CN100406591C - Method for extracting metal copper from electronical wastes - Google Patents
Method for extracting metal copper from electronical wastes Download PDFInfo
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- CN100406591C CN100406591C CNB2006101178026A CN200610117802A CN100406591C CN 100406591 C CN100406591 C CN 100406591C CN B2006101178026 A CNB2006101178026 A CN B2006101178026A CN 200610117802 A CN200610117802 A CN 200610117802A CN 100406591 C CN100406591 C CN 100406591C
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- electron wastes
- copper
- electrodeposition
- extracting copper
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
This invention relates to a method for extracting Cu from electrical wastes. The method comprises: utilizing electrical wastes such as printed circuit board as the raw materials, dissolving Cu by oxygen via indirect oxidation in a three-phase bed, extracting Cu by solvent extraction, performing back extraction, concentrating, and performing electrodeposition on the concentrate to obtain Cu with purity up to 99.99%. The method can recover Cu from electrical wastes such as printed circuit board, thus reducing environmental pollution.
Description
Technical field
The invention belongs to domain of inorganic chemistry, particularly relate to and from electron wastes, extract method of metal copper.
Background technology
Electron wastes such as printed circuit board (PCB) contain tens kinds of elements, and so multiple element has brought very big difficulty for the comprehensive treating process of electron wastes.And wherein contain the element of a lot of severe toxicity, if deal with improperly, bring very big harm will for environment and mankind itself's health.Simultaneously, also contain a lot of metal values in these elements, wherein the content of copper is the highest, is directly discarded if copper does not recycle to be significant wastage to resource.There are data to show, from 1 ton of electronics integrated circuit board (mobile phone and computer), can isolate 130 kilograms of copper.Therefore, exploitation not only can be eliminated it to environment and human harm, and have good economic benefits from the technology of electron wastes such as extracting metal from printed circuit board.
In existing technology, utilize the mechanical sorting printed circuit board (PCB), isolate nonmetal and metal, and the recovery method of copper in the metal mixture is mainly contained physics method, chemical method and microbial method.The physics method mainly adopts methods such as gravitational segregation, magnetic separation, electrostatic separation that the copper in the metal mixture is sorted out, and its shortcoming is that the rate of recovery and the grade of copper is not high; Microbial method is ripe not enough, still is in the stage of fumbling; In chemical process, at first with the vitriol oil or nitric acid oxidation circuit card, add other metal again cupric ion is cemented out, or the solution direct heating is obtained copper sulfate crystal, these methods exist all that the rate of recovery is not high, corrodibility is high or shortcoming such as processing costs height.
Summary of the invention
Technical problem to be solved
Technical problem to be solved by this invention provides a kind of method of extracting copper from electron wastes, to remedy the above-mentioned deficiency and the defective of prior aries such as mechanical sorting method, physics method, chemical method and microbial method.
Technical scheme
The invention provides a kind of method of from electron wastes, extracting copper, in turn include the following steps:
But a) in the three-phase bed of aerating oxygen and oxygen carrier, the aqueous solution of electron wastes and oxygen carrier is mixed with weight ratio 1: 1～20, to less than 1.0, the catalyzed oxidation electron wastes is to complete reaction under the condition in 60～90 ℃ of temperature and 4～10 hours reaction times with the pH value of acid-conditioning solution;
B) post reaction mixture is filtered, with solvent extration copper is extracted from filtrate, strip with ferrous sulfate, strip liquor concentrates;
C) with electrodeposition method concentrated solution is carried out electrodeposition and extract copper, and solution behind the reservation electrodeposition;
D) solution behind the electrodeposition is regenerated recycle to the step c).
One of preferred version of the above-mentioned method of extracting copper from electron wastes is to be oxynitride, Mn ion or Mn oxide compound at the oxygen carrier described in the step a).
Two of the preferred version of the above-mentioned method of extracting copper from electron wastes is, is 0.01～5mol/L at the concentration of aqueous solution of the oxygen carrier described in the step a).
Three of the preferred version of the above-mentioned method of extracting copper from electron wastes is, is sulfuric acid in the acid of the pH of the regulator solution described in step a) value.
Four of the preferred version of the above-mentioned method of extracting copper from electron wastes is to also have the step that electron wastes is pulverized before step a).
Five of the preferred version of the above-mentioned method of extracting copper from electron wastes is to be concentrated into more than the concentration 40g/L at the strip liquor described in the step b).
Six of the preferred version of the above-mentioned method of extracting copper from electron wastes is, in step b) the extraction agent that uses be Li * 984.
Seven of the preferred version of the above-mentioned method of extracting copper from electron wastes is to be the printed circuit board (PCB) that household PC, TV, mobile phone, game machine, electronic cards or industrial equipments use at the electron wastes described in the step a).
Principle of work of the present invention is as follows:
Contain many metals and non-metallic element in electron wastes such as the printed circuit board (PCB), because these metals and plastics are closely linked, be difficult to realize separating fully of metal and plastics with mechanical process, therefore utilize oxygen indirect oxidation circuit card under the oxygen carrier function, easily oxidized burning is an ion, separates fully with metal that is difficult to oxidation and plastics.Then, with extraction agent copper extracting and separating from pretreatment fluid is come out and strips to obtain the strong solution of cupric ion.
The reaction of oxygen indirect oxidation is:
3Cu+2HNO
3+3H
2SO
4＝3CuSO
4+2NO+4H
2O (1)
NO
2+H
2O→HNO
3 (3)
NO+NO
2+H
2O→2HNO
2 (4)
3HNO
2→HNO
3+H
2O+2NO (5)
H
++Mn
2++O
2→H
2O+Mn
3+ (6)
Mn
3++Cu→Cu
2+ (7)
Extractive reaction is:
2RH(o)+Cu
2+(a)＝R
2Cu(o)+2H
+ (8)
The reaction of stripping is:
R
2Cu(o)+2H
+(a)＝2RH(o)+Cu
2+ (9)
The strong solution of the cupric ion that obtains is carried out electrodeposition with electrodeposition method more just can obtain highly purified electro deposited copper.Wherein, cathodic reaction is: Cu
2++ 2e=Cu (10)
The anodic reaction is: 2OH
-=1/2O
2+ H
2O+2e (11)
For realizing the present invention, said extraction and subsequent step are as follows: at ambient temperature, extraction agent and filtrate are mixed, compare (O/A) and be (10～1): 1, the concentration of extraction agent is (10%～100%), with inorganic acid for adjusting pH value is (1.0～3.5), with setting stirring velocity for (100r/min～1300r/min) agitator stirs mixed solution, by secondary extraction and one-level back extraction, every grade time is that (1min～10min) can obtain meeting the copper-bath (40g/L～50g/L) of electrodeposition requirement.Again copper-bath is put into electrolyzer and carry out electrodeposition, the groove temperature is (20 ℃～60 ℃), and the cathode surface flow of electrolyte is (0.05m
3/ (m
2H)～1.0m
3/ (m
2H)), regulating current density is (190A/m
2～340A/m
2), bath voltage is (1.2v～3.2v).
Beneficial effect
The present invention is carrying out under the pretreated prerequisite printed-wiring board (PWB) with wet method, from the printed-wiring board (PWB) pretreatment fluid of complicated component, extract copper with extraction-electrodeposition process, realized innoxious, minimizing, the resource utilization of electronic waste, extraction-electrodeposition process that the present invention adopts can reclaim copper to greatest extent.
The rate of recovery of method copper provided by the present invention and of high grade, copper purity is up to 99.99%; Corrodibility is because of catalytic oxidation reduces, treatment condition are not harsh, processing costs is low.
Description of drawings
Fig. 1 is technical process of the present invention.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Inorganic chemical reagent is available from Shanghai chemical reagent factory, Li * 984 (the hydroxyl-ketoxime copper extractant is from Henkel KGaA company).
Embodiment 1
To pulverize the back printed circuit board (PCB) and put into the three-phase bed, add oxygen carrier 5mol/L then, the weight ratio of the two is 1: 10, adjust the pH value of solution greater than 1.0 with sulfuric acid, with high-pressure pump oxygen pneumatic is gone in the three-phase bed, reactant is heated to 60 ℃ then, reacted 6 hours, after printed circuit board (PCB) is by complete oxidation, filters and obtain filtrate.At ambient temperature, extraction agent and filtrate are mixed, comparing (O/A) is 2: 1, the concentration of extraction agent is 30%, is 2.0 with inorganic acid for adjusting pH value, is 910r/min with the setting stirring velocity, agitator stirs mixed solution, by secondary extraction and one-level back extraction, every grade time is 3min, can obtain meeting the copper-bath 40g/L of electrodeposition requirement.Again copper-bath is put into electrolyzer and carry out electrodeposition, the groove temperature is 45 ℃, and the cathode surface flow of electrolyte is 0.12m
3/ (m
2H), regulating current density is 240A/m
2, bath voltage is 2.3v, the purity that obtains copper is 99.99%.
Embodiment 2
To pulverize the back printed circuit board (PCB) and put into the three-phase bed, evenly stir, add oxygen carrier 2.5mol/L then, the weight ratio of the two is 1: 1, and the pH value of adjusting solution with sulfuric acid is gone into oxygen pneumatic in the three-phase bed with high-pressure pump greater than 1.0, reactant is heated to 90 ℃ then, reacted 4 hours, and after printed circuit board (PCB) is by complete oxidation, filtered and obtain filtrate.At ambient temperature, extraction agent and filtrate are mixed, comparing (O/A) is 10: 1, the concentration of extraction agent is 10%, is 1.0 with inorganic acid for adjusting pH value, is 100r/min with the setting stirring velocity, agitator stirs mixed solution, by secondary extraction and one-level back extraction, every grade time is 1min, can obtain meeting the copper-bath 45g/L of electrodeposition requirement.Again copper-bath is put into electrolyzer and carry out electrodeposition, the groove temperature is 20 ℃, and the cathode surface flow of electrolyte is 0.05m
3/ (m
2H), regulating current density is 190A/m
2, bath voltage is 1.2v, the purity that obtains copper is 99.9%.
Embodiment 3
To pulverize the back printed circuit board (PCB) and put into the three-phase bed, add oxygen carrier 0.01mol/L then, adjust the pH value of solution greater than 1.0 with sulfuric acid, with high-pressure pump oxygen pneumatic is gone in the three-phase bed, reactant is heated to 80 ℃ then, reacted 4 hours, and after printed circuit board (PCB) is by complete oxidation, filtered and obtain filtrate.At ambient temperature, extraction agent and filtrate are mixed, comparing (O/A) is 1: 1, the concentration of extraction agent is 100%, is 3.5 with inorganic acid for adjusting pH value, is 1300r/min with the setting stirring velocity, agitator stirs mixed solution, by secondary extraction and one-level back extraction, every grade time is 10min, can obtain meeting the copper-bath 50g/L of electrodeposition requirement.Again copper-bath is put into electrolyzer and carry out electrodeposition, the groove temperature is 60 ℃, and the cathode surface flow of electrolyte is 1.0m
3/ (m
2H), regulating current density is 340A/m
2, bath voltage is 3.2v, the purity that obtains copper is 99.8%.
Claims (8)
1. method of extracting copper from electron wastes in turn includes the following steps:
But a) in the three-phase bed of aerating oxygen and oxygen carrier, the aqueous solution of electron wastes and oxygen carrier is mixed with weight ratio 1: 1～20, to less than 1.0, the catalyzed oxidation electron wastes is to complete reaction under the condition in 60～90 ℃ of temperature and 4～10 hours reaction times with the pH value of acid-conditioning solution;
B) post reaction mixture is filtered, with solvent extration copper is extracted from filtrate, strip with ferrous sulfate, strip liquor concentrates;
C) with electrodeposition method concentrated solution is carried out electrodeposition and extract copper, and solution behind the reservation electrodeposition;
D) solution behind the electrodeposition is regenerated recycle to the step c).
2. the method for extracting copper from electron wastes according to claim 1 is characterized in that, is oxynitride, Mn ion or Mn oxide compound at the oxygen carrier described in the step a).
3. the method for extracting copper from electron wastes according to claim 1 is characterized in that, is 0.01～5mol/L at the concentration of aqueous solution of the oxygen carrier described in the step a).
4. the method for extracting copper from electron wastes according to claim 1 is characterized in that, is sulfuric acid in the acid of the pH of the regulator solution described in step a) value.
5. the method for extracting copper from electron wastes according to claim 1 is characterized in that, also has the step that electron wastes is pulverized before step a).
6. the method for extracting copper from electron wastes according to claim 1 is characterized in that, is concentrated into more than the concentration 40g/L at the strip liquor described in the step b).
7. the method for extracting copper from electron wastes according to claim 1 is characterized in that the extraction agent that uses is Lix984 in step b).
8. the method for extracting copper from electron wastes according to claim 1 is characterized in that, is the printed circuit board (PCB) that household PC, TV, mobile phone, game machine, electronic cards or industrial equipments use at the electron wastes described in the step a).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101178026A CN100406591C (en) | 2006-10-31 | 2006-10-31 | Method for extracting metal copper from electronical wastes |
Applications Claiming Priority (1)
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|---|---|---|---|
| CNB2006101178026A CN100406591C (en) | 2006-10-31 | 2006-10-31 | Method for extracting metal copper from electronical wastes |
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| CN101003857A CN101003857A (en) | 2007-07-25 |
| CN100406591C true CN100406591C (en) | 2008-07-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9689055B2 (en) | 2010-05-28 | 2017-06-27 | University Of Science And Technology Beijing | Complete non-cyanogens wet process for green recycling of waste printed circuit board |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392387B (en) * | 2008-10-21 | 2010-04-14 | 四会市鸿明贵金属有限公司 | Method for electrowinning copper nitrate solution |
| CN101812591B (en) * | 2009-02-20 | 2012-04-04 | 国立云林科技大学 | Method for recovering gold, copper, copper sulfate and copper chloride waste liquid of waste circuit board |
| JP6068341B2 (en) * | 2010-08-20 | 2017-01-25 | インテグリス・インコーポレーテッド | Sustainable methods for recovering precious and base metal from electrical and electronic equipment waste |
| CN103484669B (en) * | 2012-06-12 | 2016-08-10 | 林于丰 | The copper scrap recovery method of reusable edible solvent |
| CN103540748B (en) * | 2012-07-16 | 2015-10-28 | 中国科学院化学研究所 | A kind of metal of waste printed circuit board substrate and nonmetallic separation method |
| CN104178629B (en) * | 2013-05-23 | 2017-05-31 | 汨罗市绿岩金属有限公司 | The method that valuable metal is reclaimed from many metal dusts of waste electronic wiring board |
| CN104694978B (en) * | 2013-12-05 | 2018-03-23 | 阳谷祥光铜业有限公司 | The processing method and processing unit of a kind of waste electrolyte |
| CN108707926A (en) * | 2018-06-19 | 2018-10-26 | 福建洋屿环保科技股份有限公司 | A kind of useless diamond segment electroleaching recycling process for copper |
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|---|---|---|---|---|
| FR2634674A1 (en) * | 1988-08-01 | 1990-02-02 | Sepulcre Patrick | Process for recovery of components of electrical equipment containing polychlorobiphenyl residues and treatment devices |
| US6045763A (en) * | 1995-06-12 | 2000-04-04 | Henkel Kommanditgesellschaft Auf Aktien | Process for working up ammoniacal metal solutions including treating the wash water with an organic extraction solution |
| CN1172009C (en) * | 2001-11-09 | 2004-10-20 | 清华大学 | Technological method for reextracting gold from cyanide gold refining wast slag |
| CN1614046A (en) * | 2004-10-20 | 2005-05-11 | 东华大学 | Extraction of gold from PCB by catalyst oxidation |
-
2006
- 2006-10-31 CN CNB2006101178026A patent/CN100406591C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2634674A1 (en) * | 1988-08-01 | 1990-02-02 | Sepulcre Patrick | Process for recovery of components of electrical equipment containing polychlorobiphenyl residues and treatment devices |
| US6045763A (en) * | 1995-06-12 | 2000-04-04 | Henkel Kommanditgesellschaft Auf Aktien | Process for working up ammoniacal metal solutions including treating the wash water with an organic extraction solution |
| CN1172009C (en) * | 2001-11-09 | 2004-10-20 | 清华大学 | Technological method for reextracting gold from cyanide gold refining wast slag |
| CN1614046A (en) * | 2004-10-20 | 2005-05-11 | 东华大学 | Extraction of gold from PCB by catalyst oxidation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9689055B2 (en) | 2010-05-28 | 2017-06-27 | University Of Science And Technology Beijing | Complete non-cyanogens wet process for green recycling of waste printed circuit board |
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| CN101003857A (en) | 2007-07-25 |
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