Method for electrolysis-assisted oxidative regeneration of alkaline copper-ammonia chloride etching working solution, and apparatus using same

Abstract

Provided are a method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution, and an apparatus using the same. The method includes the following steps: (1) selecting an electrolytic cell provided with an electrolytic cell separator; (2) with the alkaline copper-ammonia chloride etching working solution as an anode electrolyte, conducting electrolysis in the electrolytic cell, where a reaction of oxidatively regenerating a copper-etching agent occurs in the anode cell zone; and during the electrolysis, an etching working solution circularly flows between the etching machine and the anode cell zone of the electrolytic cell; and (3) during the electrolysis, controlling an oxidation-reduction potential (ORP) potential value of the anode electrolyte at 300 mV or less, and feeding an etching replenisher into the alkaline copper-ammonia chloride etching working solution to participate in the reaction of oxidatively regenerating the copper-etching agent.

What is claimed is: 
     
         1 . A method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution, wherein the alkaline copper-ammonia chloride etching working solution is used for etching on an etching machine, and the method comprises the following steps:
 (1) selecting an electrolytic cell provided with an electrolytic cell separator, wherein the electrolytic cell is divided by the electrolytic cell separator into an anode cell zone and a cathode cell zone; an anode is provided in the anode cell zone and is connected to a positive electrode of an electrolytic power supply; and a cathode is provided in the cathode cell zone and is connected to a negative electrode of the electrolytic power supply;   (2) with the alkaline copper-ammonia chloride etching working solution as an anode electrolyte, conducting electrolysis in the electrolytic cell, wherein a reaction of oxidatively regenerating a copper-etching agent occurs in the anode cell zone; and   during the electrolysis, the alkaline copper-ammonia chloride etching working solution circularly flows between the etching machine and the anode cell zone of the electrolytic cell; and   (3) during the electrolysis, controlling an oxidation-reduction potential (ORP) value of the anode electrolyte at 300 mV or less, and feeding an etching replenisher into the alkaline copper-ammonia chloride etching working solution to participate in the reaction of oxidatively regenerating the copper-etching agent, such that a pH value and/or a copper ion concentration of the alkaline copper-ammonia chloride etching working solution on the etching machine are/is controlled within a set process range.   
     
     
         2 . The method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution according to  claim 1 , wherein the electrolytic cell separator is a material capable of effectively blocking entrance of copper ions and ammonium ions from the anode cell zone into the cathode cell zone. 
     
     
         3 . The method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution according to  claim 2 , wherein the electrolytic cell separator is at least one selected from the group consisting of a reverse osmosis membrane, a bipolar membrane, a proton exchange membrane, and an ion selectivity-free membrane, and a cathode electrolyte is an ammonia and/or ammonium-containing alkaline solution. 
     
     
         4 . The method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution according to  claim 3 , wherein the electrolytic cell separator is the reverse osmosis membrane and/or the bipolar membrane and/or the ion selectivity-free membrane, and the cathode electrolyte of the electrolytic cell is a spent etching solution from the same etching solution system as the anode electrolyte. 
     
     
         5 . The method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution according to  claim 2 , wherein the electrolytic cell separator is an anion-exchange membrane, and the cathode electrolyte is ammonia water. 
     
     
         6 . The method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution according to  claim 1 , wherein in order to effectively avoid excessive consumption of reductive substances other than a monovalent copper-ammonia complex in the alkaline copper-ammonia chloride etching working solution, at least one of the following measures is adopted:
 measure 1: during the electrolysis, reducing the ORP value of the anode electrolyte to control the ORP value of the anode electrolyte at less than or equal to 280 mV;   measure 2: during the electrolysis, increasing an effective electrolytic area of the anode in the electrolytic cell;   measure 3: increasing a solution circulation flow rate between the anode cell zone of the electrolytic cell and the etching machine to allow solution exchange and mixing; and   measure 4: providing a solution mixing-exchange tank on a connecting pipeline between the anode cell zone of the electrolytic cell and the etching machine, and connecting the solution mixing-exchange tank to the anode cell zone of the electrolytic cell and the etching machine; and increasing a solution circulation flow rate between the anode cell zone of the electrolytic cell and the solution mixing-exchange tank or increasing a solution circulation flow rate between the anode cell zone of the electrolytic cell and the etching machine and the solution circulation flow rate between the anode cell zone of the electrolytic cell and the solution mixing-exchange tank to allow solution exchange and mixing.   
     
     
         7 . The method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution according to  claim 6 , wherein at least two parameters selected from the group consisting of an ORP value, the pH value, and a specific gravity value of the alkaline copper-ammonia chloride etching working solution on the etching machine are detected and monitored, and operations of the electrolytic cell and a feeding device for the etching replenisher are controlled based on detected parameter results. 
     
     
         8 . The method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution according to  claim 7 , wherein the ORP value of the anode electrolyte and/or an ORP value of a solution in the solution mixing-exchange tank are/is detected and monitored, and an output working current or start/stop of the electrolytic power supply of the electrolytic cell is controlled according to a preset ORP value for the anode electrolyte and/or a preset ORP value for the solution in the solution mixing-exchange tank; and at least one selected from the group consisting of an ORP value, a pH value, and a specific gravity value of the cathode electrolyte is detected and monitored to control an electrochemical reaction in the cathode cell zone. 
     
     
         9 . The method for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution according to  claim 8 , wherein a measure is taken to make an exhaust air volume in a spray-oxygen absorption-exhausting system on the etching machine adjustable, which reduces a fresh air supply volume while enabling the reaction of oxidatively regenerating a copper-etching agent and optimizes overall production conditions for a spray-oxygen absorption reaction based on a fresh air supply and discharge of an ammonia-polluted tail gas. 
     
     
         10 . An apparatus for electrolysis-assisted oxidative regeneration of an alkaline copper-ammonia chloride etching working solution using the method according to  claim 1 , comprising an etching machine, an etching replenisher tank, and an electrolytic cell,
 wherein an electrolytic cell separator is provided in the electrolytic cell, and the electrolytic cell is divided by the electrolytic cell separator into an anode cell zone and a cathode cell zone; an anode is provided in the anode cell zone and is connected to a positive electrode of an electrolytic power supply; a cathode is provided in the cathode cell zone and is connected to a negative electrode of the electrolytic power supply; the anode cell zone of the electrolytic cell is connected to the etching machine through a pipeline to allow a liquid circulation flow between the anode cell zone of the electrolytic cell and the etching machine, such that the alkaline copper-ammonia chloride etching working solution undergoes an oxidative regeneration reaction in the electrolytic cell during the liquid circulation flow; and   the etching replenisher tank is connected to the etching machine and/or the anode cell zone of the electrolytic cell, and is configured to store an etching replenisher.   
     
     
         11 . The apparatus according to  claim 10 , wherein the etching machine is connected to the anode cell zone of the electrolytic cell through at least two pipelines, and at least one of the at least two pipelines is provided with a pump to achieve a circulation flow of an etching working solution. 
     
     
         12 . The apparatus according to  claim 11 , wherein the electrolytic cell separator is at least one selected from the group consisting of a bipolar membrane, a reverse osmosis membrane, an anion-exchange membrane, a proton exchange membrane, and an ion selectivity-free membrane. 
     
     
         13 . The apparatus according to  claim 12 , wherein at least one pipeline between the anode cell zone of the electrolytic cell and the etching machine is provided with a solution mixing-exchange tank; the solution mixing-exchange tank is connected to each of the etching machine and the anode cell zone of the electrolytic cell through a pipeline, and is connected to at least one of the etching machine and the anode cell zone of the electrolytic cell through at least two pipelines to form a liquid flow circulation, such that solutions in the solution mixing-exchange tank, the etching machine, and the anode cell zone of the electrolytic cell undergo mixing and exchange; and the etching replenisher tank is connected to at least one of the etching machine, the anode cell zone of the electrolytic cell, and the solution mixing-exchange tank. 
     
     
         14 . The apparatus according to  claim 13 , wherein a temporary storage tank configured to store a material or serve as a chemical reaction tank is provided; and the temporary storage tank is connected to at least one of the etching machine, the electrolytic cell, and the solution mixing-exchange tank through a pipeline, or is arranged on a connecting pipeline between any two of the etching machine, the electrolytic cell, and the solution mixing-exchange tank. 
     
     
         15 . The apparatus according to  claim 14 , wherein a sensor is provided in at least one of the etching machine, the electrolytic cell, the solution mixing-exchange tank, and the temporary storage tank, and the sensor is one or more selected from the group consisting of an ORP meter, a pH meter, a liquid level meter, a thermometer, and a gravimeter; an automatic detection/feeding controller is provided; and a control signal output terminal of the automatic detection/feeding controller is connected to a control signal input terminal of at least one pump and/or a feeding device and/or the electrolytic power supply in the apparatus, and the automatic detection/feeding controller is configured to control the apparatus according to a preset time program and/or a value measured by the sensor.