CN109652807A - A kind of copper nitrate spent solution regeneration and copper recovery method - Google Patents
A kind of copper nitrate spent solution regeneration and copper recovery method Download PDFInfo
- Publication number
- CN109652807A CN109652807A CN201910020815.9A CN201910020815A CN109652807A CN 109652807 A CN109652807 A CN 109652807A CN 201910020815 A CN201910020815 A CN 201910020815A CN 109652807 A CN109652807 A CN 109652807A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- copper
- copper nitrate
- added
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention discloses a kind of copper nitrate spent solution regeneration and copper recovery method, this method key step are as follows: step 1, and copper nitrate waste liquid is added additive containing Ammonia and carries out inhibition reaction；Step 2, the copper nitrate waste liquid after reaction is electrolysed, and obtains copper, waste liquid and nitrogen dioxide；Nitrogen dioxide, which is exported to absorption plant, to be absorbed, and the first acid solution is obtained；Step 3, the waste liquid after electrolysis is transferred to transferring device, and oxidant is added and carries out oxidation reaction, after cooling, nitric acid is added, obtains the second acid solution；Step 4, the first acid solution in step 2 is mixed with the second acid solution in step 3, obtains regenerated liquid.Waste liquid after electrolytic recovery copper is added oxidizing substance and oxidation reaction occurs, and adds nitric acid after being cooled to room temperature again, restores the corrosion strength of waste liquid; it realizes the circular regeneration of copper nitrate waste liquid, reduces the discharge of copper nitrate waste liquid, mitigate the processing pressure of total nitrogen; environment is protected, is economized on resources.
Description
Technical field
The present invention relates to copper nitrate waste water recovery technology fields, and in particular, to a kind of copper nitrate spent solution regeneration and copper return
Receiving method.
Background technique
Nitric acid stripping and hanging is the important procedure in PCB processing procedure, and with the progress of stripping and hanging process, copper content is gradually saturated, and loses copper
It slows, solution is extremely unstable, is not able to satisfy stripping and hanging procedure calls, and nitric acid copper liquid is just used as liquid waste processing at this time.Existing skill
Processing method in art, which can only recycle, is wherein worth higher copper, cannot achieve circular regeneration to waste liquid.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of copper nitrate spent solution regeneration and copper recovery method.
A kind of copper nitrate spent solution regeneration and copper recovery method disclosed by the invention, comprising the following steps:
Step 1, copper nitrate waste liquid is added additive containing Ammonia and carries out inhibition reaction, wherein additive containing Ammonia and nitric acid
The volume ratio of copper waste liquid is 6-9:1000；
Step 2, the copper nitrate waste liquid after reaction is electrolysed, and obtains copper, waste liquid and nitrogen dioxide；The nitrogen dioxide is defeated
It is absorbed out to absorption plant, obtains the first acid solution；
Step 3, the waste liquid after electrolysis is transferred to transferring device, and oxidant is added and carries out oxidation reaction, after cooling, is added
Nitric acid obtains the second acid solution；Wherein the volume ratio of the oxidant and the waste liquid is 2-5:1000, the nitric acid and institute
The volume ratio for stating waste liquid is 10-15:1000；
Step 4, the first acid solution in the step 2 is mixed with the second acid solution in the step 3, is obtained again
Raw liquid.
According to an embodiment of the present invention, in step 1, the stirring of additive containing Ammonia is added and carries out inhibiting reaction 10-15
Minute.
According to an embodiment of the present invention, in step 2, electrolysis temperature is 30-35 DEG C.
According to an embodiment of the present invention, in step 3, oxidant is added and carries out oxidation reaction, oxidizing reaction temperature is
It 40-50 DEG C, reacts 15-20 minutes.
According to an embodiment of the present invention, in step 3, after the waste liquid after oxidation reaction is cooled to room temperature, nitric acid is added.
Compared with prior art, the present invention can be obtained including following effect:
Oxidizing substance is added in waste liquid after electrolytic recovery copper, and oxidation reaction occurs with remaining additive containing Ammonia, cold
But to appropriate nitric acid is added again after room temperature, restore the corrosion strength of waste liquid, realize the circular regeneration of copper nitrate waste liquid, reduce copper nitrate
The discharge of waste liquid mitigates the processing pressure of total nitrogen, protects environment, economizes on resources.
Specific embodiment
Multiple embodiments of the application will be disclosed below, as clearly stated, details in many practices will with
Illustrate together in lower narration.It should be appreciated, however, that the details in these practices is not applied to limit the application.That is,
In some embodiments of the application, the details in these practices is non-essential.
A kind of copper nitrate spent solution regeneration and copper recovery method in the present embodiment the following steps are included:
Step 1, copper nitrate waste liquid is added additive containing Ammonia and carries out inhibition reaction, wherein additive containing Ammonia and nitric acid
The volume ratio of copper waste liquid is 6-9:1000.In specific embodiment, 10L copper nitrate waste water is introduced into transfer cylinder, and transfer cylinder is for containing
It puts copper nitrate waste water and carries out inhibition reaction, part can also be held for other.Preferably, the copper ion concentration in copper nitrate waste water is
20-35g/L, hydrogen ion concentration 5.2mol/L.The additive containing Ammonia that 0.06-0.09L is added is inhibited into transfer cylinder
Reaction, is stirred to react 10-15 minutes, so that copper nitrate waste water and the mixing of additive containing Ammonia are abundant.Further, inhibit reaction
Refer to that additive containing Ammonia reacts with nitric acid, to inhibit corrosion of the nitric acid to copper in waste liquid.After reaction, with 20 millis
Waste liquid after rising reaction is reacted with copper sheet, and whether test copper nitrate waste liquid inhibits to complete, if copper nitrate waste liquid corrodes copper sheet,
Copper nitrate waste liquid need to continue to add additive containing Ammonia, it is preferable that additive containing Ammonia is 99% o-chloraniline of mass percent
Solution.
Step 2, the copper nitrate waste liquid after reaction is electrolysed, and obtains copper, waste liquid and nitrogen dioxide；Nitrogen dioxide export to
Absorption plant is absorbed, and the first acid solution is obtained.In specific embodiment, the copper nitrate waste liquid after reaction draws as electrolyte
Enter in electrolysis unit, it is preferable that electrolysis unit is using stainless steel as cathode, using bellows titanium sheet as anode, so that producing in electrolytic process
Raw nitrogen dioxide is delivered to absorption plant absorption.Amberplex is welded in PV plate face for example, bellows titanium sheet refers to, it will
PV plate is welded into rectangular box-like, and the specification that PV intralamellar part corresponds to titanium sheet is equipped with slot, and slot is equipped with conduit on one side, and the other end of conduit connects
The jet pump being connected in absorption plant.In use, by the slot of titanium sheet insertion PV plate, ion in copper nitrate waste liquid can by from
Proton exchange, which enters, occurs cell reaction in slot.The nitrogen dioxide that electrolytic process generates, which is ion exchanged film, to be stopped and stays in slot
In, since jet stream pump startup extracts, negative pressure is generated, nitrogen dioxide is delivered to absorption plant by conduit and is absorbed, it is preferable that
Water is held in absorption plant, nitrogen dioxide is dissolved in water and generates nitric acid, obtains the first acid solution.In energization electrolytic process, electricity
Temperature control is solved at 30-35 DEG C, in case temperature is excessively high, nitric acid volatilization；Temperature is too low, reacts too slow.If hair in electrolytic process
The copper that existing nitric acid corrosion reduction is precipitated, should continuously add suitable additive containing Ammonia.When solution copper ion is dense in electrolysis unit
When degree is lower than 5g/L, stop electrolysis.After electrolysis, the copper that cathode is precipitated is obtained.
Step 3, the waste liquid after electrolysis is transferred to transferring device, and oxidant is added and carries out oxidation reaction, after cooling, is added
Nitric acid obtains the second acid solution；Wherein the volume ratio of oxidant and waste liquid is 2-5:1000, and the volume ratio of nitric acid and waste liquid is
10-15:1000.In specific embodiment, the waste liquid after electrolysis is transferred in regenerated liquid transferring device, and regenerated liquid transferring device is used for
It holds waste liquid and carries out regeneration adjusting.In specific embodiment, the oxidizing substance that 0.02-0.05L is added carries out oxidation reaction, heating
It to 40-50 DEG C, reacts 15-20 minutes, the remaining additive containing Ammonia of step before ruing out of.Preferably, oxidant is quality hundred
The hydrogen peroxide solution of score 27.5%.Solution is cooled to room temperature after oxidation reaction, and 0.1-0.15L nitric acid is added to regenerated liquid transfer
Device obtains the second acid solution.Preferably, nitric acid is the nitric acid solution of mass percent 68%.
Step 4, the first acid solution in step 2 is mixed with the second acid solution in step 3, obtains regenerated liquid.Tool
In body embodiment, the second acid solution in the first acid solution and step 3 of step 2 is mixed, obtains regenerated liquid.It is preferred that
Ground, the hydrionic concentration of regenerated liquid are at least 6mol/L or more.
To sum up, oxidizing substance and nitric acid is added by the waste liquid after electrolysis in the present invention, restores the corrosion of copper nitrate waste liquid
Ability realizes the circular regeneration of copper nitrate waste liquid, reduces using and discharging for nitric acid, mitigate the processing pressure of total nitrogen.This dispatch from foreign news agency
The nitrogen dioxide generated in solution preocess is dissolved and absorbed through absorption plant, and after dissolving and absorbing nitrogen dioxide, solution acidic is reinforced, and is realized
The recycling of nitrogen dioxide, avoids the wasting of resources.
The upper only embodiments of the present invention, are not intended to restrict the invention.For those skilled in the art
For, the invention may be variously modified and varied.All any modifications made in spirit and principles of the present invention are equally replaced
It changes, improve, should all include in scope of the presently claimed invention.
Claims (5)
1. a kind of copper nitrate spent solution regeneration and copper recovery method, which comprises the following steps:
Step 1, copper nitrate waste liquid is added additive containing Ammonia and carries out inhibition reaction, wherein additive containing Ammonia and copper nitrate are useless
The volume ratio of liquid is 6-9:1000；
Step 2, the copper nitrate waste liquid after reaction is electrolysed, and obtains copper, waste liquid and nitrogen dioxide；The nitrogen dioxide export to
Absorption plant is absorbed, and the first acid solution is obtained；
Step 3, the waste liquid after electrolysis is transferred to transferring device, and oxidant is added and carries out oxidation reaction, and after cooling, nitre is added
Acid obtains the second acid solution；Wherein the volume ratio of the oxidant and the waste liquid is 2-5:1000, the nitric acid with it is described
The volume ratio of waste liquid is 10-15:1000；
Step 4, the first acid solution in the step 2 is mixed with the second acid solution in the step 3, is regenerated
Liquid.
2. copper nitrate spent solution regeneration according to claim 1 and copper recovery method, which is characterized in that in the step 1, add
Enter the stirring of additive containing Ammonia to carry out inhibiting reaction 10-15 minutes.
3. copper nitrate spent solution regeneration according to claim 1 and copper recovery method, which is characterized in that in the step 2, electricity
Solving temperature is 30-35 DEG C.
4. copper nitrate spent solution regeneration according to claim 1 and copper recovery method, which is characterized in that in the step 3, add
Enter oxidant and carry out oxidation reaction, oxidizing reaction temperature is 40-50 DEG C, is reacted 15-20 minutes.
5. copper nitrate spent solution regeneration according to claim 1 and copper recovery method, which is characterized in that in the step 3, oxygen
After waste liquid after changing reaction is cooled to room temperature, nitric acid is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910020815.9A CN109652807A (en) | 2019-01-09 | 2019-01-09 | A kind of copper nitrate spent solution regeneration and copper recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910020815.9A CN109652807A (en) | 2019-01-09 | 2019-01-09 | A kind of copper nitrate spent solution regeneration and copper recovery method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109652807A true CN109652807A (en) | 2019-04-19 |
Family
ID=66119424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910020815.9A Pending CN109652807A (en) | 2019-01-09 | 2019-01-09 | A kind of copper nitrate spent solution regeneration and copper recovery method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109652807A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
| CN113249775A (en) * | 2021-04-07 | 2021-08-13 | 深圳市祺鑫环保科技有限公司 | Copper dissolution inhibitor and application thereof |
| CN113415785A (en) * | 2021-07-22 | 2021-09-21 | 盛隆资源再生（无锡）有限公司 | Method for separating and recovering hydrofluoric acid from fluorine-containing mixed acid |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167461A (en) * | 2011-05-06 | 2011-08-31 | 中国石油化工集团公司 | Method for treating production wastewater of o-chloroaniline |
| CN107699697A (en) * | 2017-10-19 | 2018-02-16 | 惠州市臻鼎环保科技有限公司 | A kind of copper recovery method of copper nitrate waste water |
-
2019
- 2019-01-09 CN CN201910020815.9A patent/CN109652807A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167461A (en) * | 2011-05-06 | 2011-08-31 | 中国石油化工集团公司 | Method for treating production wastewater of o-chloroaniline |
| CN107699697A (en) * | 2017-10-19 | 2018-02-16 | 惠州市臻鼎环保科技有限公司 | A kind of copper recovery method of copper nitrate waste water |
Non-Patent Citations (1)
| Title |
|---|
| 中国医药工业公司: "《医药工业环境保护经验汇编》", 30 June 1982 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
| CN113249775A (en) * | 2021-04-07 | 2021-08-13 | 深圳市祺鑫环保科技有限公司 | Copper dissolution inhibitor and application thereof |
| CN113415785A (en) * | 2021-07-22 | 2021-09-21 | 盛隆资源再生（无锡）有限公司 | Method for separating and recovering hydrofluoric acid from fluorine-containing mixed acid |
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109652807A (en) | A kind of copper nitrate spent solution regeneration and copper recovery method | |
| CN106910959B (en) | Method for selectively recovering lithium from lithium iron phosphate waste | |
| CN113629244B (en) | Lithium supplementing and repairing method for invalid lithium iron phosphate cathode material under low lithium consumption | |
| KR20150063159A (en) | Method for the hydrometallurgical recovery of lithium, nickel and cobalt from the lithium transition metal oxide-containing fraction of used galvanic cells | |
| CN106835194A (en) | A kind of cobalt chloride electrodeposition process | |
| JP2016500753A (en) | Method for recovering lithium from wet galvanic cell containing lithium iron phosphate by wet metallurgy | |
| CN113174486A (en) | Method for recovering valuable metals of waste lithium ion batteries | |
| Yang et al. | Progress and prospect on the recycling of spent lithium‐ion batteries: Ending is beginning | |
| CN108503167B (en) | Method for synthesizing water purifying agent by using steel pickling waste liquid | |
| CN108893742A (en) | Acidic etching waste liquid processing and reclaiming system | |
| CN111446478B (en) | Method for preparing vanadium battery electrolyte by taking vanadium-rich liquid as raw material | |
| CN113151682A (en) | Leaching method of lithium iron phosphate black powder | |
| CN111137869A (en) | Preparation method of lithium iron phosphate | |
| CN114214643A (en) | Lithium ion cycle method electrochemical ammonia synthesis process and application | |
| CN110172701A (en) | Acidic etching liquid system for regenerating and recycling | |
| US10711326B2 (en) | Method for the hydrometallurgical recovery of lithium from the lithium manganese oxide-containing fraction of used galvanic cells | |
| CN106684421B (en) | Method for preparing vanadium electrolyte | |
| CN101792862B (en) | Method for recovering metal through purified flue gas of scrap nickel-hydrogen battery | |
| JP5090036B2 (en) | A fuel cell system in which a humidifier is connected to a fuel cell unreacted mixed gas discharge duct | |
| CN100438148C (en) | Alloy powder surface treatment method | |
| CN106745951A (en) | A kind of production wastewater treatment method of ADC foaming agents | |
| CN210506530U (en) | Device for online regeneration treatment of hardware etching waste liquid | |
| CN112919440A (en) | Method for extracting lithium from retired lithium battery | |
| CN102694174B (en) | Activating treatment method for graphite applied to lithium-ion negative pole | |
| WO2019206121A1 (en) | Manufacturing method and device of flow battery electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190419 |