CN111850604A - System and process for copper extraction by electrolysis regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent - Google Patents

System and process for copper extraction by electrolysis regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent Download PDF

Info

Publication number
CN111850604A
CN111850604A CN202010682142.6A CN202010682142A CN111850604A CN 111850604 A CN111850604 A CN 111850604A CN 202010682142 A CN202010682142 A CN 202010682142A CN 111850604 A CN111850604 A CN 111850604A
Authority
CN
China
Prior art keywords
liquid
etching
ammonia
absorption device
regeneration
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
CN202010682142.6A
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 CN202010682142.6A priority Critical patent/CN111850604A/en
Publication of CN111850604A publication Critical patent/CN111850604A/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
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention discloses a system and a process for electrolyzing and regenerating copper from waste chloride alkaline etching solution and recovering ammonia by negative pressure countercurrent, wherein an MOD electrolysis device is used for electrolyzing the waste etching solution to reduce copper ions in the waste etching solution into copper simple substances and generate NH4Cl is dissolved in the regenerating liquid, NH is generated3The ammonia water is prepared by low-temperature injection absorption and negative-pressure countercurrent recovery of ammonia, the problems of an extraction regeneration circulating system or a direct electrolysis regeneration circulating system which is independently used can be solved by MOD electrolysis regeneration copper extraction and negative-pressure countercurrent recovery of ammonia, and loss in the etching solution is compensatedNH of (2)4Cl and NH3The consumption can be reduced, the cost is reduced, and the ammonia gas is recycled; in addition, the injection pipeline mixer directly conveys ammonia gas to the etching machine, so that the etching capacity is improved, and the etching speed is ensured. In addition, the system is simple in structure, can really realize zero emission and low-cost regeneration and circulation of the etching solution, and achieves the aims of clean production and improvement of economic benefits of PCB enterprises.

Description

System and process for copper extraction by electrolysis regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent
Technical Field
The invention relates to a system and a process for recycling alkaline etching waste liquid, in particular to a system and a process for extracting copper by electrolyzing and regenerating chloride alkaline etching liquid and recovering ammonia by negative pressure countercurrent, belonging to the technical field of recycling alkaline etching waste liquid of a printed circuit board.
Background
At present, two methods for regenerating and recycling the chlorine salt alkaline etching waste liquid exist.
One is an extraction method, namely, an organic extractant is used, the copper in the etching waste liquid is transferred into the organic extractant to achieve the purpose of separating the copper by mixing the organic extractant and the etching waste liquid according to the different distribution ratio of the copper ions in the organic extractant and the etching waste liquid, the copper ions in the organic extractant are back extracted by using a sulfuric acid solution, and the obtained copper sulfate solution is subjected to electrolytic copper extraction. Although the method can achieve the effect of regenerating the etching waste liquid, the method also has the defects that: the concentration of copper ions in the extracted etching waste liquid is still high, generally about 60-80g/L, and the copper ions are recycled as regeneration liquid to the etching process for many times, so that the load capacity of equipment is reduced; if the copper ion concentration of the regeneration liquid is to be reduced, multistage extraction is required, which increases the equipment cost. ② in the extraction process, the organic extractant will carry a small amount of NH4Cl、NH3、SO4 2-The copper sulfate solution is susceptible to contamination resulting in phase reduction of the electrolytic copper product, and SO4 2-The etching rate is decreased.
In the direct electrolysis method, the waste etching solution is directly introduced into an electrolytic bath to perform copper electrolysis, and the regenerated solution having a low copper concentration formed after the electrolysis is returned to the etching step. The method is simple to operate, has low equipment cost, but also has the defects that a large amount of ammonia gas is volatilized in the electrolytic process, so that the material is consumed.
Disclosure of Invention
Aiming at the defects in the conventional chloride salt alkaline etching waste liquid recycling technology, the invention provides a system and a process for extracting copper by electrolytic regeneration of chloride salt alkaline etching waste liquid and recovering ammonia by negative pressure countercurrent, which can overcome the defects in the prior art, really realize zero emission and low cost of the regeneration and circulation of the etching waste liquid, 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 process for extracting copper by electrolyzing and regenerating waste chloride alkaline etching liquid and recovering ammonia by negative pressure countercurrent, which mainly comprises the following steps:
s1: step S1-2, the etching waste liquid to be treated stored in the etching waste liquid storage cylinder enters an MOD electrolysis device and undergoes an electrolysis reaction in the MOD electrolysis device, copper ions in the etching waste liquid are reduced into elemental copper, and simultaneously ammonium chloride and a large amount of free ammonia gas are generated, wherein the elemental copper is subsequently precipitated, filtered and taken out, and the ammonium chloride is directly dissolved in the etching waste liquid to be treated;
s2: in the step S1, a small part of free ammonia gas generated by the MOD electrolysis device is conveyed to the working procedure of the etching machine for the online alkaline etching production line through the injection pipeline mixer, and the pH value and the ORP value of the online etching working solution are adjusted;
S3: the etching waste liquid treated by the MOD electrolysis device in the step S1 enters a regenerated liquid ejection and absorption device and is stored in the regenerated liquid ejection and absorption device; the rest part of the free ammonia gas generated by the MOD electrolysis device enters the regeneration liquid ejection and absorption device, and part of the rest part is absorbed and dissolved by the electrolyzed regeneration liquid in the regeneration liquid ejection and absorption device to form etching liquid regeneration sub-liquid; discharging the regenerated sub-liquid of the etching liquid into a regenerated sub-liquid preparation barrel for preparing components of the etching liquid, and then feeding the regenerated sub-liquid into a working etching liquid used by an online alkaline etching production line for an etching process after passing through a regenerated sub-liquid storage cylinder;
s4: the other part of the remaining part of the free ammonia gas entering the regeneration liquid ejection and absorption device in the step S3 enters the negative-pressure countercurrent ammonia absorption device after volatilizing from the regeneration liquid ejection and absorption device, and is absorbed and dissolved by the absorption liquid in the negative-pressure countercurrent ammonia absorption device to form ammonia water;
s5: and returning a part of the ammonia water formed in the step S4 to the regenerated sub-liquid preparation barrel for preparing the regenerated sub-liquid, and returning the other part of the formed ammonia water to the working etching liquid used by the online alkaline etching production line to be used as a supplementary liquid.
The further technical scheme is as follows:
the step S1 further includes a step S1-1:
after the etching waste liquid generated by the online alkaline etching production line is subjected to an alkaline etching waste liquid extraction regeneration process, storing the obtained etching waste liquid subjected to extraction regeneration in an etching waste liquid storage tank to form etching waste liquid to be treated;
or the etching waste liquid generated by the online alkaline etching production line is stored in the etching waste liquid storage cylinder to form the etching waste liquid to be treated.
The further technical scheme is as follows:
in the step S2, the injection pipeline mixer mixes the etching working solution pumped by the etching machine circulating pump through the etching machine circulating pump arranged on the online alkaline etching production line with a small amount of free ammonia generated by the MOD electrolysis device in the step S1, so as to stabilize the pH value and ORP value of the online etching working solution.
The further technical scheme is as follows:
the temperature of the liquid medicine in the cylinder body of the regeneration liquid ejection and absorption device is kept between 20 and 30 ℃; and the temperature of the liquid medicine in the cylinder body of the negative pressure countercurrent ammonia absorption device is kept at 10-15 ℃.
The further technical scheme is as follows:
the regenerated liquid injection absorption device is characterized in that a regenerated liquid conductivity controller is arranged in a cylinder body of the regenerated liquid injection absorption device, an ammonia water conductivity controller is arranged in a cylinder body of the negative-pressure countercurrent ammonia absorption device, the regenerated liquid conductivity controller detects the conductivity of liquid medicine in the cylinder body of the regenerated liquid injection absorption device, the ammonia water conductivity controller detects the conductivity of the liquid medicine in the cylinder body of the negative-pressure countercurrent ammonia absorption device, corresponding discharge valves are respectively and automatically started to discharge the liquid medicine up to the standard after the conductivity parameter of the liquid medicine reaches a control standard, and the corresponding liquid medicine is automatically replenished until the liquid level of the liquid medicine in the cylinder body reaches a low level.
The invention also discloses a system for electrolyzing, regenerating and extracting copper from the chlorine salt alkaline etching waste liquid and recovering ammonia by negative pressure countercurrent, which comprises an MOD electrolysis device, a regenerated liquid injection absorption device and a negative pressure countercurrent ammonia absorption device,
wherein the liquid inlet of the MOD electrolyzer is communicated with the liquid outlet of a device for storing etching waste liquid, the liquid outlet of the MOD electrolyzer is communicated with the liquid inlet of a regenerated liquid injection absorption device, one path of the gas outlet of the MOD electrolyzer is communicated with the gas inlet of the regenerated liquid injection absorption device, and the other path of the gas outlet of the MOD electrolyzer is communicated with equipment for an online etching process after passing through an injection pipeline mixer;
wherein the gas outlet of the regenerated liquid ejection and absorption device is communicated with the gas inlet of the negative-pressure countercurrent ammonia absorption device, and the liquid outlet of the negative-pressure countercurrent ammonia absorption device is communicated with an ammonia water storage barrel; the liquid outlet of the regenerated liquid injection absorption device is communicated with a regenerated sub-liquid mixing barrel, and the regenerated sub-liquid mixing barrel is communicated with equipment for an online etching process after passing through a regenerated sub-liquid storage cylinder; the ammonia water storage barrel is respectively communicated with the regeneration sub-liquid preparation barrel and the online etching process equipment.
The further technical scheme is as follows:
the device for storing the etching waste liquid is an etching waste liquid storage cylinder, and the etching waste liquid storage cylinder is communicated with equipment for an online etching process or alkaline etching liquid extraction and regeneration equipment.
The further technical scheme is as follows:
the MOD electrolyzer comprises electrolyzer modules including direct current electrolyzers and MOD electrolyzers, and the number of the electrolyzer modules is not more than 18; the anode of the MOD electrolysis device is one of a graphite electrode, a graphene electrode, a carbon felt electrode and a ruthenium oxide coating electrode, and the cathode of the MOD electrolysis device is a stainless steel alloy electrode or a titanium alloy electrode.
The further technical scheme is as follows:
the regeneration liquid ejection and absorption device comprises an ejector, a first cooling device, a regeneration liquid temperature controller, a regeneration liquid conductivity controller and a regeneration liquid level controller, wherein the ejector is used for introducing electrolytic waste gas generated by the MOD electrolysis device into the regeneration liquid ejection and absorption device; the first cooling device comprises a titanium cooling pipe and a condenser which are arranged inside the regenerated liquid ejection absorption device, and a cooling water circulating device which is arranged outside and communicated with the cooling pipe.
The further technical scheme is as follows:
the negative-pressure countercurrent ammonia absorption device comprises a negative-pressure countercurrent absorber for introducing ammonia gas into the negative-pressure countercurrent ammonia absorption device to be absorbed and dissolved, a second cooling device for cooling the negative-pressure countercurrent ammonia absorption device, an ammonia water temperature controller for detecting the temperature of ammonia water, an ammonia water conductivity controller for detecting the conductivity of the ammonia water and an ammonia water level controller; the second cooling device comprises a titanium cooling pipe and a condenser which are arranged inside the negative-pressure countercurrent ammonia absorption device, and a cooling water circulating device which is arranged outside and communicated with the cooling pipe.
The further technical scheme is as follows:
the injection pipeline mixer is communicated with a working etching solution circulating pump arranged on equipment for an on-line etching process.
The further technical scheme is as follows:
the tail gas outlet of the negative pressure countercurrent ammonia absorption device is communicated with the air inlet of a waste gas treatment tower, the tail gas discharge outlet of the waste gas treatment tower is communicated with the outside, and the waste water discharge outlet of the waste gas treatment tower is communicated with a waste water pool.
The beneficial technical effects of the invention are as follows: this application processing technology and processing system carry copper and retrieve ammonia with negative pressure countercurrent recovery through MOD electrolytic regeneration and compensate the problem that single use extraction regeneration circulation system or direct electrolysis regeneration circulation system exist, specifically as follows:
(1) When the extraction regeneration circulating system is used, the concentration of copper ions in the extracted etching waste liquid is higher, generally about 60-80g/L, the etching waste liquid is recycled as the regeneration liquid to the etching process for a plurality of times, the load capacity of equipment can be reduced, the treatment capacity is low, and if the concentration of the copper ions in the regeneration liquid is reduced, multi-stage extraction is required, so that the equipment cost is increased. This application is through alkaline etching solution extraction regeneration and direct electrolysis regeneration series connection, and the etching solution after will extracting regeneration is through direct electrolysis regeneration again, falls to below 30g/L copper ion concentration from 60-80g/L, improves the load capacity of equipment, greatly increased the equipment handling capacity.
(2) When an extraction regeneration circulation system is used, in the extraction processOrganic extractant will entrain small amount of NH4Cl、NH3、SO4 2-SO that the copper sulfate solution is easy to be polluted to cause the reduction of the electrolytic copper product phase, SO4 2-Resulting in a decrease in the etch rate. The application recovers ammonia by MOD electrolytic regeneration copper extraction and negative pressure countercurrent, and NH generated in the direct electrolysis process4Cl is dissolved in the regenerating liquid, NH produced3The ammonia water is prepared by low-temperature ejection absorption and negative-pressure countercurrent recovery of ammonia, thereby supplementing NH lost in the extraction process4Cl、NH3The material consumption is reduced, the cost is reduced, and the ammonia gas is recycled; in addition, the injection pipeline mixer directly conveys ammonia gas to the etching machine, so that the etching capacity is improved, and the etching speed is ensured.
(3) When the existing direct electrolysis regeneration system is used, ammonia is volatilized in the electrolysis process and is not reused, so that the ammonia loss is serious, and the cost is increased. The ammonia gas is recycled by using injection absorption and negative pressure countercurrent absorption, so that the alkaline chloride etching waste liquid is recycled, and green production is formed.
(4) Volatile ammonia of MOD electrolytic device mixes with online alkaline etching machine etching working solution through drawing penetrating the pipeline mixer in this application, can stabilize the pH value of etching working solution and promote the ORP value of stabilizing work, makes the etching ability further promote.
(5) The regeneration liquid that uses in this application draws penetrates absorbing device can absorb the ammonia that volatilizees among the direct electrolytic device and dissolve, and the regeneration etching solution that forms returns the etching process and participates in the etching, can reduce the consumptive material, reduces the cost.
(6) Surplus ammonia that MOD electrolytic device produced in this application passes through the negative pressure and prepares formation aqueous ammonia under the low temperature condition against current ammonia absorption device, can reduce the son liquid of regenerating and allot the material and purchase outward and reduce exhaust emission.
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-MOD electrolyzer; 101-a direct current electrolytic cell; 102-MOD electrolytic cell;
2-regenerated liquid ejection absorption device; 201-an ejector; 202-a first cooling device; 205-regenerated liquid level controller;
3-negative pressure countercurrent ammonia absorption device; 302-a second cooling device; 305-ammonia water level controller;
4-ejecting a pipeline mixer;
5-equipment for on-line etching process;
6-ammonia water storage barrel;
7-regenerating seed liquid blending barrel;
8-regeneration seed liquid storage cylinder;
9-etching waste liquid storage cylinder;
10-cooling water circulation device;
11-a waste gas treatment tower;
12-wastewater basin.
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 specific embodiment of the invention describes a system for electrolyzing, regenerating, extracting copper and recovering ammonia by negative-pressure countercurrent from waste chloride alkaline etching liquid in detail, which mainly comprises an MOD electrolyzing device 1, a regenerated liquid injection and absorption device 2 and a negative-pressure countercurrent ammonia absorption device 3.
The liquid inlet of the MOD electrolyzer 1 is communicated with the liquid outlet of a device for storing etching waste liquid, the liquid outlet of the MOD electrolyzer 1 is communicated with the liquid inlet of the regenerated liquid injection absorption device 2, one path of the gas outlet of the MOD electrolyzer 2 is communicated with the gas inlet of the regenerated liquid injection absorption device 2, and the other path of the gas outlet of the MOD electrolyzer 2 is communicated with the equipment 5 for the online etching process after passing through the injection pipeline mixer 4;
the gas outlet of the regenerated liquid ejection and absorption device 2 is communicated with the gas inlet of a negative-pressure countercurrent ammonia absorption device 3, and the liquid outlet of the negative-pressure countercurrent ammonia absorption device is communicated with an ammonia water storage barrel 6; the liquid outlet of the regenerated liquid injection absorption device 2 is communicated with a regenerated sub-liquid blending barrel 7, and the regenerated sub-liquid blending barrel is communicated with the online etching process equipment 5 after passing through a regenerated sub-liquid storage cylinder 8; the ammonia water storage barrel 6 is respectively communicated with the regenerated sub-liquid preparation barrel 7 and the on-line etching process equipment 5.
In the embodiment, the device for storing the etching waste liquid is an etching waste liquid storage cylinder 9, and the etching waste liquid storage cylinder 9 is communicated with the device 5 for the online etching process or the alkaline etching liquid extraction and regeneration device; the apparatus 5 for the in-line etching process is an alkaline etcher.
In this embodiment, the MOD electrolyzer 1 is composed of electrolyzer modules including the DC electrolyzer 101 and the MOD electrolyzer 102, and the number of the electrolyzer modules does not exceed 18. Preferably, in this embodiment, the anode of the MOD electrolysis device is one of a graphite electrode, a graphene electrode, a carbon felt electrode and a ruthenium oxide coated electrode, and the cathode of the MOD electrolysis device is a stainless steel alloy electrode or a titanium alloy electrode.
In this embodiment, the regenerated liquid injection and absorption device 2 includes an injector 201 for introducing the electrolytic waste gas generated by the MOD electrolysis device into the regenerated liquid injection and absorption device, a first cooling device 202 for cooling the regenerated liquid injection and absorption device, a regenerated liquid temperature controller for detecting the temperature of the regenerated liquid, a regenerated liquid conductivity controller for detecting the conductivity of the regenerated liquid, and a regenerated liquid level controller 205; the first cooling device 202 comprises a titanium cooling pipe and a condenser which are arranged inside the regenerated liquid injection absorption device, and a cooling water circulation device 10 which is arranged outside and communicated with the cooling pipe. The first cooling device can ensure that the temperature of the liquid medicine in the cylinder body is kept between 20 and 30 ℃ in the operation process of the whole system; the regenerated liquid conductivity controller is used for detecting the conductivity of the liquid medicine in the cylinder body of the regenerated liquid injection absorption device, when the conductivity parameter of the liquid medicine reaches the control standard, the discharge valve is automatically started to discharge the liquid medicine up to the standard, and corresponding liquid medicine is automatically supplied until the liquid level of the liquid medicine in the cylinder body reaches the lowest position.
In this embodiment, the negative-pressure countercurrent ammonia absorption device 3 includes a negative-pressure countercurrent absorber for introducing ammonia gas into the negative-pressure countercurrent ammonia absorption device for absorption and dissolution, a second cooling device 302 for cooling the negative-pressure countercurrent ammonia absorption device, an ammonia water temperature controller for detecting the temperature of ammonia water, an ammonia water conductivity controller for detecting the conductivity of ammonia water, and an ammonia water level controller 305; wherein the second cooling device 302 comprises a titanium cooling pipe and a condenser which are arranged inside the negative pressure countercurrent ammonia absorption device, and a cooling water circulation device 10 which is arranged outside and communicated with the cooling pipe. The second cooling device can ensure that the temperature of liquid medicine in the cylinder body is kept at 10-15 ℃ in the operation process of the whole system; the ammonia water conductivity controller is used for detecting the conductivity of the liquid medicine in the cylinder body of the negative-pressure countercurrent ammonia absorption device, when the conductivity parameter of the liquid medicine reaches the control standard, the discharge valve is automatically started to discharge the liquid medicine up to the standard, and corresponding liquid medicine is automatically supplied until the liquid level of the liquid medicine in the cylinder body reaches the lowest position.
In this embodiment, the injection pipeline mixer 4 is communicated with a working etching solution circulating pump arranged on the equipment for the on-line etching process.
In this embodiment, the tail gas outlet of the negative pressure countercurrent ammonia absorption device 3 is communicated with the air inlet of a waste gas treatment tower 11, the tail gas discharge outlet of the waste gas treatment tower 11 is communicated with the outside, the treated tail gas reaching the standard is discharged to the outside, and the waste water discharge outlet of the waste gas treatment tower 11 is communicated with a waste water tank 12.
The invention also describes a process for carrying out the electrolytic regeneration copper extraction and the negative pressure countercurrent recovery ammonia on the chlorine salt alkaline etching waste liquid by using the system in detail, which mainly comprises the following steps:
s1: including step S1-1 and step S1-2,
step S1-1, after the etching waste liquid generated by the online alkaline etching production line is subjected to alkaline etching waste liquid extraction regeneration technology, storing the obtained etching waste liquid subjected to extraction regeneration in an etching waste liquid storage cylinder to form the etching waste liquid to be treated, wherein the adopted alkaline etching waste liquid extraction regeneration technology is an extraction method conventionally used in the field; or, the etching waste liquid generated by the online alkaline etching production line is directly stored in the etching waste liquid storage cylinder to form the etching waste liquid to be treated without adopting the conventional extraction method to extract the etching waste liquid generated by the online alkaline etching production line. In the present embodiment, the step S1-1 adopts the former treatment method, that is, the treatment is performed by using an extraction process, and when an extraction regeneration circulation system is used, the concentration of copper ions in the extracted etching waste liquid is high, generally 60 to 80 g/L.
And step S1-2, the etching waste liquid to be treated stored in the etching waste liquid storage cylinder enters an MOD electrolysis device and undergoes an electrolysis reaction in the MOD electrolysis device, copper ions in the etching waste liquid are reduced into elemental copper, and simultaneously ammonium chloride and a large amount of free ammonia gas are generated, wherein the elemental copper is subsequently precipitated, filtered and taken out, and the ammonium chloride is directly dissolved in the etching waste liquid to be treated. After the etching waste liquid is treated by the electrolysis step, the concentration of copper ions in the etching waste liquid can be reduced from 60-80g/L to below 30g/L, and in the specific embodiment, the concentration of copper ions can be reduced to below 10 g/L.
The MOD electrolyzer in this embodiment is a modular electrolyzer, and the principles of electrolysis are as follows: by utilizing the electrolytic reduction effect, copper ions in the etching waste liquid are reduced to be simple substance copper on the cathode under the action of an external electric field, meanwhile, the anode generates ammonium chloride, and a large amount of free ammonia is generated and volatilized in the electrolytic process, and the chemical reaction formula is as follows:
a cathode; cu (NH)3)4 2++2e-→Cu+4NH3↑
Figure BDA0002586244270000091
S2: in the step S1, a small part of free ammonia gas generated by the MOD electrolysis device is conveyed to the process of the etching machine for the online alkaline etching production line through the injection pipeline mixer, and the pH value and the ORP value of the online etching working solution are adjusted. Specifically, in step S2, the injection pipeline mixer mixes the etching working solution pumped by the etching machine circulating pump with a small amount of free ammonia generated by the MOD electrolysis device in step S1 by the etching machine circulating pump arranged on the online alkaline etching production line, so as to stabilize the pH value and ORP value of the online etching working solution and improve the etching capability of the online etching working solution. More specifically, the pH controller, the electric air valve and other devices can be used for linkage management and control in the mixing process.
S3: the etching waste liquid treated by the MOD electrolysis device in step S1 (in this specific embodiment, the copper ion concentration of the etching waste liquid is reduced to below 15 g/L) enters the regenerated liquid injection absorption device and is stored therein, in this specific embodiment, the temperature of the liquid medicine in the cylinder of the regenerated liquid injection absorption device is maintained at 20-30 ℃ by the cooling device. The rest part of the free ammonia gas generated by the MOD electrolysis device enters the regeneration liquid ejection and absorption device, and part of the rest part is absorbed and dissolved by the electrolyzed regeneration liquid in the regeneration liquid ejection and absorption device to form etching liquid regeneration sub-liquid; the regenerated sub-liquid of the etching liquid is discharged into a regenerated sub-liquid preparation barrel for preparing the components of the etching liquid, passes through a regenerated sub-liquid storage cylinder and then enters the working etching liquid used by the online alkaline etching production line for etching process, thereby achieving the aim of regeneration.
S4: in the step S3, the other part of the remaining part of the free ammonia gas entering the regeneration liquid ejection and absorption device enters the negative-pressure countercurrent ammonia absorption device after volatilizing from the regeneration liquid ejection and absorption device, and is absorbed and dissolved by the absorption liquid (in this embodiment, water is used as the absorption liquid) located in the negative-pressure countercurrent ammonia absorption device to form ammonia water, and the temperature of the liquid medicine (ammonia water) in the cylinder of the negative-pressure countercurrent ammonia absorption device is kept at 10-15 ℃.
In the above steps S3 and S4, a regenerated liquid conductivity controller is disposed in the cylinder of the regenerated liquid ejection absorption device, an ammonia water conductivity controller is disposed in the cylinder of the negative-pressure countercurrent ammonia absorption device, the regenerated liquid conductivity controller detects the conductivity of the liquid medicine in the cylinder of the regenerated liquid ejection absorption device, the ammonia water conductivity controller detects the conductivity of the liquid medicine in the cylinder of the negative-pressure countercurrent ammonia absorption device, when the conductivity parameter of the liquid medicine reaches a control standard, corresponding discharge valves are respectively and automatically started to discharge the liquid medicine up to the standard, and corresponding liquid medicine is automatically replenished until the liquid level of the liquid medicine in the cylinder reaches the lowest level.
S5: and returning a part of the ammonia water formed in the step S4 to the regenerated sub-liquid preparation barrel for preparing the regenerated sub-liquid, and returning the other part of the formed ammonia water to the working etching liquid used by the online alkaline etching production line for use as a replenishing liquid for new liquid washing. Therefore, the ammonia gas is fully regenerated and used, and the aim of recycling the ammonia gas is fulfilled.
According to the process and the system, the problems of an extraction regeneration circulating system or a direct electrolysis regeneration circulating system which is singly used are solved by MOD electrolysis regeneration copper extraction and negative pressure countercurrent recovery ammonia, and the process and the system are as follows:
(1) When the extraction regeneration circulating system is used, the concentration of copper ions in the extracted etching waste liquid is higher, generally about 60-80g/L, the etching waste liquid is recycled as the regeneration liquid to the etching process for a plurality of times, the load capacity of equipment can be reduced, the treatment capacity is low, and if the concentration of the copper ions in the regeneration liquid is reduced, multi-stage extraction is required, so that the equipment cost is increased. This application is through alkaline etching solution extraction regeneration and direct electrolysis regeneration series connection, and the etching solution after will extracting regeneration is through direct electrolysis regeneration again, falls to below 30g/L copper ion concentration from 60-80g/L, improves the load capacity of equipment, greatly increased the equipment handling capacity.
(2) When an extraction regeneration circulation system is used, a small amount of NH is carried in the organic extractant during the extraction process4Cl、NH3、SO4 2-SO that the copper sulfate solution is easy to be polluted to cause the reduction of the electrolytic copper product phase, SO4 2-Resulting in a decrease in the etch rate. The application recovers ammonia by MOD electrolytic regeneration copper extraction and negative pressure countercurrent, and NH generated in the direct electrolysis process4Cl is dissolved in the regenerating liquid, NH produced3The ammonia water is prepared by low-temperature ejection absorption and negative-pressure countercurrent recovery of ammonia, thereby supplementing NH lost in the extraction process4Cl、NH3The material consumption is reduced, the cost is reduced, and the ammonia gas is recycled; in addition, the injection pipeline mixer directly conveys ammonia gas to the etching machine, so that the etching capacity is improved, and the etching speed is ensured.
(3) When the existing direct electrolysis regeneration system is used, ammonia is volatilized in the electrolysis process and is not reused, so that the ammonia loss is serious, and the cost is increased. The ammonia gas is recycled by using injection absorption and negative pressure countercurrent absorption, so that the alkaline chloride etching waste liquid is recycled, and green production is formed.
(4) Volatile ammonia of MOD electrolytic device mixes with online alkaline etching machine etching working solution through drawing penetrating the pipeline mixer in this application, can stabilize the pH value of etching working solution and promote the ORP value of stabilizing work, makes the etching ability further promote.
(5) The regeneration liquid that uses in this application draws penetrates absorbing device can absorb the ammonia that volatilizees among the direct electrolytic device and dissolve, and the regeneration etching solution that forms returns the etching process and participates in the etching, can reduce the consumptive material, reduces the cost.
(6) Surplus ammonia that MOD electrolytic device produced in this application passes through the negative pressure and prepares formation aqueous ammonia under the low temperature condition against current ammonia absorption device, can reduce the son liquid of regenerating and allot the material and purchase outward and reduce exhaust emission.
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 (12)

1. A process for extracting copper by electrolyzing and regenerating waste etching liquid containing chlorine salt and recovering ammonia by negative pressure countercurrent is characterized by mainly comprising the following steps:
s1: step S1-2, the etching waste liquid to be treated stored in the etching waste liquid storage cylinder enters an MOD electrolysis device and undergoes an electrolysis reaction in the MOD electrolysis device, copper ions in the etching waste liquid are reduced into elemental copper, and simultaneously ammonium chloride and a large amount of free ammonia gas are generated, wherein the elemental copper is subsequently precipitated, filtered and taken out, and the ammonium chloride is directly dissolved in the etching waste liquid to be treated;
s2: in the step S1, a small part of free ammonia gas generated by the MOD electrolysis device is conveyed to the working procedure of the etching machine for the online alkaline etching production line through the injection pipeline mixer, and the pH value and the ORP value of the online etching working solution are adjusted;
s3: the etching waste liquid treated by the MOD electrolysis device in the step S1 enters a regenerated liquid ejection and absorption device and is stored in the regenerated liquid ejection and absorption device; the rest part of the free ammonia gas generated by the MOD electrolysis device enters the regeneration liquid ejection and absorption device, and part of the rest part is absorbed and dissolved by the electrolyzed regeneration liquid in the regeneration liquid ejection and absorption device to form etching liquid regeneration sub-liquid; discharging the regenerated sub-liquid of the etching liquid into a regenerated sub-liquid preparation barrel for preparing components of the etching liquid, and then feeding the regenerated sub-liquid into a working etching liquid used by an online alkaline etching production line for an etching process after passing through a regenerated sub-liquid storage cylinder;
S4: the other part of the remaining part of the free ammonia gas entering the regeneration liquid ejection and absorption device in the step S3 enters the negative-pressure countercurrent ammonia absorption device after volatilizing from the regeneration liquid ejection and absorption device, and is absorbed and dissolved by the absorption liquid in the negative-pressure countercurrent ammonia absorption device to form ammonia water;
s5: and returning a part of the ammonia water formed in the step S4 to the regenerated sub-liquid preparation barrel for preparing the regenerated sub-liquid, and returning the other part of the formed ammonia water to the working etching liquid used by the online alkaline etching production line to be used as a supplementary liquid.
2. The process for copper extraction by electrolytic regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent flow as claimed in claim 1, wherein the step S1 further comprises the step S1-1:
after the etching waste liquid generated by the online alkaline etching production line is subjected to an alkaline etching waste liquid extraction regeneration process, storing the obtained etching waste liquid subjected to extraction regeneration in an etching waste liquid storage tank to form etching waste liquid to be treated;
or the etching waste liquid generated by the online alkaline etching production line is stored in the etching waste liquid storage cylinder to form the etching waste liquid to be treated.
3. The process for extracting copper by electrolytic regeneration of waste chlorine salt etching solution and recovering ammonia by negative pressure countercurrent according to claim 1, which is characterized in that: in the step S2, the injection pipeline mixer mixes the etching working solution pumped by the etching machine circulating pump through the etching machine circulating pump arranged on the online alkaline etching production line with a small amount of free ammonia generated by the MOD electrolysis device in the step S1, so as to stabilize the pH value and ORP value of the online etching working solution.
4. The process for extracting copper by electrolytic regeneration of waste chlorine salt etching solution and recovering ammonia by negative pressure countercurrent according to claim 1, which is characterized in that: the temperature of the liquid medicine in the cylinder body of the regeneration liquid ejection and absorption device is kept between 20 and 30 ℃; and the temperature of the liquid medicine in the cylinder body of the negative pressure countercurrent ammonia absorption device is kept at 10-15 ℃.
5. The process for extracting copper by electrolytic regeneration of waste chlorine salt etching solution and recovering ammonia by negative pressure countercurrent according to claim 1, which is characterized in that: the regenerated liquid injection absorption device is characterized in that a regenerated liquid conductivity controller is arranged in a cylinder body of the regenerated liquid injection absorption device, an ammonia water conductivity controller is arranged in a cylinder body of the negative-pressure countercurrent ammonia absorption device, the regenerated liquid conductivity controller detects the conductivity of liquid medicine in the cylinder body of the regenerated liquid injection absorption device, the ammonia water conductivity controller detects the conductivity of the liquid medicine in the cylinder body of the negative-pressure countercurrent ammonia absorption device, corresponding discharge valves are respectively and automatically started to discharge the liquid medicine up to the standard after the conductivity parameter of the liquid medicine reaches a control standard, and the corresponding liquid medicine is automatically replenished until the liquid level of the liquid medicine in the cylinder body reaches a low level.
6. A system for electrolyzing and regenerating copper extraction and negative-pressure countercurrent ammonia recovery from waste chlorine salt alkaline etching solution used in the process of any one of claims 1 to 5, which is characterized in that: comprises an MOD electrolysis device (1), a regenerated liquid ejection and absorption device (2) and a negative pressure countercurrent ammonia absorption device (3),
Wherein the liquid inlet of the MOD electrolyzer (1) is communicated with the liquid outlet of a device for storing etching waste liquid, the liquid outlet of the MOD electrolyzer (1) is communicated with the liquid inlet of the regenerated liquid injection absorption device (2), one path of the gas outlet of the MOD electrolyzer (2) is communicated with the gas inlet of the regenerated liquid injection absorption device (2), and the other path of the gas outlet of the MOD electrolyzer (2) is communicated with the equipment (5) for the online etching process after passing through the injection pipeline mixer (4);
wherein the gas outlet of the regenerated liquid ejection and absorption device (2) is communicated with the gas inlet of the negative-pressure countercurrent ammonia absorption device (3), and the liquid outlet of the negative-pressure countercurrent ammonia absorption device is communicated with an ammonia water storage barrel (6); the liquid outlet of the regenerated liquid ejection absorption device (2) is communicated with a regenerated sub-liquid blending barrel (7), and the regenerated sub-liquid blending barrel is communicated with the equipment (5) for the online etching process after passing through a regenerated sub-liquid storage cylinder (8); the ammonia water storage barrel (6) is respectively communicated with the regenerated sub-liquid preparation barrel (7) and the equipment (5) for the online etching process.
7. The system for copper extraction and negative-pressure countercurrent ammonia recovery by electrolysis and regeneration of waste chlorine salt alkaline etching solution according to claim 6, characterized in that: the device for storing the etching waste liquid is an etching waste liquid storage cylinder (9), and the etching waste liquid storage cylinder (9) is communicated with equipment (5) for an online etching process or alkaline etching liquid extraction and regeneration equipment.
8. The system for copper extraction and negative-pressure countercurrent ammonia recovery by electrolysis and regeneration of waste chlorine salt alkaline etching solution according to claim 6, characterized in that: the MOD electrolyzer (1) consists of electrolyzer modules comprising direct current electrolyzers (101) and MOD electrolyzers (102), and the number of the electrolyzer modules is not more than 18; the anode of the MOD electrolysis device is one of a graphite electrode, a graphene electrode, a carbon felt electrode and a ruthenium oxide coating electrode, and the cathode of the MOD electrolysis device is a stainless steel alloy electrode or a titanium alloy electrode.
9. The system for copper extraction and negative-pressure countercurrent ammonia recovery by electrolysis and regeneration of waste chlorine salt alkaline etching solution according to claim 6, characterized in that: the regenerated liquid ejection and absorption device (2) comprises an ejector (201) for introducing electrolytic waste gas generated by the MOD electrolysis device into the regenerated liquid ejection and absorption device, a first cooling device (202) for cooling the regenerated liquid ejection and absorption device, a regenerated liquid temperature controller for detecting the temperature of regenerated liquid, a regenerated liquid conductivity controller for detecting the conductivity of the regenerated liquid and a regenerated liquid level controller (205); the first cooling device (202) comprises a titanium cooling pipe and a condenser which are arranged inside the regenerated liquid injection absorption device, and a cooling water circulating device (10) which is arranged outside and communicated with the cooling pipe.
10. The system for copper extraction and negative-pressure countercurrent ammonia recovery by electrolysis and regeneration of waste chlorine salt alkaline etching solution according to claim 6, characterized in that: the negative-pressure countercurrent ammonia absorption device (3) comprises a negative-pressure countercurrent absorber for introducing ammonia gas into the negative-pressure countercurrent ammonia absorption device to be absorbed and dissolved, a second cooling device (302) for cooling the negative-pressure countercurrent ammonia absorption device, an ammonia water temperature controller for detecting the temperature of ammonia water, an ammonia water conductivity controller for detecting the conductivity of the ammonia water and an ammonia water level controller (305); the second cooling device (302) comprises a titanium cooling pipe and a condenser which are arranged inside the negative-pressure countercurrent ammonia absorption device, and a cooling water circulating device (10) which is arranged outside and communicated with the cooling pipe.
11. The system for copper extraction and negative-pressure countercurrent ammonia recovery by electrolysis and regeneration of waste chlorine salt alkaline etching solution according to claim 6, characterized in that: the injection pipeline mixer (4) is communicated with a working etching solution circulating pump arranged on equipment for an on-line etching process.
12. The system for copper extraction and negative-pressure countercurrent ammonia recovery by electrolysis and regeneration of waste chlorine salt alkaline etching solution according to claim 6, characterized in that: the tail gas outlet of the negative pressure countercurrent ammonia absorption device (3) is communicated with the air inlet of a waste gas treatment tower (11), the tail gas discharge outlet of the waste gas treatment tower (11) is communicated with the outside, and the waste water discharge outlet of the waste gas treatment tower (11) is communicated with a waste water pool (12).
CN202010682142.6A 2020-07-15 2020-07-15 System and process for copper extraction by electrolysis regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent Pending CN111850604A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010682142.6A CN111850604A (en) 2020-07-15 2020-07-15 System and process for copper extraction by electrolysis regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010682142.6A CN111850604A (en) 2020-07-15 2020-07-15 System and process for copper extraction by electrolysis regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent

Publications (1)

Publication Number Publication Date
CN111850604A true CN111850604A (en) 2020-10-30

Family

ID=72983132

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010682142.6A Pending CN111850604A (en) 2020-07-15 2020-07-15 System and process for copper extraction by electrolysis regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent

Country Status (1)

Country Link
CN (1) CN111850604A (en)

Similar Documents

Publication Publication Date Title
CN205973941U (en) Ammonia nitrogen wastewater treatment device
CN109252168A (en) A kind of devices and methods therefor of efficient activated acid etching solution
CN104152905A (en) Acidic copper chloride etching liquid electrolytic regeneration recycling and copper plate recovery device and method
CN104313584A (en) Method and system for electrolyzing copper-containing etching liquid to obtain copper plate and regenerating and recycling etching liquid
CN204779821U (en) Etching solution recycle and regeneration and carry copper device
CN115135806B (en) Method and equipment for regenerating and recycling alkaline etching waste liquid
CN102839379A (en) On-line treatment method of acidic etching solution
CN103265094A (en) Method for recycling nitric acid and copper from waste water generated in production of printed circuit board
CN102586851A (en) Electrolytic method for relieving and reducing tin sludge generated in tin plating solution
CN111926331A (en) Alkaline etching solution and in-situ electrolysis copper extraction recycling device and method thereof
CN103025667A (en) System and method for recovering spent etching solution
CN212610926U (en) System for electrolyzing and regenerating waste chlorine salt etching liquid to extract copper and recovering ammonia in negative pressure countercurrent mode
CN111663155B (en) Comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate
CN112225302A (en) Ammonia nitrogen wastewater treatment method and system
CN111850604A (en) System and process for copper extraction by electrolysis regeneration of waste chlorine salt alkaline etching solution and ammonia recovery by negative pressure countercurrent
CN113026003A (en) Reduction regeneration method for chemical nickel plating aging solution
CN112110532A (en) Method for treating chloride ions in chlorine-containing solution by using copper powder
CN208087748U (en) Two-component acidity etching liquid recycling device
CN104651880B (en) The method that a kind of decopper(ing) point cyanogen simultaneous PROCESS FOR TREATMENT silver smelts the lean solution containing cyanogen
CN209412325U (en) A kind of device of efficient activated acid etching solution
CN214004793U (en) Alkaline etching waste liquid electrolysis recycling equipment
CN102807294A (en) Recirculation system for treating used etching liquid
CN210683950U (en) Acid etching solution recycling and regenerating device
CN211339693U (en) Alkaline copper-containing etching waste liquid regeneration and ammonia nitrogen wastewater circulation system
CN114045394A (en) Method for separating copper from nickel chloride solution by extraction method

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