CN111748826A - Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process - Google Patents

Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process Download PDF

Info

Publication number
CN111748826A
CN111748826A CN202010736207.0A CN202010736207A CN111748826A CN 111748826 A CN111748826 A CN 111748826A CN 202010736207 A CN202010736207 A CN 202010736207A CN 111748826 A CN111748826 A CN 111748826A
Authority
CN
China
Prior art keywords
liquid
regenerated
etching
gas
chlorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010736207.0A
Other languages
Chinese (zh)
Inventor
张良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunshan Kezhiyuan Environmental Protection Technology Co ltd
Original Assignee
Kunshan Kezhiyuan Environmental Protection Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kunshan Kezhiyuan Environmental Protection Technology Co ltd filed Critical Kunshan Kezhiyuan Environmental Protection Technology Co ltd
Priority to CN202010736207.0A priority Critical patent/CN111748826A/en
Publication of CN111748826A publication Critical patent/CN111748826A/en
Pending legal-status Critical Current

Links

Images

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
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • 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
    • C25C7/04—Diaphragms; Spacing elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a single-film double-chamber electrolytic copper and chlorine regeneration system and process for acidic chloride etching waste liquid, and belongs to the technical field of equipment for recycling acidic etching waste liquid of printed circuit boards, acidic waste liquid of hardware etching and acidic chloride copper-containing waste liquid of mines. The system comprises an online acid etching machine, a single-film double-chamber electrolysis device, a regenerated liquid blending device, a regenerated liquid injection absorption device, a chlorine recycling and regenerating device, a low-temperature water curtain absorption device, a dynamic wave absorption device and a rotational flow spraying device, wherein a process for carrying out chlorine recycling and regeneration on acid etching waste liquid generated by the acid etching machine by a single-film double-chamber electrolysis device through electrolytic copper and a chlorine recycling and regenerating device is adopted, so that the problems of processes such as a displacement method, an ion-exchange membrane electrolysis method, a sulfuric acid distillation method, a diaphragm electrolysis method and the like adopted in the prior art are solved, the regeneration and circulation of the acid chloride etching waste liquid with low cost can be really realized, and the aims of clean production and high economic benefit of PCB enterprises are fulfilled.

Description

Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process
Technical Field
The invention relates to a system and a process for recycling acidic waste etching solution, in particular to a system and a process for recycling acidic chloride waste etching solution with a single membrane and double chambers for electrolyzing copper and chlorine, belonging to the technical field of equipment for recycling acidic waste etching solution of printed circuit boards, acidic waste etching solution of hardware and acidic waste copper-containing solution of mine acidic chloride.
Background
The PCB industry is the same as the paper industry, the textile industry, the decoration and electroplating industry and the like, is a water-consuming household and an environment-polluting household, and generates a large amount of corrosive waste liquid every year. In the process of producing Printed Circuit Boards (PCBs) and hardware fittings, an acid chloride etching process and an alkaline chloride etching process are generally used, wherein the acid chloride etching waste liquid generated by the acid chloride etching process mainly comprises hydrochloric acid, sodium chlorate, copper chloride and ferric chloride, the content of copper in the acid chloride etching waste liquid can reach 50-140g/L, and the acid chloride etching waste liquid belongs to hazardous waste, and the current method for recovering copper from the acid chloride etching waste liquid comprises the following steps:
the first, replacement method: the method generally uses acidic waste etching solution and a small amount of alkaline waste etching solution or ammonia water for neutralization to reduce the acidity in the acidic waste etching solution, and then industrial iron flakes or aluminum powder is added into the acidic waste etching solution to replace copper by utilizing the activity of iron or aluminum. The method can release heat and generate a large amount of water vapor, chlorine and hydrogen chloride gas in the production reaction process, and a large amount of waste water is discharged after the replacement is finished, wherein the discharged waste water contains a large amount of Cl-Ammonia nitrogen and Fe3+Or Al3+Not only pollutes the environment, but also the effective components in the etching solution can not be recycled.
II, ion membrane electrolysis: the method adopts Cl with activity resistance-The anode of (2) performs diaphragm electrolysis on the acidic etching waste liquid. The electrolytic copper produced by the method after electrolysis is powdery, the operation strength is high, the consumption of the ionic membrane is very fast, and the production and operation cost is high.
Thirdly, a sulfuric acid distillation method: the method is to add sulfuric acid into the acidic etching waste liquid for reduced pressure distillation, and to separate and recover HCl and produce copper sulfate by utilizing the difference of boiling points and volatility of the sulfuric acid and hydrochloric acid. The method needs to add a large amount of sulfuric acid to replace copper chloride with copper sulfate, and the copper chloride cannot be completely replaced with the copper sulfate by the sulfuric acid, so the production process is complex and has high danger.
Fourthly, diaphragm electrolysis: the currently used diaphragm electrolysis is influenced by the distance between workshops and the production capacity, so that the chlorine recycling efficiency is low, and meanwhile, the liquid medicine expands by 20 to 30 percent in the cyclic regeneration process of the etching waste liquid, and a large amount of by-products of ferric trichloride and sodium hypochlorite solution are generated; in addition, the equipment structure is complex to install and the electrolysis efficiency is low.
Disclosure of Invention
Aiming at the defects in the existing acidic chloride etching waste liquid recycling technology, the invention provides a system and a process for single-film double-chamber electrolytic copper and chlorine recycling of acidic chloride etching waste liquid, which can overcome the defects in the prior art, really realize low-cost acidic chloride etching waste liquid recycling, and achieve the aims of clean production and improvement of economic benefits of PCB enterprises.
The technical scheme of the invention is as follows:
the invention discloses a single-film double-chamber electrolytic copper and chlorine regeneration process for acidic chloride etching waste liquid, which mainly comprises the following steps:
s1: the method comprises the following steps that waste etching solution to be treated generated by an online acid etching machine is stored in a waste etching solution storage device, the waste etching solution to be treated enters a single-film double-chamber electrolytic device from the waste etching solution storage device and is subjected to circular electrolytic reaction by a positive pressure micro-permeable membrane electrolytic method, copper ions in the waste etching solution to be treated are reduced into elemental copper at a cathode in the electrolytic process, chlorine is generated at an anode at the same time, acid gas is generated in the electrolytic process, and the elemental copper is subsequently precipitated, filtered and taken out;
s2: the electrolyte generated after the etching waste liquid to be treated is electrolyzed in the step S1 is stored by the regenerated liquid storage device and then enters the regenerated liquid blending device, and the components of the part of the etching waste liquid to be treated which is conveyed by the waste liquid storage device are blended to form regenerated liquid; the regenerated liquid enters a regenerated liquid injection absorption device, and is subjected to gas-liquid mixing reaction with part of chlorine generated by electrolysis in the step S1 to form regenerated sub-liquid, the regenerated sub-liquid is conveyed and stored in a regenerated sub-liquid storage device through a liquid pipeline, and the regenerated sub-liquid is conveyed through the liquid pipeline and enters working etching liquid used by an online acid etching machine for an acid etching process to form a recycling closed cycle of the etching waste liquid;
s3: removing the residual part of the waste etching solution to be treated after being electrolyzed in the step S1 after being used in the step S2 and entering the regenerated solution guiding and absorbing device, recycling the chlorine gas in the regenerated device and entering the working etching solution of the online acid etching machine for circular reaction, and ensuring the ORP value of the working etching solution;
s4: after the on-line acid etching machine is shut down and the production requirements are met, redundant chlorine and acid gas in the regeneration liquid ejection absorption device and acid gas generated in the step S1 sequentially enter the low-temperature water curtain absorption device, the dynamic wave absorption device and the rotary spray tower for absorption treatment, and the treated tail gas is discharged after reaching the standard.
The further technical scheme is as follows:
in the step S2, the ORP value of the liquid medicine in the cylinder body of the regenerated liquid injection absorption device is detected by the ORP controller of the regenerated liquid to control the mixing proportion of the chlorine gas entering the cylinder body of the device and the regenerated liquid, so that the ORP value of the regenerated sub-liquid reaches the control standard, the up-to-standard regenerated sub-liquid is discharged into the regenerated sub-liquid storage device, and then the prepared liquid medicine in the regenerated liquid preparation device is automatically supplemented into the cylinder body of the regenerated liquid injection absorption device; the regeneration liquid is injected into the absorption device to generate and the untreated tail gas enters the low-temperature water curtain absorption device through the gas pipeline to be treated.
The further technical scheme is as follows:
the temperature of the liquid medicine in the cylinder body of the regenerated liquid ejection and absorption device is kept within 15-25 ℃ in the whole system operation process; the temperature of the liquid medicine in the cylinder body of the regeneration sub-liquid storage device is kept within 35-40 ℃ in the whole system operation process.
The further technical scheme is as follows:
in the step S3, the chlorine recycling and regenerating device comprises a titanium centrifugal fan, an injection pipeline mixer and an etching machine ORP controller arranged on the injection pipeline mixer, which are sequentially arranged along the gas flow direction, and the amount of the redundant chlorine in the regenerating liquid injection absorption device, which enters the online acid etching machine and is mixed with the etching working liquid after passing through the titanium centrifugal fan and the injection pipeline mixer, is controlled according to the ORP value of the working etching liquid detected by the etching machine ORP controller, so that the ORP value of the online working etching liquid is ensured to be within the working range.
The further technical scheme is as follows:
when the single-film double-chamber electrolytic device is used for electrolysis in the step S1, the high-frequency power supply automatic regulator and the etching machine ORP controller arranged on the single-film double-chamber electrolytic device carry out current regulation and voltage monitoring on the electrolytic cell through information signals, and the electrolytic current of the single-film double-chamber electrolytic device can be remotely regulated according to the control value of the etching machine ORP controller, so that the ORP value of the working solution of the etching machine is ensured to be within the working range; and when the etching machine ORP controller monitors that the ORP value of the working etching solution is low, the regeneration sub-solution storage device can be synchronously started to replenish the regeneration sub-solution into the online acid etching machine, so that the working parameters of the working etching solution are ensured.
The further technical scheme is as follows:
in step S4, the chlorine and the acid gas entering the low-temperature water curtain absorption device are absorbed by the low-temperature water curtain absorption device through water curtain flow and a gas condenser at 15-20 ℃, and absorption liquid generated by the low-temperature water curtain absorption device enters the dynamic wave absorption device and is used for preparing the absorption liquid in the dynamic wave absorption device and recovering hydrochloric acid; chlorine and acid gas which are not treated by the low-temperature water curtain absorption device enter the dynamic wave absorption device, are washed by dynamic waves and are sprayed and dissolved, then the untreated chlorine and acid gas enter the rotary spray tower again and are neutralized by using an alkaline solution, and the treated tail gas is discharged after reaching the standard.
The invention also discloses a single-film double-chamber electrolytic copper and chlorine regeneration system for the acidic chloride etching waste liquid used in the process, which comprises an online acidic etching machine, a single-film double-chamber electrolytic device, a regenerated liquid blending device, a regenerated liquid injection absorption device, a chlorine recycling regeneration device, a low-temperature water curtain absorption device, a dynamic wave absorption device and a rotational flow spraying device, wherein the single-film double-chamber electrolytic device is connected with the regenerated liquid injection absorption device through a pipeline, and the low-temperature water curtain absorption device is connected with the dynamic wave absorption
The waste liquid outlet of the online acid etching machine is communicated with the liquid inlet of the single-film double-chamber electrolytic device after passing through an etching waste liquid storage device, the electrolyte outlet of the single-film double-chamber electrolytic device is communicated with the liquid inlet of the regenerated liquid preparation device after passing through a regenerated liquid storage device, the liquid outlet of the regenerated liquid preparation device is communicated with the liquid inlet of the regenerated liquid injection absorption device, and the regenerated sub-liquid outlet of the regenerated liquid injection absorption device is communicated with the etching liquid inlet of the online acid etching machine after passing through a regenerated sub-liquid storage device;
an anode gas outlet of the single-membrane double-chamber electrolysis device is communicated with a gas inlet and outlet of the regenerated liquid injection absorption device, and the gas inlet and outlet of the regenerated liquid injection absorption device is communicated with a gas inlet of the online acid etching machine after passing through the chlorine recycling regeneration device;
the cathode gas outlet and the acid gas outlet of the single-membrane double-chamber electrolysis device are communicated with the gas inlet of the low-temperature water curtain absorption device, the gas outlet of the low-temperature water curtain absorption device is communicated with the gas inlet of the dynamic wave absorption device, and the gas outlet of the dynamic wave absorption device is communicated with the gas inlet of the rotational flow spraying device.
The further technical scheme is as follows:
the single-membrane double-chamber electrolysis device comprises two electrolysis baths which are adjacently arranged, a cooling bath which is adjacently arranged with one of the electrolysis baths, and a circulating cylinder which is adjacently arranged with the cooling bath, wherein a plurality of anode boxes which are formed by adopting positive pressure micro-permeation membranes and have frame-type structures are respectively arranged in the two electrolysis baths at intervals, a cathode chamber is formed between the inner wall of the electrolysis bath and the outer wall of the anode box, and the liquid level of liquid in the cathode chamber is higher than that of liquid in the anode box;
the anode box is internally provided with one of a graphite electrode, a graphene electrode, a carbon felt electrode and a reticular ruthenium-titanium coating electrode, the cathode chamber is internally provided with a stainless steel alloy electrode or a titanium alloy electrode, and the positive pressure micro-permeation film is a polyester positive pressure micro-permeation film.
The further technical scheme is as follows:
the anode gas outlets of the single-membrane double-chamber electrolysis device are respectively arranged on the plurality of anode boxes and communicated and converged through gas pipelines; the cathode gas outlet of the single-membrane double-chamber electrolysis device is respectively arranged on two corresponding cathode chambers on the electrolysis bath, the acid gas outlet of the single-membrane double-chamber electrolysis device is arranged on the circulating cylinder, and the cathode gas outlet is communicated with the acid gas outlet through another gas pipeline to be converged.
The further technical scheme is as follows:
the regenerated liquid injection and absorption device comprises an injector for introducing part of chlorine generated by the single-membrane double-chamber electrolysis device into the regenerated liquid injection and absorption device, a cooling device for cooling the regenerated liquid injection and absorption device, a regenerated liquid temperature controller for detecting the temperature of regenerated liquid, a gas-liquid mixer for mixing gas and liquid and a regenerated liquid ORP controller for detecting the ORP value of the regenerated liquid.
The further technical scheme is as follows:
the chlorine recycling and regenerating device comprises a titanium centrifugal fan, an electric air valve and an ejector pipeline mixer which are sequentially arranged along the gas flowing direction; the ejector pipeline mixer is communicated with the air inlet of the online acid etching machine, and an etching machine ORP controller for detecting the ORP value of the online working etching liquid is positioned on the ejector pipeline mixer;
a high-frequency power supply automatic regulator is positioned on the single-film double-chamber electrolysis device and is communicated with the etching machine ORP controller;
and the injection pipeline mixer is communicated with a working etching solution circulating pump arranged on the online acid etching machine.
The further technical scheme is as follows:
and a regenerated sub-liquid ORP controller for detecting an ORP value of the regenerated sub-liquid is positioned on a liquid pipeline between the regenerated sub-liquid storage device and the online acid etching machine.
The further technical scheme is as follows:
the low-temperature water curtain absorption device comprises a water curtain flowing device for absorbing gas and a gas condensation device for condensing the gas, and an absorption liquid outlet of the low-temperature water curtain absorption device is communicated with an absorption liquid inlet of the dynamic wave absorption device; the dynamic wave absorption device comprises a dynamic wave washing device for dynamic wave washing and a spraying and dissolving device for spraying and dissolving.
The beneficial technical effects of the invention are as follows:
the system and the process of the invention carry out the copper electrolysis and the chlorine recycling and regenerating device to recycle and regenerate the chlorine by the single-membrane double-chamber electrolysis device, improve the problems of the replacement method, the ion membrane electrolysis method, the sulfuric acid distillation method, the diaphragm electrolysis method and other processes adopted in the prior art, and are as follows:
1. in the replacement process used in the replacement method in the prior art, a large amount of effective components of the acidic etching waste liquid can be wasted, and the produced copper is sponge copper powder and has very low purity. The system and the process can recycle 95% of effective components in the acid chloride etching waste liquid, and the purity of the finished copper can reach more than 97%.
2. In the prior art, the membrane resistance is high when the ion membrane is used for electrolysis, so that the power consumption is high during electrolysis, and the ion membrane is required to be replaced once after being used for 3-6 months, so that the overall production cost is high. According to the acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process, the power consumption can be reduced by 30%, and the polyester positive-pressure micro-permeation film is adopted as the film, so that the replacement frequency of the film can be increased to once per year, and the overall production cost is reduced.
3. When diaphragm electrolytic regeneration is carried out by using a diaphragm electrolytic method in the prior art, the diaphragm electrolytic regeneration system and the diaphragm electrolytic regeneration process which are commonly used in the industry can cause increment or expansion of etching waste liquid due to the fact that the reuse rate of the etching waste liquid is only 70% -80%, so that the amount of by-products, namely ferric trichloride and sodium hypochlorite is large, and further secondary treatment difficulty is caused. According to the acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process, the reuse rate of the etching waste liquid can be increased to 95%, the condition of increment or expansion of the etching waste liquid is basically avoided, and the by-product can be used for treating plant wastewater to achieve resource recycling.
4. The single-membrane double-chamber electrolysis device used in the invention optimizes the structure of the electrolysis bath and adjusts the area ratio of the cathode and the anode, thereby reducing the edge effect of electrolysis; meanwhile, the gas collecting pipeline and the outlet are optimized, so that the gas is conveniently conveyed, and the gas recovery rate is further improved. During electrolysis, the high-frequency power supply and the etching machine ORP controller carry out current regulation and voltage monitoring on the electrolytic cell through analog signals or communication signals. In addition, the single-membrane double-chamber electrolysis device adopts a single membrane to form an anode box and a cathode chamber, the anode box adopts a frame structure, and the positive pressure micro-permeation membrane is utilized to reduce the electrolysis resistance. The liquid level of the cathode chamber is slightly higher than the liquid level of the anode box to form positive pressure, so that the liquid in the anode box cannot enter the cathode chamber, electrolytic copper is prevented from being corroded back, and the electrolytic efficiency is improved.
5. The regeneration liquid injection absorption device used in the invention improves the structure optimization and temperature control, improves the gas-liquid reaction area and speed, and adjusts the concentration of the absorption liquid before absorption, so that chlorine can be fully recovered at this stage.
6. In the prior art, in the aspect of etching working solution recycling of an on-line acid etching machine, one of the common practices in the industry at present is to recycle etching solution by absorbing gas through liquid circulation through a pipeline; the second common method is to use a pipeline to convey gas to an auxiliary groove beside the online acid etching machine or to regenerate the etching solution by jet vacuum pumping. The two modes have the condition of untimely reaction, which causes low reuse rate; in addition, the liquid conveying mode has the problems of easy leakage and pipeline temperature resistance due to the temperature (about 50 ℃) of the liquid; in addition, the jet vacuum pumping has a distance problem, which means that the electrolysis system and the etching machine are usually too far (more than 200 m), and the gas cannot effectively reach the etching machine, so that the gas cannot be regenerated in time. According to the invention, by adopting the acidic chlorine salt etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process, the mode of combining gas delivery and high-concentration regenerated sub-liquid according to an ORP (oxidation-reduction potential) control mode is adopted, and the problem that gas cannot effectively participate in etching reaction due to long distance is avoided through the combined action of the titanium centrifugal fan and the injection pipeline mixer, and meanwhile, the adopted high-concentration regenerated sub-liquid can reduce the parameter control of an online acidic etching machine, only the pressure, the temperature, the speed and the ORP value need to be controlled, so that the production intensity and the outsourcing and waste gas discharge of regenerated sub-liquid materials are reduced.
Drawings
FIG. 1 is a schematic diagram of the system of the present invention; the dashed lines with arrows in the figure are gas paths and the solid lines with arrows in the figure are liquid paths;
FIG. 2 is a process flow diagram of the process of the present invention;
wherein:
1-on-line acid etcher; 101-etcher ORP controller; 102-waste outlet of on-line acid etcher; 103-an etching solution inlet of an online acid etching machine; 104-gas inlet of on-line acid etcher;
2-single membrane double-chamber electrolysis device; 201-an electrolytic cell; 201 a-anode box; 201 b-cathode chamber; 202-a cooling tank; 203-circulation cylinder; 204-a liquid inlet of the single-membrane double-chamber electrolysis device; 205-electrolyte outlet of single membrane double chamber electrolyzer; 206-anode gas outlet of single membrane two-chamber electrolyzer; 207-cathode gas outlet of single membrane double chamber electrolyser; 208-acid gas outlet;
3-a regenerated liquid blending device;
4-regenerated liquid ejection absorption device; 401-an ejector; 402-injecting a regenerating liquid into a liquid inlet of an absorption device; 403-a regenerated sub-liquid outlet of the regenerated liquid ejection absorption device; 404-gas inlet and outlet of regenerated liquid ejection absorption device; 405-a tail gas outlet;
5-low temperature water curtain absorption device; 501-an absorption liquid outlet of a low-temperature water curtain absorption device; 502-a tail gas treatment inlet of a low temperature water curtain absorption device;
6-a dynamic wave absorbing device; 601-an absorption liquid inlet of the dynamic wave absorption device;
7-a rotational flow spraying device;
8-etching waste liquid storage device;
9-a regeneration liquid storage device;
10-a regenerated seed solution storage device;
11-titanium centrifugal fan;
12-an electric air valve;
13-ejector line mixer;
14-regeneration subpool ORP controller.
Detailed Description
In order to make the technical means of the present invention clearer and to make the technical means of the present invention capable of being implemented according to the content of the specification, the following detailed description of the embodiments of the present invention is made with reference to the accompanying drawings and examples, which are provided for illustrating the present invention and are not intended to limit the scope of the present invention.
The following specific embodiment describes in detail an acidic chlorine salt etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system, which mainly comprises an online acidic etching machine 1, a single-film double-chamber electrolysis device 2, a regeneration liquid blending device 3, a regeneration liquid injection absorption device 4, a chlorine recycling regeneration device, a low-temperature water curtain absorption device 5, a dynamic wave absorption device 6 and a rotational flow spraying device 7.
The structure of the device related to the extraction of copper from the etching waste liquid in the system is as follows: the waste liquid outlet 102 of the on-line acid etching machine 1 is communicated with the liquid inlet 204 of the single-film double-chamber electrolysis device 2 after passing through an etching waste liquid transfer device and an etching waste liquid storage device 8 in sequence. An electrolyte outlet 205 of the single-membrane double-chamber electrolytic device 2 is communicated with a liquid inlet of the regenerated liquid preparation device 3 after passing through a regenerated liquid storage device 9, a liquid outlet of the regenerated liquid preparation device 3 is communicated with a liquid inlet 402 of the regenerated liquid injection absorption device 4, and a regenerated sub-liquid outlet 403 of the regenerated liquid injection absorption device 4 is communicated with an etching liquid inlet 103 of the online acid etching machine 1 after passing through a regenerated sub-liquid storage device 10; in addition, an adding cylinder for adding the regenerated seed solution can be arranged between the regenerated seed solution storage device 10 and the online acid etching machine 1.
The structure of the device related to the recycling of the chlorine and the acid gas in the system is as follows: the anode gas outlet 206 of the single-film double-chamber electrolysis device 2 is communicated with a gas inlet 404 of a regenerated liquid injection absorption device 4, and the gas inlet 404 of the regenerated liquid injection absorption device is communicated with the gas inlet 104 of the online acid etching machine 1 after being recycled and regenerated by chlorine; the cathode gas outlet 207 and the acid gas outlet 208 of the single-membrane double-chamber electrolysis device 2 are communicated with the gas inlet of the low-temperature water curtain absorption device 5, the gas outlet of the low-temperature water curtain absorption device 5 is communicated with the gas inlet of the dynamic wave absorption device 6, and the gas outlet of the dynamic wave absorption device 6 is communicated with the gas inlet of the rotational flow spraying device 7.
The more specific device structure in the above system is as follows:
the on-line acid etching machine 1 is an acid etching apparatus used in an acid etching production line, and generates a large amount of acid etching waste liquid during etching. The on-line acid etching machine is provided with a liquid level controller in a positioning way, and in addition, a system for automatically adding and adjusting the components of the etching liquid can be additionally added according to the requirements of customers.
The single-film double-chamber electrolysis device 2 is used for single-film double-chamber electrolysis, performs circular electrolysis by a positive pressure micro-permeable membrane electrolysis method, reduces copper ions in the acidic etching waste liquid into elemental copper on a cathode under the action of an external electric field by utilizing the action of electrolytic reduction, simultaneously generates chlorine at an anode, generates and volatilizes a large amount of acidic gas in the electrolysis process, and has the following chemical reaction formula:
cathode: cu2++e－＝Cu+Cu++e－＝Cu
Anode: 2Cl－－2e－＝Cl2↑
The single-film double-chamber electrolyzer 2 comprises two electrolytic tanks 201 arranged adjacently, a cooling tank 202 arranged adjacently to one of the electrolytic tanks, and a circulating cylinder 203 arranged adjacently to the cooling tank. Two of the electrolytic cells 201 are used for electrolyzing acidic etching waste liquid to convert copper ions into elemental copper and simultaneously generate chlorine and a large amount of acidic gas. A plurality of anode boxes 201a of a frame structure formed by adopting positive pressure micro-permeation films are respectively arranged in the two electrolytic tanks 201 at intervals, one of a graphite electrode, a graphene electrode, a carbon felt electrode and a reticular ruthenium-titanium coating electrode is arranged in each anode box and is used as an anode, and chlorine is generated at the anode in the electrolytic process. A cathode chamber 201b is formed between the inner wall of the electrolytic cell and the outer wall of the anode box, a stainless steel alloy electrode or a titanium alloy electrode is arranged in the cathode chamber and serves as a cathode, and copper ions are converted into elemental copper at the cathode in the electrolytic process. In addition, the positive pressure micro-permeable membrane is a polyester positive pressure micro-permeable membrane, and the adoption of the polyester positive pressure micro-permeable membrane can reduce the electrolytic resistance; meanwhile, the liquid level of liquid in the cathode chamber is higher than the liquid level of liquid in the anode box, and positive pressure is formed by controlling the liquid level of the cathode chamber to be slightly higher than the liquid level of the anode box, so that the liquid in the anode box cannot enter the cathode chamber, electrolytic copper is prevented from being corroded back, and the electrolytic efficiency is improved. Wherein, a cooling pipe communicated with cooling circulating water is arranged in the cooling tank 202, and the acidic waste etching solution initially entering the single-film double-chamber electrolytic device is circularly cooled by utilizing the cooling effect of the cooling pipe, so that the acidic waste etching solution is kept at a lower temperature. Wherein the main function of the circulation cylinder 203 is for circulation of the electrolyte generated after electrolysis.
The arrangement of the gas and liquid inlets and outlets on the single-membrane double-chamber electrolyzer 2 is as follows: a cooling tank 202 in the single-film double-chamber electrolytic device 2 is provided with a liquid inlet 204 of the single-film double-chamber electrolytic device for acidic etching waste liquid to enter the single-film double-chamber electrolytic device (the cooling tank 202), and the acidic etching waste liquid enters the cooling tank from the liquid inlet 204, is cooled, then flows out of the cooling tank, enters the two electrolytic tanks and circulates between the two electrolytic tanks. The circulating cylinder 203 of the single-film double-chamber electrolyzer 2 is provided with an electrolyte outlet 205 of the single-film double-chamber electrolyzer, wherein the electrolyte generated after electrolysis flows out of the single-film double-chamber electrolyzer (the circulating cylinder 203), and the electrolytes generated after electrolytic reaction in the two electrolyzers are gathered, enter the circulating cylinder, are circulated, flow out of the electrolyte outlet 205 and enter the regenerated liquid storage device 9. Two electrolytic tanks of the single-film double-chamber electrolytic device 2 are respectively provided with a cathode gas outlet 207 for overflowing a large amount of acid gas generated by the electrolytic tanks in the electrolytic process, the circulating cylinder 203 is provided with an acid gas outlet 208 for overflowing the acid gas in the circulating cylinder, and the cathode gas outlet 207 and the acid gas outlet 208 are gathered by a gas pipeline and then enter the low-temperature water curtain absorption device 5. Each anode box 201a in the single-membrane double-chamber electrolysis device 2 is provided with an anode gas outlet 206 of the single-membrane double-chamber electrolysis device for chlorine generated by the anode to overflow, and all the anode gas outlets are gathered by a gas pipeline and then enter the regenerated liquid injection absorption device 4.
The regenerated liquid storage device 9 is used for storing the electrolyte flowing out of the single-membrane double-chamber electrolytic device and conveying the electrolyte into the regenerated liquid blending device 3 according to the amount required by the regenerated liquid blending device. A liquid level controller for detecting and controlling the liquid level is positioned in the regenerated liquid storage device 9.
The regenerated liquid preparing device 3 is used for adjusting the component content of the electrolyte conveyed by the regenerated liquid storage device 9 to form regenerated liquid. The regenerated liquid blending device 3 is provided with a liquid level controller for detecting and controlling the liquid level and a stirring device for fully stirring. In addition, the regenerated liquid preparing device 3 is provided with a liquid inlet for electrolyte to enter, a liquid outlet for prepared regenerated liquid to flow out and an etching waste liquid inlet for etching waste liquid to flow in, wherein the etching waste liquid flowing in from the etching waste liquid inlet is also used for adjusting the electrolyte to form regenerated liquid, and the source of the flowing etching waste liquid is the etching waste liquid storage device 8.
The regenerated liquid ejection and absorption device 4 is used for fully mixing the regenerated liquid prepared by the regenerated liquid preparation device 3 and part of chlorine generated by the single-film double-chamber electrolysis device to form regenerated sub-liquid. The regenerated liquid injection and absorption device 4 comprises an injector 401 for introducing part of chlorine generated by the single-membrane double-chamber electrolytic device into the regenerated liquid injection and absorption device, a cooling device for cooling the regenerated liquid injection and absorption device, a regenerated liquid temperature controller for detecting the temperature of regenerated liquid, a gas-liquid mixer for mixing gas and liquid, and a regenerated liquid ORP controller for detecting the ORP value of the regenerated liquid. The ejector 401 introduces part of chlorine generated by the single-film double-chamber electrolysis device into a cylinder of the regenerated liquid ejection and absorption device at a gas inlet and outlet 404, and simultaneously, the gas introduced into the cylinder and the regenerated liquid in the regenerated liquid ejection and absorption device are fully mixed by a gas-liquid mixer to form regenerated sub-liquid. The cooling device and the regenerated liquid temperature controller are used jointly, and the temperature of liquid medicine in a cylinder body of the regenerated liquid injection absorption device can be monitored and controlled to be kept within 15-25 ℃ all the time in the whole system operation process. The regeneration liquid ORP controller detects the ORP value of the liquid medicine in the cylinder body of the regeneration liquid injection absorption device, when the detected parameters reach the control standard, the discharge valve is automatically started to discharge the liquid medicine in the cylinder body into the regeneration sub-liquid storage device 10, and the prepared liquid medicine in the regeneration liquid preparation device 3 is automatically supplemented into the cylinder body of the regeneration liquid injection absorption device 4. In addition, still fix a position on this regenerating liquid draws and penetrates absorbing device and be equipped with the liquid level controller that is used for detecting the control liquid level, and this regenerating liquid draws and penetrates absorbing device and go up still to have seted up tail gas outlet 405, this tail gas outlet pass through the gas pipeline with low temperature cascade absorbing device's tail gas treatment import 502 intercommunication, make regenerating liquid draw and penetrate absorbing device production and untreated tail gas gets into low temperature cascade absorbing device and handles.
The regenerated sub-liquid storage device 10 is used for storing the regenerated sub-liquid discharged by the regenerated liquid injection absorption device 4 and conveying the regenerated sub-liquid into the on-line acid etching machine 1 for recycling. A liquid level controller for detecting and controlling the liquid level, a temperature detector for detecting the temperature and a cooling device for cooling are positioned in the regeneration sub-liquid storage device 10, wherein the temperature detector and the cooling device jointly act to keep the temperature of the liquid medicine in the cylinder body of the regeneration sub-liquid storage device at 35-40 ℃. In addition, a regeneration sub-liquid ORP controller 14 for detecting an ORP value of the regeneration sub-liquid is provided in a position on a liquid pipe between the regeneration sub-liquid storage device 10 and the on-line acid etching machine 1. In addition, the copper ion concentration in the regeneration subphase is 60-110g/L, ORP value which is more than or equal to 600mv, and the liquid temperature is 35-40 ℃.
The chlorine recycling and regenerating device is used for introducing chlorine generated by the single-film double-chamber electrolytic device 2 which is not treated after being treated by the regenerated liquid injection and absorption device 4 into the online acid etching machine 1. The chlorine recycling and regenerating device comprises a titanium centrifugal fan 11, an electric air valve 12 and an injection pipeline mixer 13 which are sequentially arranged along the gas flowing direction, wherein the injection pipeline mixer 13 is communicated with the gas inlet of the online acid etching machine 1, and an etching machine ORP controller 101 for detecting the ORP value of the online working etching liquid is positioned on the injection pipeline mixer. According to the ORP value of the working etching liquid detected by the ORP controller 101 of the etching machine, the redundant chlorine of the regenerated liquid injection absorption device 4 passes through the titanium centrifugal fan 11, the electric air valve 12 and the injection pipeline mixer 13 in turn to carry out the circulating reaction with the etching working liquid in the on-line acid etching machine 1, so that the ORP value and other related parameters of the etching working liquid are ensured. In addition, a high-frequency power supply automatic regulator is positioned on the single-film double-chamber electrolytic device 2 and is communicated with the etching machine ORP controller 101 in a communication mode, when electrolysis is carried out, the high-frequency power supply automatic regulator and the etching machine ORP controller 101 carry out current regulation and voltage monitoring on the electrolytic tank through analog signals or communication signals, the electrolytic current of the single-film double-chamber electrolytic device can be remotely regulated according to the control value of the etching machine ORP controller, and the ORP value of working liquid of the etching machine is guaranteed to be within the working range. In addition, when the ORP value of the working etching solution is low, the electrolytic current can be automatically adjusted, an adding pump and an adding valve which are arranged in a regenerated sub-solution storage device can be started, and the regenerated sub-solution is replenished into the online acid etching machine, so that the working parameters of the working etching solution are ensured. The injection pipeline mixer 13 is communicated with a working etching solution circulating pump arranged on the online acid etching machine, wherein the injection pipeline mixer mixes the etching working solution extracted by the working etching solution circulating pump and the redundant chlorine discharged by the regenerated liquid injection absorption device.
The low-temperature water curtain absorption device 5 is mainly used for carrying out absorption and dissolution treatment on gas entering the low-temperature water curtain absorption device in a low-temperature state (15-20 ℃). The low-temperature water curtain absorption device 5 comprises a water curtain flowing device for absorbing gas and a gas condensing device for condensing the gas, the gas is absorbed and dissolved through the water curtain flowing device, and the gas is condensed through the gas condensing device. In addition, an absorption liquid outlet 501 of the low-temperature water curtain absorption device 5 is communicated with an absorption liquid inlet 601 of the dynamic wave absorption device, the absorption liquid flowing out of the low-temperature water curtain absorption device can be used for preparing the absorption liquid in the dynamic wave absorption device and recovering hydrochloric acid, and untreated gas enters the subsequent dynamic wave absorption device for treatment.
The dynamic wave absorption device 6 is mainly used for further absorbing and dissolving the gas treated by the low-temperature water curtain absorption device. The dynamic wave absorption device 6 comprises a dynamic wave washing device for dynamic wave washing and a spraying and dissolving device for spraying and dissolving, the adopted dynamic wave washing device is not easy to block and high in reaction efficiency when used for dynamic wave washing, and the dynamic wave washing device is matched with the spraying and dissolving device to further improve the absorption and regeneration efficiency of ferrous solution.
And in the rotational flow spraying device 7, the tail gas treated by the dynamic wave absorption device is subjected to neutralization reaction treatment in a rotational flow spraying tower by adopting an alkaline solution, so that the gas treated by the rotational flow spraying device is discharged after reaching the standard.
The invention also describes a process for performing single-film double-chamber electrolytic copper and chlorine regeneration on the acidic chloride etching waste liquid by using the system in detail, which mainly comprises the following steps:
s1: the method comprises the following steps that waste etching solution to be treated generated by an online acid etching machine is stored in a waste etching solution storage device, the waste etching solution to be treated enters a single-film double-chamber electrolytic device from the waste etching solution storage device and is subjected to circular electrolytic reaction by a positive pressure micro-permeable membrane electrolytic method, copper ions in the waste etching solution to be treated are reduced into elemental copper at a cathode in the electrolytic process, chlorine is generated at an anode at the same time, acid gas is generated in the electrolytic process, and the elemental copper is subsequently precipitated, filtered and taken out;
s2: the electrolyte generated after the etching waste liquid to be treated is electrolyzed in the step S1 is stored by the regenerated liquid storage device and then enters the regenerated liquid blending device, and the components of the part of the etching waste liquid to be treated which is conveyed by the waste liquid storage device are blended to form regenerated liquid; the regenerated liquid enters a regenerated liquid injection absorption device, and is subjected to gas-liquid mixing reaction with part of chlorine generated by electrolysis in the step S1 to form regenerated sub-liquid, the regenerated sub-liquid is conveyed and stored in a regenerated sub-liquid storage device through a liquid pipeline, and the regenerated sub-liquid is conveyed through the liquid pipeline and enters working etching liquid used by an online acid etching machine for an acid etching process to form a recycling closed cycle of the etching waste liquid;
s3: removing the residual part of the waste etching solution to be treated after being electrolyzed in the step S1 after being used in the step S2 and entering the regenerated solution guiding and absorbing device, recycling the chlorine gas in the regenerated device and entering the working etching solution of the online acid etching machine for circular reaction, and ensuring the ORP value of the working etching solution;
s4: after the on-line acid etching machine is shut down and the production requirements are met, redundant chlorine and acid gas in the regeneration liquid ejection absorption device and acid gas generated in the step S1 sequentially enter the low-temperature water curtain absorption device, the dynamic wave absorption device and the rotary spray tower for absorption treatment, and the treated tail gas is discharged after reaching the standard.
In the step S2, the ORP value of the chemical liquid in the cylinder of the regenerative liquid injection absorption device is detected by the regenerative liquid ORP controller to control the mixing ratio of the chlorine gas and the regenerative liquid entering the cylinder of the device, so that the ORP value of the regenerative sub-liquid reaches the control standard, the up-to-standard regenerative sub-liquid is discharged into the regenerative sub-liquid storage device, and then the prepared chemical liquid in the regenerative liquid preparation device is automatically supplemented into the cylinder of the regenerative liquid injection absorption device; the regeneration liquid is injected into the absorption device to generate and the untreated tail gas enters the low-temperature water curtain absorption device through the gas pipeline to be treated. In addition, the temperature of the liquid medicine in the cylinder body of the regenerated liquid ejection and absorption device is kept within 15-25 ℃ in the whole system operation process; the temperature of the liquid medicine in the cylinder body of the regeneration sub-liquid storage device is kept within 35-40 ℃ in the whole system operation process.
In the step S3, the chlorine recycling and regenerating device includes a titanium centrifugal fan, an injection pipeline mixer, and an etching machine ORP controller disposed on the injection pipeline mixer, which are sequentially disposed along the gas flow direction, and the amount of the excess chlorine in the regenerating liquid injection and absorption device, which enters the online acidic etching machine and is mixed with the etching working liquid, is controlled according to the ORP value of the working etching liquid detected by the etching machine ORP controller, after passing through the titanium centrifugal fan and the injection pipeline mixer, so as to ensure that the ORP value of the online working etching liquid is within the working range.
When the single-film double-chamber electrolytic device is used for electrolysis in the step S1, the high-frequency power supply automatic regulator and the etching machine ORP controller arranged on the single-film double-chamber electrolytic device perform current regulation and voltage monitoring on the electrolytic cell through information signals, so that the electrolytic current of the single-film double-chamber electrolytic device can be remotely regulated according to the control value of the etching machine ORP controller, and the ORP value of the working solution of the etching machine is ensured to be within the working range; and when the etching machine ORP controller monitors that the ORP value of the working etching solution is low, the regeneration sub-solution storage device can be synchronously started to replenish the regeneration sub-solution into the online acid etching machine, so that the working parameters of the working etching solution are ensured.
In the step S4, the chlorine gas and the acidic gas entering the low-temperature water curtain absorption device are absorbed by the low-temperature water curtain absorption device through water curtain flow and a gas condenser at 15-20 ℃, and the absorption liquid generated by the low-temperature water curtain absorption device enters the dynamic wave absorption device and is used for blending the absorption liquid in the dynamic wave absorption device and recovering hydrochloric acid; chlorine and acid gas which are not treated by the low-temperature water curtain absorption device enter the dynamic wave absorption device, are washed by dynamic waves and are sprayed and dissolved, then the untreated chlorine and acid gas enter the rotary spray tower again and are neutralized by using an alkaline solution, and the treated tail gas is discharged after reaching the standard.
The system and the process are not only suitable for the cyclic regeneration of the acidic waste etching solution of the printed circuit board, but also suitable for the cyclic regeneration of the acidic waste etching solution of hardware and the cyclic regeneration of the acidic waste copper-containing solution of mine chloride.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (13)

1. A single-film double-chamber electrolytic copper and chlorine regeneration process for acidic chlorine salt etching waste liquid is characterized by mainly comprising the following steps:
s1: the method comprises the following steps that waste etching solution to be treated generated by an online acid etching machine is stored in a waste etching solution storage device, the waste etching solution to be treated enters a single-film double-chamber electrolytic device from the waste etching solution storage device and is subjected to circular electrolytic reaction by a positive pressure micro-permeable membrane electrolytic method, copper ions in the waste etching solution to be treated are reduced into elemental copper at a cathode in the electrolytic process, chlorine is generated at an anode at the same time, acid gas is generated in the electrolytic process, and the elemental copper is subsequently precipitated, filtered and taken out;
s2: the electrolyte generated after the etching waste liquid to be treated is electrolyzed in the step S1 is stored by the regenerated liquid storage device and then enters the regenerated liquid blending device, and the components of the part of the etching waste liquid to be treated which is conveyed by the waste liquid storage device are blended to form regenerated liquid; the regenerated liquid enters a regenerated liquid injection absorption device, and is subjected to gas-liquid mixing reaction with part of chlorine generated by electrolysis in the step S1 to form regenerated sub-liquid, the regenerated sub-liquid is conveyed and stored in a regenerated sub-liquid storage device through a liquid pipeline, and the regenerated sub-liquid is conveyed through the liquid pipeline and enters working etching liquid used by an online acid etching machine for an acid etching process to form a recycling closed cycle of the etching waste liquid;
s3: removing the residual part of the waste etching solution to be treated after being electrolyzed in the step S1 after being used in the step S2 and entering the regenerated solution guiding and absorbing device, recycling the chlorine gas in the regenerated device and entering the working etching solution of the online acid etching machine for circular reaction, and ensuring the ORP value of the working etching solution;
s4: after the on-line acid etching machine is shut down and the production requirements are met, redundant chlorine and acid gas in the regeneration liquid ejection absorption device and acid gas generated in the step S1 sequentially enter the low-temperature water curtain absorption device, the dynamic wave absorption device and the rotary spray tower for absorption treatment, and the treated tail gas is discharged after reaching the standard.
2. The single-membrane double-chamber electrolytic copper and chlorine regeneration process of the acidic chloride etching waste liquid according to claim 1, characterized in that: in the step S2, the ORP value of the liquid medicine in the cylinder body of the regenerated liquid injection absorption device is detected by the ORP controller of the regenerated liquid to control the mixing proportion of the chlorine gas entering the cylinder body of the device and the regenerated liquid, so that the ORP value of the regenerated sub-liquid reaches the control standard, the up-to-standard regenerated sub-liquid is discharged into the regenerated sub-liquid storage device, and then the prepared liquid medicine in the regenerated liquid preparation device is automatically supplemented into the cylinder body of the regenerated liquid injection absorption device; the regeneration liquid is injected into the absorption device to generate and the untreated tail gas enters the low-temperature water curtain absorption device through the gas pipeline to be treated.
3. The single-membrane double-chamber electrolytic copper and chlorine regeneration process of the acidic chloride etching waste liquid according to claim 2, characterized in that: the temperature of the liquid medicine in the cylinder body of the regenerated liquid ejection and absorption device is kept within 15-25 ℃ in the whole system operation process; the temperature of the liquid medicine in the cylinder body of the regeneration sub-liquid storage device is kept within 35-40 ℃ in the whole system operation process.
4. The single-membrane double-chamber electrolytic copper and chlorine regeneration process of the acidic chloride etching waste liquid according to claim 1, characterized in that: in the step S3, the chlorine recycling and regenerating device comprises a titanium centrifugal fan, an injection pipeline mixer and an etching machine ORP controller arranged on the injection pipeline mixer, which are sequentially arranged along the gas flow direction, and the amount of the redundant chlorine in the regenerating liquid injection absorption device, which enters the online acid etching machine and is mixed with the etching working liquid after passing through the titanium centrifugal fan and the injection pipeline mixer, is controlled according to the ORP value of the working etching liquid detected by the etching machine ORP controller, so that the ORP value of the online working etching liquid is ensured to be within the working range.
5. The single-membrane double-chamber electrolytic copper and chlorine regeneration process of the acidic chloride etching waste liquid according to claim 4, characterized in that: when the single-film double-chamber electrolytic device is used for electrolysis in the step S1, the high-frequency power supply automatic regulator and the etching machine ORP controller arranged on the single-film double-chamber electrolytic device carry out current regulation and voltage monitoring on the electrolytic cell through information signals, and the electrolytic current of the single-film double-chamber electrolytic device can be remotely regulated according to the control value of the etching machine ORP controller, so that the ORP value of the working solution of the etching machine is ensured to be within the working range; and when the etching machine ORP controller monitors that the ORP value of the working etching solution is low, the regeneration sub-solution storage device can be synchronously started to replenish the regeneration sub-solution into the online acid etching machine, so that the working parameters of the working etching solution are ensured.
6. The single-membrane double-chamber electrolytic copper and chlorine regeneration process of the acidic chloride etching waste liquid according to claim 1, characterized in that: in step S4, the chlorine and the acid gas entering the low-temperature water curtain absorption device are absorbed by the low-temperature water curtain absorption device through water curtain flow and a gas condenser at 15-20 ℃, and absorption liquid generated by the low-temperature water curtain absorption device enters the dynamic wave absorption device and is used for preparing the absorption liquid in the dynamic wave absorption device and recovering hydrochloric acid; chlorine and acid gas which are not treated by the low-temperature water curtain absorption device enter the dynamic wave absorption device, are washed by dynamic waves and are sprayed and dissolved, then the untreated chlorine and acid gas enter the rotary spray tower again and are neutralized by using an alkaline solution, and the treated tail gas is discharged after reaching the standard.
7. A single-membrane double-chamber electrolytic copper and chlorine regeneration system for waste etching solution of acidic chloride salt used in the process of any one of claims 1 to 6, characterized in that: comprises an online acid etching machine (1), a single-film double-chamber electrolysis device (2), a regenerated liquid blending device (3), a regenerated liquid injection absorption device (4), a chlorine recycling regeneration device, a low-temperature water curtain absorption device (5), a dynamic wave absorption device (6) and a rotational flow spraying device (7), wherein the online acid etching machine is connected with the single-film double-chamber electrolysis device through a pipeline, and the dynamic wave absorption device is connected with the low-temperature water curtain absorption device through
A waste liquid outlet (102) of the online acid etching machine (1) is communicated with a liquid inlet (204) of the single-film double-chamber electrolytic device (2) after passing through an etching waste liquid storage device (8), an electrolyte outlet (205) of the single-film double-chamber electrolytic device (2) is communicated with a liquid inlet of the regenerated liquid blending device (3) after passing through a regenerated liquid storage device (9), a liquid outlet of the regenerated liquid blending device (3) is communicated with a liquid inlet (402) of the regenerated liquid injection absorption device (4), and a regenerated sub-liquid outlet (403) of the regenerated liquid injection absorption device (4) is communicated with an etching liquid inlet (103) of the online acid etching machine (1) after passing through a regenerated sub-liquid storage device (10);
an anode gas outlet (206) of the single-membrane double-chamber electrolysis device (2) is communicated with a gas inlet and outlet (404) of the regenerated liquid injection absorption device (4), and the gas inlet and outlet of the regenerated liquid injection absorption device (4) is communicated with a gas inlet (104) of the online acid etching machine (1) after passing through the chlorine recycling regeneration device;
the cathode gas outlet (207) and the acid gas outlet (208) of the single-membrane double-chamber electrolysis device (2) are communicated with the gas inlet of the low-temperature water curtain absorption device (5), the gas outlet of the low-temperature water curtain absorption device (5) is communicated with the gas inlet of the dynamic wave absorption device (6), and the gas outlet of the dynamic wave absorption device (6) is communicated with the gas inlet of the rotational flow spraying device (7).
8. The single-membrane double-chamber electrolytic copper and chlorine regeneration system for acidic chloride etching waste liquid according to claim 7, characterized in that: the single-membrane double-chamber electrolysis device (2) comprises two electrolysis baths (201) which are adjacently arranged, a cooling bath (202) which is adjacently arranged with one electrolysis bath and a circulating cylinder (203) which is adjacently arranged with the cooling bath, a plurality of anode boxes (201a) which are formed by adopting positive pressure micro-permeation membranes and have frame-type structures are respectively arranged in the two electrolysis baths at intervals, a cathode chamber (201b) is formed between the inner wall of the electrolysis bath and the outer wall of the anode box, and the liquid level of liquid in the cathode chamber is higher than that of liquid in the anode boxes;
be equipped with in positive pole box (201a) graphite electrode, graphite alkene electrode, carbon felt electrode and netted ruthenium titanium coating electrode, be equipped with stainless steel alloy electrode or titanium alloy electrode in cathode chamber (201b), the little infiltration film of malleation is the little infiltration film of polyester malleation.
9. The single-membrane double-chamber electrolytic copper and chlorine regeneration system for acidic chloride etching waste liquid according to claim 7, characterized in that: the anode gas outlets of the single-membrane double-chamber electrolysis device (2) are respectively arranged on the plurality of anode boxes and communicated and converged through gas pipelines; the cathode gas outlet of the single-membrane double-chamber electrolysis device (2) is respectively arranged on two corresponding cathode chambers on the electrolysis bath, the acid gas outlet of the single-membrane double-chamber electrolysis device (2) is arranged on the circulating cylinder, and the cathode gas outlet is communicated with the acid gas outlet through another gas pipeline to be converged.
10. The single-membrane double-chamber electrolytic copper and chlorine regeneration system for acidic chloride etching waste liquid according to claim 7, characterized in that: the regenerated liquid ejection and absorption device (4) comprises an ejector (401) used for introducing part of chlorine generated by the single-membrane double-chamber electrolysis device into the regenerated liquid ejection and absorption device, a cooling device used for cooling the regenerated liquid ejection and absorption device, a regenerated liquid temperature controller used for detecting the temperature of regenerated liquid, a gas-liquid mixer used for mixing gas and liquid and a regenerated liquid ORP controller used for detecting the ORP value of the regenerated liquid.
11. The single-membrane double-chamber electrolytic copper and chlorine regeneration system for acidic chloride etching waste liquid according to claim 7, characterized in that: the chlorine recycling and regenerating device comprises a titanium centrifugal fan (11), an electric air valve (12) and an ejector pipeline mixer (13) which are sequentially arranged along the gas flowing direction; the ejector pipeline mixer (13) is communicated with the air inlet of the online acid etching machine (1), and an etching machine ORP controller (101) for detecting the ORP value of the online working etching liquid is positioned on the ejector pipeline mixer;
a high-frequency power supply automatic regulator is positioned on the single-film double-chamber electrolytic device (2) and is communicated with the etching machine ORP controller (101);
the injection pipeline mixer (13) is communicated with a working etching solution circulating pump arranged on the online acid etching machine.
12. The single-membrane double-chamber electrolytic copper and chlorine regeneration system for acidic chloride etching waste liquid according to claim 7, characterized in that: and a regenerated sub-liquid ORP controller (14) for detecting an ORP value of the regenerated sub-liquid is positioned on a liquid pipeline between the regenerated sub-liquid storage device (8) and the online acid etching machine (1).
13. The single-membrane double-chamber electrolytic copper and chlorine regeneration system for acidic chloride etching waste liquid according to claim 7, characterized in that: the low-temperature water curtain absorption device (5) comprises a water curtain flowing device for absorbing gas and a gas condensing device for condensing the gas, and an absorption liquid outlet (501) of the low-temperature water curtain absorption device (5) is communicated with an absorption liquid inlet (601) of the dynamic wave absorption device; the dynamic wave absorption device (6) comprises a dynamic wave washing device for dynamic wave washing and a spraying and dissolving device for spraying and dissolving.
CN202010736207.0A 2020-07-28 2020-07-28 Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process Pending CN111748826A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010736207.0A CN111748826A (en) 2020-07-28 2020-07-28 Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010736207.0A CN111748826A (en) 2020-07-28 2020-07-28 Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process

Publications (1)

Publication Number Publication Date
CN111748826A true CN111748826A (en) 2020-10-09

Family

ID=72712099

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010736207.0A Pending CN111748826A (en) 2020-07-28 2020-07-28 Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process

Country Status (1)

Country Link
CN (1) CN111748826A (en)

Similar Documents

Publication Publication Date Title
CN105858990A (en) Technology and device for preparing sodium hypochlorite solution with zero-emission saline solution of desulfurization waste water
CN104313584A (en) Method and system for electrolyzing copper-containing etching liquid to obtain copper plate and regenerating and recycling etching liquid
CN105483707B (en) A kind of method that alkaline copper chloride etching waste liquid proposes copper reuse
CN107129011A (en) A kind of device and method of the high villaumite organic wastewater of electrolysis-ionic membrane coupling processing
CN111254455B (en) Device and method for decomposing chlorate generated by side reaction of anode chamber of electrolytic cell in chlor-alkali production and related acid adding process
CN109252168A (en) A kind of devices and methods therefor of efficient activated acid etching solution
CN115135806B (en) Method and equipment for regenerating and recycling alkaline etching waste liquid
CN106835194A (en) A kind of cobalt chloride electrodeposition process
WO2018103621A1 (en) Acid copper electroplating process using insoluble anode and equipment therefor
CN105329988A (en) Electrolytic bath for treating high-salt industrial waste water by combining Fenton method with bipolar membrane technology
CN102002729A (en) Copper-containing waste etching solution treatment method and etching solution regeneration method
WO2020130222A1 (en) Method for treating ship ballast water and ship exhaust gas by using electrolysis
CN106011929A (en) Method for recycling copper extracted from alkaline copper chloride etching waste liquid
CN212533147U (en) Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system
KR20130078834A (en) Treating and reusing method of high salinity waste water
CN111748826A (en) Acid chloride etching waste liquid single-film double-chamber electrolytic copper and chlorine regeneration system and process
CN112281180A (en) Method for preparing chlorine by electrolyzing concentrated seawater through bipolar membrane
CN108588723A (en) A kind of regeneration cycle system and method for alkaline etching waste liquid for producing
CN215251227U (en) Chlorate decomposition device in production of caustic soda by ion-exchange membrane method
CN209412325U (en) A kind of device of efficient activated acid etching solution
CN203613055U (en) Treatment device for wastewater with high salinity and chlorine
CN102807294A (en) Recirculation system for treating used etching liquid
CN208087748U (en) Two-component acidity etching liquid recycling device
CN214087709U (en) Water system for preparing weak-acid hypochlorous acid from etching waste liquid
CN117385359A (en) Method for regenerating acidic etching solution by chlorine-free electrolysis

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination