CN108517410A - A kind of method of metallic copper in hydrometallurgical recovery printed wiring board (PCB) - Google Patents
A kind of method of metallic copper in hydrometallurgical recovery printed wiring board (PCB) Download PDFInfo
- Publication number
- CN108517410A CN108517410A CN201810429072.6A CN201810429072A CN108517410A CN 108517410 A CN108517410 A CN 108517410A CN 201810429072 A CN201810429072 A CN 201810429072A CN 108517410 A CN108517410 A CN 108517410A
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- Prior art keywords
- copper
- printed wiring
- solution
- hydrochloric acid
- pcb
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- 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)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of hydrometallurgical recovery printed wiring boards（PCB）The method of middle metallic copper.Technological process is as shown in Figure 1, wherein, certain density hydrochloric acid is used in leaching process, it leaches at normal temperatures, the acid solution of certain copper content is obtained after to be leached, solution is aoxidized as anolyte after leaching, catholyte electro-deposition is re-used as after oxidation and obtains copper metal, noble metal does not dissolve in hydrochloric acid, and enrichment is deposited in solution bottom.The present invention mainly recycles the metallic copper in printed wiring board, and product is copper coin, entire technological process closed cycle, and entrance is hydrochloric acid and PCB, and outlet only has copper metal, noble metal and construction material.The method have the advantages that PCB electronic wastes are turned waste into wealth, is simple for process, process intermediate recycles.
Description
Technical field
The invention belongs to technical field of resource recovery, it is related to a kind of side of metallic copper in hydrometallurgical recovery printed wiring board
Method.
Background technology
In PCB contain a large amount of metallics, wherein gold content be gold ore tens arrive hundred times.If profit can be recycled
With just more than 50000 RMB, the recycling of metal can not only accelerate to locate for copper recyclable 1 ton of PCB, gold, nickel value
Electronic waste is managed, huge economic benefit can be more obtained.
Currently, hydrometallurgy is to be handled the discarded PCB containing metal with strong acid or strong oxidizer using wet method, obtain
The precipitation of inertia noble metal and the acid solution of active metal handle the stripping sediment of noble metal with chloroazotic acid etc., then divide
It is not reduced into the metal products such as gold, silver, palladium, this method obtains extensive concern because its chemical reaction is easily controllable.Mesh
Before, in terms of patented invention, peak etc. is built in vain（CN104073639B）It invents and discloses a kind of using ionic liquid leaching substep
The method for recycling metal in waste and old printed wiring board, ionic liquid is first added in the method and the aqueous solution of oxidant carries out PCB
It leaches, the copper and zinc in filtrate is restored by filtering, being electrolysed after leaching, then with ammonia solvent filter residue, water is used after filtering
It closes trap reduction filtrate and obtains thick silver.Sodium hydroxide solution is added in filter residue, then is restored in filtrate by dissolving, filtering, electrolysis
Tin, with the nickel in dissolving with hydrochloric acid filter residue, condensing crystallizing recycles nickel chloride, finally uses the gold in aqua regia dissolution filter residue, reduction filter
Gold in liquid.This method is there are some disadvantages, and valuable metal recovery is at twice weight in the spent acid processing and waste residue in technique
Difficulty is wanted, it is simple and practicable to handle spent acid with neutralisation, but acid fails to be utilized, and also alkaline consumption is very big, 1% in leached mud
The copper and noble metal of left and right are also recycled without feasible solution.Exactly these problems make several years hydrometallurgical processes of prosperity, by
Copper metallurgy field is gradually exited.
The present invention is directed to detach the noble metals such as copper and deposition gold, silver, palladium from PCB, in conventional wet metallurgical technology
The economic benefit and environmental benefit of sour consumption big, spent acid processing hardly possible problem and enterprise, creative uses the regenerated side of anode
Method, technique closed cycle, allows leachate to recycle.Copper is set to leach into solution with HCl systems, noble metal is then deposited on liquid
In body, noble metal is collected by enrichment, copper isolates solution by electro-deposition again, to reach the recycling of metal in PCB,
Such as Fig. 1.
The present invention is compared with the prior art mainly following three points：（1）Anodic dissolution repeatedly leaches regeneration, and PCB is made to leach
Rate improves, and noble metal reaches abundant enrichment, and anodic dissolution is fully utilized.（2）Entire technique closed cycle, into technological process
Be PCB waste materials and hydrochloric acid, out be noble metal, deposition copper coin and building filler.（3）Technique is generated without waste water and gas,
Without the concern for the process problem for taking acid, environmental protection, high financial profit.
Invention content
Present invention aims at the method for metallic copper in a kind of hydrometallurgical recovery printed wiring board of offer, mainly solve to pass
Secondary pollution is serious in hydrometallurgy of uniting, the big technical problem of chemical reagent consumption amount.
To achieve the above object, the recovery process of metal is as shown in Figure 1 in PCB of the present invention.It has main steps that：By salt
Acid leaches printed wiring board at a certain temperature, and noble metal is enriched in leachate bottom, and the solution after leaching is as anode, cathode
Solution is the solution after anode is anodized, and cathode is copper sheet, and anode is graphite electrode, and fine and close copper is obtained after electro-deposition
Metal, solution after electro-deposition recycle, and technological process entrance is PCB and hydrochloric acid, exported product be copper metal, noble metal and
Construction material.
The present invention makes anodic dissolution repeatedly leach regeneration using above-mentioned technical proposal, and PCB leaching rates improve, and noble metal reaches
Fully enrichment, anodic dissolution are fully utilized.The present invention greatly reduces the generation of waste liquid in conventional wet metallurgical process, solves
Secondary pollution and the big problem of chemical reagent consumption amount, entire technique closed cycle, into technological process be PCB waste materials and
Hydrochloric acid, out be noble metal, deposition copper coin and building filler.
Description of the drawings
Fig. 1 is metallic copper recovery process flow chart in printed wiring board.
Specific implementation mode
Embodiment 1：
In the triangular flask of 250 mL, 10 g are crushed to the hydrochloric acid of a concentration of 2 mol/L of PCB and 50 mL of 0.5 mm of diameter
Mixing is placed in 15 DEG C of water-bath the mixing speed with 100 r/min and leaches 6 h, and copper ion concentration can reach in solution
108 g/L are filtered after the completion of leaching, and solid is construction material and noble metal, and liquid carries out electro-deposition as anode.In electrolytic cell
Anode slot in be added 1 L extracted liquids, the extracted liquid after being anodized for 2 L in cathode can, with 250 at 25 DEG C
A/m2Current density carry out 10 h of electro-deposition, wherein cathode be 2 cm2Copper sheet, anode be 4 cm2Graphite electrode, herein
Under the conditions of, the rate of recovery of current efficiency 94.6%, copper is 98.7%.
Embodiment 2：
In the triangular flask of 250 mL, the hydrochloric acid that 10 g are crushed to a concentration of 4 mol/L of PCB and 100 mL of 1 mm of diameter mixes
It closes, is placed in 25 DEG C of water-bath the mixing speed with 200 r/min and leaches 6 h, copper ion concentration can reach 74 in solution
G/L is filtered after the completion of leaching, and solid is construction material and noble metal, and liquid carries out electro-deposition as anode.In the sun of electrolytic cell
1 L extracted liquids, the extracted liquid after being anodized for 1 L in cathode can, with 250 A/m at 25 DEG C are added in the slot of pole2
Current density carry out 10 h of electro-deposition, wherein cathode be 2 cm2Copper sheet, anode be 2 cm2Graphite electrode, in this condition
Under, the rate of recovery of current efficiency 95.5%, copper is 98.2%.
Embodiment 3：
In the triangular flask of 250 mL, the hydrochloric acid that 10 g are crushed to a concentration of 6 mol/L of PCB and 510 mL of 2 mm of diameter mixes
It closes, is placed in 35 DEG C of water-bath the mixing speed with 300 r/min and leaches 6 h, copper ion concentration can reach 48 in solution
G/L is filtered after the completion of leaching, and solid is construction material and noble metal, and liquid carries out electro-deposition as anode.In the sun of electrolytic cell
2 L extracted liquids, the extracted liquid after being anodized for 1 L in cathode can, with 250 A/m at 25 DEG C are added in the slot of pole2
Current density carry out 10 h of electro-deposition, wherein cathode be 4 cm2Copper sheet, anode be 2 cm2Graphite electrode, in this condition
Under, the rate of recovery of current efficiency 91.3%, copper is 92.6%.
Embodiment 4：
In the triangular flask of 250 mL, 10 g are crushed to the hydrochloric acid of a concentration of 8 mol/L of PCB and 50 mL of 0.5 mm of diameter
Mixing is placed in 25 DEG C of water-bath the mixing speed with 200 r/min and leaches 6 h, and copper ion concentration can reach in solution
115 g/L are filtered after the completion of leaching, and solid is construction material and noble metal, and liquid carries out electro-deposition as anode.In electrolytic cell
Anode slot in be added 1 L extracted liquids, the extracted liquid after being anodized for 1 L in cathode can, with 250 at 25 DEG C
A/m2Current density carry out 10 h of electro-deposition, wherein cathode be 2 cm2Copper sheet, anode be 10 cm2Graphite electrode, herein
Under the conditions of, current efficiency 98.2%, deposition copper efficiency is 99.1%.
Embodiment 5：
In the triangular flask of 250 mL, the hydrochloric acid that 10 g are crushed to a concentration of 10 mol/L of PCB and 50 mL of 2 mm of diameter mixes
It closes, is placed in 25 DEG C of water-bath the mixing speed with 200 r/min and leaches 6 h, copper ion concentration can reach 118 in solution
G/L is filtered after the completion of leaching, and solid is construction material and noble metal, and liquid carries out electro-deposition as anode.In the sun of electrolytic cell
1 L extracted liquids, the extracted liquid after being anodized for 1 L in cathode can, with 250 A/m at 25 DEG C are added in the slot of pole2
Current density carry out 10 h of electro-deposition, wherein cathode be 2 cm2Copper sheet, anode be 10 cm2Graphite electrode, in this condition
Under, current efficiency 97.9%, deposition copper efficiency is 98.4%.
Claims (9)
1. the method for metallic copper, has main steps that in a kind of hydrometallurgical recovery printed wiring board as shown in Figure 1：Printed wiring
Plate leaches in hydrochloric acid, and metallic copper leaches into solution, and noble metal is enriched in leachate bottom；Solution after leaching is as sun
Pole, cathode solution are the solution aoxidized in anode, and cathode is copper sheet, and anode is graphite electrode, and densification is obtained after electro-deposition
Copper metal, the solution after electro-deposition recycle, such as Fig. 1.
2. according to the method described in claim 1, it is characterized in that：The hydrochloric acid is 2 mol/L ~ 12 of market purchase
The hydrochloric acid of mol/L.
3. according to the method described in claim 1, it is characterized in that：Extraction time of the printed wiring board in hydrochloric acid is 1 h ~ 48
h。
4. according to the method described in claim 1, it is characterized in that：The grain size of printed wiring board is in 0.1 ~ 5.0 mm.
5. according to the method described in claim 1, it is characterized in that：Printed wiring board quality is 1 g with hydrochloric acid volume ratio:1
mL~1 g:15 mL。
6. according to the method described in claim 1, it is characterized in that：Extraction temperature is 5 DEG C ~ 95 DEG C.
7. according to the method described in claim 1, it is characterized in that：Mixing speed is the r/min of 100 r/min ~ 800 when leaching.
8. according to the method described in claim 1, it is characterized in that：The anode and cathode area ratio is 1：10~5：1.
9. according to the method described in claim 1, it is characterized in that：Anode and cathode liquid volume ratio is 1：10~10：1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810429072.6A CN108517410A (en) | 2018-05-08 | 2018-05-08 | A kind of method of metallic copper in hydrometallurgical recovery printed wiring board (PCB) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810429072.6A CN108517410A (en) | 2018-05-08 | 2018-05-08 | A kind of method of metallic copper in hydrometallurgical recovery printed wiring board (PCB) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108517410A true CN108517410A (en) | 2018-09-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810429072.6A Pending CN108517410A (en) | 2018-05-08 | 2018-05-08 | A kind of method of metallic copper in hydrometallurgical recovery printed wiring board (PCB) |
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| Country | Link |
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| CN (1) | CN108517410A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609767A (en) * | 2018-12-26 | 2019-04-12 | 北京工业大学 | A kind of waste printed circuit board noble metal based on ultrasonic wave added efficiently separates recovery method |
| CN110484744A (en) * | 2019-08-26 | 2019-11-22 | 珠海格力电器股份有限公司 | A method of recycling noble metal from waste and old patch capacitor |
| IT202100021962A1 (en) | 2021-08-17 | 2023-02-17 | Envin S R L | Hydrometallurgical process for the recovery of pure metals from electronic boards and printed circuits. |
-
2018
- 2018-05-08 CN CN201810429072.6A patent/CN108517410A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609767A (en) * | 2018-12-26 | 2019-04-12 | 北京工业大学 | A kind of waste printed circuit board noble metal based on ultrasonic wave added efficiently separates recovery method |
| CN110484744A (en) * | 2019-08-26 | 2019-11-22 | 珠海格力电器股份有限公司 | A method of recycling noble metal from waste and old patch capacitor |
| CN110484744B (en) * | 2019-08-26 | 2020-07-24 | 珠海格力电器股份有限公司 | Method for recovering precious metal from waste chip capacitor |
| IT202100021962A1 (en) | 2021-08-17 | 2023-02-17 | Envin S R L | Hydrometallurgical process for the recovery of pure metals from electronic boards and printed circuits. |
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| PB01 | Publication | ||
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Application publication date: 20180911 |