CN114427092A - Regeneration copper extraction method of nitric acid etching solution - Google Patents
Regeneration copper extraction method of nitric acid etching solution Download PDFInfo
- Publication number
- CN114427092A CN114427092A CN202210095991.0A CN202210095991A CN114427092A CN 114427092 A CN114427092 A CN 114427092A CN 202210095991 A CN202210095991 A CN 202210095991A CN 114427092 A CN114427092 A CN 114427092A
- Authority
- CN
- China
- Prior art keywords
- copper
- solution
- electrolysis
- nitric acid
- extraction method
- 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
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 207
- 239000010949 copper Substances 0.000 title claims abstract description 207
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 196
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 53
- 238000005530 etching Methods 0.000 title claims abstract description 51
- 238000000605 extraction Methods 0.000 title claims abstract description 39
- 230000008929 regeneration Effects 0.000 title claims abstract description 30
- 238000011069 regeneration method Methods 0.000 title claims abstract description 30
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 76
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 33
- 238000011084 recovery Methods 0.000 claims abstract description 31
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 29
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical group CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 22
- 238000005341 cation exchange Methods 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 230000001172 regenerating effect Effects 0.000 claims description 8
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- 230000003647 oxidation Effects 0.000 abstract description 17
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 238000000034 method Methods 0.000 description 17
- 239000002699 waste material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 4
- 229940112669 cuprous oxide Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- -1 phenolic aldehyde Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a regeneration copper extraction method of nitric acid etching solution. The regeneration copper extraction method of the nitric acid etching solution comprises the following steps: 1) separating the copper-containing nitric acid etching solution by an ion exchange membrane to obtain a high copper solution and a low copper solution; 2) adding a strong oxidant into the high copper solution, carrying out primary electrolysis, crystallizing copper ions into a copper plate at a cathode after electrifying and electrolysis, and obtaining a copper-containing solution after electrolysis; 3) electrifying the low-copper solution and the copper-containing solution for secondary electrolysis to obtain a solution to be recovered; 4) and adding concentrated nitric acid into the solution to be recovered to obtain the etching solution meeting the recovery standard. According to the regeneration copper extraction method of the nitric acid etching solution, the recovery rate of copper is more than 99%, the purity is more than 99%, and the recovered copper is high in quality by adopting a small amount of strong oxidant, and has no corrosion and oxidation phenomena, so that the high-efficiency recovery of the nitric acid etching solution is realized.
Description
Technical Field
The invention relates to the technical field of copper extraction methods, in particular to a regeneration copper extraction method of nitric acid etching solution.
Background
With the continuous development of society, a large amount of waste can be generated in the production process, so that the production cost can be increased, in the production of the circuit board, a large amount of waste liquid can be generated, but a large amount of metal substances can be contained in the waste liquid, if the metal substances in the waste liquid can not be extracted, the serious waste of the substances can be caused, and through the copper extraction method, the copper substances in the waste liquid can be extracted, so that the production benefit can be increased.
The copper-containing waste nitric acid etching liquid is waste water generated in the electronic industry, and can be generated in the process of deplating or cleaning the waste water of a printed circuit board. With the increasing output of printed circuit boards, copper-containing waste nitric acid etching liquid is increased, the content of copper ions in waste liquid greatly exceeds the national sewage discharge standard, and if the copper ions are directly discharged, the environment is polluted greatly, and the copper has a certain recovery value, so that measures must be taken to treat the copper-containing waste water.
In the prior art, the processes for directly treating the copper-containing waste nitric acid etching solution mainly comprise methods such as an ion exchange method and a chemical precipitation method, wherein the chemical precipitation method is to add caustic soda, lime or sulfide into the etching solution to precipitate copper, but the chemical precipitation method has large dosage of the added medicament and low product purity; the ion exchange method is to separate copper ions from wastewater by using ion exchange resin, but the generated eluent needs to be reprocessed, otherwise, secondary pollution is generated. The two technologies are only used for wastewater treatment, the wastewater treatment is discharged after reaching the standard, and the economic value of the product is high without producing copper plates.
In the actual electrolysis of the waste nitric acid containing copper, how to prevent the occurrence of corrosion copper products and black cuprous oxide is always the key for improving the quality and the yield of the copper products.
CN112708885A discloses a method and a system for recycling copper etching waste nitric acid, relating to the technical field of etching waste liquid treatment. According to the method for recycling the copper-etching waste nitric acid, the concentration of copper ions of the high-copper waste nitric acid which loses the copper etching capacity can be reduced to about 10g/L from 50-70g/L after electrolysis, and the copper is prevented from being corroded and cuprous oxide is prevented from being generated by a strong oxidation agent. The system provided by the invention realizes the recycling of the waste nitric acid and low-cost operation on the basis of ensuring high quality and high yield of the elemental copper product, is a set of resource utilization process system with good environmental protection benefit and economic benefit, but causes certain pollution due to more usage amount of the strong oxidation agent.
Therefore, it is necessary to develop a method for effectively extracting copper, preventing the occurrence of corrosion copper products and black cuprous oxide, improving the quality of copper products and realizing the efficient recovery of nitric acid etching solution.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for regenerating and extracting copper from nitric acid etching solution, the recovery rate of copper is more than 99%, the purity is more than 99%, and the recovered copper has high quality by adopting a small amount of strong oxidant, has no phenomena of corrosion and oxidation, and realizes the high-efficiency recovery of the nitric acid etching solution.
In order to achieve the purpose, the invention adopts the following technical scheme:
a regeneration copper extraction method of nitric acid etching solution comprises the following steps:
1) separating the copper-containing nitric acid etching solution by an ion exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 20-70g/L, and the concentration of copper ions in the low copper solution is less than 10 g/L;
2) adding a strong oxidant into the high copper solution obtained in the step 1), carrying out primary electrolysis, crystallizing copper ions into a copper plate at a cathode after electrifying and electrolysis, and obtaining a copper-containing solution after electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis to obtain a solution to be recovered;
4) adding concentrated nitric acid into the solution to be recovered obtained in the step 3) to obtain the etching solution meeting the recovery standard.
According to the regeneration copper extraction method of the nitric acid etching solution, the high copper solution and the low copper solution are obtained through ion exchange membrane separation, the high copper solution is electrolyzed to extract copper for the first time, a small amount of strong oxidant is added to effectively prevent a corrosion copper product and black cuprous oxide from appearing, the low copper solution is further electrolyzed for the second time to extract copper, the high-efficiency recovery of copper ions is realized, and concentrated nitric acid is added into the solution to be recovered to realize the recycling of the etching solution.
In the step 1), the ion exchange membrane is a strong-acid cation exchange membrane.
The strong acid cation exchange membrane is a phenolic aldehyde series strong acid cation exchange membrane and/or a vinylpyridine series strong acid cation exchange membrane.
In step 2), the volume of the strong oxidant accounts for 0.5-1.5% of the volume of the high copper solution, such as 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, or 1.5%.
The strong oxidant is sodium chlorate.
The concentration of sodium chlorate is 10-20%, for example, sodium chlorate having a sodium chlorate concentration of 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% is obtained after the sodium chlorate is diluted with water.
In step 2), the current of the primary electrolysis is 1000-3000A, for example, the current is 1000A, 1100A, 1200A, 1300A, 1400A, 1500A, 1600A, 1700A, 1800A, 1900A, 2000A, 2100A, 2200A, 2300A, 2400A, 2500A, 2600A, 2700A, 2800A, 2900A or 3000A, and the temperature of the primary electrolysis is 10-25 deg.C, for example, 10 deg.C, 11 deg.C, 12 deg.C, 13 deg.C, 14 deg.C, 15 deg.C, 17 deg.C, 18 deg.C, 19 deg.C, 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C or 25 deg.C.
In step 3), the current of the secondary electrolysis is 2000-4000A, for example, the current is 2000A, 2100A, 2200A, 2300A, 2400A, 2500A, 2600A, 2700A, 2800A, 2900A, 3000A, 3100A, 3200A, 3300A, 3400A, 3500A, 3600A, 3700A, 3800A, 3900A or 4000A, and the temperature of the secondary electrolysis is 10-25 ℃, for example, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃ or 25 ℃.
In step 4), the volume of the concentrated nitric acid accounts for 1-5% of the volume of the solution to be recovered, such as 1%, 2%, 3%, 4%, or 5%.
As a preferable scheme of the invention, the regeneration copper extraction method of the nitric acid etching solution comprises the following steps:
1) separating the copper-containing nitric acid etching solution by using a strong acid cation exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 20-70g/L, and the concentration of copper ions in the low copper solution is less than 10 g/L;
2) adding sodium chlorate with the concentration of 10-20 percent into the high copper solution obtained in the step 1), wherein the volume of the sodium chlorate accounts for 0.5-1.5 percent of the volume of the high copper solution, carrying out primary electrolysis, wherein the current of the primary electrolysis is 3000A, the temperature of the primary electrolysis is 10-25 ℃, copper ions are crystallized into a copper plate at a cathode after the electrolysis by electrifying, and the copper-containing solution is obtained after the electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis, wherein the current of the secondary electrolysis is 2000-4000A, and the temperature of the secondary electrolysis is 10-25 ℃ to obtain a solution to be recovered;
4) adding concentrated nitric acid which accounts for 1-5% of the volume of the liquid to be recovered into the liquid to be recovered obtained in the step 3), and obtaining the etching liquid meeting the recovery standard.
Compared with the prior art, the invention has the beneficial effects that:
according to the regeneration copper extraction method of the nitric acid etching solution, the recovery rate of copper is more than 99%, the purity is more than 99%, and the recovered copper is high in quality by adopting a small amount of strong oxidant, and has no corrosion and oxidation phenomena, so that the high-efficiency recovery of the nitric acid etching solution is realized.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
Example 1
The regeneration copper extraction method of the nitric acid etching solution comprises the following steps:
1) separating the copper-containing nitric acid etching solution by a vinylpyridine strong-acid cation exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 70g/L, and the concentration of copper ions in the low copper solution is 6 g/L;
2) adding 18% sodium chlorate in the volume of 1% of the high copper solution obtained in the step 1), carrying out primary electrolysis at the temperature of 18 ℃ and the current of 1500A, crystallizing copper ions into a copper plate at a cathode after electrifying and electrolysis, and obtaining a copper-containing solution after electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis, wherein the current of the secondary electrolysis is 3500A, and the temperature of the secondary electrolysis is 18 ℃ to obtain a solution to be recovered;
4) adding concentrated nitric acid accounting for 5% of the volume of the liquid to be recovered into the liquid to be recovered obtained in the step 3) to obtain the etching liquid meeting the recovery standard.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.95%, the purity is 99.8%, and the recovered copper has high quality and no corrosion and oxidation phenomena.
Example 2
The regeneration copper extraction method of the nitric acid etching solution comprises the following steps:
1) separating the copper-containing nitric acid etching solution by a vinylpyridine strong-acid cation exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 60g/L, and the concentration of copper ions in the low copper solution is 5 g/L;
2) adding sodium chlorate with the concentration of 15 percent into the high copper solution obtained in the step 1), wherein the volume of the sodium chlorate accounts for 1.2 percent of the volume of the high copper solution, carrying out primary electrolysis, wherein the current of the primary electrolysis is 1600A, the temperature of the primary electrolysis is 18 ℃, copper ions are crystallized into a copper plate at a cathode after electrifying and electrolysis, and obtaining the copper-containing solution after electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis, wherein the current of the secondary electrolysis is 2500A, and the temperature of the secondary electrolysis is 18 ℃, so as to obtain a solution to be recovered;
4) adding concentrated nitric acid accounting for 4% of the volume of the liquid to be recovered into the liquid to be recovered obtained in the step 3) to obtain the etching liquid meeting the recovery standard.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.94%, the purity is 99.6%, and the recovered copper has high quality and no corrosion and oxidation phenomena.
Example 3
The regeneration copper extraction method of the nitric acid etching solution comprises the following steps:
1) separating the copper-containing nitric acid etching solution by a phenolic strongly acidic cation exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 50g/L, and the concentration of copper ions in the low copper solution is 4 g/L;
2) adding 13% sodium chlorate in the volume of 0.8% of the high copper solution into the high copper solution obtained in the step 1), carrying out primary electrolysis at the current of 1500A and the temperature of 18 ℃ to crystallize copper ions into a copper plate at a cathode after electrifying and electrolysis, and obtaining the copper-containing solution after electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis, wherein the current of the secondary electrolysis is 2400A, and the temperature of the secondary electrolysis is 18 ℃, so as to obtain a solution to be recovered;
4) adding concentrated nitric acid which accounts for 3% of the volume of the liquid to be recovered into the liquid to be recovered obtained in the step 3), and obtaining the etching liquid meeting the recovery standard.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.954%, the purity is 99.6%, and the recovered copper has high quality and no corrosion and oxidation phenomena.
Example 4
The regeneration copper extraction method of the nitric acid etching solution comprises the following steps:
1) separating the copper-containing nitric acid etching solution by a vinylpyridine strong-acid cation exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 30g/L, and the concentration of copper ions in the low copper solution is 3 g/L;
2) adding sodium chlorate with the concentration of 11 percent into the high copper solution obtained in the step 1), wherein the volume of the sodium chlorate accounts for 0.6 percent of the volume of the high copper solution, carrying out primary electrolysis, wherein the current of the primary electrolysis is 1500A, the temperature of the primary electrolysis is 20 ℃, copper ions are crystallized into a copper plate at a cathode after electrifying and electrolysis, and obtaining the copper-containing solution after electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis, wherein the current of the secondary electrolysis is 2800A, and the temperature of the secondary electrolysis is 20 ℃, so as to obtain a solution to be recovered;
4) adding concentrated nitric acid which accounts for 3% of the volume of the liquid to be recovered into the liquid to be recovered obtained in the step 3), and obtaining the etching liquid meeting the recovery standard.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.96%, the purity is 99.7%, and the recovered copper has high quality and no corrosion and oxidation phenomena.
Example 5
The regeneration copper extraction method of the nitric acid etching solution comprises the following steps:
1) separating the copper-containing nitric acid etching solution by a phenolic aldehyde strong-acid cation exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 25g/L, and the concentration of copper ions in the low copper solution is 2 g/L;
2) adding sodium chlorate with the concentration of 10 percent into the high copper solution obtained in the step 1), wherein the volume of the sodium chlorate accounts for 0.6 percent of the volume of the high copper solution, carrying out primary electrolysis, wherein the current of the primary electrolysis is 1300A, the temperature of the primary electrolysis is 15 ℃, copper ions are crystallized into a copper plate at a cathode after electrifying and electrolysis, and obtaining the copper-containing solution after electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis, wherein the current of the secondary electrolysis is 2200A, and the temperature of the secondary electrolysis is 15 ℃, so as to obtain a solution to be recovered;
4) adding concentrated nitric acid accounting for 1% of the volume of the liquid to be recovered into the liquid to be recovered obtained in the step 3) to obtain the etching liquid meeting the recovery standard.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.97%, the purity is 99.8%, and the recovered copper has high quality and no corrosion and oxidation phenomena.
Example 6
This example is different from example 1 in that the ion exchange membrane is a sodium sulfonate type cation exchange membrane, and the other examples are the same as example 1.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.8%, the purity is 99.1%, and the recovered copper has high quality and no corrosion and oxidation phenomena.
Example 7
This example is different from example 1 in that the sodium chlorate concentration was 5%, and the other examples were the same as example 1.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.6%, the purity is 99.1%, and the recovered copper has high quality and no corrosion and oxidation phenomena.
Example 8
This example is different from example 1 in that the concentration of sodium chlorate was 30%, and the other examples were the same as example 1.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.1%, the purity is 99%, the quality of the recovered copper is high, and the phenomena of corrosion and oxidation are avoided, but the purification of the copper is influenced by the hypochlorous acid with too high concentration.
Example 9
This example differs from example 1 in that the volume of sodium chlorate represents 0.1% of the volume of the high copper solution, and is otherwise the same as example 1.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.2%, the purity is 99.1%, and the recovered copper has high quality and has no corrosion and oxidation phenomena.
Example 10
This example differs from example 1 in that the volume of sodium chlorate represents 2% of the volume of the high copper solution, and is otherwise the same as example 1.
By adopting the regeneration copper extraction method of the embodiment, the recovery rate of copper reaches 99.2%, the purity is 99.1%, and the recovered copper has high quality and no corrosion and oxidation phenomena, but the purification of copper is influenced by much hypochlorous acid.
Comparative example 1
This comparative example differs from example 1 in that the oxidizing agent was not enhanced in step 2), and is otherwise the same as example 1.
By adopting the regeneration copper extraction method of the comparative example, the copper recovery rate reaches 98.3%, the purity is 99.3%, and the recovered copper has the phenomena of corrosion and oxidation blackening.
Comparative example 2
The comparative example differs from example 1 in that the copper-containing nitric acid etching solution was directly subjected to electrolysis under conditions of an electrolysis current of 3000A and an electrolysis temperature of 18 ℃.
By adopting the regeneration copper extraction method of the comparative example, the copper recovery rate reaches 95.9%, the purity is 97.5%, and the recovered copper has the phenomena of corrosion and oxidation blackening.
The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A regeneration copper extraction method of nitric acid etching solution is characterized by comprising the following steps:
1) separating the copper-containing nitric acid etching solution by an ion exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 20-70g/L, and the concentration of copper ions in the low copper solution is less than 10 g/L;
2) adding a strong oxidant into the high copper solution obtained in the step 1), carrying out primary electrolysis, crystallizing copper ions into a copper plate at a cathode after electrifying and electrolysis, and obtaining a copper-containing solution after electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis to obtain a solution to be recovered;
4) adding concentrated nitric acid into the solution to be recovered obtained in the step 3) to obtain the etching solution meeting the recovery standard.
2. The regeneration copper extraction method according to claim 1, wherein in step 1), the ion exchange membrane is a strong acid cation exchange membrane.
3. The regeneration copper extraction method according to claim 2, wherein the strong acid cation exchange membrane is a phenolic strongly acid cation exchange membrane and/or a vinylpyridine strongly acid cation exchange membrane.
4. The regenerative copper extraction process according to any one of claims 1 to 3, characterized in that in step 2), the volume of the strong oxidant is 0.5 to 1.5% of the volume of the high copper solution.
5. The regenerative copper extraction method according to any one of claims 1 to 4, wherein the strong oxidant is sodium chlorate.
6. The regenerative copper extraction method of claim 5, wherein the concentration of sodium chlorate is 10-20%.
7. The regenerative copper extraction method as claimed in one of claims 1 to 6, wherein the current of the primary electrolysis in step 2) is 1000-3000A, and the temperature of the primary electrolysis is 10-25 ℃.
8. The regenerative copper extraction method as claimed in one of claims 1 to 7, wherein the current of the secondary electrolysis in step 3) is 2000-4000A, and the temperature of the secondary electrolysis is 10-25 ℃.
9. The regenerative copper extraction method according to any one of claims 1 to 8, characterized in that in step 4), the volume of the concentrated nitric acid is 1 to 5% of the volume of the solution to be recovered.
10. The regenerative copper extraction method according to one of claims 1 to 9, characterized by comprising the steps of:
1) separating the copper-containing nitric acid etching solution by using a strong acid cation exchange membrane to obtain a high copper solution and a low copper solution, wherein the concentration of copper ions in the high copper solution is 20-70g/L, and the concentration of copper ions in the low copper solution is less than 10 g/L;
2) adding 10-20% sodium chlorate with the volume accounting for 0.5-1.5% of the volume of the high copper solution into the high copper solution obtained in the step 1), carrying out primary electrolysis with the current of 1000-3000A, the temperature of the primary electrolysis being 10-25 ℃, crystallizing copper ions into a copper plate at a cathode after electrifying and electrolysis, and obtaining a copper-containing solution after electrolysis;
3) electrifying the low-copper solution obtained in the step 1) and the copper-containing solution obtained in the step 2) for secondary electrolysis, wherein the current of the secondary electrolysis is 2000-4000A, and the temperature of the secondary electrolysis is 10-25 ℃ to obtain a solution to be recovered;
4) adding concentrated nitric acid which accounts for 1-5% of the volume of the liquid to be recovered into the liquid to be recovered obtained in the step 3) to obtain the etching liquid meeting the recovery standard.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210095991.0A CN114427092A (en) | 2022-01-26 | 2022-01-26 | Regeneration copper extraction method of nitric acid etching solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210095991.0A CN114427092A (en) | 2022-01-26 | 2022-01-26 | Regeneration copper extraction method of nitric acid etching solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114427092A true CN114427092A (en) | 2022-05-03 |
Family
ID=81313118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210095991.0A Pending CN114427092A (en) | 2022-01-26 | 2022-01-26 | Regeneration copper extraction method of nitric acid etching solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114427092A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112647096A (en) * | 2020-12-01 | 2021-04-13 | 苏州美源达环保科技股份有限公司 | Method for recovering copper ions in acidic etching solution |
| CN112708885A (en) * | 2020-12-16 | 2021-04-27 | 华润环保发展有限公司 | Recycling method and system for copper-etching waste nitric acid |
-
2022
- 2022-01-26 CN CN202210095991.0A patent/CN114427092A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112647096A (en) * | 2020-12-01 | 2021-04-13 | 苏州美源达环保科技股份有限公司 | Method for recovering copper ions in acidic etching solution |
| CN112708885A (en) * | 2020-12-16 | 2021-04-27 | 华润环保发展有限公司 | Recycling method and system for copper-etching waste nitric acid |
Non-Patent Citations (1)
| Title |
|---|
| 马兴冠等: "《辽河流域水环境突发污染事故应急处理技术与管理体系》", vol. 1, 辽宁科学技术出版社, pages: 75 - 77 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100240470B1 (en) | Retrieving and recycling method for sn plating solution | |
| EP2397444B1 (en) | Method and facility for processing waste water containing fluorine and silicon | |
| CN1904142B (en) | Copper extraction method of etching waste liquid or low copper containing waste liquid | |
| WO2016206418A1 (en) | Recycling and reusing process for spent tin stripper solution | |
| CN103510107B (en) | A kind of method reclaiming copper from brown oxide waste liquid | |
| CN100473617C (en) | Treatment method for recycling zinc electrolysis washing wastewater | |
| CN109868476B (en) | Method for recycling etching liquid containing copper ions and nitrate radicals | |
| CN112981428B (en) | Method for stepwise extracting hydroxide from multi-ion mixed solution | |
| CN103755082A (en) | System and method for resource recovery of regenerated wastewater of ion exchange resin | |
| CN102295321A (en) | Method for treating acid copper-containing waste liquor of printed-circuit board and producing electrolytic copper | |
| CN111573640A (en) | Method and system for producing high-purity nitric acid by recovering fluorine-containing dilute nitric acid waste liquid | |
| KR20100008783A (en) | Method for the treatment and reuse of a stripper solution | |
| CN108249649B (en) | Chemical copper plating waste liquid resource utilization method | |
| CN111591967A (en) | Recovery processing method of phosphoric acid waste acid | |
| CN107540142B (en) | Combined treatment process and method for high-salt-content reclaimed water in lead-zinc smelting | |
| CN114427092A (en) | Regeneration copper extraction method of nitric acid etching solution | |
| US20110293506A1 (en) | Method for processing waste water containing fluorine and silicon, method for producing calcium fluoride, and facility for processing fluorine-containing waste water | |
| US6936177B2 (en) | Method for removing metal from wastewater | |
| CN112299615A (en) | Device and method for recycling nickel-containing wastewater resources | |
| CN112794510A (en) | Method for harmlessly treating low-concentration manganese-containing ammonia-nitrogen wastewater in electrolytic manganese industry | |
| CN203768157U (en) | Ion exchange resin regenerated waste water resource recycling system | |
| JPH07112559B2 (en) | Method for treating alkaline fluoride waste liquid containing metal ions and oils | |
| CN114317969A (en) | Method for recycling tin and copper from PCB tin waste liquid in recycling mode | |
| CN107253781B (en) | Method for recycling acidic copper-containing 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 |