CN111663155B - Comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate - Google Patents
Comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate Download PDFInfo
- Publication number
- CN111663155B CN111663155B CN202010637375.4A CN202010637375A CN111663155B CN 111663155 B CN111663155 B CN 111663155B CN 202010637375 A CN202010637375 A CN 202010637375A CN 111663155 B CN111663155 B CN 111663155B
- Authority
- CN
- China
- Prior art keywords
- copper
- solution
- concentration
- nitrate
- copper nitrate
- 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.)
- Active
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000010949 copper Substances 0.000 title claims abstract description 88
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 88
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000007788 liquid Substances 0.000 title claims abstract description 45
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 238000005520 cutting process Methods 0.000 title claims abstract description 37
- 238000011084 recovery Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 48
- 238000004070 electrodeposition Methods 0.000 claims abstract description 46
- 238000005530 etching Methods 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003672 processing method Methods 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 87
- 238000001816 cooling Methods 0.000 claims description 35
- 229910001431 copper ion Inorganic materials 0.000 claims description 35
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims description 28
- 238000005868 electrolysis reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 13
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 13
- 239000004571 lime Substances 0.000 claims description 13
- -1 nitrate ions Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- APTUIUORLSQNEF-UHFFFAOYSA-N dicopper tetranitrate Chemical compound [Cu++].[Cu++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APTUIUORLSQNEF-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 241000287828 Gallus gallus Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013330 chicken meat Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- 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
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a comprehensive recovery processing method of waste copper cutting liquid of copper nitrate, which relates to a metal recovery technology and aims to solve the problems that the purity can not meet the requirement of standard cathode copper No. 1 and the liquid after electrodeposition can not be recycled, and the key points of the technical scheme are as follows: concentrating the waste copper cutting liquid of the copper nitrate; adding a proper amount of concentrated sulfuric acid into the concentrated copper nitrate solution; adding a proper amount of corrosion inhibitor into the concentrated copper nitrate; and electrodepositing the prepared copper nitrate solution by an electrolytic system to obtain a cathode copper product with chemical components reaching the standard of No. 1 copper products. The comprehensive recovery processing method of the waste copper cutting liquid of copper nitrate improves the purity of copper products, ensures that chemical components of the copper products meet the requirement of No. 1 standard cathode copper, realizes the cycle of electrodeposition extraction copper-PCB etching, effectively reduces the production cost and reduces the discharge.
Description
Technical Field
The invention relates to a metal recovery technology, in particular to a comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate.
Background
In recent years, the rapid development of the copper product industry has led to the generation of large amounts of copper-containing waste solutions. Meanwhile, the national requirements for environmental protection are increasing day by day, so that the treatment and discharge of copper-containing waste materials become a great problem for enterprises. Technically, the removal of free divalent copper ions is mature, and the mass concentration of residual copper ions in the solution after treatment can be reduced to below 1 mg/L. However, in industries such as dye, electroplating, and circuit board (PCB), copper-containing wastewater often contains a large amount of copper ions, wherein the copper ions are most representative of the waste liquid in the PCB industry. The waste copper cutting liquid contains a large amount of resources, each ton of the waste copper cutting liquid contains over 90kg of copper, and the single extraction process of metal ions is relatively simple. Therefore, the selection of the waste copper scrap treatment technology and the quality of the treatment effect are not only related to the recycling of resources, but also related to the environmental safety, the economy and the sustainable development of the society in the peripheral areas of the factory.
At present, the treatment method of copper cutting liquid mainly focuses on two technologies, namely a copper sulfate processing technology and a recycling regeneration technology, and other new technologies are developed on the basis of the two technologies. The technical principle of the copper sulfate processing technology is as follows: the method is characterized in that a precipitator is used for precipitating copper ions in waste liquid, then precipitated copper salt reacts with sulfuric acid to produce copper sulfate, but because acid etching solution generally contains high acid, a large amount of alkaline precipitator is consumed, the copper content of the precipitated waste liquid is still high, the waste liquid can reach the national discharge standard after further copper removal, and a large amount of nitrate is generated due to the addition of the precipitator, so that the method is used for killing chickens to remove eggs and recycling part of resources with short and shallow eyes, and is harmful to the environment.
The Chinese patent publication with publication number CN101906644B discloses a method for recovering copper from copper nitrate wastewater, which has the technical key points that: (1) taking iron as an anode and copper as a cathode; (2) the method comprises the steps of introducing copper nitrate wastewater into an electrolytic cell, wherein the initial concentration of nitric acid in the copper nitrate wastewater is less than 6.3g/L, the initial concentration of copper nitrate in the copper nitrate wastewater introduced into the electrolytic cell is not less than 53g/L, carrying out gas stirring on the copper nitrate wastewater in the electrolytic cell, and simultaneously introducing direct current between two electrodes to electrolyze the copper nitrate wastewater, so that copper in the copper nitrate wastewater is deposited on a copper cathode plate, and the electrolytic recovery of copper is realized.
In practical application, the scheme is found that copper deposited on a copper cathode plate is soaked in nitric acid liquid containing iron during recovery and taking out, certain corrosion exists, the purity of the copper is affected, and the requirement of standard cathode copper No. 1 cannot be met, and on the other hand, the scheme is essentially that the copper in the solution is replaced by iron, and the nitric acid solution is polluted due to the fact that a large amount of iron is dissolved in the solution by nitric acid, so that the post-electrodeposition liquid after copper extraction cannot be fully utilized.
Therefore, a new solution is needed to solve this problem.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a comprehensive recovery and treatment method for copper nitrate waste copper cutting liquid, which aims to improve the purity of a copper product, ensure that the chemical composition of the copper product meets the requirement of No. 1 standard cathode copper, realize the cycle of electrodeposition extraction copper-PCB etching, effectively reduce the production cost and reduce the emission on the premise of not introducing new metal impurities.
The technical purpose of the invention is realized by the following technical scheme: a comprehensive recovery treatment method for copper nitrate waste copper cutting liquid comprises the following steps: 1) concentrating the waste copper cutting liquid of the copper nitrate to obtain a high-concentration copper nitrate solution, wherein the concentration of copper ions is 50-120g/L, and the concentration of nitrate ions is 100-350 g/L; 2) adding concentrated sulfuric acid with the concentration of 98% to the high-concentration copper nitrate solution obtained in the step 1) through a pipette to the bottom of the solution, and preparing a high-concentration copper nitrate mixed pre-solution; 3) adding the prepared nitric acid corrosion inhibitor into the high-concentration copper nitrate mixed pre-solution prepared in the step 2) to prepare a copper nitrate pre-electrodeposition solution; 4) Directly introducing the copper nitrate pre-electrodeposition solution prepared in the step 3) into an electrodeposition tank, producing an electrodeposited copper product by electrolysis and configuring a cooling system at a current density of 300-2Extracting under the conditions that the electrolysis circulation amount is 400-500L/h and the electrodeposition temperature is below 20 ℃ to obtain a No. 1 standard copper cathode copper product and a low-copper ion-containing post-electrodeposition solution; 5) conveying the electro-deposition solution containing low copper ions obtained in the step 4) to a PCB etching process, using the electro-deposition solution as an etching solution to produce an etched circuit board, and resupplying the generated copper nitrate solution to the step 1).
By adopting the technical scheme, the step 1) concentrates the waste copper cutting liquid of the copper nitrate, so that the concentration of copper ions is improved, copper can be obtained by electrolysis more easily, and the energy consumption of electrolysis is effectively reduced; step 2) adding concentrated sulfuric acid to drive nitric acid in a free state, wherein the chemical formula is as follows: h2SO4 (concentrated) + NO3- ═ HSO4- + HNO3 (gas), SO that the back dissolution of electrodeposited copper is inhibited, and the recovery rate and the actual electrolysis efficiency of copper are effectively improved; step 3) adding a nitric acid corrosion inhibitor to effectively reduce the corrosivity of nitric acid, thereby improving the electrochemical crystallization speed of copper, improving the purity of a copper product, ensuring that the chemical composition of the copper product meets the requirement of standard cathode copper No. 1, improving the economic benefit, and further improving the recovery rate of copper to be more than 99%; after the electrodeposited copper product is produced by electrolysis, cooling the electrodeposited copper by using a cooling system, so that the electrodeposited copper is extracted in a low-temperature environment, the back dissolution of the electrodeposited copper is further avoided, the volatilization of nitric acid is reduced, and the recovery rate of the nitric acid is improved; and 5) supplying the solution after electrodeposition to a PCB etching process, and supplying the generated copper nitrate solution to the step 1) again, thereby realizing the cycle of electrodeposition extraction copper-PCB etching, effectively reducing the production cost and reducing the discharge.
The invention is further configured to: step 1) concentrating the copper nitrate waste copper cutting liquid by adopting a reduced pressure distillation method under a reduced pressure environment with the air pressure value lower than 30mmHg, and pumping the generated distilled water vapor into a lime pool at normal temperature and normal pressure by adopting an oil pump
The invention is further configured to: the concentration of copper ions in the high-concentration copper nitrate solution in the step 1) is preferably 70 g/L; the nitrate ion concentration is preferably 350 g/L.
The invention is further configured to: the addition amount of the concentrated sulfuric acid in the step 2) is 5-10g/L, and the generated gas is conveyed into a lime pool through a gas pump.
The invention is further configured to: the concentration of the prepared aqueous solution of the nitric acid corrosion inhibitor added in the step 3) is 5-15%, preferably 10%; the addition amount is 2-4%, preferably 3%.
The invention is further configured to: the cooling system of the step 4) is an indirect cooling process, and the indirect cooling is indirect cooling by using cooling circulating water.
The invention is further configured to: and (3) after the liquid solution with low copper ion content after electrodeposition in the step 5) is conveyed to a PCB etching process, adding water to dilute the liquid solution until the concentration of copper ions is 3-4g/L and the concentration of nitrate ions is 140 g/L.
In conclusion, the invention has the following beneficial effects: 1. the concentration of copper ions is improved, so that copper can be obtained more easily by electrolysis, and the electrolysis energy consumption is effectively reduced;
2. concentrated sulfuric acid is added to drive nitric acid in a free state, so that the back dissolution of electrodeposited copper is inhibited, and the recovery rate and the actual electrolysis efficiency of copper are effectively improved;
3. the nitric acid corrosion inhibitor is added to effectively reduce the corrosivity of nitric acid, so that the purity of a copper product is improved, the chemical components of the copper product meet the requirements of standard cathode copper No. 1, the economic benefit is improved, and the recovery rate of copper is further improved to be more than 99%;
4. the cooling system is utilized to cool the electro-deposition liquid, so that electro-deposition copper is extracted in a low-temperature environment, anti-dissolution of the electro-deposition copper is further avoided, volatilization of nitric acid is reduced, and recovery rate of the nitric acid is improved;
5. the cycle of electrodeposition extraction copper-PCB etching is realized, the production cost is effectively reduced, and the emission is reduced;
6. the vacuum distillation method is adopted for concentration, so that low-temperature distillation below 30 ℃ is realized, and the volatilization of nitric acid is effectively inhibited and reduced;
7. a lime pool is adopted to neutralize and absorb the volatilized acidic pollutants, so that the pollutant emission is reduced;
8. the concentration of nitrate radical is adjusted by adding water to further improve the applicability of the PCB etching process.
Detailed Description
The present invention will be described in further detail below.
Taking certain copper nitrate waste copper cutting liquid, and measuring the specific chemical components as follows:
| component (A) | Cu2+(g.L-1) | NO3 -(g.L-1) |
| Copper cutting liquid | 24.3 | 113.2 |
The first embodiment is as follows: a comprehensive recovery treatment method for copper nitrate waste copper cutting liquid comprises the following steps:
1) concentrating the waste copper cutting liquid to obtain a high-concentration copper nitrate solution, wherein the concentration of copper ions is 50-120g/L, and the concentration of nitrate ions is 100-350 g/L; specifically, the copper nitrate waste copper cutting liquid is concentrated by adopting a reduced pressure distillation method under a reduced pressure environment with the air pressure value lower than 30mmHg (lower than 30 ℃), and the generated distilled water vapor is pumped into a lime pool at normal temperature and normal pressure by adopting an oil pump.
2) Adding concentrated sulfuric acid with the concentration of 98% into the high-concentration copper nitrate solution obtained in the step 1) to the bottom of the solution through a pipette according to the addition amount of 5-10g/L, preparing a high-concentration copper nitrate mixed pre-solution, and conveying the generated gas into a lime pool through an air pump; here, when the sulfate concentration in the high-concentration copper nitrate solution reached 50g/L, it was not necessary to add concentrated sulfuric acid.
3) Adding the prepared nitric acid corrosion inhibitor into the high-concentration copper nitrate mixed pre-solution prepared in the step 2) to prepare a copper nitrate pre-electrodeposition solution; the concentration of the added nitric acid corrosion inhibitor preparation aqueous solution is 5-15%, preferably 10%; the addition amount is 2-4%, preferably 3 ‰
4) Directly introducing the copper nitrate pre-electrodeposition solution prepared in the step 3) into an electrodeposition tank, producing an electrodeposited copper product by electrolysis and configuring a cooling system at a current density of 300-2Extracting under the conditions that the electrolysis circulation amount is 400-500L/h and the electrodeposition temperature is below 20 ℃ to obtain a No. 1 standard copper cathode copper product and a low-copper ion-containing post-electrodeposition solution; the cooling system adopts an indirect cooling process, and the indirect cooling process is indirect cooling by using circulating cooling water.
5) And (3) conveying the solution obtained in the step 4) and containing low copper ions to a PCB etching process, adding water to dilute the solution until the concentration of the copper ions is 3-4g/L and the concentration of the nitrate ions is 130-140g/L, so that the solution can be used as an etching solution to produce an etched circuit board, and the generated copper nitrate solution is supplied to the step 1) again.
Example two:
a comprehensive recovery treatment method for copper nitrate waste copper cutting liquid comprises the following steps:
1) concentrating the waste copper nitrate copper cutting liquid to obtain a high-concentration copper nitrate solution, wherein the concentration of copper ions is 70g/L, and the concentration of nitrate ions is 350.025 g/L; specifically, the copper nitrate waste copper cutting liquid is concentrated by adopting a reduced pressure distillation method under a reduced pressure environment with the air pressure value lower than 30mmHg (lower than 30 ℃), and the generated distilled water vapor is pumped into a lime pool at normal temperature and normal pressure by adopting an oil pump.
2) Adding 10g/L of 98% concentrated sulfuric acid to the bottom of the high-concentration copper nitrate solution obtained in the step 1) through a pipette to prepare a high-concentration copper nitrate solution before mixing, and conveying the generated gas into a lime pool through an air pump;
3) adding 3 per mill of prepared nitric acid corrosion inhibitor into the high-concentration copper nitrate mixed pre-solution prepared in the step 2) to prepare copper nitrate electro-deposition pre-solution; the concentration of the prepared aqueous solution of the nitric acid corrosion inhibitor is 10 percent.
4) Directly introducing the copper nitrate pre-electrodeposition solution prepared in the step 3) into an electrodeposition tank, electrolyzing to produce an electrodeposited copper product, preparing a cooling system, and extracting under the conditions of current density of 350A/m2, electrolysis circulation amount of 450L/h and electrodeposition temperature of below 20 ℃ to obtain a No. 1 standard copper cathode copper product and a low-copper ion-containing post-electrodeposition solution; the cooling system adopts an indirect cooling process, and the indirect cooling process is indirect cooling by using circulating cooling water.
5) And (3) conveying the solution obtained in the step 4) and containing low copper ions to a PCB etching process, adding water to dilute the solution until the concentration of the copper ions is 3-4g/L and the concentration of the nitrate ions is 130-140g/L, so that the solution can be used as an etching solution to produce an etched circuit board, and the generated copper nitrate solution is supplied to the step 1) again.
Example three:
a comprehensive recovery treatment method for copper nitrate waste copper cutting liquid comprises the following steps:
1) concentrating the waste copper nitrate copper cutting liquid to obtain a high-concentration copper nitrate solution, wherein the concentration of copper ions is 85.4g/L, and the concentration of nitrate ions is 268.1 g/L; specifically, the copper nitrate waste copper cutting liquid is concentrated by adopting a reduced pressure distillation method under a reduced pressure environment with the air pressure value lower than 30mmHg (lower than 30 ℃), and the generated distilled water vapor is pumped into a lime pool at normal temperature and normal pressure by adopting an oil pump.
2) Adding 8g/L of 98% concentrated sulfuric acid to the bottom of the high-concentration copper nitrate solution obtained in the step 1) through a pipette to prepare a high-concentration copper nitrate solution before mixing, and conveying the generated gas into a lime pool through an air pump;
3) adding 2.5 per mill of prepared nitric acid corrosion inhibitor into the high-concentration copper nitrate mixed pre-solution prepared in the step 2) to prepare copper nitrate pre-electrodeposition solution; the concentration of the prepared aqueous solution of the nitric acid corrosion inhibitor is 10 percent.
4) Directly introducing the copper nitrate pre-electrodeposition solution prepared in the step 3) into an electrodeposition tank, electrolyzing to produce an electrodeposited copper product, preparing a cooling system, and extracting under the conditions of current density of 380A/m2, electrolysis circulation amount of 450L/h and electrodeposition temperature of below 20 ℃ to obtain a No. 1 standard copper cathode copper product and a post-electrodeposition solution containing low copper ions; the cooling system adopts an indirect cooling process, and the indirect cooling process is indirect cooling by using circulating cooling water.
5) And (3) conveying the solution obtained in the step 4) and containing low copper ions to a PCB etching process, adding water to dilute the solution until the concentration of the copper ions is 3-4g/L and the concentration of the nitrate ions is 130-140g/L, so that the solution can be used as an etching solution to produce an etched circuit board, and the generated copper nitrate solution is supplied to the step 1) again.
Example four:
a comprehensive recovery treatment method for copper nitrate waste copper cutting liquid comprises the following steps:
1) concentrating the waste copper nitrate copper cutting liquid to obtain a high-concentration copper nitrate solution, wherein the concentration of copper ions is 75.6g/L, and the concentration of nitrate ions is 208.1 g/L; specifically, the copper nitrate waste copper cutting liquid is concentrated by adopting a reduced pressure distillation method under a reduced pressure environment with the air pressure value lower than 30mmHg (lower than 30 ℃), and the generated distilled water vapor is pumped into a lime pool at normal temperature and normal pressure by adopting an oil pump.
2) Adding 13g/L of 98% concentrated sulfuric acid to the bottom of the high-concentration copper nitrate solution obtained in the step 1) through a pipette to prepare a high-concentration copper nitrate solution before mixing, and conveying the generated gas into a lime pool through an air pump;
3) adding 2 per mill of prepared nitric acid corrosion inhibitor into the high-concentration copper nitrate mixed pre-solution prepared in the step 2) to prepare copper nitrate pre-electrodeposition solution; the concentration of the prepared aqueous solution of the nitric acid corrosion inhibitor is 10 percent.
4) Directly introducing the copper nitrate pre-electrodeposition solution prepared in the step 3) into an electrodeposition tank, electrolyzing to produce an electrodeposited copper product, preparing a cooling system, and extracting under the conditions of current density of 400A/m2, electrolysis circulation amount of 480L/h and electrodeposition temperature of below 20 ℃ to obtain a No. 1 standard copper cathode copper product and a low-copper ion-containing post-electrodeposition solution; the cooling system adopts an indirect cooling process, and the indirect cooling process is indirect cooling by using circulating cooling water.
5) And (3) conveying the solution obtained in the step 4) and containing low copper ions to a PCB etching process, adding water to dilute the solution until the concentration of the copper ions is 3-4g/L and the concentration of the nitrate ions is 130-140g/L, so that the solution can be used as an etching solution to produce an etched circuit board, and the generated copper nitrate solution is supplied to the step 1) again.
The specific embodiments are only for explaining the present invention, and the present invention is not limited thereto, and those skilled in the art can make modifications without inventive contribution to the present embodiments as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (7)
1. A comprehensive recovery processing method of copper nitrate waste copper cutting liquid is characterized in that: the method comprises the following steps:
1) concentrating the waste copper cutting liquid of the copper nitrate to obtain a high-concentration copper nitrate solution, wherein the concentration of copper ions is 50-120g/L, and the concentration of nitrate ions is 100-350 g/L;
2) adding concentrated sulfuric acid with the concentration of 98% to the high-concentration copper nitrate solution obtained in the step 1) through a pipette to the bottom of the solution, and preparing a high-concentration copper nitrate mixed pre-solution;
3) adding the prepared nitric acid corrosion inhibitor into the high-concentration copper nitrate mixed pre-solution prepared in the step 2) to prepare a copper nitrate pre-electrodeposition solution;
4) directly introducing the copper nitrate pre-electrodeposition solution prepared in the step 3) into an electrodeposition tank, producing an electrodeposited copper product by electrolysis and configuring a cooling system at a current density of 300-2Extracting under the conditions that the electrolysis circulation amount is 400-500L/h and the electrodeposition temperature is below 20 ℃ to obtain a No. 1 standard copper cathode copper product and a low-copper ion-containing post-electrodeposition solution;
5) conveying the electro-deposition solution containing low copper ions obtained in the step 4) to a PCB etching process, using the electro-deposition solution as an etching solution to produce an etched circuit board, and resupplying the generated copper nitrate solution to the step 1).
2. The comprehensive recovery and treatment method for the copper nitrate waste copper cutting liquid according to claim 1, which is characterized in that: and in the step 1), the copper nitrate waste copper cutting liquid is concentrated under the reduced pressure environment with the air pressure value lower than 30mmHg by adopting a reduced pressure distillation method, and the generated distilled water vapor is pumped into a lime pool at normal temperature and normal pressure by adopting an oil pump.
3. The comprehensive recovery and treatment method for the copper nitrate waste copper cutting liquid according to claim 1, which is characterized in that: the concentration of copper ions in the high-concentration copper nitrate solution in the step 1) is 70 g/L; the nitrate ion concentration was 350 g/L.
4. The comprehensive recovery and treatment method for the copper nitrate waste copper cutting liquid according to claim 1, which is characterized in that: the adding amount of the concentrated sulfuric acid in the step 2) is 5-10g/L, and the generated gas is conveyed into the lime pool through an air pump.
5. The comprehensive recovery and treatment method for the copper nitrate waste copper cutting liquid according to claim 1, which is characterized in that: the concentration of the prepared aqueous solution of the nitric acid corrosion inhibitor added in the step 3) is 10 percent; the addition amount is 3 per mill.
6. The comprehensive recovery and treatment method for the copper nitrate waste copper cutting liquid according to claim 1, which is characterized in that: the cooling system in the step 4) is an indirect cooling process, and the indirect cooling is indirect cooling by using cooling circulating water.
7. The comprehensive recovery and treatment method for the copper nitrate waste copper cutting liquid according to claim 1, which is characterized in that: and (3) after the electrodeposition solution containing low copper ions in the step 5) is conveyed to a PCB etching process, adding water to dilute the solution until the concentration of the copper ions is 3-4g/L and the concentration of the nitrate ions is 140 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010637375.4A CN111663155B (en) | 2020-07-03 | 2020-07-03 | Comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010637375.4A CN111663155B (en) | 2020-07-03 | 2020-07-03 | Comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111663155A CN111663155A (en) | 2020-09-15 |
| CN111663155B true CN111663155B (en) | 2021-05-11 |
Family
ID=72391281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010637375.4A Active CN111663155B (en) | 2020-07-03 | 2020-07-03 | Comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111663155B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115196667B (en) * | 2022-09-15 | 2023-01-13 | 阮氏化工（常熟）有限公司 | Method and device for producing copper sulfate and nitric acid by using stripping and hanging liquid |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB643668A (en) * | 1947-03-04 | 1950-09-27 | Benoy Kumar Bose | Improvements relating to the recovery of metals from base metal nitrates |
| US4545850A (en) * | 1984-08-20 | 1985-10-08 | Psi Star | Regenerative copper etching process and solution |
| JPH089791B2 (en) * | 1987-07-08 | 1996-01-31 | 日立電線株式会社 | Copper electrolytic refining method |
| US6596053B2 (en) * | 1999-07-08 | 2003-07-22 | Cognis Corporation | Processes for the recovery of copper from aqueous solutions containing nitrate ions |
| WO2006134724A1 (en) * | 2005-06-15 | 2006-12-21 | Nippon Mining & Metals Co., Ltd. | Ultrahigh-purity copper and process for producing the same, and bonding wire comprising ultrahigh-purity copper |
| CN101280430A (en) * | 2008-05-15 | 2008-10-08 | 金川集团有限公司 | Preparation of hyperpure copper |
| CN103265094A (en) * | 2013-06-01 | 2013-08-28 | 山东天维膜技术有限公司 | Method for recycling nitric acid and copper from waste water generated in production of printed circuit board |
| CN106222697B (en) * | 2016-07-26 | 2018-05-01 | 深圳市京中康科技有限公司 | A kind of technique that copper is recycled in the waste liquid from copper nitrate |
| CN106319563A (en) * | 2016-09-13 | 2017-01-11 | 广沣金源（北京）科技有限公司 | Electrolytic copper and method for producing electrolytic copper from concentrated nitric acid copper-containing wastewater |
| CN108677214A (en) * | 2018-07-09 | 2018-10-19 | 南京舜业环保科技有限公司 | A kind of the copper retracting device and recovery method of nitric acid deplating liquid |
| CN109972180B (en) * | 2019-04-12 | 2020-12-18 | 博敏电子股份有限公司 | New application of 2,2'-dithiodipyridine, electroplating hole filling additive using the same, and electroplating method using the additive |
-
2020
- 2020-07-03 CN CN202010637375.4A patent/CN111663155B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111663155A (en) | 2020-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101768742B (en) | Regenerated acidic etching solution, copper recycling method and special device thereof | |
| CN101693997B (en) | Method for processing acidic etching waste solution of printed circuit board | |
| CN103060844B (en) | Resource recovering method for nitric acid type waste solder stripping solution | |
| CN105523668B (en) | A kind of PCB nitrogen-containing wastewaters Zero discharge treatment method and device | |
| CN101353795A (en) | Method for extracting copper from printed circuit board acidic spent etching solution and preparing poly ferric chloride | |
| CN115449849B (en) | Microetching solution on-line electrolytic copper extraction cyclic regeneration process | |
| CN105483707B (en) | A kind of method that alkaline copper chloride etching waste liquid proposes copper reuse | |
| CN204779821U (en) | Etching solution recycle and regeneration and carry copper device | |
| CN103936081A (en) | Method and system for preparing ferric chloride, electrodeposited copper and copper powder from copper-containing hydrochloric acid waste liquid | |
| CN104911596A (en) | Device and method for cyclic regeneration and copper extraction of etching liquid | |
| CN111663155B (en) | Comprehensive recovery treatment method for waste copper cutting liquid of copper nitrate | |
| CN108359990A (en) | A kind of alkaline etching liquid and its recycling method | |
| CN102912375B (en) | Method and the special purpose device thereof of copper is reclaimed from acidic etching liquid | |
| CN202201979U (en) | Acid etching solution recycling and copper recovery device | |
| CN106222697B (en) | A kind of technique that copper is recycled in the waste liquid from copper nitrate | |
| CN102839379A (en) | On-line treatment method of acidic etching solution | |
| CN105692977A (en) | Treatment method of high-concentration acidic copper-containing wastewater | |
| CN103265094A (en) | Method for recycling nitric acid and copper from waste water generated in production of printed circuit board | |
| CN106350678A (en) | Method of recycling corrosion inhibitor and copper from brownification waste liquid | |
| CN115928150A (en) | Method for recovering silver from silver-containing waste | |
| CN202440550U (en) | Alkaline etching liquid recycling and regenerating system | |
| CN201704154U (en) | Integrated PCB cupric waste liquid treatment system | |
| CN103290415B (en) | Treatment process and system of acid etching solution | |
| CN218710923U (en) | Device system for regenerating and extracting copper from acidic etching solution of printed circuit board | |
| CN208087748U (en) | Two-component acidity etching liquid recycling device |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |