CN115572975A - Method and device for recycling copper chloride hydrochloride etching waste liquid - Google Patents
Method and device for recycling copper chloride hydrochloride etching waste liquid Download PDFInfo
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- CN115572975A CN115572975A CN202211256939.5A CN202211256939A CN115572975A CN 115572975 A CN115572975 A CN 115572975A CN 202211256939 A CN202211256939 A CN 202211256939A CN 115572975 A CN115572975 A CN 115572975A
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- anolyte
- copper
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- waste liquid
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- 238000005530 etching Methods 0.000 title claims abstract description 67
- 239000007788 liquid Substances 0.000 title claims abstract description 67
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000004064 recycling Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 34
- GJCXHYNLSNVSQZ-UHFFFAOYSA-L [Cu](Cl)Cl.Cl Chemical compound [Cu](Cl)Cl.Cl GJCXHYNLSNVSQZ-UHFFFAOYSA-L 0.000 title claims abstract description 29
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 57
- 239000010949 copper Substances 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006722 reduction reaction Methods 0.000 claims abstract description 22
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 238000012546 transfer Methods 0.000 claims description 44
- 230000007704 transition Effects 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 19
- 230000007246 mechanism Effects 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000011156 evaluation Methods 0.000 abstract description 6
- 238000012946 outsourcing Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses a method and a device for recycling copper chloride hydrochloride etching waste liquid, wherein the method comprises the following steps: continuously carrying out electrolytic reduction reaction, wherein a photovoltaic solar generator is adopted for supplying power, a cathode ion membrane is used for isolating anolyte and catholyte, low-copper etching solution obtained after metal copper is reduced by cathode electrolysis is used as anolyte, and high-copper etching solution is used as catholyte; continuously circulating the electrolyte, and leading out part of anolyte in the period; detecting the concentration of the copper ions of the anode liquor; when the concentration of copper ions in the guided anolyte is within a set concentration threshold range, recovering the guided anolyte; and when the concentration of the copper ions in the derived anolyte is not within the set concentration threshold range, injecting the derived anolyte into the catholyte. The method solves the problems that the copper chloride etching waste liquid is subjected to outsourcing centralized treatment or an electrolysis recovery method is adopted inside an enterprise, more power is consumed by a power grid for power supply, and the enterprise energy consumption evaluation is higher.
Description
Technical Field
The invention relates to the field of regeneration and recovery, in particular to a method and a device for recycling copper chloride hydrochloride etching waste liquid.
Background
With the development of electronic technology, such as the increase of advanced electronic products of mobile phones, automobiles, new energy sources, aerospace and the like, a circuit board is used as an essential basic product in the packaging of various electronic components, the market demand is very large, china develops from hundreds of small processing plants in 90 years to more than 4000 large-scale production enterprises, the annual output is more than 4 to 5 hundred million square meters, and the scale productivity is first worldwide, hydrochloric acid + ammonium chloride + oxidant and a bank protecting agent are used as copper plate etching agents in the production process, also called as acid etching solutions, and after saturated copper ions are exhausted after failure, a large amount of copper chloride etching waste liquid hydrochloric acid is generated, also called as high copper etching liquid, the content of copper ions is about 150g/L, the copper etching waste liquid belongs to dangerous waste and is very serious in pollution, so that the country encourages recycling and reduces the emission, but the energy consumption problem of enterprises is not considered in the recycling process mainly by outsourcing centralized treatment or an electrolytic recycling method inside the enterprises, more power grids are consumed, and the electrolytic copper reduction enterprise recycling method causes higher energy consumption evaluation.
Disclosure of Invention
The invention mainly aims to provide a method and a device for recycling copper chloride hydrochloride etching waste liquid, which aim to solve the problems that the copper chloride hydrochloride etching waste liquid is subjected to outsourcing centralized treatment or an electrolysis recycling method is adopted in an enterprise, more power is consumed by a power grid, and higher enterprise energy consumption evaluation is caused.
The invention provides a method for recycling copper chloride hydrochloride etching waste liquid, which comprises the following steps:
continuously carrying out electrolytic reduction reaction, wherein a photovoltaic solar generator is adopted for supplying power, a cathode ion membrane is used for isolating anolyte and catholyte, low-copper etching solution obtained after metal copper is reduced by cathode electrolysis is used as anolyte, and high-copper etching solution is used as catholyte;
continuously circulating the electrolyte, and leading out part of anolyte in the period;
detecting the concentration of the copper ions of the anode liquor;
when the concentration of copper ions in the guided anolyte is within a set concentration threshold range, recovering the guided anolyte;
and when the concentration of the copper ions in the derived anolyte is not within the set concentration threshold range, injecting the derived anolyte into the catholyte.
Further, the current density and voltage of electrolysis are positively adjusted following the copper ion concentration of the catholyte.
Further, the current density of electrolysis is controlled at 180A/square meter;
the voltage of electrolysis is controlled at 1.8V/square meter.
Furthermore, the concentration threshold value range is set to be 55-65g/L.
Further, the step of continuously performing the circulation of the electrolyte includes:
injecting a set amount of high copper etching solution into the cathode electrolytic tank through a liquid inlet pump;
part of the catholyte flows into a transfer tank for cooling treatment;
injecting the catholyte subjected to temperature reduction treatment in the transit tank into an anode electrolytic tank;
and part of the anolyte in the anode electrolytic cell flows into the circulating rotary cylinder to obtain the exported anolyte.
Further, the step of detecting the concentration of copper ions in the derived anolyte may include:
detecting whether the volume of liquid in the rotary cylinder in the circulation reaches a preset value or not;
if yes, the step of detecting the concentration of the copper ions in the derived anolyte is carried out.
Further, the step of recovering the derived anolyte includes:
starting the cut-off device to enable the anolyte flowing out of the anode electrolytic cell to flow into the standby cavity;
pumping the guided anolyte into a set container through a circulating transfer cylinder;
and after the extraction action is finished, closing the cut-off device to enable the anolyte in the standby cavity to flow into the circulating transfer cylinder.
Further, part of the catholyte flows into a transfer tank to be subjected to a temperature reduction treatment step, and the temperature of the catholyte in the transfer tank is reduced to below 50 ℃.
The invention also discloses a device for recycling the copper chloride hydrochloride etching waste liquid, which is applied to the method for recycling the copper chloride hydrochloride etching waste liquid;
the device for recycling the copper chloride hydrochloride etching waste liquid comprises:
a photovoltaic solar generator;
a liquid inlet pump;
the cathode electrolytic tank is communicated with the liquid inlet pump and is electrically connected with the photovoltaic solar generator;
the transfer tank is communicated with the cathode electrolytic tank;
the cooling device is connected with the transfer tank and is used for cooling the liquid in the transfer tank;
the transfer pump is communicated with the transfer groove;
the anode electrolytic tank is communicated with the transfer pump and is electrically connected with the photovoltaic solar generator;
the circulating rotary cylinder is communicated with the anode electrolytic tank;
the circulating pump is respectively communicated with the circulating rotary cylinder and the cathode electrolytic tank;
and the extraction pump is communicated with the circulating transfer cylinder.
Further, the device for recycling the copper chloride hydrochloride etching waste liquid also comprises:
the standby cavity is communicated with the circulating transfer cylinder through a communicating channel, and the bottom of the standby cavity is higher than an outlet of the communicating channel at the circulating transfer cylinder;
the cut-off device comprises a transition groove and a transition groove control mechanism, wherein the transition groove control mechanism drives the transition groove to rotate so as to enable the transition groove to be changed between a first parking position and a second parking position;
when the transition groove is positioned at the first parking position, the communicating channel is smooth;
when the transition groove is positioned at the second stopping position, the communicating channel is blocked, and the transition groove leads the anolyte flowing out of the anode electrolytic cell into the standby cavity.
According to the method and the device for recycling the copper chloride hydrochloric etching waste liquid, the copper ions in the high-copper etching liquid are electrolyzed and reduced into the metal copper through the electrolytic reduction reaction by the power supply of the photovoltaic solar generator, the content of the copper ions is reduced, the recycled anolyte can be used as a copper plate etching agent after being prepared, the copper chloride hydrochloric etching waste liquid is recycled, the electrolytic power supply is realized by utilizing the solar power generation, the direct power supply through a power grid can be avoided, and the problems that the power grid power supply is consumed more and the enterprise energy consumption evaluation is higher due to the fact that the copper chloride hydrochloric etching waste liquid is subjected to outsourcing centralized treatment or the electrolytic recovery method is adopted inside an enterprise are solved.
Drawings
FIG. 1 is a schematic view showing the steps of an embodiment of the method for recycling copper chloride hydrochloride etching waste liquid according to the present invention;
FIG. 2 is a schematic structural diagram of an embodiment of the apparatus for recycling waste copper chloride hydrochloride etching solution according to the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
Referring to fig. 1, in an embodiment of the present invention, the present invention provides a method for recycling copper chloride hydrochloride etching waste liquid, including the following steps:
s1, continuously carrying out electrolytic reduction reaction, wherein a photovoltaic solar generator 10 is adopted for supplying power, a cathode ion membrane is used for isolating anolyte and catholyte, low-copper etching solution obtained after metal copper is subjected to cathodic electrolytic reduction is used as anolyte, and high-copper etching solution is used as catholyte;
s2, continuously circulating the electrolyte, and leading out part of anolyte in the electrolyte;
s3, detecting the concentration of the copper ions of the derived anolyte;
s4, when the concentration of copper ions in the guided anolyte is within a set concentration threshold range, the guided anolyte is recovered;
and S5, when the concentration of the copper ions in the derived anolyte is not within the set concentration threshold range, injecting the derived anolyte into the catholyte.
In the step S1, the photovoltaic solar generator 10 includes a high-efficiency solar cell panel and an energy storage battery, converts solar energy into electric energy through the high-efficiency solar cell panel, stores the electric energy into the energy storage battery, supplies power for an electrolytic reduction reaction through the energy storage battery, and obtains a byproduct, namely metallic copper through the electrolytic reduction reaction; during the electrolytic reduction reaction, hydrochloric acid etching solution enters from the lower position of the cathode area of the ion-exchange membrane electrolytic cell, and copper ions in the etching waste solution are reduced into copper simple substances at the cathode under the electrolysis action, so that the concentration of the copper ions is reduced; during electrolytic reduction reaction, the anode: 2Cl- → Cl2+2e2CuCl + Cl2 → 2CuCl2, cu + will preferentially oxidize to Cu2+, cathode: cu2+ +2e = Cu; during electrolysis, copper ions in the anolyte migrate to the cathode through the cathode film and are reduced into metal copper at the cathode, so that the concentration of the copper ions in the catholyte and the anolyte can be reduced.
In the step S2, the electrolyte circulation can continuously inject the liquid with a lower temperature into the cathode electrolytic cell and the anode electrolytic cell to reduce the temperature in the cathode electrolytic cell and the anode electrolytic cell, so as to ensure the normal operation of the electrolytic reduction reaction.
In the step S3, the concentration of the copper ions in the anolyte is detected, which is not described herein for the prior art.
In the step S4, the derived anolyte can be recycled to the production line as a copper plate etchant after being regenerated by adding a small amount of hydrochloric acid and chloride ion ammonium chloride through an oxidation-reduction potential and a hydrometer; the concentration threshold range is set to a value that allows the derived anolyte to be more preferably formulated as a copper plate etchant.
In step S5, when the concentration of the copper ions in the derived anolyte is not within the set concentration threshold range, the derived anolyte is injected into the catholyte to reduce the temperature to a certain extent so as to avoid affecting the concentration of the copper ions in the anode electrolytic cell.
According to the method for recycling the copper chloride hydrochloric etching waste liquid, the photovoltaic solar generator 10 supplies power to perform an electrolytic reduction reaction, copper ions in the high-copper etching liquid are electrolytically reduced into metal copper, the content of the copper ions is reduced, the recycled anolyte can be used as a copper plate etching agent after being blended, recycling of the copper chloride hydrochloric etching waste liquid is achieved, power can be prevented from being directly supplied through a power grid due to the fact that solar power generation is used for supplying power for electrolysis, and the problems that more power grid power is consumed and higher enterprise energy consumption evaluation is caused due to the fact that the copper chloride hydrochloric etching waste liquid is subjected to outsourcing centralized treatment or an electrolysis recycling method is adopted inside an enterprise are solved.
Further, the current density of electrolysis is controlled to be 180-200A/square meter;
the electrolytic voltage is controlled to be 1.5V-2.0V/square meter.
Specifically, the electrolytic current density can be controlled to be 180-200A/square meter, and the electrolytic current density includes, but is not limited to, 180A/square meter, 185A/square meter, 190A/square meter, 195A/square meter and the like, and can be adjusted according to actual requirements; the electrolytic voltage is controlled to be 1.5V-2.0V/square meter, and the electrolytic voltage comprises but is not limited to 1.5V/square meter, 1.55V/square meter, 1.6V/square meter, 1.65V/square meter, 1.7V/square meter, 1.75V/square meter, 1.8V/square meter, 1.85V/square meter, 1.9V/square meter, 1.95V/square meter, 2V/square meter and the like, and can be adjusted according to actual requirements.
Further, the current density and voltage of the electrolysis are adjusted positively following the copper ion concentration of the catholyte.
Specifically, low current and voltage are used when the concentration of copper ions is low, and the main purpose is to ensure the tightness of the cathode for reducing metal copper, ensure that the metal copper is reduced into bulk metal copper instead of copper powder, ensure the recovery of the reduced metal copper and be beneficial to the actual reduction of the copper ions; for example, in some embodiments, when the concentration of copper ions (Cu 2 +) in the catholyte is 130g/L, the current density in the cell is 200A/m2 and the voltage is 2V/m2; when the concentration of copper ions in the catholyte is reduced to 100g/L, the current density in the tank is 180A per square meter and the voltage is 1.8V per square meter; when the concentration of copper ions and copper ions in the catholyte is reduced to 80g/L, the current density in the tank is 160A per square meter, and the voltage is 1.6V per square meter; when the concentration of copper ions and copper ions in the catholyte is reduced to 60g/L, the current density in the tank is 150A per square meter, and the voltage is 1.5V per square meter; the forward adjustment, namely high current density and voltage are used when the concentration of copper ions is high;
it should be noted that, in some embodiments, the concentration of copper ions may be detected from time to time, and the current density and voltage may be controlled according to the detection result; in some embodiments, through a concentration change rule of copper ions, when it is predicted that copper ions will reach a set concentration value, performing multiple copper ion concentration detection, and when the detection meets the copper ion concentration, correspondingly adjusting current density and voltage, so to speak, when the detection does not detect the corresponding node copper ion concentration, and after the detected copper ion concentration reaches another interval, correspondingly adjusting the current density and voltage, for example, when the detected copper ion concentration is from 82g/L to 79g/L, adjusting the current density in a groove to be 160A/square meter, and the voltage to be 1.6V/square meter; in some embodiments, the current density and the voltage are adjusted according to the concentration variation rule of the copper ions when the copper ions reach the set concentration value.
Further, the concentration threshold value range is set to be 55-65g/L.
Specifically, the set concentration threshold range may be a range of values, including, but not limited to, 55-60g/L,60-65g/L,56-64g/L, etc., in some embodiments, the set concentration threshold range may be a single value, such as 55g/L,58g/L,60g/L,63g/L,65g/L, etc., or the set concentration threshold range may be determined according to a set value, such as 60 + -1 g/L,60 + -2 g/L, etc.
Further, the step S2 of continuously performing the circulation of the electrolyte includes:
s21, injecting a set amount of high-copper etching solution into the cathode electrolytic tank 1 through the liquid inlet pump 8;
s22, allowing part of catholyte to flow into the transfer tank 2 for cooling treatment;
s23, injecting the catholyte subjected to temperature reduction treatment in the transit tank 2 into an anode electrolytic tank 4;
s24, part of the anolyte in the anode electrolytic tank 4 flows into the circulating rotary cylinder 5 to obtain the exported anolyte.
In the above step S21, the high copper etching solution (high copper chloride etching waste solution) can be quantitatively injected by the liquid inlet pump 8, so as to increase the copper ion concentration in the catholyte, and lower the temperature of the catholyte to make the catholyte more uniform.
In the step S22, the catholyte in the cathode electrolytic cell 1 flows out at a high level, and can directly flow into the transit trough 2 for cooling treatment, so as to reduce energy loss, wherein the cooling treatment can be performed by water temperature heat transfer, the transit trough 2 is provided with cooling fins to realize cooling by using a single cooling mode such as wind energy cooling, and the like, or can be a combined cooling mode combining multiple cooling modes to realize cooling.
In step S23, the catholyte after the temperature reduction process in the transfer tank 2 is pumped into the anolyte tank 4 by a pump when necessary, for example, the anolyte in the circulating rotary cylinder 5 is detected, so that the concentration of copper ions in the anolyte is controlled not to be too high.
In step S24, the anolyte in the anolyte tank 4 directly flows out to the circulation transfer cylinder 5 at a high level to obtain the derived anolyte, so that energy loss can be reduced.
It should be noted that, in some embodiments, the steps S22 and S24 may be continuously performed at all times, and the steps S21 and S23 may be programmed to be performed appropriately, for example, when the catholyte temperature in the catholyte tank 1 is judged to be too high or the quantity of the catholyte in the transfer tank 2 is judged to be too low, the step S21 is triggered, and when the anolyte temperature in the anolyte tank 4 is judged to be too high or the anolyte in the transfer cylinder 5 is too low and the anolyte discharge is not performed, the step S23 is triggered.
Further, before the step S3 of detecting the copper ion concentration of the derived anolyte, the method includes:
z1, detecting whether the volume of liquid in the rotary cylinder 5 in the circulation reaches a preset value;
and Z2, if so, entering a step S3 of detecting the concentration of the copper ions of the derived anolyte.
In the above steps Z1 to Z2, it is determined whether the volume of the liquid in the circulating rotary cylinder 5 reaches a preset value by detecting whether the upper surface of the anolyte reaches a set height, and when the upper surface of the anolyte reaches the set height, it is determined that the volume of the liquid in the circulating rotary cylinder 5 reaches the preset value.
Further, the step S4 of recovering the derived anolyte includes:
s41, opening the cut-off device 9 to enable the anolyte flowing out of the anode electrolytic tank 4 to flow into the standby cavity;
s42, pumping the guided anolyte out of the circulating transfer cylinder 5 into a set container;
and S43, after the extraction action is finished, closing the cut-off device 9 to enable the anolyte in the standby cavity to flow into the circulating transfer cylinder 5.
In the above steps S41 to S43, in general, the anolyte flowing out from the anode electrolytic cell 4 at a high level flows into the circulating transfer cylinder 5, and flows into the backup cavity buffer under the intervention of the cut-off device 9, so as to prevent the anolyte flowing in subsequently from affecting the copper ion concentration of the anolyte in the circulating transfer cylinder 5, when the derived anolyte is pumped out from the circulating transfer cylinder 5 into the set container, the cut-off device 9 is closed to make the anolyte in the backup cavity flow into the circulating transfer cylinder 5, and in some embodiments, a set amount of anolyte, for example, one hundred liters, is led out from the circulating transfer cylinder 5 every time; in some embodiments, the entire anolyte is drawn out of the transfer cylinder 5 each time, and the anolyte is recovered to the maximum extent and is blended into the copper plate etchant.
Further, a part of the catholyte flows into the relay tank 2 to be cooled in step S22, and the temperature of the catholyte in the relay tank 2 is reduced to below 50 ℃. The phenomenon that the temperature of the cathode liquid in the transit tank 2 is too high and the good cooling effect cannot be achieved is avoided.
Referring to fig. 2, the invention also discloses a device for recycling the copper chloride hydrochloride etching waste liquid, which is applied to the method for recycling the copper chloride hydrochloride etching waste liquid;
the device for recycling the copper chloride hydrochloride etching waste liquid comprises a photovoltaic solar generator 10, a liquid inlet pump 8, a cathode electrolytic tank 1, a transfer tank 2, a cooling device, a transfer pump 3, an anode electrolytic tank 4, a circulating transfer cylinder 5, a circulating pump 6 and a pumping-out pump 7; the cathode electrolytic tank 1 is communicated with the liquid inlet pump 8 and is electrically connected with the photovoltaic solar generator 10; the transit tank 2 is communicated with the cathode electrolytic tank 1; the cooling device is connected with the transit tank 2 and is used for cooling the liquid in the transit tank 2; the transfer pump 3 is communicated with the transfer tank 2; the anode electrolytic tank 4 is communicated with the transfer pump 3 and is electrically connected with the photovoltaic solar generator 10; the circulating rotary cylinder 5 is communicated with the anode electrolytic tank 4; the circulating pump 6 is respectively communicated with the circulating rotary cylinder 5 and the cathode electrolytic tank 1; the suction pump 7 is communicated with the circulation cylinder 5.
Specifically, the photovoltaic solar generator 10 is used for converting solar energy into electric energy, supplying power for an electrolytic reduction reaction, and reducing the power consumption of an enterprise to a power grid; the liquid inlet pump 8 is used for pumping high copper etching liquid in the storage container into the cathode electrolytic tank 1; the anode electrolytic tank 4 and the cathode electrolytic tank 1 are respectively used for storing anode liquid and cathode liquid for electrolytic reduction reaction, and the anode electrolytic tank 4 is communicated with the cathode electrolytic tank 1 and is isolated by a cathode ionic membrane; the high-level flow of the catholyte in the cathode electrolytic tank 1 enters a transit tank 2, the catholyte in the transit tank 2 is cooled under the action of a cooling device and then enters and exits an anode electrolytic tank 4 through a transit pump 3, and the high-level flow of the anolyte in the anode electrolytic tank 4 enters a circulating transit cylinder 5; the anolyte in the circulating rotary cylinder 5 may be pumped into the cathode electrolytic cell 1 by the circulating pump 6, or may be pumped into a predetermined container for preparation by the pump 7 for preparation.
Further, in some embodiments, the apparatus for recycling the waste etching solution of copper chloride hydrochloride further comprises a spare cavity and a cut-off device 9; the standby cavity is communicated with the circulating transfer cylinder 5 through a communication channel, and the bottom of the standby cavity is higher than an outlet of the communication channel at the circulating transfer cylinder 5; the cut-off device 9 comprises a transition groove 91 and a transition groove control mechanism 92, wherein the transition groove control mechanism 92 drives the transition groove 91 to rotate so as to enable the transition groove 91 to be changed between a first parking position and a second parking position; when the transition groove is positioned at the first parking position, the communicating channel is unblocked; when the transition groove is positioned at the second stopping position, the communicating channel is blocked, and the transition groove leads the anolyte flowing out of the anode electrolytic tank 4 into the standby cavity.
Specifically, when the cut-off equipment 9 is opened, the transition groove is in the second parking position, and when the cut-off equipment 9 is closed, the transition groove is in the first parking position; the transition groove control mechanism 92 can be a motor or a combination of a motor and a transmission mechanism, and the photovoltaic solar generator 10 supplies power to drive the transition groove to work.
According to the method and the device for recycling the copper chloride hydrochloric etching waste liquid, the photovoltaic solar generator 10 is used for supplying power to perform an electrolytic reduction reaction, copper ions in the high-copper etching liquid are electrolytically reduced into metal copper, the content of the copper ions is reduced, the recycled anolyte can be used as a copper plate etching agent after being prepared, the copper chloride hydrochloric etching waste liquid is recycled, power is supplied by using solar power generation for electrolysis, the problem that the copper chloride hydrochloric etching waste liquid consumes more power supplied by a power grid and causes higher enterprise energy consumption evaluation due to the fact that the copper chloride hydrochloric etching waste liquid is subjected to outsourcing centralized treatment or an electrolysis recycling method is adopted inside an enterprise is solved.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A method for recycling copper chloride hydrochloride etching waste liquid is characterized by comprising the following steps:
continuously carrying out electrolytic reduction reaction, wherein a photovoltaic solar generator is adopted for supplying power, an anolyte and a catholyte are separated by a cathode ionic membrane, a low-copper etching solution obtained after metal copper is reduced by cathodic electrolysis is taken as the anolyte, and a high-copper etching solution is taken as the catholyte;
continuously circulating the electrolyte, and leading out part of anolyte in the period;
detecting the concentration of copper ions in the derived anolyte;
when the concentration of copper ions in the guided anolyte is within a set concentration threshold range, recovering the guided anolyte;
and when the concentration of the copper ions in the led anolyte is not within a set concentration threshold range, injecting the led anolyte into the catholyte.
2. The method for recycling the copper chloride hydrochloride etching waste liquid according to claim 1, wherein the current density of electrolysis is controlled to be 180-200A/square meter;
the electrolytic voltage is controlled to be 1.5V-2.0V/square meter.
3. The method for recycling the copper chloride hydrochloride etching waste liquid according to claim 2, wherein the current density and voltage of the electrolysis are adjusted along with the positive adjustment of the copper ion concentration of the catholyte.
4. The method for recycling copper chloride hydrochloride etching waste liquid according to claim 1, wherein the set concentration threshold range is 55-65g/L.
5. The method for recycling copper chloride hydrochloride etching waste liquid according to claim 1, wherein the step of continuously circulating the electrolyte comprises:
injecting a set amount of high-copper etching solution into the cathode electrolytic tank through a liquid inlet pump;
part of the catholyte flows into a transfer tank to be subjected to cooling treatment;
injecting the catholyte subjected to temperature reduction treatment in the transit tank into an anode electrolytic tank;
and part of the anolyte in the anode electrolytic cell flows into the circulating middle revolving cylinder to obtain the exported anolyte.
6. The method for recycling a copper chloride hydrochloride etching waste liquid according to claim 5, wherein the step of detecting the concentration of copper ions in the derived anolyte is preceded by:
detecting whether the volume of liquid in the circulating rotary cylinder reaches a preset value;
and if so, entering the step of detecting the concentration of the copper ions of the exported anolyte.
7. The method according to claim 5, wherein the step of recovering the guided anolyte comprises:
starting the cut-off device to enable the anolyte flowing out of the anode electrolytic cell to flow into the standby cavity;
pumping the guided anolyte out of the circulating rotary cylinder into a set container;
and after the extraction action is finished, closing the cut-off device to enable the anolyte in the standby cavity to flow into the circulating rotary cylinder.
8. The method for recycling the copper chloride hydrochloride etching waste liquid according to claim 5, wherein the catholyte flows into a transit tank to be cooled, and the temperature of the catholyte in the transit tank is reduced to below 50 ℃.
9. A device for recycling and reusing a copper chloride hydrochloride etching waste liquid is characterized by being applied to the method for recycling and reusing the copper chloride hydrochloride etching waste liquid according to any one of claims 1 to 8;
the device for recycling the copper chloride hydrochloride etching waste liquid comprises:
a photovoltaic solar generator;
a liquid inlet pump;
the cathode electrolytic tank is communicated with the liquid inlet pump and is electrically connected with the photovoltaic solar generator;
the transfer tank is communicated with the cathode electrolytic tank;
the temperature reduction device is connected with the transfer tank and is used for reducing the temperature of the liquid in the transfer tank;
the transfer pump is communicated with the transfer groove;
the anode electrolytic tank is communicated with the transfer pump and is electrically connected with the photovoltaic solar generator;
the circulating rotary cylinder is communicated with the anode electrolytic tank;
the circulating pump is respectively communicated with the circulating rotary cylinder and the cathode electrolytic tank;
and the extraction pump is communicated with the circulating transfer cylinder.
10. The apparatus for recycling and reusing an etching waste solution of copper chloride hydrochloride according to claim 9, further comprising:
the standby cavity is communicated with the circulating rotary cylinder through a communication channel, and the bottom of the standby cavity is higher than an outlet of the communication channel at the circulating rotary cylinder;
the cut-off device comprises a transition groove and a transition groove control mechanism, wherein the transition groove control mechanism drives the transition groove to rotate so as to enable the transition groove to be changed between a first parking position and a second parking position;
when the transition groove is in the first parking position, the communication channel is unblocked;
when the transition groove is located at the second parking position, the communication channel is blocked, and the transition groove introduces anolyte flowing out of the anode electrolytic cell into the standby cavity.
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