液被泵浦133-11和133-12泵送到暂存槽27中暂储。其中，暂存槽27中溶液的铜离子浓度设定控制在60g/L。
通过传感器108测得的数据，自动检测投料控制器131对泵浦133-13控制将溶液256投到电解槽C的阴极槽区中。传感器108比重计控制电解槽C的阴极电解液的铜离子浓度为5g/L，电解过程中会产生海绵铜并被阴极布滤袋294作收集。随着电解槽C的作业进行，其阴极电解液溢流到溢流缓冲槽56中并通过泵浦133-18泵送到暂存槽30中暂储。
暂存槽31用作氯气氧化反应槽，其槽顶安装真空射流气液混合器71和槽内安装传感器109液位计。过程中将各电解槽的阳极槽区所逸出的氯气引流到暂存槽31中与槽内溶液反应。其传感器109液位计控制泵浦133-19投入暂存槽31的溶液，传感器107ORP计控制泵浦133-20将暂存槽31的溶液投到电解槽C的阳极槽区中，使电解槽C的阴极电解液在电解取铜后能将其中的氯化亚铜和氯化亚铁氧化为蚀铜剂以满足再生蚀刻子液的部分标准要求。
所述的暂存槽28作为配制再生蚀刻子液使用。投入暂存槽29的溶液后跟随投入盐酸、三氯化铁、氯化铵、启动液流循环搅拌器84作配制所述再生蚀刻子液252。通过人工检验合格后将配制完成的再生蚀刻子液252泵送到暂存槽23中暂存。
所述的尾气处理槽281是用于对各槽逸出的酸性尾气S吸收作环保处理。
在蚀刻生产过程中，蚀刻工作液其氧化还原电位数值控制在580mv。
本实施例的酸性含铁蚀刻废液主要成分为：盐酸、氯化铜、氯化铵和氯化铁的水溶液。其中酸度为1.6mol/L，铜离子浓度为100g/L，总铁离子浓度为140g/L。
一种递进式电解回用线路板酸性蚀刻废液的装置操作步骤如下。
1.向电解槽A的阳极槽区加投蚀刻工作液和阴极槽区中加投蚀刻废液251，其电解槽A的阴极槽区中安装有氧化还原电位控制器7，在电解过程中控制蚀刻废液251向电解槽A的阴极槽区电的加投量，其阴极电解液的ORP值控为200mv。
2.向两个电解槽B的阳极槽区加投蚀刻工作液，向电解槽B的阴极槽区加投暂存槽26中的电解槽A阴极槽区的溢出液268，分别使用传感器105和106比重计在过程中控制电解槽A阴极槽区的溢出液268向电解槽B的各阴极槽区的加投量。
3.通过传感器107ORP计向电解槽C的阳极槽区作控制加投暂存槽31的溶液，通过传感器108比重计向电解槽C的阴极槽区中控制泵浦133-13加投暂存槽27中已作回收铜处理的电解槽B溢出的阴极电解液256。
4.接通各电解电源，使各电解槽进行电解作业，过程中利用所述的蚀刻生产线257中的蚀刻工作液在电解槽A和B的各阳极槽区之间的循环流动，使各电解阳极对蚀刻工作液进行氧化再生的电化学反应。电解槽A和B 的阳极槽区所析出的氯气被引流到暂存槽31中用于氧化已作回收铜处理后的电解槽C阴极槽区溢出的电解液，电解槽B和电解槽C的阴极均电析出金属铜253。
5.将已作氧化处理的溶液在暂存槽28中进行加投盐酸、氯化铁和氯化铵来配制再生蚀刻子液，经人工检验合格后将槽28中溶液通过泵浦133-15抽送到暂存槽23中暂存。其再生蚀刻子液252的参数为酸度5.5M/L、铜离子浓度为5g/L、三价铁离子浓度为140g/L。
6.将各槽罐所逸出的酸性尾气S被引流到尾气处理槽281中作环保处理。
7.整套设备系统的工艺流程由自动检测投料控制器131按程序作自动控制，并将暂存槽23中的再生蚀刻子液投到蚀刻线中作循环使用。
以上是采用图3的装置并按上述步骤来实现一种递进式电解回用线路板酸性蚀刻废液的100％循环回用工艺。
实施例4
如图4所示为一种递进式电解回用线路板酸性蚀刻废液的方法及其装置的实施例4，其包括有电解槽A 1、两个电解槽B 2-1和2-2、电解槽A的阴极槽区氧化还原电位控制器7、电解槽A分隔物3、电解槽B分隔物4-1和4-2、电解槽A的电解电源5、两个电解槽B的电解电源6-1和6-2、暂存槽23～28、溢流缓冲槽51～56、水油分离器96、传感器101～112、自动检测投料控制器131、阀门132-1～132-20、泵浦1331～133-20、酸性蚀刻废液251、再生蚀刻子液252、回收金属铜253、已作回收铜处理的电解槽B溢出的阴极电解液256、线路板蚀刻生产线257、氧化再生蚀刻液260、电解槽A阴极槽区的溢出液268。
所述的电解槽A分隔物3为阴离子交换膜。电解槽B分隔物4-1为双极膜，4-2为反渗透膜。
所述的电解槽A的阳极材料为钛基涂层不溶性阳极，阴极材料为钛金属。
所述的电解槽B 2-1的阳极材料为钛基涂层不溶性阳极，阴极材料为金属铜片；电解槽B 2-2的阳极材料为导电石墨，阴极材料为金属铜片。
所述的传感器101为酸度计，传感器102、106、111为氧化还原电位计即ORP计，传感器103、107为温度计，传感器104、109为比重计，传感器105、112为液位计，传感器110为光电比色计。所有传感器的现场检测数据均传送 到自动检测投料控制器131处理并按程序控制整套装置工作运转。
所述的线路板蚀刻生产线257里安装有传感器101至103，其中传感器101酸度计控制阀门加投外来酸性三氯化铁溶液作蚀刻工作液的酸度控制；传感器102ORP计控制变频泵浦133-4转速使蚀刻工作液氧化还原电位按工艺控于510mv；传感器103温度计使蚀刻工作液的温度控为50℃。其中，蚀刻工作液的比重是通过安装在循环混和交换槽的传感器104比重计来作检测控制，当循环混和交换槽的溶液比重因蚀铜增大后，以控制泵浦133-1将暂存槽23的溶液泵送入循环混和交换槽中来降低溶液中的铜离子浓度。所以使线路板蚀刻生产线257通过以上控投使蚀刻工作液维持其酸度为1摩尔/升、比重为1.33克/毫升、ORP为510mv来稳定蚀刻性能。
所述的线路板蚀刻生产线257溢出的蚀刻废液先流入所述的水油分离器96作油墨和菲林渣的有机物分离后流入到液流缓冲槽51中，后通过泵浦133-3泵送到作为循环混和交换槽使用的暂存槽24中，当暂存槽24中氧化再生蚀刻液260在液满后受传感器105液位计控制启动泵浦133-7将暂存槽24中的部分溶液泵送到暂存槽25中暂存。
所述的循环混和交换槽即暂存槽24分别与线路板蚀刻生产线257作循环液流的管道连接，与电解槽A和电解槽B的阳极槽区作循环液流管道连接，暂存槽24中的氧化再生蚀刻液260的氧化还原电位值是通过传感器107ORP计将现场参数传送到自动检测投料控制器131处理并对两个电解电源B的工作电流作调节控制，使循环混和交换槽溶液260的氧化还原电位数值范围受控在750～800mv。根据安装在所述的循环混和交换槽的传感器104比重计检测数值，将暂存槽23里的再生蚀刻子液不投往蚀刻线而是直接投到所述的循环混和交换槽中，既能迅速平衡蚀刻工作液的铜离子浓度，又能快速氧化再生蚀刻子液中仍余有的Fe2+亚铁离子，使蚀刻工作液的ORP值更稳定。
所述的氧化还原电位控制器7按工艺设定值控制泵浦133-11将暂存槽25中蚀刻废液251向电解槽A的阴极槽区作加投，经过电解处理后的溢出液268被泵浦133-10抽送到暂存槽26中暂存。电解作业时因电解槽A的阴极没有电析出金属铜，故暂存槽26中溶液的铜离子浓度仍为120g/L。电解槽A的阳极用于氧化蚀刻工作液。
所述的电解槽B是电解槽A的递进式电解取铜的电解槽，其阴极作电解取铜，阳极作氧化所述的氧化再生蚀刻液260来维持蚀刻进行。传感器109比重计和传感器110光电比色计分别控制泵浦133-12和133-13将暂存槽26中的电解槽A阴极槽区的溢出液268加投到两个电解槽B的阴极槽区中以实现递进式电解取铜。过程中电解槽B的阴极电解液中铜离子浓度控制设定值为30g/L，电解槽B中的阴极均电析出铜金属253。
所述的已作回收铜处理的从电解槽B溢出的阴极电解液256通过泵浦133-15和133-17被泵送到暂存槽27中，再由传感器111ORP计和传感器112液位计控制泵浦133-18抽送到暂存槽28中通过喷淋塔抽吸电解槽阳极电解液逸出的氯气对已作回收铜处理的电解槽B溢出的阴极电解液256作氧化反应，使其溶液中部分氯化亚铜、氯化亚铁氧化生成为氯化铜和氯化铁蚀铜剂，制得低铜离子浓度的再生蚀刻子液。其中再生蚀刻子液中仍存在一定数量未被氯气氧化的二价铁离子。
本实施例的酸性含铁蚀刻废液主要成分为：盐酸、氯化铜、氯化钠、氯化铵、氯化铁和氯化亚铁的水溶液。其中酸度为1mol/L，铜离子浓度为120g/L，总铁离子浓度为120g/L。
一种递进式电解回用线路板酸性蚀刻废液的装置其主要使用步骤如下。
1.向电解槽A的阳极槽区加投蚀刻工作液和阴极槽区中加投蚀刻废液251作为起始的电解液，其中所述的电解槽A的阴极槽区中安装的氧化还原电位控制器7，在电解作业过程中将氧化还原电位控制器7的设定值设为470mV以控制蚀刻废液251向电解槽A的阴极槽区的加投量，并且其阴极上无金属铜生成，仅发生消除蚀铜剂的反应，电解槽A的阳极槽区用于对蚀刻工作液的氧化反应。
2.向两个电解槽B的阴极槽区加投暂存槽26中的溶液，其阳极槽的电解液与用作循环混合交换槽的暂存槽24中溶液作循环流动。
3.接通电解电源5和电解电源6，使电解槽A和电解槽B进行电解作业，过程中氧化还原电位控制器7监控蚀刻废液251投向电解槽A的阴极槽区，电解槽B 2-1中传感器109比重计监控暂存槽26中的电解槽A阴极槽区的溢出液268通过泵浦133-13投向电解槽B的阴极槽区，电 解槽B 2-2中的传感器110光电比色计控制泵浦133-12加投暂存槽26溶液到电解槽B的阴极槽区中，使电解槽B中的阴极均电析上铜；电解槽B的阳极对氧化再生蚀刻液260进行电化学氧化反应，使蚀刻生产线257通过控制泵浦133-4的转速投送量来维持蚀刻生产；同时各电解槽的阳极槽区所逸出的少量氯气通过喷淋式气液混合器76吸收处理器对已作回收铜处理的电解槽B溢出的阴极电解液256进行配制再生蚀刻子液252。
4.对回配的所述的再生蚀刻子液252的工作参数指标为酸度6M/L，铜离子浓度为30g/L，铁离子浓度为120g/L。
以上是通过使用示意图4中的装置和按照上述的工艺步骤，能实现一种递进式电解回用的线路板酸性含铁蚀刻废液的100％循环回用工艺。
实施例5
采用图1的装置，对以下酸性蚀刻废液进行处理。
本实施例的酸性蚀刻废液主要成分为：盐酸、氯化铜和水。其中酸度为3.2mol/L，铜离子浓度为120g/L。其氧化还原电位值ORP值为500mv。
本实施例的具体步骤如下。
1.向电解槽A的阳极槽区和阴极槽区加投酸性蚀刻废液251作为起始的电解液，电解作业过程中控制酸性蚀刻废液251向电解槽A的阴极槽区的加投量，使蚀刻废液中的二价铜离子进行电化学的还原反应，所述阴极槽区因满液溢流到暂存槽25中。
2.向电解槽B的阴极槽区加投暂存槽25中的电解槽A阴极槽区的溢出液268，向其阳极槽区加投暂存槽27中已作回收铜处理的电解槽B溢出的阴极电解液256。
3.人工操作接通电解电源5和电解电源6使电解槽A和电解槽B进行电解作业；电解过程中，电解槽A的阳极槽区电解产出氯气；氧化还原电位控制器7设置控制氧化还原电位为300mV，监控酸性蚀刻废液251投向电解槽A的阴极槽区，使其中的阴极电解液中的蚀铜剂浓度降低且控制电解槽A的电解阴极上没有电析出金属铜；电解槽B中传感器103比重计监控暂存槽25中的电解槽A阴极槽区的溢出液268通过泵浦 133-3投向电解槽B的阴极槽区并在工艺上控制阴极电解液的铜离子浓度。电解槽A的阳极和电解槽B的阳极分别对酸性蚀刻废液251和已作回收铜处理的电解槽B溢出的阴极电解液256进行电化学氧化反应，同时电解槽A和电解槽B的阳极槽区所逸出氯气通过射流器71作气液混合来氧化暂存槽28中的溶液生成再生蚀刻子液252；电解槽A的阴极电解液作还原反应消除蚀铜剂，电解槽B的阴极电析出金属铜253。电解槽B的阳极用来氧化已作回收铜处理的电解槽B溢出的阴极电解液256作再生蚀刻子液的配制。
4.再生蚀刻子液的参数值为酸度4.0M/L，铜离子浓度为60g/L，ORP值为520mv。
以上是通过使用图1中的装置和按照上述的工艺步骤，能实现一种递进式电解回用线路板酸性蚀刻废液的循环回用工艺。
实施例6
采用图3的装置，对以下酸性蚀刻废液进行处理。
本实施例的酸性蚀刻废液主要成分为：盐酸、氯化铜、氯化铵和水。其中酸度为2.5mol/L，铜离子浓度为120g/L。其氧化还原电位值ORP值为520mv。
本实施例的具体步骤如下。
1.向电解槽A的阳极槽区加投蚀刻工作液和阴极槽区中加投酸性蚀刻废液251，其阴极槽区中安装有氧化还原电位控制器7，在电解过程中控制蚀刻废液251向电解槽A的阴极槽区的加投量，其阴极电解液的ORP值控为350mv。
2.向两个电解槽B的阳极槽区加投蚀刻工作液，向其电解槽B的阴极槽区加投暂存槽26中的电解槽A阴极槽区的溢出液268，分别使用传感器105和106比重计在过程中控制电解槽A阴极槽区的溢出液268向电解槽B的各阴极槽区的加投量。
3.通过传感器107ORP计向电解槽C的阳极槽区作控制加投暂存槽31的溶液，通过传感器108比重计向电解槽C的阴极槽区中控制133-13加投暂存槽27中已作回收铜处理的电解槽B溢出的阴极电解液256。
4.接通各电解电源，使各电解槽进行电解作业，过程中利用所述的线路板 蚀刻生产线257中的蚀刻工作液在电解槽A和B的各阳极槽区之间的循环流动，使各电解阳极对蚀刻工作液进行氧化再生的电化学反应。电解槽A和B的阳极槽区所析出的氯气被引流到暂存槽31中用于氧化已作回收铜处理后的电解槽C阴极槽区溢出的电解液，电解槽B和电解槽C的阴极均电析出金属铜253。
5.将已作氧化处理的溶液在暂存槽28中进行加投盐酸和氯化铵来配制再生蚀刻子液，经人工检验合格后将槽28中溶液通过泵浦133-15抽送到暂存槽23中暂存。其再生蚀刻子液252的参数为酸度6.1M/L、铜离子浓度为5g/L。
6.将各槽罐所逸出的酸性尾气S被引流到尾气处理槽281中作环保处理。
7.整套设备系统的工艺流程由自动检测投料控制器131按程序作自动控制，并将暂存槽23中的再生蚀刻子液投到蚀刻线中作循环使用。
以上是采用图3的装置并按上述步骤来实现一种递进式电解回用线路板酸性蚀刻废液的100％循环回用工艺。
实施例7
采用图4的装置，对以下酸性蚀刻废液进行处理。
本实施例的酸性蚀刻废液主要成分为：盐酸、氯化铜、氯化钠和水。其中酸度为2.7mol/L，铜离子浓度为110g/L。其氧化还原电位值ORP值为480mv。
本实施例的具体步骤如下。
1.向电解槽A的阳极槽区电加投蚀刻工作液和阴极槽区中加投酸性蚀刻废液251作为起始的电解液，其中所述电解槽A的阴极槽区中安装的氧化还原电位控制器7，在电解作业过程中将氧化还原电位控制器7的设定值设为300mV以控制酸性蚀刻废液251向电解槽A的阴极槽区的加投量，并且其阴极上无金属铜生成，仅发生消除蚀铜剂的反应，电解槽A的阳极槽区用于对蚀刻工作液的氧化反应。
2.向两个电解槽B的阴极槽区加投暂存槽26中的溶液，其阳极槽的电解液与用作循环混合交换槽的暂存槽24中溶液作循环流动。
3.接通电解电源5和电解电源6，使电解槽A和电解槽B进行电解作业，过程中氧化还原电位控制器7监控蚀刻废液251投向电解槽A的阴极槽 区，电解槽B 2-1中传感器109比重计监控暂存槽26中的电解槽A阴极槽区的溢出液268通过泵浦133-13投向电解槽B的阴极槽区，电解槽B 2-2中的传感器110光电比色计控制泵浦133-12加投暂存槽26溶液到电解槽B的阴极槽区中，使电解槽B中的阴极均电析上铜；电解槽B的阳极对氧化再生蚀刻液260进行电化学氧化反应，使蚀刻生产线257通过控制泵浦133-4的转速投送量来维持蚀刻生产；同时各电解槽的阳极槽区所逸出的少量氯气通过喷淋式气液混合器76吸收处理器对已作回收铜处理的电解槽B溢出的阴极电解液256进行配制再生蚀刻子液252。
4.对回配的所述的再生蚀刻子液252的工作参数指标为酸度5.2M/L，铜离子浓度为30g/L。
以上是通过使用示意图4中的装置和按照上述的工艺步骤，能实现一种递进式电解回用的线路板酸性蚀刻废液的100％循环回用工艺。
实施例8
如图5所示为一种递进式电解回用线路板酸性蚀刻废液的方法及其装置的实施例8，其包括有两个电解槽A 1-1和1-2、两个电解槽B 2-1和2-2、电解槽A 1-1的阴极槽区安装氧化还原电位控制器7-1，电解槽A 1-2的阴极槽区安装氧化还原电位控制器7-2，电解槽A分隔物3-1和3-2、电解槽B分隔物4-1和4-2、两个电解电源5-1和5-2、两个电解电源6-1和6-2、暂存槽23～28、溢流缓冲槽共9个、水油分离器96、传感器101～116、自动检测投料控制器131、阀门132、泵浦133、尾气处理槽281、阴极槽区蚀刻废液投料管134、酸性蚀刻废液251、再生蚀刻子液252、回收金属铜253、已作回收铜处理的电解槽B溢出的阴极电解液256、线路板蚀刻生产线257、氧化再生蚀刻液260、电解槽A阴极槽区的溢出液268。
所述的两个电解槽A分隔物3-1和3-2均为阴离子交换膜。电解槽B分隔物4-1和4-2均为阴离子交换膜。
所述的两个电解槽A 1-1和1-2的阳极材料均为钛基涂层不溶性阳极，阴极材料均为钛金属。
所述的电解槽B 2-1和2-2的阳极材料均为钛基涂层不溶性阳极；电解槽 B 2-1和2-2的阴极材料均为金属铜片。
所述的传感器101、111、112和113均为比重计，传感器102和114为酸度计，传感器103、106、109和111为氧化还原电位计(即ORP计)，传感器104和107为温度计，传感器105、108、110和116为液位计。所有传感器的现场数据均传送到自动检测投料控制器131处理并按程序控制整套装置工作运转。
所述的线路板蚀刻生产线257里安装有传感器101、102、103、104，其中传感器101比重计控制泵浦133-1加投再生蚀刻子液252对蚀刻工作液作氯盐浓度控制；传感器102酸度计控制阀门132-2加投盐酸283以控制蚀刻工作液的酸度；传感器103ORP计控制变频泵浦133-4转速使蚀刻工作液氧化还原电位按工艺控于530mv；传感器104温度计使蚀刻工作液的温度控为50℃。所以使线路板蚀刻线257通过以上控投使蚀刻工作液维持其酸度为0.9mol/L、比重为1.35g/ml、ORP为530mv来稳定蚀刻性能。
所述的线路板蚀刻生产线257溢出的蚀刻废液先流入所述的水油分离器96作油墨和菲林渣的有机物分离后流入到液流缓冲槽51中，后通过泵浦泵送到作为循环混和交换槽使用的暂存槽24中，当暂存槽24中氧化再生蚀刻液260在液满后受传感器105液位计控制启动泵浦133-7将暂存槽24中的部分溶液泵送到暂存槽25中暂存。
所述的两个电解槽A 1-1和1-2的工作状态分别受液位计110和116的现场检测数值作关联控制。其中电解槽A 1-2用于将电解槽B已取铜的256溶液在配制后电解氧化再生蚀刻子液。
所述的循环混和交换槽即暂存槽24分别与线路板蚀刻线257作循环液流的管道连接，分别与电解槽A 1-1、电解槽B 2-1和2-2的阳极槽区作循环液流管道连接，循环混和交换槽中的溶液即为氧化再生蚀刻液260。暂存槽24中的氧化再生蚀刻液260的氧化还原电位值是通过传感器106ORP计将现场参数传送到自动检测投料控制器131处理并分别对电解电源5-1和电解电源6-1和6-2的工作电流作调节控制，使氧化再生蚀刻液260的氧化还原电位数值范围受控在750～850mv。
所述的氧化还原电位控制器7-1和7-2分别控制泵浦133-14和133-13将暂存槽25中蚀刻废液251向两个电解槽A的阴极槽区作加投，经过电解处理后 的溢出液268被泵浦抽送到暂存槽26中暂存。两个电解槽A在电解作业时因两个阴极都没有电析出金属铜，故暂存槽26中溶液的铜离子浓度仍为约140g/L。
所述的电解槽B 2-1和2-2是一递进式电解取铜的电解槽，其功能是阴极作电解取铜，阳极作氧化所述的氧化再生蚀刻液260来维持蚀刻进行。传感器111和112比重计分别控制泵浦133-18和133-17将暂存槽26中两个电解槽A阴极槽区的溢出液268加投到电解槽B 2-1和2-2的阴极槽区中以实现递进式电解取铜。过程中电解槽B 2-1和2-2的阴极电解液中铜离子浓度控制设定值均为40g/L，电解槽B 2-1和2-2的阴极均电析出铜金属253。
所述的已作回收铜处理的电解槽B 2-1和2-2溢出的阴极电解液256被泵送到暂存槽27中，再由传感器113比重计和传感器114酸度计控制泵浦113-23抽送槽27的溶液到暂存槽28中作配制，过程中开启叶轮搅拌器92，向槽28投入盐酸283、氯化铵285、氢氧化铁297，配制得到电解槽A 1-2的阳极电解液。
所述的电解槽B 2-1和2-2的阴极槽区蚀刻废液投料管296和297用于加投蚀刻废液反应去除电解槽B分隔物4-1和4-2上面的氯化亚铜铜泥，避免分隔物发生铜泥堵塞。
所述的尾气处理槽281是采用喷淋塔将废气引入作处理。
本实施例的酸性含铁蚀刻废液主要成分为：盐酸、氯化铜、氯化钠、氯化铵、氯化铁和氯化亚铁的水溶液。其中酸度为0.9mol/L，铜离子浓度为140g/L，总铁离子浓度为30g/L。
一种递进式电解回用线路板酸性蚀刻废液的装置其主要使用步骤如下。
1.向电解槽A 1-1的阳极槽区加投蚀刻工作液和阴极槽区中加投蚀刻废液251作为起始的电解液，并且电解槽A 1-1的阳极电解液与循环混合交换槽溶液能作循环流动，向电解槽A 1-2的阳极槽区加投需要再生氧化的蚀刻子液(槽28溶液)。其中电解槽A 1-1的阳极槽区安装传感器101液位计，电解槽A 1-2的阳极槽区安装传感器109ORP计，两个电解槽A的阴极槽区中分别安装的氧化还原电位控制器7-1和7-2。
2.向电解槽B 2-1和2-2的阴极槽区加投暂存槽26中的溶液，其阳极槽区的电解液与作为循环混合交换槽的暂存槽24中溶液作循环流动。
3.接通两个电解槽A的电解电源5-1和5-2、两个电解槽B的电解电源6-1和6-2使两个电解槽A和两个电解槽B进行电解作业；过程中将氧化还原电位控制器7-1和7-2的设定值均设为480mV以控制酸性含铁蚀刻废液251投向两个电解槽A的阴极槽区，其两个阴极和上面无金属铜生成，仅发生消除蚀铜剂的反应，两个电解槽A的阳极分别对阳极电解液进行氧化反应；电解槽B 2-1中传感器111比重计监控暂存槽26中电解槽A阴极槽区的溢出液268通过泵浦133-18投向电解槽B 2-1的阴极槽区，电解槽B 2-2中的传感器112比重计控制泵浦133-17加投暂存槽26内溶液到电解槽B的两个阴极槽区中，使电解槽B 2-1和2-2中的阴极均电析上铜；电解槽B 2-1和2-2的阳极对氧化再生蚀刻液260进行电化学氧化反应，使线路板蚀刻生产线257通过控制泵浦174的转速投送量来维持蚀刻生产；电解过程中，采用计量泵浦分别按时间控制加投小量蚀刻废液251到电解槽B 2-1和2-2的阴极槽中，以去除电解槽B分隔物上的氯化亚铜。
4.将两个电解槽B的阴极溢出液收集到暂存槽27，根据暂存槽28中的传感器113和114所检测得到数据分别控制向槽28中加投256溶液，盐酸和氯化铵、氢氧化铁进行配制，制得电解槽A 1-2的阳极电解液。
5.根据传感器109ORP计的现场检测数值控制泵浦133-24向电解槽A 1-2的阳极槽区投入槽28中的溶液，通过电化学氧化制得符合工艺要求的再生蚀刻子液作蚀刻生产循环回用。
以上是通过使用示意图5中的装置和按照上述的工艺步骤，能实现一种递进式电解回用的线路板酸性蚀刻废液的100％循环回用工艺。

Claims (10)

  1. 一种递进式电解回用线路板酸性蚀刻废液的方法，其特征在于，包括以下步骤：
    步骤一：采用至少一个电解槽A，所述的电解槽A内部采用电解槽分隔物分隔有阳极槽区和阴极槽区；电解作业时所述电解槽A的阳极槽区和阴极槽区中分别设置有电解阳极和电解阴极，分别对电解槽A的阳极电解液和阴极电解液进行电解作业；所述的电解槽A的阴极电解液包含酸性蚀刻废液；
    步骤二：采用至少一个电解槽B作递进式电解取铜，所述的电解槽B内分有阳极槽区和阴极槽区；电解作业时所述的电解槽B阳极槽区和阴极槽区中分别设置有电解阳极和电解阴极，分别对电解槽B阳极电解液和阴极电解液进行电解作业，令所述电解槽B的电解阴极上发生铜离子被还原为金属铜的电化学反应；所述电解槽B的阴极电解液包含经过电解处理后的电解槽A的阴极电解液或者其与酸性蚀刻废液的混合液；
    步骤三：所述电解槽B的电解阴极上因电化学反应沉积的金属铜达到预先设定的电析目标量时，将所述电解槽B的电解阴极从电解槽B取出。
  2. 根据权利要求1所述的递进式电解回用线路板酸性蚀刻废液的方法，其特征在于：所述电解槽A的阳极电解液包含蚀刻工作液、蚀刻废液、经过电解处理后电解槽B的阴极电解液中的至少一种；所述电解槽B的阳极电解液包含经过电解处理后的电解槽B的阴极电解液、蚀刻工作液、蚀刻废液中的至少一种。
  3. 根据权利要求1所述的递进式电解回用线路板酸性蚀刻废液的方法，其特征在于：根据电解槽A的阴极槽区中阴极电解液的氧化还原电位数值按工艺要求对电解槽A的电解电源的输出电流大小作调整或者启动关停，和/或向电解槽A的阴极槽区加投补充包含酸性蚀刻废液的溶液，以保持其阴极电解液中蚀铜剂的浓度令其电解阴极上少电析出金属铜甚至不电析出金属铜，而主要作电化学还原反应使电解槽A的阴极电解液中的蚀铜剂CuCl2，或者CuCl2和FeCl3浓度降低甚至消除其蚀铜能力。
  4. 根据权利要求1所述的递进式电解回用线路板酸性蚀刻废液的方法，其特征在于：电解过程中将所述的电解槽A的阴极电解液的氧化还原电位数值控制在200～580mv，即采取其外投废液的氧化还原电位值ORP值投控点范围控制在200～580mv之间。
  5. 根据权利要求1所述的递进式电解回用线路板酸性蚀刻废液的方法，其特征在于：增设排序在电解槽B后的至少一个电解槽C，所述的电解槽C内分有阳极槽区和阴极槽区；电解作业时所述电解槽C的阳极槽区和阴极槽区中分别设置有电解阳极和电解阴极，分别对其阳极电解液和阴极电解液进行电解作业；所述电解槽C的阳极电解液包含酸性蚀刻工 作液、经过电解处理后的电解槽B的阴极电解液、经过电解处理后的电解槽C的阴极电解液中的至少一种，或者在此基础上进一步包含蚀刻废液；所述电解槽C的阴极电解液包含经过电解处理后的电解槽B的阴极电解液，或者在此基础上进一步包含电解槽A的阴极电解液和/或蚀刻废液。
  6. 根据权利要求5所述的递进式电解回用线路板酸性蚀刻废液的方法，其特征在于：控制所述电解槽B的电解阴极和电解槽C的阴极电解液的铜离子浓度不低于5g/L。
  7. 根据权利要求5所述的递进式电解回用线路板酸性蚀刻废液的方法，其特征在于：对方法中至少一种电解液的参数值进行检测，并以现场测得的数据作为依据控制电解槽A的电解电源和/或电解槽B的电解电源和/或电解槽C的电解电源的输出电流大小和/或开启关停，和/或控制各种物料的加投，所检测的参数值包括但不限于酸度值、比重值、氧化还原电位值、光电比色值、液位、温度、流量、有害气体浓度中的任意一种或以上。
  8. 根据权利要求5所述的递进式电解回用线路板酸性蚀刻废液的方法，其特征在于：将设有电解分隔物电解槽中的电解槽A的阳极电解液和/或电解槽B的阳极电解液和/或电解槽C的阳极电解液与蚀刻生产线上的蚀刻工作液循环混和，令蚀刻生产线上的蚀刻工作液能进行在线补充蚀铜剂。
  9. 一种运用权利要求1至8任意一项所述的递进式电解回用线路板酸性蚀刻废液的方法的装置，其特征在于，包括：
    使用至少一个电解槽A和至少一个电解槽B，所述的电解槽A内部采用电解槽分隔物作分隔有阳极槽区和阴极槽区，所述的电解槽B内部划分有阳极槽区和阴极槽区；电解槽A的阴极槽区中安装有氧化还原电位计，电解槽A的阴极槽区与电解槽B的阴极槽区通过液流管道连接将电解槽A的阴极槽区中经过电解反应的溶液加投到电解槽B的阴极槽区中作递进式电解取铜；电解槽A的阳极槽区和电解槽A的阴极槽区中分别设置有电解阳极和电解阴极，所述的电解阳极和电解阴极分别与电解槽A的电解电源的正极和负极连接；电解槽B的阳极槽区和电解槽B的阴极槽区中分别设置有电解槽B的电解阳极和电解阴极，所述的电解阳极和电解阴极分别与电解槽B的电解电源的正极和负极连接。
  10. 根据权利要求1所述的装置，其特征在于：增设排序在电解槽B后的至少一个电解槽C，所述的电解槽C中分有阳极槽区和阴极槽区；电解槽B的阴极槽区与电解槽C的阴极槽区通过液流管道连接将电解槽B的阴极槽区中经电解处理后的溶液加投到电解槽C的阴极槽区中；电解槽C的阳极槽区和电解槽C的阴极槽区中分别设置有电解阳极和电解 阴极，电解阳极和电解阴极分别与电解电源C的正极和负极连接；电解过程中，电解槽C的阳极槽区和阴极槽区中分别装有阳极电解液和阴极电解液；所述的电解槽C的阳极电解液包含蚀刻工作液、经过电解处理后的电解槽B的阴极电解液、经过电解处理后的电解槽C的阴极电解液中的至少一种，或者在此基础上进一步包含蚀刻废液；所述电解槽C的阴极电解液包含经过电解处理后的电解槽B的阴极电解液，或者在此基础上进一步包含电解槽A的阴极电解液和/或蚀刻废液。
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WO2025166981A1 (zh) * 2024-02-05 2025-08-14 叶涛 一种处理垃圾渗滤液的气液混合式电化学反应装置及其处理垃圾渗滤液的方法
WO2025166977A1 (zh) * 2024-02-05 2025-08-14 叶涛 一种气液混合式电化学反应装置及其对蚀刻液氧化处理的方法

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