CN114016034A - Recycling treatment method of etching waste liquid mixed acid - Google Patents
Recycling treatment method of etching waste liquid mixed acid Download PDFInfo
- Publication number
- CN114016034A CN114016034A CN202111300149.8A CN202111300149A CN114016034A CN 114016034 A CN114016034 A CN 114016034A CN 202111300149 A CN202111300149 A CN 202111300149A CN 114016034 A CN114016034 A CN 114016034A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- etching
- copper
- mixed acid
- nickel
- 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
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 189
- 239000002699 waste material Substances 0.000 title claims abstract description 180
- 238000005530 etching Methods 0.000 title claims abstract description 83
- 239000002253 acid Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000460 chlorine Substances 0.000 claims abstract description 39
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 39
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 52
- 229910001431 copper ion Inorganic materials 0.000 claims description 52
- 210000003298 dental enamel Anatomy 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- 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
-
- 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)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses a recycling treatment method of etching waste liquid mixed acid, which comprises the following steps: s1: filtering the mixed acid etching waste liquid; s2: carrying out electrolytic treatment on the mixed acid etching waste liquid; s3: collecting and treating chlorine generated by electrolysis; s4: processing and separating nickel ions; s5: the waste liquid is subjected to concentration pretreatment, copper simple substances and chlorine are formed by electrolyzing the waste etching liquid, the copper in the waste etching liquid is extracted for recycling, the mixed liquid generated by the reaction of the chlorine and alkali liquor can be used as an oxidant required to be added in the production of the original etching liquid, nickel ions in the waste liquid II are precipitated by adding a nickel ion precipitator oxalate, the nickel is separated, and the waste liquid IV after the concentration treatment can be reused on an etching line.
Description
Technical Field
The invention relates to the technical field of etching waste liquid treatment, in particular to a recycling treatment method of etching waste liquid mixed acid.
Background
The acid etching is widely applied in printed circuit, electronic and metal finishing industries, and mainly comprises three types of ferric trichloride etching liquid, sulfuric acid/hydrogen peroxide system etching liquid and acid copper chloride etching liquid, wherein the acid copper chloride system etching liquid is the most widely used etching liquid at present, is suitable for etching inner layers of circuit boards and outer layers of positive wafer methods, and the amount of waste liquid generated by the acid etching of the printed boards is greatly increased along with the increase of the yield of highly refined circuits and high-layer printed boards.
The main raw materials of the acidic etching solution comprise ammonium chloride, hydrochloric acid and copper chloride, have strong oxidizing property, and can perform oxidation-reduction reaction with the copper plate and the nickel plate, so that the copper plate and the nickel plate are dissolved, and the copper plate and the nickel plate are etched. The small-size circuit board mill not only can utilize the etching line to etch the copper, but also can be used for the etching of a small amount of nickel boards, like this, there are a large amount of copper ions and a small amount of nickel ions in the etching waste liquid, however, the etching waste liquid that contains copper ions and nickel ions, current processing mode is all direct outsourcing as the waste liquid treatment, does not realize the used repeatedly of etching waste liquid, is unfavorable for energy-concerving and environment-protective simultaneously.
Disclosure of Invention
The invention aims to provide a method for recycling and treating mixed acid of etching waste liquid, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for recycling and reusing etching waste liquid mixed acid comprises the following steps:
s1: filtering the mixed acid etching waste liquid;
s2: carrying out electrolytic treatment on the mixed acid etching waste liquid;
s3: collecting and treating chlorine generated by electrolysis;
s4: processing and separating nickel ions;
s5: and carrying out concentration pretreatment on the waste liquid.
As a further scheme of the invention: in S1, the mixed acid etching waste liquid is filtered through a filter, large solid impurities in the waste liquid are filtered, it is guaranteed that no macroscopic solid impurities exist in the waste liquid, and the filtered waste liquid I is obtained.
As a still further scheme of the invention: and S2, conveying the filtered waste liquid I to a collecting tank for collection, then carrying out electrolysis treatment, conveying the waste liquid I to a membrane electrolytic cell, carrying out electrolysis reaction on the waste liquid I in a cathode chamber and an anode chamber of the membrane electrolytic cell, reducing and converting a large amount of copper ions in the waste liquid I into copper in the cathode chamber, and generating chlorine in the anode chamber.
As a still further scheme of the invention: in the step S3, chlorine generated by electrolysis in the anode chamber is absorbed by chlorine absorption equipment, the absorbed chlorine is introduced into alkali liquor, the temperature of the alkali liquor is controlled to be 40-70 ℃, the introduced chlorine reacts with the alkali liquor to generate a mixed solution which can replace an oxidant added in the original etching production, so that copper ions in the etching waste liquid can be effectively electrolyzed and converted into copper, and the converted copper is precipitated at the bottom of the tank.
As a still further scheme of the invention: in S4, copper is precipitated at the bottom of a cathode chamber of the membrane electrolytic cell, the upper layer of waste liquid without copper ions is extracted and placed in a collecting tank I, copper ions in the waste liquid are separated, at the moment, waste liquid II without copper ions is formed, only a small amount of nickel ions are contained in the waste liquid II, a nickel ion precipitator is added into the collecting tank I and is oxalate, the nickel ions in the waste liquid II are precipitated for 6-8 hours, the nickel ions in the waste liquid II are precipitated at the bottom of the collecting tank I, the waste liquid above the precipitated nickel in the collecting tank I is extracted and conveyed to the collecting tank II, and at the moment, waste liquid III which is located in the collecting tank II and is removed with the copper ions and the nickel ions is obtained.
As a still further scheme of the invention: in the step S5, the waste liquid III from which copper ions and nickel ions are removed is conveyed to an enamel kettle and is heated and concentrated, water begins to evaporate when the temperature in the enamel kettle reaches above 90 ℃, the temperature of the enamel kettle is gradually raised according to the distillation speed, the final heating temperature in the enamel kettle is controlled at 140-.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the etching waste liquid is electrolyzed to form a copper simple substance and chlorine gas, so that copper in the etching waste liquid is extracted for recycling, the mixed liquid generated by the reaction of the chlorine gas and alkali liquor can be used as an oxidant required to be added in the production of the original etching liquid, nickel ions in the waste liquid II are precipitated by adding a nickel ion precipitator oxalate, so that nickel is separated, and the concentrated waste liquid IV can be reused on an etching line.
Drawings
FIG. 1 is a method step diagram of a recycling treatment method of etching waste liquid mixed acid.
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.
Referring to fig. 1, in an embodiment of the present invention, a method for recycling and reusing mixed acid from etching waste liquid includes the following steps:
s1: filtering the mixed acid etching waste liquid;
s2: carrying out electrolytic treatment on the mixed acid etching waste liquid;
s3: collecting and treating chlorine generated by electrolysis;
s4: separating nickel ions;
s5: and carrying out concentration pretreatment on the waste liquid.
In S1, the mixed acid etching waste liquid is filtered through a filter, large solid impurities in the waste liquid are filtered, it is guaranteed that no macroscopic solid impurities exist in the waste liquid, and the filtered waste liquid I is obtained.
And S2, conveying the filtered waste liquid I to a collecting tank for collection, then carrying out electrolysis treatment, conveying the waste liquid I to a membrane electrolytic cell, carrying out electrolysis reaction on the waste liquid I in a cathode chamber and an anode chamber of the membrane electrolytic cell, reducing and converting a large amount of copper ions in the waste liquid I into copper in the cathode chamber, and generating chlorine in the anode chamber.
In S3, chlorine generated by electrolysis of the anode chamber is absorbed by chlorine absorption equipment, the absorbed chlorine is introduced into alkali liquor, the temperature of the alkali liquor is controlled to be 40-70 ℃, the introduced chlorine reacts with the alkali liquor to generate a mixed solution which can replace an oxidant required to be added in the original etching production, the current density of the membrane electrolysis cell is adjusted to be 200A/square meter to 250A/square meter, so that copper ions in the etching waste liquid can be effectively electrolyzed and converted into copper, the converted copper is deposited at the bottom of the cell, because the reducibility of the copper ions is higher than that of the nickel ions, the current density is adjusted to 200A/square meter to 250A/square meter, so that the copper ions in the mixed acid etching waste liquid are effectively reduced by electrolysis, and simultaneously, the nickel ions in the mixed acid etching waste liquid are prevented from being reduced, and the purity of the precipitated copper is ensured.
In S4, copper is precipitated at the bottom of a cathode chamber of the membrane electrolytic cell, the upper layer of waste liquid without copper ions is extracted and placed in a collecting tank I, copper ions in the waste liquid are separated, at the moment, waste liquid II without copper ions is formed, only a small amount of nickel ions are contained in the waste liquid II, a nickel ion precipitator is added into the collecting tank I and is oxalate, the nickel ions in the waste liquid II are precipitated for 6-8 hours, the nickel ions in the waste liquid II are precipitated at the bottom of the collecting tank I, the waste liquid above the precipitated nickel in the collecting tank I is extracted and conveyed to the collecting tank II, and at the moment, waste liquid III which is located in the collecting tank II and is removed with the copper ions and the nickel ions is obtained.
In the step S5, the waste liquid III from which copper ions and nickel ions are removed is conveyed to an enamel kettle and is heated and concentrated, water begins to evaporate when the temperature in the enamel kettle reaches above 90 ℃, the temperature of the enamel kettle is gradually raised according to the distillation speed, the final heating temperature in the enamel kettle is controlled at 140-.
Example 1
A method for recycling and reusing etching waste liquid mixed acid comprises the following steps:
s1: filtering the mixed acid etching waste liquid;
s2: carrying out electrolytic treatment on the mixed acid etching waste liquid;
s3: collecting and treating chlorine generated by electrolysis;
s4: separating nickel ions;
s5: and carrying out concentration pretreatment on the waste liquid.
In S1, the mixed acid etching waste liquid is filtered through a filter, large solid impurities in the waste liquid are filtered, it is guaranteed that no macroscopic solid impurities exist in the waste liquid, and the filtered waste liquid I is obtained.
And S2, conveying the filtered waste liquid I to a collecting tank for collection, then carrying out electrolysis treatment, conveying the waste liquid I to a membrane electrolytic cell, carrying out electrolysis reaction on the waste liquid I in a cathode chamber and an anode chamber of the membrane electrolytic cell, reducing and converting a large amount of copper ions in the waste liquid I into copper in the cathode chamber, and generating chlorine in the anode chamber.
In the step S3, chlorine generated by electrolysis of the anode chamber is absorbed by chlorine absorption equipment, the absorbed chlorine is introduced into alkali liquor, the temperature of the alkali liquor is controlled at 40 ℃, the introduced chlorine reacts with the alkali liquor to generate a mixed solution which can replace an oxidant added in the original etching production, the current density of the membrane electrolysis cell is adjusted to 200A/square meter, so that copper ions in the etching waste liquid can be effectively electrolyzed and converted into copper, and the converted copper is precipitated at the bottom of the cell, because the reducibility of the copper ions is higher than that of the nickel ions, and the current density is adjusted to 200A/square meter, so that the copper ions in the mixed acid etching waste liquid are effectively reduced by electrolysis, the nickel ions in the mixed acid etching waste liquid are prevented from being reduced, and the purity of the precipitated copper is ensured.
In S4, the copper deposits in membrane electrolytic cell' S cathode chamber bottom, take out the upper strata waste liquid that does not contain copper ion, and place in collecting vat I, the copper ion separation in the waste liquid is realized, waste liquid II that does not contain copper ion has been formed this moment, and only contain a small amount of nickel ion in the waste liquid II, through adding nickel ion precipitant to collecting vat I, the nickel ion precipitant is the oxalate, precipitate the nickel ion in waste liquid II for 6 hours, make the nickel ion in waste liquid II precipitate in collecting vat I bottom, take out the waste liquid of the nickel top of sediment in the collecting vat I, and carry to collecting vat II, obtain the waste liquid III that has got rid of copper ion and nickel ion in being located collecting vat II this moment.
And S5, conveying the waste liquid III from which the copper ions and the nickel ions are removed into an enamel kettle, heating and concentrating, evaporating water when the temperature in the enamel kettle reaches above 90 ℃, gradually increasing the temperature of the enamel kettle according to the distillation speed, controlling the final heating temperature in the enamel kettle to be 140 ℃, collecting and cooling the evaporated water vapor, collecting the collected cooling water for reuse, obtaining concentrated waste liquid IV, collecting the obtained waste liquid IV, and reusing the obtained waste liquid IV on an etching line when the waste liquid III is required to be used.
Example 2
A method for recycling and reusing etching waste liquid mixed acid comprises the following steps:
s1: filtering the mixed acid etching waste liquid;
s2: carrying out electrolytic treatment on the mixed acid etching waste liquid;
s3: collecting and treating chlorine generated by electrolysis;
s4: separating nickel ions;
s5: and carrying out concentration pretreatment on the waste liquid.
In S1, the mixed acid etching waste liquid is filtered through a filter, large solid impurities in the waste liquid are filtered, it is guaranteed that no macroscopic solid impurities exist in the waste liquid, and the filtered waste liquid I is obtained.
And S2, conveying the filtered waste liquid I to a collecting tank for collection, then carrying out electrolysis treatment, conveying the waste liquid I to a membrane electrolytic cell, carrying out electrolysis reaction on the waste liquid I in a cathode chamber and an anode chamber of the membrane electrolytic cell, reducing and converting a large amount of copper ions in the waste liquid I into copper in the cathode chamber, and generating chlorine in the anode chamber.
In the step S3, chlorine generated by electrolysis of the anode chamber is absorbed by chlorine absorption equipment, the absorbed chlorine is introduced into alkali liquor, the temperature of the alkali liquor is controlled to be 55 ℃, the introduced chlorine reacts with the alkali liquor to generate a mixed solution which can replace an oxidant added in the original etching production, the current density of the membrane electrolysis cell is adjusted to 225A/square meter, so that copper ions in the etching waste liquid can be effectively electrolyzed and converted into copper, the converted copper is precipitated at the bottom of the cell, and the current density is adjusted to 225A/square meter because the reducibility of the copper ions is higher than that of the nickel ions, so that the reduction of the nickel ions in the mixed acid etching waste liquid is prevented while the copper ions in the mixed acid etching waste liquid are effectively reduced by electrolysis, and the purity of the precipitated copper is ensured.
In S4, the copper deposits in membrane electrolytic cell' S cathode chamber bottom, take out the upper strata waste liquid that does not contain copper ion, and place in collecting vat I, the copper ion separation in the waste liquid is realized, waste liquid II that does not contain copper ion has been formed this moment, and only contain a small amount of nickel ion in the waste liquid II, through adding nickel ion precipitant to collecting vat I, the nickel ion precipitant is the oxalate, precipitate the nickel ion in waste liquid II for 7 hours, make the nickel ion in waste liquid II precipitate in collecting vat I bottom, take out the waste liquid of the nickel top of sediment in the collecting vat I, and carry to collecting vat II, obtain the waste liquid III that has got rid of copper ion and nickel ion in being located collecting vat II this moment.
And S5, conveying the waste liquid III from which the copper ions and the nickel ions are removed into an enamel kettle, heating and concentrating, evaporating water when the temperature in the enamel kettle reaches above 90 ℃, gradually increasing the temperature of the enamel kettle according to the distillation speed, controlling the final heating temperature in the enamel kettle to be 150 ℃, collecting and cooling the evaporated water vapor, collecting the collected cooling water for reuse to obtain concentrated waste liquid IV, collecting the obtained waste liquid IV, and reusing the obtained waste liquid IV on an etching line when the waste liquid III is required to be used.
Example 3
A method for recycling and reusing etching waste liquid mixed acid comprises the following steps:
s1: filtering the mixed acid etching waste liquid;
s2: carrying out electrolytic treatment on the mixed acid etching waste liquid;
s3: collecting and treating chlorine generated by electrolysis;
s4: separating nickel ions;
s5: and carrying out concentration pretreatment on the waste liquid.
In S1, the mixed acid etching waste liquid is filtered through a filter, large solid impurities in the waste liquid are filtered, it is guaranteed that no macroscopic solid impurities exist in the waste liquid, and the filtered waste liquid I is obtained.
And S2, conveying the filtered waste liquid I to a collecting tank for collection, then carrying out electrolysis treatment, conveying the waste liquid I to a membrane electrolytic cell, carrying out electrolysis reaction on the waste liquid I in a cathode chamber and an anode chamber of the membrane electrolytic cell, reducing and converting a large amount of copper ions in the waste liquid I into copper in the cathode chamber, and generating chlorine in the anode chamber.
In the step S3, chlorine generated by electrolysis of the anode chamber is absorbed by chlorine absorption equipment, the absorbed chlorine is introduced into alkali liquor, the temperature of the alkali liquor is controlled at 70 ℃, the introduced chlorine reacts with the alkali liquor to generate a mixed solution which can replace an oxidant added in the original etching production, the current density of the membrane electrolysis cell is adjusted to be 250A/square meter, so that copper ions in the etching waste liquid can be effectively electrolyzed and converted into copper, the converted copper is precipitated at the bottom of the cell, and the current density is adjusted to be 200A/square meter to 250A/square meter because the reducibility of the copper ions is higher than that of the nickel ions, so that the copper ions in the mixed acid etching waste liquid are effectively electrolytically reduced, the nickel ions in the mixed acid etching waste liquid are prevented from being reduced, and the purity of the precipitated copper is ensured.
In S4, the copper deposits in membrane electrolytic cell' S cathode chamber bottom, take out the upper strata waste liquid that does not contain copper ion, and place in collecting vat I, the copper ion separation in the waste liquid is realized, waste liquid II that does not contain copper ion has been formed this moment, and only contain a small amount of nickel ion in the waste liquid II, through adding nickel ion precipitant to collecting vat I, the nickel ion precipitant is the oxalate, precipitate the nickel ion in waste liquid II for 8 hours, make the nickel ion in waste liquid II precipitate in collecting vat I bottom, take out the waste liquid of the nickel top of sediment in the collecting vat I, and carry to collecting vat II, obtain the waste liquid III that has got rid of copper ion and nickel ion in being located collecting vat II this moment.
And S5, conveying the waste liquid III from which the copper ions and the nickel ions are removed into an enamel kettle, heating and concentrating, evaporating water when the temperature in the enamel kettle reaches above 90 ℃, gradually increasing the temperature of the enamel kettle according to the distillation speed, controlling the final heating temperature in the enamel kettle to be 160 ℃, collecting and cooling the evaporated water vapor, collecting the collected cooling water for reuse, obtaining concentrated waste liquid IV, collecting the obtained waste liquid IV, and reusing the obtained waste liquid IV on an etching line when the waste liquid III is required to be used.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (6)
1. A recycling treatment method of etching waste liquid mixed acid is characterized in that: the method comprises the following steps:
s1: filtering the mixed acid etching waste liquid;
s2: carrying out electrolytic treatment on the mixed acid etching waste liquid;
s3: collecting and treating chlorine generated by electrolysis;
s4: processing and separating nickel ions;
s5: and carrying out concentration pretreatment on the waste liquid.
2. The method for recycling and treating the etching waste liquid mixed acid according to claim 1, characterized in that: in S1, the mixed acid etching waste liquid is filtered through a filter, large solid impurities in the waste liquid are filtered, it is guaranteed that no macroscopic solid impurities exist in the waste liquid, and the filtered waste liquid I is obtained.
3. The method for recycling and treating the etching waste liquid mixed acid according to claim 1, characterized in that: and S2, conveying the filtered waste liquid I to a collecting tank for collection, then carrying out electrolysis treatment, conveying the waste liquid I to a membrane electrolytic cell, carrying out electrolysis reaction on the waste liquid I in a cathode chamber and an anode chamber of the membrane electrolytic cell, reducing and converting a large amount of copper ions in the waste liquid I into copper in the cathode chamber, and generating chlorine in the anode chamber.
4. The method for recycling and treating the etching waste liquid mixed acid according to claim 1, characterized in that: in the step S3, chlorine generated by electrolysis in the anode chamber is absorbed by chlorine absorption equipment, the absorbed chlorine is introduced into alkali liquor, the temperature of the alkali liquor is controlled to be 40-70 ℃, the introduced chlorine reacts with the alkali liquor to generate a mixed solution which can replace an oxidant added in the original etching production, so that copper ions in the etching waste liquid can be effectively electrolyzed and converted into copper, and the converted copper is precipitated at the bottom of the tank.
5. The method for recycling and treating the etching waste liquid mixed acid according to claim 1, characterized in that: in S4, copper is precipitated at the bottom of a cathode chamber of the membrane electrolytic cell, the upper layer of waste liquid without copper ions is extracted and placed in a collecting tank I, copper ions in the waste liquid are separated, at the moment, waste liquid II without copper ions is formed, only a small amount of nickel ions are contained in the waste liquid II, a nickel ion precipitator is added into the collecting tank I and is oxalate, the nickel ions in the waste liquid II are precipitated for 6-8 hours, the nickel ions in the waste liquid II are precipitated at the bottom of the collecting tank I, the waste liquid above the precipitated nickel in the collecting tank I is extracted and conveyed to the collecting tank II, and at the moment, waste liquid III which is located in the collecting tank II and is removed with the copper ions and the nickel ions is obtained.
6. The method for recycling and treating the etching waste liquid mixed acid according to claim 1, characterized in that: in the step S5, the waste liquid III from which copper ions and nickel ions are removed is conveyed to an enamel kettle and is heated and concentrated, water begins to evaporate when the temperature in the enamel kettle reaches above 90 ℃, the temperature of the enamel kettle is gradually raised according to the distillation speed, the final heating temperature in the enamel kettle is controlled at 140-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111300149.8A CN114016034A (en) | 2021-11-04 | 2021-11-04 | Recycling treatment method of etching waste liquid mixed acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111300149.8A CN114016034A (en) | 2021-11-04 | 2021-11-04 | Recycling treatment method of etching waste liquid mixed acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114016034A true CN114016034A (en) | 2022-02-08 |
Family
ID=80061098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111300149.8A Pending CN114016034A (en) | 2021-11-04 | 2021-11-04 | Recycling treatment method of etching waste liquid mixed acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114016034A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114990339A (en) * | 2022-05-23 | 2022-09-02 | 广东鑫菱环境科技有限公司 | Method for recovering and recycling semiconductor copper alloy etching solution |
| CN115449852A (en) * | 2022-10-26 | 2022-12-09 | 东莞市科佳电路有限公司 | Technical method for self-making electrolytic copper ion recovery from microetching waste liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013176111A1 (en) * | 2012-05-24 | 2013-11-28 | 水ｉｎｇ株式会社 | Processing method and apparatus for copper chloride-containing acidic waste liquids |
| US20170058408A1 (en) * | 2015-08-31 | 2017-03-02 | Yiting YE | Method for electrolytic recycling and regenerating acidic cupric chloride etchants |
| CN106498401A (en) * | 2017-01-06 | 2017-03-15 | 深圳市新锐思环保科技有限公司 | A kind of recoverying and utilizing method of acidic etching waste liquid and recovery and processing system |
| CN110453225A (en) * | 2019-08-29 | 2019-11-15 | 深圳市祺鑫天正环保科技有限公司 | The processing method of acidic etching waste liquid |
-
2021
- 2021-11-04 CN CN202111300149.8A patent/CN114016034A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013176111A1 (en) * | 2012-05-24 | 2013-11-28 | 水ｉｎｇ株式会社 | Processing method and apparatus for copper chloride-containing acidic waste liquids |
| US20170058408A1 (en) * | 2015-08-31 | 2017-03-02 | Yiting YE | Method for electrolytic recycling and regenerating acidic cupric chloride etchants |
| CN106498401A (en) * | 2017-01-06 | 2017-03-15 | 深圳市新锐思环保科技有限公司 | A kind of recoverying and utilizing method of acidic etching waste liquid and recovery and processing system |
| CN110453225A (en) * | 2019-08-29 | 2019-11-15 | 深圳市祺鑫天正环保科技有限公司 | The processing method of acidic etching waste liquid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114990339A (en) * | 2022-05-23 | 2022-09-02 | 广东鑫菱环境科技有限公司 | Method for recovering and recycling semiconductor copper alloy etching solution |
| CN115449852A (en) * | 2022-10-26 | 2022-12-09 | 东莞市科佳电路有限公司 | Technical method for self-making electrolytic copper ion recovery from microetching waste liquid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101768742B (en) | Regenerated acidic etching solution, copper recycling method and special device thereof | |
| CN111560615B (en) | Method for on-line recovery of copper and chlorine from acidic etching waste liquid and regeneration of etching liquid | |
| CN114016034A (en) | Recycling treatment method of etching waste liquid mixed acid | |
| CN101906654B (en) | Method for purifying copper electrolyte with minimal chemical reacting dose | |
| KR100742088B1 (en) | A reusing method of copper nitrate waste water as etching solution and copper ingot by etching process | |
| CN113957459A (en) | Method for producing bromine and caustic soda by electrolyzing sodium bromide through ion membrane | |
| CN106185810B (en) | A kind of joint disposal technique of acidic copper chloride waste etching solution | |
| CN104911596A (en) | Device and method for cyclic regeneration and copper extraction of etching liquid | |
| CN204779821U (en) | Etching solution recycle and regeneration and carry copper device | |
| CN110453225B (en) | Method for treating acidic waste etching solution | |
| CN103936081A (en) | Method and system for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid | |
| CN102912375B (en) | Method and the special purpose device thereof of copper is reclaimed from acidic etching liquid | |
| CN106566927A (en) | Efficient gradient separation recovery process for copper anode slime leachate | |
| CN107012466A (en) | A kind of acidic etching liquid method for recycling and system | |
| CN104726894A (en) | Gallium recycling method | |
| JP2010059502A (en) | Treatment method and device for copper etching waste solution | |
| CN106350678A (en) | Method of recycling corrosion inhibitor and copper from brownification waste liquid | |
| CN108505043A (en) | A kind of method of PCB regenerating waste acidic etching liquids reuse | |
| CN111020633A (en) | Treatment method of acidic etching waste liquid | |
| CN104711636B (en) | Method for processing acidic etching waste solution of printed circuit board | |
| CN111501064A (en) | Production method of 6N copper | |
| CN103290415B (en) | Treatment process and system of acid etching solution | |
| WO2019071642A1 (en) | Method for recovering lead from waste lead-acid battery lead paste in wet process | |
| JP2006176353A (en) | Method for recovering hydrochloric acid and copper from copper etching waste liquid | |
| CN112125449B (en) | Method for treating brownification waste liquid |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220208 |
|
| RJ01 | Rejection of invention patent application after publication |