CN112708885A - Recycling method and system for copper-etching waste nitric acid - Google Patents
Recycling method and system for copper-etching waste nitric acid Download PDFInfo
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 69
- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000005530 etching Methods 0.000 title claims abstract description 52
- 238000004064 recycling Methods 0.000 title claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 147
- 229910052802 copper Inorganic materials 0.000 claims abstract description 134
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000007788 liquid Substances 0.000 claims abstract description 84
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 70
- 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 27
- 239000007800 oxidant agent Substances 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 23
- 210000004027 cell Anatomy 0.000 claims description 23
- 238000001556 precipitation Methods 0.000 claims description 22
- 238000003860 storage Methods 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- 239000011550 stock solution Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 9
- 235000015073 liquid stocks Nutrition 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000003814 drug Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 210000003040 circulating cell Anatomy 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 22
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract description 15
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 9
- 229940112669 cuprous oxide Drugs 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 32
- 229910002651 NO3 Inorganic materials 0.000 description 22
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 101100493710 Caenorhabditis elegans bath-40 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- GIKNHHRFLCDOEU-UHFFFAOYSA-N 4-(2-aminopropyl)phenol Chemical compound CC(N)CC1=CC=C(O)C=C1 GIKNHHRFLCDOEU-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 101150035718 Pno1 gene Proteins 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000008961 swelling Effects 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
-
- 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)
- 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)
- Electrolytic Production Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method and a system for recycling copper etching waste nitric acid, and relates 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 oxidizing agent; the scheme creatively adopts a secondary electrolysis method to realize the recycling of the nitric acid, and the volume expansion of each batch is not concentrated within 5 percent; meanwhile, the copper product produced by electrolysis can be sold. The method can be popularized in the PCB production industry and industrial enterprises which produce the same kind of waste acid in different industries, and has good environmental benefit, social benefit and economic benefit. The system provided by the invention realizes the recycling of the waste nitric acid and the low-cost operation on the basis of ensuring the high quality and high yield of the elemental copper product, and is a set of resource utilization process system with good environmental protection benefit and economic benefit.
Description
Technical Field
The invention relates to the technical field of etching waste liquid treatment, in particular to a method and a system for recycling copper etching waste nitric acid.
Background
In the electroplating process of the microelectronic processing industry, people can use etching liquid to corrode redundant copper foil on a circuit board, copper ions in the etching liquid are increased continuously along with the etching process, and when the content of the copper ions in the etching liquid reaches a certain concentration, the efficiency of the etching liquid for corroding the copper is gradually reduced until the etching liquid loses efficacy, so that the etching liquid becomes etching waste liquid and is discharged. The corresponding etching waste liquid is generated in the processes of cleaning, deoiling, activating, derusting, deplating and the like of a plated part, heavy metal copper ions in the waste liquid have high toxicity, the discharge concentration of copper is lower than 0.5mg/L according to the discharge standard of China, and the copper-containing etching waste acid liquid must be treated as hazardous waste. The main components are shown in the following table 1 (in addition, a small amount of impurity metal mainly containing tin):
table 1:
| copper ion concentration (g/L) | Hydrogen ion concentration (mol/L) | Nitric acid (%) |
| 45-70 | 4.0-5.0 | 20-25 |
The traditional treatment process of the etching solution mainly comprises a chemical precipitation method, an adsorption method, an electrolytic ion exchange method, a redox method, a neutralization method and the like, and the treatment processes have respective advantages and disadvantages. Among them, the application of the electrolytic method is common. At present, the electrolytic refining method is mainly divided into two types, namely sulfuric acid system electrolysis and nitric acid system electrolysis. The electrolysis process of the sulfuric acid system is mature and widely applied to industrial production, but the higher requirement on the purity of copper cannot be met due to the limitation of the sulfuric acid self condition. The electrolysis of the nitric acid system is not limited by sulfuric acid, the solubility of copper nitrate in water is much higher than that of copper sulfate at the temperature of 20 ℃, the nitric acid system can be electrolyzed at normal temperature, heating is not needed, and a large amount of energy is saved. Meanwhile, the requirement of the nitric acid system on the content of electrolytic acid is low, and the pH value is about 1. But the existence of nitrate affects the stability of electrolytic production (the black material Cu is generated from the cathode plate)2O, copper will start to corrode to some extent) and is currently less industrially used.
At present, the resource research of the nitric acid system etching solution is most based on the copper recovery treatment of flat electrolysis, but the research on the rotational flow electrolysis technology at home and abroad is less; in addition, 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, and related researches and patents do not provide effective methods; most researches on the recycling method of the waste nitric acid after electrolysis are simple addition of additives and supplement of concentrated nitric acid, and the recycling efficiency is not high. For example, patent CN205223353U adopts "settling detinning-flat electrolytic copper extraction-chemical addition recycling" process to treat nitric acid type tin-stripping copper-containing waste liquid; patent CN207391170U uses a process of "diffusion dialysis-plate electrolysis for copper extraction".
Disclosure of Invention
The invention aims to solve the technical problem of how to recover the copper simple substance in the nitric acid system etching waste liquid under the condition of high-concentration nitric acid, and simultaneously realize the recycling of the waste nitric acid and the low-cost operation on the basis of ensuring the high quality and high yield of the simple substance copper product.
In order to solve the above problems, the present invention proposes the following technical solutions:
in a first aspect, the invention provides a resource recycling method of copper etching waste nitric acid, which comprises the following steps:
s1, carrying out tin precipitation treatment on the copper nitrate waste liquid stock solution, and reserving supernatant;
s2, taking out the supernatant, adding a strong oxidation agent into the supernatant, and carrying out first electrolysis until the concentration of copper ions in the electrolyte is less than or equal to 10g/L to obtain a low-copper liquid;
s3, collecting the low-copper liquid in the step S2 until the long copper amount of the cathode plate of the electrolytic cell exceeds 15kg in the step S2, and stopping the first electrolysis;
s4, carrying out secondary electrolysis on the low-copper liquid collected in the step S3 in batches until the copper etching capacity of the electrolyte in each batch reaches the standard, and obtaining a liquid to be recycled;
s5, adding concentrated nitric acid with the volume of 5-8% into the solution to be recycled to obtain the etching solution meeting the recycling standard.
The further technical scheme is that the strong oxidation medicament is selected from 50% hydrogen peroxide or mixture of sulfamic acid and 50% hydrogen peroxide.
The further technical scheme is that if the strong oxidation medicament is selected from 50% hydrogen peroxide, the dosage is 2-2.5% V (volume of waste liquid);
if the strong oxidizing agent is selected from the mixture of sulfamic acid and 50% hydrogen peroxide, the dosage of the sulfamic acid is 0.7-1V (volume of waste liquid) 1 kg/L; the amount of hydrogen peroxide is 0.8-1% V (volume of waste liquid).
The method further comprises the following steps between the steps S2 and S3: removing residual strongly oxidizing agent from the low copper liquid.
The further technical scheme is that the residual strong oxidizing agent is removed from the low-copper liquid, and the specific operation is that the low-copper liquid is heated for 2 hours at 50-60 ℃.
The further technical proposal is that the first electrolysis condition is that the temperature of the electrolyte is 16-24 ℃, the current density is 100-200A/m2。
The further technical proposal is that when the concentration of copper ions in the electrolyte is less than 15g/L, the current is denseThe degree is 100-120A/m2。
The further technical proposal is that the current density of the second electrolysis is 380-420A/m2And the temperature of the electrolyte is 16-24 ℃.
In a second aspect, the invention provides a copper etching waste nitric acid recycling and reusing system, which comprises a secondary electrolytic storage tank, a tin precipitation tank, a raw material storage tank, a filter, a circulating tank, an electrolytic tank and a tank to be reused, wherein the tin precipitation tank, the raw material storage tank, the filter, the circulating tank, the electrolytic tank and the tank to be reused are sequentially connected; wherein the content of the first and second substances,
the tin precipitation tank is used for carrying out tin precipitation treatment on the copper nitrate waste liquid stock solution;
the circulating tank is connected with the additive tank, and the additive tank adds a strong oxidation medicament into liquid in the circulating tank;
the electrolytic cell is communicated with the circulating cell through a circulating pump, and the electrolytic cell performs first electrolysis on the liquid in the circulating cell;
the secondary electrolytic storage tank is connected with the electrolytic cell and is used for storing the low-copper liquid obtained by the first electrolysis of the electrolytic cell; or conveying the low-copper liquid to an electrolytic bath for second electrolysis;
and the tank to be recycled is used for collecting the liquid to be recycled obtained by the second electrolysis of the electrolytic cell.
The technical scheme is that the electrolytic cell is single-group or multi-group rotational flow electrolytic equipment or flat plate electrolytic equipment.
The further technical proposal is that an additive removing tank is arranged between the secondary electrolytic storage tank and the electrolytic tank; the additive removing tank is used for removing strong oxidizing agents in the low-copper liquid from the electrolytic tank and then delivering the low-copper liquid without the strong oxidizing agents to the secondary electrolytic storage tank.
Compared with the prior art, the invention can achieve the following technical effects:
according to the method and the system 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 capability can be reduced to about 10g/L from 50-70g/L after the high-copper waste nitric acid is electrolyzed, and the copper is prevented from being corroded and cuprous oxide is prevented from being generated by a strong oxidizing agent; the scheme creatively adopts a secondary electrolysis method to realize the recycling of the nitric acid, and the volume expansion of each batch is not concentrated within 5 percent; meanwhile, the copper product produced by electrolysis can be sold. The method can be popularized in the PCB production industry and industrial enterprises which produce the same kind of waste acid in different industries, and has good environmental benefit, social benefit and economic benefit.
The copper etching waste nitric acid recycling system provided by the invention realizes waste nitric acid recycling and low-cost operation on the basis of ensuring high quality and high yield of elemental copper products, and is a set of resource utilization process system with good environmental protection benefit and economic benefit.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a process route diagram of a copper etching waste nitric acid recycling system provided by the invention;
fig. 2 is a process flow diagram of the copper etching waste nitric acid recycling system provided by the invention.
Reference numerals
A raw material storage tank 10, a filter 20, a circulating tank 30, an electrolytic tank 40, an additive removing tank 50, a secondary electrolytic storage tank 60 and a tank to be recycled 70.
Detailed Description
The technical solutions in the embodiments will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, wherein like reference numerals represent like elements in the drawings. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. 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.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Referring to fig. 1-2, the present embodiment provides a method for recycling copper etching waste nitric acid, which includes the following steps:
and S1, carrying out tin precipitation treatment on the copper nitrate waste liquid stock solution, and keeping the supernatant.
In specific implementation, the stripping and hanging piece cleaning copper nitrate waste liquid stock solution collected from a production line is firstly subjected to tin precipitation treatment, for example, the stock solution enters a tin precipitation tank, divalent tin is aerated and oxidized to be naturally precipitated, the conversion from alpha-metastannic acid to beta-metastannic acid can be accelerated by proper heating, and the supernatant is left to prepare for the subsequent process.
For example, in one embodiment, the oxidation is accelerated by introducing air and the copper nitrate waste liquid is left to stand, so that most of tin in the copper nitrate waste liquid stock solution can be settled in a solid form within 1-2 days, and the tin content of the upper liquid is only about 30 mg/L.
S2, taking out the supernatant, adding a strong oxidation agent into the supernatant, and carrying out first electrolysis until the concentration of copper ions in the electrolyte is less than or equal to 10g/L to obtain the low-copper liquid.
Adding strong oxidizing agent to prevent nitrous acid from being generated in the electrolytic process. In the electrolytic process, the temperature of the electrolyte, the concentration of copper ions, the acidity, the current and other parameters are monitored, samples can be taken from the buffer circulation tank every 4 hours for assay, and the electrolysis of the solution in the batch is stopped until the concentration of the copper ions in the electrolyte is less than or equal to 10g/L, so that the low-copper liquid is obtained.
It should be noted that, in the conventional electrolytic process, nitrate is generated during electrolysisThe existence of acid radicals can cause the negative plate in the electrolytic cell to generate black Cu2O, electrolysis to some extent, copper will start to corrode by the following specific mechanism:
reaction mechanism of Cu2O with black appearance of copper product
In the copper nitrate electrolyte, Cu is excluded2+In addition, it also contains H+、OH-A small amount of impurity ions and a large amount of NO3 -. H in the electrolyte+The content is less, the pH value is about 0, the theoretical precipitation potential of hydrogen ions is 0.0V, which is lower than the theoretical potential of copper ions, and hydrogen gas is precipitated at a cathode to have a certain overpotential, so that the hydrogen gas is difficult to react at the cathode; OH group-The content is less, and the possibility of precipitation at the cathode is lower; NO3 -The content of Cu in the electrolyte is high2+2 times the concentration, at pH 0, NO3 -The electrode potential for the reduction reaction was 0.87V ([ NO ]3 -]) lmol/L, pno 1 atm), so NO is much higher than copper3 -The influence of (a) cannot be ignored.
When the potential of the redox reaction electrode is inquired, NO is shown under the condition of the same pH value3 -The reduction electrode potential of (2) is much higher than that of copper ions, and NO in the solution should be considered as the principle that the higher the electrode potential, the more easily NO is precipitated at the cathode3 -The reaction of 1 preferentially occurs at the cathode to produce NO.
NO3 -+4H++3e＝NO+2H2O (1)
As the reaction proceeds, NO in solution3 -The concentration is reduced to a certain value, so that the precipitation potential of copper ions is larger than NO3 -At the precipitation potential of (2), copper is precipitated at the cathode to obtain cathode copper. But not when actually electrolyzed. In fact, when a copper nitrate solution is electrolyzed, copper ions preferentially gain electrons at the cathode, and copper is generated. The reason why the copper ions and the nitrate ions get electrons at the cathode in sequence and the theory is not accordant with the reality is that NO3 -The reduction reaction of (A) is carried out under certain conditionsThe method is carried out. However, the production of NO is not directly dependent on the reaction, but proceeds via equations 2 and 3.
NO3 -+3H++2e＝HNO2+H2O (2)
HNO2+H++e＝NO+H2O (3)
Due to the large amount of NO in the electrolyte3 -Is present, so in the electrolytic process, HNO2The formation of (A) is carried out according to reactions 4 to 8.
H++NO3 -＝HNO3 (4)
HNO3+HNO2＝H2O+N2O4 (5)
N2O4＝2NO2 (6)
NO2+e＝NO2 - (7)
H++NO3 -＝HNO2 (8)
In the actual reaction, NO3 -The reduction rate of the catalyst is related to the number of impurities adsorbed on the adsorption layer and the HNO existing in the catalyst2The reaction is automatically accelerated, and when the pH value is lower, the potential of the reaction formula 2 is increased and simultaneously a large amount of HNO is generated2When present, it is possible to accelerate the reaction. HNO2Sometimes it is possible to control the generation of (b) without fixed conditions, but sometimes it is accelerated. After reaction 2 occurs, reaction 3 occurs immediately, and NO gas is generated. These two reactions take place, consuming a significant amount of H + from the solution on the cathode surface, raising its pH. When the pH value exceeds 2.25, Cu2+The reduction product of (2) will be Cu2The form of O stably exists, the precipitation process of cathode copper is Cu2O is an intermediate product, and proceeds via equations 9 and 10. However, the cathode copper obtained through such a process does not have good conductivity and ductility, but exhibits properties such as brittleness and susceptibility to oxidation.
2Cu2++H2O+2e＝Cu2O+2H+ (9)
Cu2O+2H++2e＝2Cu+H2O (10)
The process of generating cathode copper by reacting 9 and 10 with Cu2+ in the solution is as follows: hydrated Cu in solution2+Getting an electron on the cathode surface to generate hydrated Cu2O, hydrated Cu2O diffuses on the surface of the electrode, reaches a growth line or a growth point, enters crystal lattices and belongs to an octahedral face-centered cubic system. Due to Cu2O has a different lattice from that of copper, not all of Cu2O can be incorporated into the lattice of copper. Cu already incorporated in the lattice2O will be dispersed on the cathode surface to obtain an electron to generate copper, and the copper form will remain the original Cu2The form of O, i.e. octahedra. As the reaction proceeds, Cu2O is preferentially precipitated on the surface of octahedral copper and is continuously accumulated, and the Cu which is not incorporated into the crystal lattice2O is adsorbed in the gaps on the surface of the cathode copper, no more electron-generated copper can be obtained, the O is easy to fall off from the surface of the cathode, and the Cu can be obtained by water flushing or brush brushing2Black powder of O, in which a small amount of copper powder is mixed. This is also the cathode plate surface energy spectrum analysis for copper and the black powder XRD analysis for Cu2The reason for O and Cu.
The formation of black copper is indeed associated with NO in solution3 -In connection with, or more specifically with, NO3 -HNO produced by the reaction2Related to HNO in the electrolyte2The larger the amount of (B), the more easily black copper is produced. Found by experiments, NO3 -Reaction to produce HNO2Having a direct relationship with current density, high current density can promote NO3 -Discharge at the cathode to accelerate HNO2Accumulation in solution. When HNO2When a certain amount is accumulated in the solution, NO will be generated NO whether the electrolysis is carried out at low current density or high current density3 -The discharge reaction at the cathode leads to the generation of black copper, which is only a problem of long discharge time.
In conclusion, HNO2Has a direct relationship with the current density, the higher the NO3 -The more easily the reaction is at the cathode, the more the HNO is accelerated2Accumulation of (i), HNO2Accumulation in the electrolyte further promotes NO3 -Ultimately resulting in the formation of black copper.
Mechanism of copper being etched back
Dilute nitric acid differs from concentrated nitric acid as an oxidizing agent in that dilute nitric acid has a slow reaction rate, a weak oxidizing power, and the oxidized substance cannot reach the maximum valence state, and the oxidation of dilute nitric acid is considered to be reduced to NO first, but because the production of NO is not so high at a slow reaction rate, it is reduced to N, NH or the like in one step without time before escaping from the reaction system. From the reaction mechanism, the oxidation of nitric acid is related to the catalytic action of NO which is decomposed by light and is often present in nitric acid, and NO plays a role in transferring electrons:
NO+e-＝NO- (11)
NO-+H+＝HNO (12)
HNO+HNO＝HO+2NO (13)
the nitric acid gains reductant electrons through NO, accelerating the reaction, and the fuming nitric acid has strong oxidizability because of the large amount of NO dissolved in the acid. I.e. NO is the catalyst in the reaction, playing a positive catalytic role.
In summary, the appearance of either black cuprous oxide or corrosion is related to NO, which is derived from electrolyte NO3 -By discharge reaction of (3), NO3 -The discharge reaction of (2) is in turn related to the current density. Therefore, the control of the current density of the electroplating and the prevention of nitrate radical reduction are the key of the whole electroplating. The best way to avoid the build-up of nitrous acid is to add to the electrolyte a substance which acts as: when nitrous acid is generated at the cathode, the nitrous acid reacts with the cathode, and the nitrous acid is consumed, and meanwhile, the generated product is ensured not to pollute the electrolyte.
The hydrogen peroxide/sulfamic acid is a better nitrogen oxide remover and can ensure that the electrolyte can be normally electroplated. Air is introduced during electrolysis, which can help to remove nitrogen oxides in time.
In specific implementation, the strong oxidation medicament is selected from 50% hydrogen peroxide or a mixture of sulfamic acid and 50% hydrogen peroxide.
The amount of the strong oxidizing agent added varies depending on the type of the strong oxidizing agent or the concentration of copper ions in the liquid, and for example, table 2 below lists examples of the amount of the strong oxidizing agent added for both of the a and B cases. In the table, V represents the volume of waste liquid (supernatant).
TABLE 2 Strong oxidant addition
In the specific implementation, the first electrolysis condition is that the temperature of the electrolyte is 16-24 ℃, the current density is 100-2。
It will be appreciated that excessive current density is responsible for the reduction of nitrate ions, and that nitrogen oxides are a direct factor in the corrosion of cuprous oxide and copper, which occurs when the concentration of nitrogen oxides in the electrolyte builds up to a certain extent.
In one embodiment, when the concentration of copper ions in the electrolyte is less than 15g/L, the current density is 100-120A/m2。
In specific implementation, when Cu2+Stopping electrolysis when the concentration of the carbon dioxide is lower than 10g/L, and if the electrolysis stopping time exceeds 3 hours, taking out the cathode plate and cleaning the cathode plate by water; when Cu2+<The electrolysis was not stopped at 15g/L and was carried out at a low current.
For example, in one embodiment, the current density is controlled according to the different stages of electrolysis (copper ion concentration), see table 3.
TABLE 3 control of the electrolyte in the cell
| Amount of copper (g/L) | Current Density (A/m)2) |
| 0-10 | ─ |
| 10-15 | 100-120 |
| 15-20 | 120-140 |
| 20-30 | 140-150 |
| 30-40 | 150-180 |
| >40 | 180-200 |
In a specific embodiment, between the steps S2 and S3, the method further includes the steps of: removing residual strongly oxidizing agent from the low copper liquid.
In specific implementation, the residual strong oxidizing agent is removed from the low-copper liquid, and the specific operation is to heat the low-copper liquid for 2 hours at 50-60 ℃.
In other embodiments, the low-copper liquid can be heated at 50-60 ℃ for 2h in cooperation with the irradiation of an ultraviolet lamp to remove residual hydrogen peroxide and/or sulfamic acid.
S3, collecting the low-copper liquid in the step S2 until the long copper amount of the cathode plate of the electrolytic cell exceeds 15kg in the step S2, and stopping the first electrolysis.
In the specific implementation, the supernatant is electrolyzed in batches, and the low-copper liquid is collected until the long copper amount of the cathode plate of the electrolytic cell exceeds 15kg, and the first electrolysis is stopped.
And (4) discharging copper (the length of the copper at the cathode of the single cyclone electrolyzer exceeds 15kg) after the copper discharge standard is met, and the copper simple substance can be recycled and sold.
S4, carrying out secondary electrolysis on the low-copper liquid collected in the step S3 in batches until the copper etching capacity of the electrolyte in each batch reaches the standard, and obtaining a liquid to be recycled;
in the embodiment of the present invention, the mechanism for performing the secondary electrolysis regeneration and reuse is introduced as follows:
Cu+4HNO3(concentrated) → Cu (NO)3)2+2NO2↑+2H2O；
3Cu+8HNO3(dilute) → 3Cu (NO)3)2+2NO↑+4H2O.
Dilute nitric acid differs from concentrated nitric acid as an oxidizing agent in that dilute nitric acid has a slow reaction rate, a weak oxidizing power, and the oxidized substance cannot reach the maximum valence state, and the oxidation of dilute nitric acid is considered to be reduced to NO first, but because the production of NO is not so high at a slow reaction rate, it is reduced to N, NH or the like in one step without time before escaping from the reaction system. From the reaction mechanism, the oxidation of nitric acid is related to the catalytic action of NO which is decomposed by light and is often present in nitric acid, and NO plays a role in transferring electrons:
NO+e-＝NO-
NO-+H+＝HNO
HNO+HNO＝HO+2NO
the nitric acid gains reductant electrons through NO, accelerating the reaction, and the fuming nitric acid has strong oxidizability because of the large amount of NO dissolved in the acid. I.e. NO is the catalyst in the reaction, playing a positive catalytic role.
The recycling principle is that nitrate radicals are discharged at the cathode through secondary electrolysis by utilizing the reverse corrosion phenomenon of the cathode, so that the concentration of nitrogen oxides in the system is improved, and the copper corrosion capability is improved.
In specific implementation, the current density of the second electrolysis is 380-420A/m2And the temperature of the electrolyte is 16-24 ℃.
The second electrolysis is carried out for a period of at least 2 hours, for example, 2 to 3 hours, to produce nitrite and oxynitride for promoting copper etching.
In the specific implementation, sampling is carried out every 10 minutes after two hours of electrolysis to verify the copper etching capacity, and whether the sectional copper etching capacity reaches the standard can be judged by the following method:
and (3) adding 250ml of electrolyte sample by adopting a standard copper bar, and completely etching the copper within 5 minutes to obtain the qualified product.
And obtaining the liquid to be recycled after the copper etching capacity of each batch of secondary electrolyte reaches the standard.
S5, adding concentrated nitric acid with the volume of 5-8% into the solution to be recycled to obtain the etching solution meeting the recycling standard.
In one embodiment, the treatment effect of the waste liquid treated by the method for recycling the copper etching waste nitric acid is shown in tables 4-5.
TABLE 4 Water quality index
TABLE 5 Water swelling after preparation and reuse
| Status of state | Increase in liquid volume |
| Concentration without evaporation | The increment is 6 to 8 percent |
| Concentrating by evaporation | 0 |
In one embodiment, the effluent is based on average Cu2+Concentration 60g/L meterThe consumption of the strong oxidant for treating each ton of waste liquid is shown in Table 6
TABLE 6 consumption of chemicals (treatment of ton of waste acid)
In one embodiment, the effluent is based on average Cu2+The concentration is 60g/L, and the copper yield of each ton of waste liquid is shown in Table 7.
TABLE 7 copper product yield (60 g/L of copper stock solution per ton of waste liquor)
| Item | Number of | Remarks for note |
| Theoretical copper yield | 55kg | - |
| Actual copper yield | 44kg | Calculated as 80% |
With continued reference to fig. 1-2, another embodiment of the present invention provides a recycling system for copper etching waste nitric acid, which includes a secondary electrolytic storage tank 60, a tin deposition tank, a raw material storage tank 10, a filter 20, a circulation tank 30, an electrolytic tank 40, and a tank to be recycled 70, which are connected in sequence; the tin precipitation tank is used for carrying out tin precipitation treatment on the copper nitrate waste liquid stock solution;
the circulating tank 30 is connected with an additive tank, and the additive tank adds a strong oxidation medicament into the liquid in the circulating tank 30;
the electrolytic tank 40 is communicated with the circulating tank 30 through a circulating pump, and the electrolytic tank 40 performs first electrolysis on the liquid in the circulating tank 30;
the secondary electrolytic storage tank 60 is connected with the electrolytic cell 40 and is used for storing the low-copper liquid obtained by the first electrolysis of the electrolytic cell 40; or conveying the low-copper liquid to the electrolytic bath 40 for second electrolysis;
the tank 70 to be recycled is used for collecting the liquid to be recycled obtained by the second electrolysis of the electrolytic cell 40.
In a specific embodiment, the electrolytic cell 40 is a single-group or multi-group cyclone electrolytic device, or a flat plate electrolytic device.
It should be noted that the cyclone electrodeposition technology is an efficient metal purification and separation technology, and compared with the traditional separation technology, the cyclone electrodeposition technology has the characteristics of strong selectivity, short process flow, low copper content of electrodeposition mother liquor, high current efficiency, high product quality and the like. The cyclone electrolysis is also based on the basic theory of electrochemistry, but the cyclone electrolysis technology is based on the difference of theoretical precipitation potential of each metal ion, namely, if the metal to be extracted has larger potential difference with other metal ions in the solution system, the metal with the positive potential is easy to preferentially precipitate at the cathode. The key point of the cyclone electrodeposition technology is that adverse factors such as concentration polarization and the like on electrolysis are eliminated through high-speed liquid flow, so that target metal is preferentially separated out; compared with the traditional electrodeposition technology, the rotational flow electrodeposition technology can carry out selective electrodeposition in multi-metal solution with low target metal ion concentration and obtain high-purity metal products.
According to the inventors' experiment using cyclone electrolysis, in one embodiment 1100L of electrolyte, Cu, was added to the cell2+：45.1g/L，H+: 4.4 mol/L. And starting cold water circulation, starting a water pump circulation, slowly and uniformly adding 27.5L 50% hydrogen peroxide into the system, and circulating for 30 min. The current density is adjusted to 165A/m2。
The experiment shows that the cyclone electrolysis is good, and 39.5kg of copper is produced. The current efficiency is more than 90%. When the concentration of copper ions is high, the current density is 165A/m2When the current efficiency is lower than 90.35%; increase the current densityThe current efficiency can be effectively improved. When the copper ion concentration is lower than 30g/L, the copper quality is poor, powdery copper exists, coarse granular copper begins to appear when the copper ion concentration is lower than 19g/L in the cyclone electrolysis, and the copper quality is good. And the current efficiency of about 95 percent can be maintained under the condition of lower copper concentration, and the acidity is improved by 1.16 mol/L.
When using a flat plate device for electrolysis, should be conducted at a low current density (e.g., 50A/m)2) Electrolyzing, and gradually increasing current to target current density (the maximum current density of the single plate should not exceed 200A/m)2The temperature of the electrolytic bath solution is preferably maintained between 16 and 24 ℃), and the current control indexes of the flat plate equipment are shown in table 3.
In a specific embodiment, an additive removing tank 50 is further arranged between the secondary electrolytic storage tank 60 and the electrolytic bath 40; the additive removing tank 50 is used for removing the strong oxidizing agent from the low copper liquid from the electrolytic tank 40, and then delivering the low copper liquid without the strong oxidizing agent to the secondary electrolytic tank 60.
In a specific embodiment, the copper etching waste nitric acid recycling system further comprises a concentrated nitric acid tank, wherein the concentrated nitric acid tank is connected with the tank to be recycled so as to supplement concentrated nitric acid to liquid in the tank to be recycled and meet the requirement of a recycling line.
The use process of the copper etching waste nitric acid recycling system is introduced as follows:
the stock solution collected from the production line firstly enters a tin precipitation tank for tin precipitation. And pumping the supernatant in the tin precipitation tank into a raw material storage tank, enabling the copper nitrate waste liquid to enter a circulating buffer tank from the raw material storage tank through a filter, opening a circulating pump between the circulating tank and an electrolytic tank, and adding a strong oxidant in a preset proportion into the circulating tank to perform first electrolysis. And stopping electrolysis when the concentration of copper ions in the electrolyte reaches 10g/L, and pumping the low-copper liquid into an additive removing tank. And (3) if the waste production unit has recycling requirements, pumping the liquid obtained after electrolysis into an additive removing tank with a heating system to remove residual hydrogen peroxide, and pumping the liquid into a secondary electrolysis storage tank to wait for centralized secondary electrolysis recycling treatment. Repeating the operation until the copper growing amount on the cathode plate reaches the copper discharging standard. Discharging copper after the copper discharging standard is met, closing the liquid cooling system, pumping the liquid in the secondary electrolysis storage tank into an electrolytic cell in batches, carrying out secondary electrolysis, and pumping the liquid to be recycled into a tank to be recycled for collection after the electrolyte meets the recycling requirement; adding preset concentrated nitric acid into the tank to be recycled until the requirement of a production line is met, and obtaining recycled liquid.
In conclusion, the technical scheme of the invention can realize the resource recycling of the copper-etching-like waste nitric acid. The concentration of copper ions of the original high-copper waste nitric acid without copper etching capability can be reduced from 50-70g/L to about 10g/L after the first electrolytic treatment, the copper ions can be recycled after the second electrolytic treatment, and the volume expansion of each batch is about 6% without concentration treatment; meanwhile, the copper product produced by the reduction electrolysis can be sold.
The technical scheme of the invention can be popularized in the PCB production industry and industrial enterprises which produce the same type of waste acid in different industries, and has good environmental benefit, social benefit and economic benefit.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A resource recycling method of copper etching waste nitric acid is characterized by comprising the following steps:
s1, carrying out tin precipitation treatment on the copper nitrate waste liquid stock solution, and reserving supernatant;
s2, taking out the supernatant, adding a strong oxidation agent into the supernatant, and carrying out first electrolysis until the concentration of copper ions in the electrolyte is less than or equal to 10g/L to obtain a low-copper liquid;
s3, collecting the low-copper liquid in the step S2 until the long copper amount of the cathode plate of the electrolytic cell exceeds 15kg in the step S2, and stopping the first electrolysis;
s4, carrying out secondary electrolysis on the low-copper liquid collected in the step S3 in batches until the copper etching capacity of the electrolyte in each batch reaches the standard, and obtaining a liquid to be recycled;
s5, adding concentrated nitric acid with the volume of 5-8% into the solution to be recycled to obtain the etching solution meeting the recycling standard.
2. The resource recycling method of copper etching waste nitric acid as claimed in claim 1, wherein the strong oxidizing agent is selected from 50% hydrogen peroxide or a mixture of sulfamic acid and 50% hydrogen peroxide.
3. The resource recycling method of copper etching waste nitric acid according to claim 2, wherein if the strong oxidizing agent is selected from 50% hydrogen peroxide, the dosage is 2-2.5% V (volume of waste liquid);
if the strong oxidizing agent is selected from the mixture of sulfamic acid and 50% hydrogen peroxide, the dosage of the sulfamic acid is 0.7-1V (volume of waste liquid) 1 kg/L; the amount of hydrogen peroxide is 0.8-1% V (volume of waste liquid).
4. The resource recycling method of copper etching waste nitric acid according to claim 1 or 3, further comprising the steps between steps S2 and S3: removing residual strongly oxidizing agent from the low copper liquid.
5. The resource recycling method of copper etching waste nitric acid according to claim 4, wherein the residual strong oxidant is removed from the low-copper liquid by heating the low-copper liquid at 50-60 ℃ for 2 h.
6. The method as claimed in claim 1, wherein the first electrolysis is carried out under conditions of an electrolyte temperature of 16-24 ℃, a current density of 100-200A/m2。
7. The method of claim 6, wherein the nitric acid is recycledThe application method is characterized in that when the concentration of copper ions in the electrolyte is less than 15g/L, the current density is 100-120A/m2。
8. The method as claimed in claim 1, wherein the current density of the second electrolysis is 380-420A/m2And the temperature of the electrolyte is 16-24 ℃.
9. A copper etching waste nitric acid recycling system is characterized by comprising a secondary electrolytic storage tank, a tin deposition tank, a raw material storage tank, a filter, a circulating tank, an electrolytic tank and a tank to be recycled, wherein the tin deposition tank, the raw material storage tank, the filter, the circulating tank, the electrolytic tank and the tank to be recycled are sequentially connected; wherein the content of the first and second substances,
the tin precipitation tank is used for carrying out tin precipitation treatment on the copper nitrate waste liquid stock solution;
the circulating tank is connected with the additive tank, and the additive tank adds a strong oxidation medicament into liquid in the circulating tank;
the electrolytic cell is communicated with the circulating cell through a circulating pump, and the electrolytic cell performs first electrolysis on the liquid in the circulating cell;
the secondary electrolytic storage tank is connected with the electrolytic cell and is used for storing the low-copper liquid obtained by the first electrolysis of the electrolytic cell; or conveying the low-copper liquid to an electrolytic bath for second electrolysis;
and the tank to be recycled is used for collecting the liquid to be recycled obtained by the second electrolysis of the electrolytic cell.
10. The copper etching waste nitric acid resource recycling system of claim 9, wherein an additive removing tank is further arranged between the secondary electrolysis storage tank and the electrolytic cell; the additive removing tank is used for removing strong oxidizing agents in the low-copper liquid from the electrolytic tank and then delivering the low-copper liquid without the strong oxidizing agents to the secondary electrolytic storage tank.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114427092A (en) * | 2022-01-26 | 2022-05-03 | 昆山华拓环保科技有限公司 | Regeneration copper extraction method of nitric acid etching solution |
| CN114855172A (en) * | 2022-05-18 | 2022-08-05 | 张锐 | Method for prolonging Lifetime of Cu etching liquid based on nitric acid system |
| CN114855221A (en) * | 2022-04-18 | 2022-08-05 | 定颖电子(黄石)有限公司 | System and method for recovering copper-containing nitric acid waste liquid of circuit board |
| CN115537816A (en) * | 2022-10-08 | 2022-12-30 | 青岛理工大学 | Rotational flow electrolysis system and method for regeneration of acidic copper chloride etchant and copper recovery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4033838A (en) * | 1976-05-19 | 1977-07-05 | Kawecki Berylco Industries, Inc. | Recovery of copper from waste nitrate liquors by electrolysis |
| JPH0461986A (en) * | 1990-06-27 | 1992-02-27 | Nec Toyama Ltd | Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching |
| KR20050065031A (en) * | 2003-12-24 | 2005-06-29 | 재단법인 포항산업과학연구원 | A reusing method of waste water comprising copper and nitric acid as etching solution and copper |
| CN109868476A (en) * | 2019-01-28 | 2019-06-11 | 湖北永绍科技股份有限公司 | A kind of etching liquid recycling and reusing method of copper ions and nitrate anion |
| CN210683962U (en) * | 2019-08-30 | 2020-06-05 | 深圳市捷骏鼎盛环保科技有限公司 | Nitric acid deplating liquid recycling system |
-
2020
- 2020-12-16 CN CN202011489376.5A patent/CN112708885A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4033838A (en) * | 1976-05-19 | 1977-07-05 | Kawecki Berylco Industries, Inc. | Recovery of copper from waste nitrate liquors by electrolysis |
| JPH0461986A (en) * | 1990-06-27 | 1992-02-27 | Nec Toyama Ltd | Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching |
| KR20050065031A (en) * | 2003-12-24 | 2005-06-29 | 재단법인 포항산업과학연구원 | A reusing method of waste water comprising copper and nitric acid as etching solution and copper |
| CN109868476A (en) * | 2019-01-28 | 2019-06-11 | 湖北永绍科技股份有限公司 | A kind of etching liquid recycling and reusing method of copper ions and nitrate anion |
| CN210683962U (en) * | 2019-08-30 | 2020-06-05 | 深圳市捷骏鼎盛环保科技有限公司 | Nitric acid deplating liquid recycling system |
Non-Patent Citations (1)
| Title |
|---|
| 戴明飞: "中和―絮凝法回收硝酸型退锡废水中的锡", 《化工环保》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114427092A (en) * | 2022-01-26 | 2022-05-03 | 昆山华拓环保科技有限公司 | Regeneration copper extraction method of nitric acid etching solution |
| CN114855221A (en) * | 2022-04-18 | 2022-08-05 | 定颖电子(黄石)有限公司 | System and method for recovering copper-containing nitric acid waste liquid of circuit board |
| CN114855221B (en) * | 2022-04-18 | 2023-12-01 | 超颖电子电路股份有限公司 | System and method for recovering copper-containing nitric acid waste liquid of circuit board |
| CN114855172A (en) * | 2022-05-18 | 2022-08-05 | 张锐 | Method for prolonging Lifetime of Cu etching liquid based on nitric acid system |
| CN115537816A (en) * | 2022-10-08 | 2022-12-30 | 青岛理工大学 | Rotational flow electrolysis system and method for regeneration of acidic copper chloride etchant and copper recovery |
| CN115537816B (en) * | 2022-10-08 | 2024-06-07 | 青岛理工大学 | Rotational flow electrolysis system and method for regenerating acidic copper chloride etchant and recycling copper |
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