CN106756091A - A kind of extracting method of Metals of Discarded Printed Circuit Boards copper - Google Patents
A kind of extracting method of Metals of Discarded Printed Circuit Boards copper Download PDFInfo
- Publication number
- CN106756091A CN106756091A CN201611179178.2A CN201611179178A CN106756091A CN 106756091 A CN106756091 A CN 106756091A CN 201611179178 A CN201611179178 A CN 201611179178A CN 106756091 A CN106756091 A CN 106756091A
- Authority
- CN
- China
- Prior art keywords
- ammonium
- metals
- printed circuit
- circuit boards
- extracting method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
- C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
-
- 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
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
Abstract
The invention discloses a kind of extracting method of Metals of Discarded Printed Circuit Boards copper, it is characterised in that comprise the following steps：Step (1)：To there is Leach reaction at a temperature of 20~90 DEG C as leaching agent by the mixed solution of the discarded circuit board after crushing as raw material, ammoniacal liquor, ammonium salt and aminated compounds, filter to obtain leachate；Step (2)：The leachate pH obtained in step (1) is adjusted to 0.5~3, oxalates is added, precipitation reaction occurs at a temperature of 30~80 DEG C, be centrifugally separating to obtain sediment；Step (3)：The sediment that will be obtained in step (2) 1~10h of calcining at constant temperature at a temperature of 200~500 DEG C, cooling obtains product.The present invention forms complex compound and forms mantoquita precipitation and extracts metallic copper in discarded circuit board WPCB using normal pressure ammonia leaching process and using foreign ion in oxalates and solution, and recovery rate is high, process is simple, low cost.
Description
Technical field
The present invention relates to the recycling field of metals resources in discarded circuit board (WPCB), more particularly, to one kind
The extracting method of Metals of Discarded Printed Circuit Boards copper.
Background technology
With the arrival of information age, the life for developing into people of electronic technology brings change with rapid changepl. never-ending changes and improvements, people
It is increasing to the demand of electronic product, but at the same time also generate substantial amounts of solid electronic rubbish, bring huge
Environmental problem.In general, average content of iron is 27.3% in discarded circuit board (WPCB), copper content is 16.4%, aluminium content
It is 11%, while also containing a number of noble metal, such valuable metal content will be significantly larger than general ore, can be with
Say it is " mine in city ".Wherein, copper scrap can turn into the weight of copper resource as a kind of copper resource existed with unique forms
Supplement source.In recent years, China attaches great importance to for the recycling of copper scrap, therefore the recovery technology of copper scrap develops very
Rapidly, the cost of investment of its recovery is low, risk is small, technological process is relatively easy.If being hidden in the copper resource in WPCB to these
It is used, can not only solves the environmental problem that WPCB is brought, while is conducive to alleviating China for import resource excessively
Rely on this present situation.Measuring copper relies primarily on extractant in traditional handicraft, but the use of extractant can cause to be mixed into water phase
Organic phase, so that the quality of final products is influenceed, and extractant obtains expensive.Therefore design invention is a kind of to metal in WPCB
Copper recovery rate is high and to be independent of the new enrichment method of extractant imperative.
The content of the invention
For problems of the prior art, it is an object of the invention to provide a kind of Metals of Discarded Printed Circuit Boards copper
Extracting method, to solve in existing discarded circuit board (WPCB), metallic copper recovery rate is low, need to cause product matter using extractant
The low problem of amount.
To achieve the above object, the technical solution adopted in the present invention is：A kind of extraction of Metals of Discarded Printed Circuit Boards copper
Method, comprises the following steps：Step (1)：Using by the discarded circuit board after crushing as raw material, ammoniacal liquor, ammonium salt and amine
There is Leach reaction in the mixed solution of compound, filter to obtain leachate as leaching agent at a temperature of 20~90 DEG C；Step (2)：
The leachate pH obtained in step (1) is adjusted to 0.5~3, oxalates is added, precipitation reaction occurs at a temperature of 30~80 DEG C,
It is centrifugally separating to obtain sediment；Step (3)：The sediment that will be obtained in step (2) calcining at constant temperature 1 at a temperature of 200~500 DEG C
~10h, cooling obtains product.
The beneficial effects of the present invention are：The present invention is using normal pressure ammonia leaching process and using oxalates and foreign ion in solution
Form complex compound and form mantoquita precipitation and extract metallic copper in discarded circuit board WPCB, recovery rate is high, extraction rate reached to 99.45%
More than, it is impure few, simplify subsequent treatment process；Using oxalates as precipitating reagent, it is to avoid easily cause product using traditional
Quality is low, high cost extractant, improves extraction yield, reduces production cost；Low temperature calcination process is placed in nitrogen, argon gas or true
Metal simple-substance copper is directly obtained under the protective atmosphere of empty condition, it is ensured that extract product purity.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail, and the description of this part is only exemplary and explains
Property, there should not be any restriction effect to protection scope of the present invention.
A kind of extracting method of Metals of Discarded Printed Circuit Boards copper of the invention, comprises the following steps：
Step (1)：Using by the discarded circuit board after crushing as raw material, ammoniacal liquor, ammonium salt and aminated compounds it is mixed
Solution is closed as leaching agent, Leach reaction occurs at a temperature of 20~90 DEG C, filter to obtain leachate；
Step (2)：The leachate pH obtained in step (1) is adjusted to 0.5~3, oxalates is added, in 30~80 DEG C of temperature
Lower generation precipitation reaction, is centrifugally separating to obtain sediment；
Step (3)：The sediment that will be obtained in step (2) 1~10h of calcining at constant temperature at a temperature of 200~500 DEG C, cooling
Obtain product.
Preferably, ammonium salt is ammonium hydrogen carbonate, ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium fluoride, acetic acid in the step (1)
One kind in ammonium, ammonium carbonate, ammonium persulfate, monoammonium phosphate, ammonium dihydrogen phosphate, ammonium persulfate, ATS (Ammonium thiosulphate) or ammonium molybdate
Or several mixtures.
Preferably, amine substance is ethylenediamine, n-octyl amine, triethanolamine, n-butylamine, diethylamine, first in the step (1)
One or more mixtures in amine, benzene methanamine, hydrazine hydrate or urea.
Preferably, in the step (2), oxalates be sodium oxalate, potassium oxalate, ammonium oxalate, potassium binoxalate, sodium bioxalate,
Or one or more mixtures in ammonium binoxalate.
Preferably, in the step (1), ammoniacal liquor, ammonium salt, the mass ratio of amine substance are (1~8):(0.5~7):
(0.2~10).
Preferably, the Leach reaction time is 1~10h in the step (1).
Preferably, the precipitation reaction time is 20~120min in the step (2).
It is furthermore preferred that in the step (3), sediment carries out calcining at constant temperature under nitrogen, argon gas or vacuum condition.
Embodiment 1
Discarded circuit board WPCB is crushed, discarded circuit board WPCB powder 1.0g are weighed, three-neck flask is respectively placed in
In, it is 4 to be added thereto to 80mL mass ratioes:2:The mixed liquor of 2.5 ammoniacal liquor, ammonium salt and triethanolamine, wherein ammonium salt are chlorination
60 DEG C are heated under ammonium, strong agitation carries out Leach reaction 4h, and leachate is obtained after filtering；Leachate pH is adjusted to 1.0 with hydrochloric acid,
Add 1.0g (NH4)2C2O4, and there is precipitation reaction 60min at 60 DEG C；The precipitation that will be obtained is in a nitrogen atmosphere in tubular type
In after calcining at constant temperature 4h at 400 DEG C in stove, furnace cooling obtains final product metallic copper powder.
With embodiment 1, difference is extraction conditions and used ammonium salt point to the extraction process of embodiment 2,3,4,5
Wei not NH4HCO3、(NH4)2SO4(NH4)2CO3、NH4HCO3(NH4)2SO4Mixture.
The extraction conditions of the Metals of Discarded Printed Circuit Boards copper of embodiment 1~5 and the leaching rate obtained by experimental calculation and
Metallic copper yield is as shown in table 1.
Table 1
The extraction process of embodiment 6,7,8,9,10 with embodiment 1, difference be used aminated compounds not
Together.
The extraction conditions of the Metals of Discarded Printed Circuit Boards copper of embodiment 6~10 and the leaching rate obtained by experimental calculation and
Metallic copper yield is as shown in table 2.
Table 2
With embodiment 1, difference is m to the extraction process of embodiment 11,12,13,14Ammoniacal liquor：mAmmonium chloride：mTriethanolamine=4.0:
2.0:X, wherein x=0.5,2.5,4.5,6.5.
The extraction conditions of the Metals of Discarded Printed Circuit Boards copper of embodiment 11~14 and the leaching rate obtained by experimental calculation
It is as shown in table 3 with metallic copper yield.
Table 3
The extraction process of embodiment 15,16,17,18 with embodiment 1, difference be pH be adjusted to 0.5 respectively, 1.0,
1.5、2.0。
The extraction conditions of the Metals of Discarded Printed Circuit Boards copper of embodiment 15~18 and the leaching rate obtained by experimental calculation
It is as shown in table 4 with metallic copper yield.
Table 4
The extraction process of embodiment 19,20,21,22 with embodiment 1, difference be calcining heat be respectively 200 DEG C,
300℃、400℃、500℃。
The extraction conditions of the Metals of Discarded Printed Circuit Boards copper of embodiment 19~22 and the leaching rate obtained by experimental calculation
It is as shown in table 5 with metallic copper yield.
Table 5
| Embodiment | Reaction temperature | Extraction time | Calcining heat | Calcination time | Metallic copper yield/% |
| 19 | 60℃ | 4h | 200℃ | 4h | 90.25 |
| 20 | 60℃ | 4h | 300℃ | 4h | 98.57 |
| 21 | 60℃ | 4h | 400℃ | 4h | 99.45 |
| 22 | 60℃ | 4h | 500℃ | 4h | 99.05 |
The above, is only presently preferred embodiments of the present invention, not makes any limitation to technical scope of the invention, therefore
Every any trickle amendment, equivalent variations and modification made to above example according to technical spirit of the invention, still belongs to
In the range of technical scheme.
Claims (8)
1. a kind of extracting method of Metals of Discarded Printed Circuit Boards copper, it is characterised in that comprise the following steps：
Step (1)：Using by the discarded circuit board after crushing as raw material, the mixing of ammoniacal liquor, ammonium salt and aminated compounds is molten
There is Leach reaction in liquid, filter to obtain leachate as leaching agent at a temperature of 20~90 DEG C；
Step (2)：The leachate pH obtained in step (1) is adjusted to 0.5~3, oxalates is added, issued in 30~80 DEG C of temperature
Raw precipitation reaction, is centrifugally separating to obtain sediment；
Step (3)：The sediment that will be obtained in step (2) 1~10h of calcining at constant temperature at a temperature of 200~500 DEG C, cooling is obtained
Product.
2. the extracting method of Metals of Discarded Printed Circuit Boards copper as claimed in claim 1, it is characterised in that：In the step (1)
Ammonium salt be ammonium hydrogen carbonate, ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium fluoride, ammonium acetate, ammonium carbonate, ammonium persulfate, monoammonium phosphate,
One or more mixtures in ammonium dihydrogen phosphate, ammonium persulfate, ATS (Ammonium thiosulphate) or ammonium molybdate.
3. the extracting method of Metals of Discarded Printed Circuit Boards copper as claimed in claim 1, it is characterised in that：In the step (1)
Amine substance is in ethylenediamine, n-octyl amine, triethanolamine, n-butylamine, diethylamine, methylamine, benzene methanamine, hydrazine hydrate or urea
Plant or several mixtures.
4. the extracting method of Metals of Discarded Printed Circuit Boards copper as claimed in claim 1, it is characterised in that：In the step (2),
Oxalates is one or more mixing in sodium oxalate, potassium oxalate, ammonium oxalate, potassium binoxalate, sodium bioxalate or ammonium binoxalate
Thing.
5. the extracting method of Metals of Discarded Printed Circuit Boards copper as claimed in claim 1, it is characterised in that：In the step (1),
Ammoniacal liquor, ammonium salt, the mass ratio of amine substance are (1~8):(0.5~7):(0.2~10).
6. the extracting method of Metals of Discarded Printed Circuit Boards copper as claimed in claim 1, it is characterised in that：In the step (1)
The Leach reaction time is 1~10h.
7. the extracting method of Metals of Discarded Printed Circuit Boards copper as claimed in claim 1, it is characterised in that：In the step (2)
The precipitation reaction time is 20~120min.
8. the extracting method of Metals of Discarded Printed Circuit Boards copper as claimed in claim 1, it is characterised in that：In the step (3),
Sediment carries out calcining at constant temperature under nitrogen, argon gas or vacuum condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611179178.2A CN106756091A (en) | 2016-12-19 | 2016-12-19 | A kind of extracting method of Metals of Discarded Printed Circuit Boards copper |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611179178.2A CN106756091A (en) | 2016-12-19 | 2016-12-19 | A kind of extracting method of Metals of Discarded Printed Circuit Boards copper |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355498A (en) * | 2018-11-22 | 2019-02-19 | 长春黄金研究院有限公司 | A kind of process of low grade copper oxide ore recycling copper |
| CN109680163A (en) * | 2019-01-14 | 2019-04-26 | 东北大学 | A method of using triethanolamine as the Leaching of Gold Using Thiosulfate of additive |
| CN112921356A (en) * | 2021-01-22 | 2021-06-08 | 西南科技大学 | Method for recovering copper from waste printed circuit board |
| CN114516654A (en) * | 2022-02-09 | 2022-05-20 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by same |
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| CN101315996A (en) * | 2008-06-20 | 2008-12-03 | 北京矿冶研究总院 | Method for selectively removing copper from waste lithium ion battery |
| CN102190326A (en) * | 2010-03-05 | 2011-09-21 | 昶昕实业股份有限公司 | Methods for recovering copper from copper-containing waste liquor |
| CN104313583A (en) * | 2014-07-16 | 2015-01-28 | 东莞市广华化工有限公司 | Precipitant for recycling acidic etching waste liquid, and processing method thereof |
Non-Patent Citations (1)
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| 张志欣 等: ""利用WPCB 制备锂离子电池Cu2O/G 复合负极材料的研究"", 《中部四省化学化工学会2016年学术年会摘要集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355498A (en) * | 2018-11-22 | 2019-02-19 | 长春黄金研究院有限公司 | A kind of process of low grade copper oxide ore recycling copper |
| CN109680163A (en) * | 2019-01-14 | 2019-04-26 | 东北大学 | A method of using triethanolamine as the Leaching of Gold Using Thiosulfate of additive |
| CN112921356A (en) * | 2021-01-22 | 2021-06-08 | 西南科技大学 | Method for recovering copper from waste printed circuit board |
| CN112921356B (en) * | 2021-01-22 | 2022-05-27 | 西南科技大学 | Method for recovering copper from waste printed circuit board |
| CN114516654A (en) * | 2022-02-09 | 2022-05-20 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by same |
| CN114516654B (en) * | 2022-02-09 | 2024-02-27 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by preparation method |
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