CN106676577B - A method of recycling copper from waste and old circuit board - Google Patents
A method of recycling copper from waste and old circuit board Download PDFInfo
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- CN106676577B CN106676577B CN201710065851.8A CN201710065851A CN106676577B CN 106676577 B CN106676577 B CN 106676577B CN 201710065851 A CN201710065851 A CN 201710065851A CN 106676577 B CN106676577 B CN 106676577B
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- 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
- 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
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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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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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
- 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 method that the present invention relates to a kind of to recycle copper from waste and old circuit board, the described method comprises the following steps: the metal layer of waste and old circuit board being separated, pole plate is prepared into；Using the pole plate being prepared as working electrode, electrolysis unit is formed with to electrode, reference electrode and electrolyte；It is powered to the electrolysis unit of composition, connects circuit and be passed through oxidizing gas into electrolyte and be electrolysed, obtain copper simple substance in cathode.The method copper dissolution rate is high, and electrode is at low cost, and electrolyte composition is simple, and environmental pollution is small, simple process and efficiently.
Description
Technical field
The invention belongs to reclaiming metals fields, are related to a kind of method that copper is recycled from waste and old circuit board.
Background technique
After the stepped into information epoch, the update of the various electronic products such as equipment such as household electrical appliances, computer and smart phone is changed
The electron wastes for being getting faster for speed, and generating therewith are also increased with the speed for being up to 22% every year, it has also become processing is difficult
Spend maximum solid waste.Core component-printed circuit board (Printed circuit board) of these electronic products
In containing can be largely one basic containing the rare precious metals and copper, iron, nickel etc. such as gold, silver, platinum, rhodium with the resource of regeneration
The resource concentration body of metal.
Currently, the method for processing waste and old circuit board mainly has physical method, chemical method, Bioleaching method etc..Physical method is main
Metal and nonmetallic is separated according to the metals such as copper in waste and old printed circuit board and nonmetallic physical characteristic difference.By broken
Broken, the techniques such as electrostatic or magnetic separation separate metal and organic matter, but have had to the enrichment body of metal and plastics, metallic element simple substance
It is not properly separated, it is also necessary to be further processed and used equipment investment is big, energy consumption is high, thus economic feasibility is relatively
Difference.
Chemical method is broadly divided into pyrogenic process and wet process, although pyrogenic process has the advantages that simply and easily, can generate two evils simultaneously
The pernicious gases such as English discharge a large amount of drosses, bring serious pollution to environment, recovery efficiency is not high.Wet process biggest advantage exists
In the generation of the harmful smokes such as no dioxin, and the dissolution rate of copper is high, but it cannot be effectively treated and speckle with having for chemical agent
Machine object and acid pickle is largely produced, is easy to bring secondary pollution to environment, which causes hydrometallurgical technology cannot
The large-scale promotion application in industry.
Bioleaching process is exactly using microbial cell or its metabolite, the effects of by physics, chemistry, biology
The process of adsorbing metal ions.Bioleaching environmental protection, operation is simple, and pollution is small, but leaching cycle is long, and needs bacterium and circuit
Plate comes into full contact with, also not high for the recovery efficiency of metal, industrially not by scale application.
CN104947155A discloses a kind of method for recycling copper from waste and old circuit board based on electrochemical process, using such as
Lower step: being dissolved in water for copper sulphate and obtain copper-bath, and model of the sulphur acid for adjusting pH 0.5~1 is added in copper-bath
In enclosing, then add lauryl sodium sulfate and/or polyethylene glycol (PEG) and micro hydrochloric acid obtains electrolyte；Waste and old circuit board
It for anode, is placed in anode, places into electrolyte, cathode is industrial titanium plate or stainless steel plate, is set between anode and cathode
There is partition, is equipped with fluid passage every bottom, maintains electrolyte temperature within the scope of 20~80 DEG C, be electrolysed using DC current
Deposition, or electrolytic deposition is carried out using pulse current.The configuration of this method electrolyte is complicated, and drug is various, and electrolyte is acid strong,
Cathode material cost is also higher.
Therefore, it is particularly significant to study a kind of new more efficient method that copper is recycled from waste and old circuit board.
Summary of the invention
For the technical problems in the prior art, the present invention provides a kind of side that copper is recycled from waste and old circuit board
Method, the method copper dissolution rate is high, and electrode is at low cost, and electrolyte composition is simple, and environmental pollution is small, simple process and efficiently.
In order to achieve the above objectives, the present invention takes following technical scheme:
The present invention provides a kind of method that copper is recycled from waste and old circuit board, the described method comprises the following steps:
(1) metal layer of waste and old circuit board is separated, is prepared into pole plate；
(2) pole plate that step (1) is prepared is as working electrode, and to electrode, reference electrode and electrolyte group
At electrolysis unit；
(3) it is powered to the electrolysis unit of step (2) composition, connects circuit and is passed through oxidizing gas progress into electrolyte
Electrolysis, obtains copper simple substance in cathode.
Wherein, step (1) metal layer by waste and old circuit board separates, and the method for preparing pole plate are as follows:
(a) by sample since room temperature, with 15~25 DEG C/min heating rate, 400~800 DEG C are heated to, stop 20~
60min, until warpage occurs for metal layer, heating process carries out under inert gas protection, the waste and old circuit board after being pyrolyzed；
(b) waste and old circuit board after the pyrolysis for obtaining step (a) is cooling, removes glass fabric and metal layer, will be golden
After category layer heats 15~30min at 1100~1500 DEG C, it is cooled to room temperature and obtains pole plate.
Preferably, step (a) heating rate can be 15 DEG C/min, 18 DEG C/min, 20 DEG C/min, 22 DEG C/min or
25 DEG C/min etc., but it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, step (a) heating temperature can be 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C,
700 DEG C, 750 DEG C or 800 DEG C etc., but it is not limited to cited numerical value, other unlisted numerical value are same in the numberical range
It is applicable in.
Preferably, the time of step (a) heating can be 20min, 25min, 30min, 35min, 40min,
45min, 50min, 55min or 60min etc., but it is not limited to cited numerical value, other unlisted numbers in the numberical range
It is worth equally applicable.
Preferably, step (a) inert gas in nitrogen, helium or argon gas any one or at least two group
It closes, the combination is typical but non-limiting example has: the combination of nitrogen and argon gas, the combination of nitrogen and helium, helium and argon gas
Combination or nitrogen, helium and the combination of argon gas etc..
Preferably, step (b) heating temperature can be 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C,
1350 DEG C, 1400 DEG C, 1450 DEG C or 1500 DEG C etc., but it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value it is equally applicable.
Preferably, the time of step (b) heating can be 15min, 18min, 20min, 22min, 25min, 28min
Or 30min etc., but it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
As currently preferred technical solution, the described step (2) includes stainless steel electrode, carbon electrode and carbon to electrode
Any one in felt electrode.
As currently preferred technical solution, step (2) described reference electrode includes Ag/AgCl electrode and/or Hg/
Hg2Cl2Electrode.
As currently preferred technical solution, step (2) electrolyte is sulfuric acid.
As currently preferred technical solution, the concentration of the sulfuric acid is 0.01~1.2mol/L, as 0.01mol/L,
0.05mol/L, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.8mol/L, 1mol/L or 1.2mol/L etc., but it is not limited to institute
The numerical value enumerated, other interior unlisted numerical value of the numberical range are equally applicable, preferably 0.01~0.5mol/L.
As currently preferred technical solution, the voltage of step (3) described energization is 0.3~1.2V, as 0.3V,
0.4V, 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1V, 1.1V or 1.2V etc., but it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing, preferably 0.3~1V.
As currently preferred technical solution, step (3) described oxidizing gas includes air, industrial oxygen and high-purity
Any one in oxygen or at least two combination, the combination is typical but non-limiting example has: the group of air and industrial oxygen
It closes, the combination of industrial oxygen and high purity oxygen gas, the combination of high purity oxygen gas and air or air, industrial oxygen and high pure oxygen etc..
As currently preferred technical solution, the flow of step (3) described oxidizing gas is 20~100mL/min,
Such as 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min or
100mL/min etc., but it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably
For 30~90mL/min.
The present invention is by the way of electrolysis, and promote copper simple substance by anode reinforcing is converted into bivalent cupric ion, with this
Meanwhile some copper is dissolved out in the form of cupprous, the present invention is passed through oxidizing gas, the oxidisability gas into electrolyte
Body generates hydrogen peroxide by electrocatalytic reaction in cathode surface, chemically reacts with monovalence copper, generates reactive oxygen species,
Such as hydroxyl free radical, negative oxygen ion etc., these reactive oxygen species are reacted with the copper simple substance of anode, further promote copper list
The dissolution of matter, therefore the present invention utilizes the synergistic effect of anode and cathode, and the dissolution rate of copper greatly improved.
When the voltage of energization is lower than 0.3V, the amount for the hydrogen peroxide that the oxidizing gas being passed through generates can be reduced, and can be subtracted
It is few, therefore the amount of the reactive oxygen species generated can also be reduced, and then reduce its facilitation to copper dissolution, and copper is caused to dissolve out
Rate reduces, and other metal dissolvings are had when voltage is greater than 1.2V, reduces the purity for the copper simple substance that cathode obtains.
As currently preferred technical solution, the temperature of step (3) described electrolysis is 20~50 DEG C, such as 20 DEG C, 25 DEG C,
30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C etc., but it is not limited to cited numerical value, other unlisted numbers in the numberical range
It is worth equally applicable.
Copper dissolution is exothermic reaction, and it is the endothermic reaction that oxidizing gas electro-catalysis, which generates hydrogen peroxide, so to electrolysis
The production quantity of hydrogen peroxide can be reduced when temperature is lower than 20 DEG C, although the low progress for being conducive to copper dissolution reaction of reaction temperature,
It is that temperature is positively correlated with reaction rate, the dissolution rate of copper can reduce, therefore to be generally unfavorable for copper molten lower than 20 DEG C for temperature
Progress out；And when temperature is higher than 50 DEG C, although improving the generation of whole reaction rate and hydrogen peroxide, the molten place of copper
Rate can reduce.
Wherein, the copper dissolution rate being mentioned herein is the copper simple substance that cathode obtains, total matter with copper in theoretically anode grid substrate
The ratio of amount.
As currently preferred technical solution, electrolysis time described in step (3) is 30~90min, as 30min,
40min, 50min, 60min, 70min, 80min or 90min etc., but be not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable, preferably 60~90min.
Compared with prior art, the present invention at least has the advantages that
(1) method that the present invention provides a kind of recycles copper from waste and old circuit board, the method copper dissolution rate are greater than
90%, and removal process is efficient, the time used is between 30~90min；
(2) method that the present invention provides a kind of recycles copper from waste and old circuit board, the component of the method electrolyte is only
It is stainless steel electrode, carbon electrode or carbon felt electrode to electrode for sulfuric acid, method is at low cost；
(3) method that the present invention provides a kind of from waste and old circuit board recycles copper, sulfuric acid in the method electrolyte
Concentration is low, and unharmful substance generates in the process, and environmental pollution is small；
(4) method that the present invention provides a kind of recycles copper from waste and old circuit board, the method simple process can carry out
Industrialized production.
Specific embodiment
Specific embodiment of the invention part provide it is a kind of from waste and old circuit board recycle copper method, the method includes with
Lower step:
(1) metal layer of waste and old circuit board is separated, is prepared into substrate；
(2) substrate that step (1) is prepared is as working electrode, and to electrode, reference electrode and electrolyte group
At electrolysis unit；
(3) it is powered to the electrolysis unit of step (2) composition, connects circuit and is passed through oxidizing gas progress into electrolyte
Electrolysis, obtains copper simple substance in cathode.
Embodiment 1
A method of it recycling copper from waste and old circuit board, the described method comprises the following steps:
(1) metal layer of waste and old circuit board is separated, is prepared into substrate；
(2) as working electrode, stainless steel electrode is used as to electrode, Ag/AgCl electricity the substrate that step (1) is prepared
Pole collectively constitutes electrolysis unit as electrolyte as reference electrode, the sulfuric acid of 0.5mol/L；
(3) it is powered to the electrolysis unit of step (2) composition, voltage 1V connects circuit and is passed through into electrolyte high-purity
Oxygen (flow 50mL/min) carries out electrolysis 90min at 25 DEG C, obtains copper simple substance in cathode.
The dissolution rate of above method copper is 91%, and the purity for the copper being prepared is 99%.
Embodiment 2
A method of it recycling copper from waste and old circuit board, the described method comprises the following steps:
(1) metal layer of waste and old circuit board is separated, is prepared into substrate；
(2) substrate that step (1) is prepared is used as working electrode, carbon electrode to electrode, Ag/AgCl electrode
As reference electrode, the sulfuric acid of 0.5mol/L collectively constitutes electrolysis unit as electrolyte；
(3) it is powered to the electrolysis unit of step (2) composition, voltage 0.8V connects circuit and is passed through height into electrolyte
Pure oxygen (flow 50mL/min) carries out electrolysis 90min at 25 DEG C, obtains copper simple substance in cathode.
The dissolution rate of above method copper is 90%, and the purity for the copper being prepared is 99%.
Embodiment 3
A method of it recycling copper from waste and old circuit board, the described method comprises the following steps:
(1) metal layer of waste and old circuit board is separated, is prepared into substrate；
(2) substrate that step (1) is prepared is used as working electrode, carbon felt electrode to electrode, Ag/AgCl electrode
As reference electrode, the sulfuric acid of 0.3mol/L collectively constitutes electrolysis unit as electrolyte；
(3) it is powered to the electrolysis unit of step (2) composition, voltage 0.3V connects circuit and is passed through height into electrolyte
Pure oxygen (flow 20mL/min) carries out electrolysis 90min at 25 DEG C, obtains copper simple substance in cathode.
The dissolution rate of above method copper is 91%, and the purity for the copper being prepared is 99%.
Embodiment 4
A method of it recycling copper from waste and old circuit board, the described method comprises the following steps:
(1) metal layer of waste and old circuit board is separated, is prepared into substrate；
(2) substrate that step (1) is prepared is used as working electrode, carbon felt electrode to electrode, Ag/AgCl electrode
As reference electrode, the sulfuric acid of 0.01mol/L collectively constitutes electrolysis unit as electrolyte；
(3) it is powered to the electrolysis unit of step (2) composition, voltage 0.3V connects circuit and is passed through height into electrolyte
Pure oxygen (flow 50mL/min) carries out electrolysis 90min at 20 DEG C, obtains copper simple substance in cathode.
The dissolution rate of above method copper is 95%, and the purity for the copper being prepared is 99%.
Embodiment 5
A method of it recycling copper from waste and old circuit board, the described method comprises the following steps:
(1) metal layer of waste and old circuit board is separated, is prepared into substrate；
(2) substrate that step (1) is prepared is used as working electrode, carbon felt electrode to electrode, Hg/Hg2Cl2Electricity
Pole collectively constitutes electrolysis unit as electrolyte as reference electrode, the sulfuric acid of 0.01mol/L；
(3) it is powered to the electrolysis unit of step (2) composition, voltage 1.2V connects circuit and is passed through sky into electrolyte
Gas (flow 100mL/min) carries out electrolysis 30min at 60 DEG C, obtains copper simple substance in cathode.
The dissolution rate of above method copper is 92%, and the purity for the copper being prepared is 99%.
Embodiment 6
A method of it recycling copper from waste and old circuit board, the described method comprises the following steps:
(1) metal layer of waste and old circuit board is separated, is prepared into substrate；
(2) substrate that step (1) is prepared is used as working electrode, carbon felt electrode to electrode, Hg/Hg2Cl2Electricity
Pole collectively constitutes electrolysis unit as electrolyte as reference electrode, the sulfuric acid of 1.2mol/L；
(3) it is powered to the electrolysis unit of step (2) composition, voltage 0.8V connects circuit and is passed through work into electrolyte
Industry oxygen (flow 80mL/min) carries out electrolysis 60min at 30 DEG C, obtains copper simple substance in cathode.
The dissolution rate of above method copper is 90%, and the purity for the copper being prepared is 99%.
Embodiment 7
A method of recycling copper from waste and old circuit board, the step (1) separates the metal layer of waste and old circuit board, and
The method for preparing pole plate are as follows:
(a) by sample since room temperature, with 15 DEG C/min heating rate, 400 DEG C is heated to, stops 60min, until metal
Warpage occurs for layer, and heating process carries out under nitrogen protection, the waste and old circuit board after being pyrolyzed；
(b) waste and old circuit board after the pyrolysis for obtaining step (a) is cooling, removes glass fabric and metal layer, will be golden
After category layer heats 30min at 1100 DEG C, it is cooled to room temperature and obtains pole plate.
Other than above-mentioned condition, other conditions are same as Example 4.
The dissolution rate of above method copper is 95%, and the purity for the copper being prepared is 99%.
Embodiment 8
A method of recycling copper from waste and old circuit board, the step (1) separates the metal layer of waste and old circuit board, and
The method for preparing pole plate are as follows:
(a) by sample since room temperature, with 25 DEG C/min heating rate, 800 DEG C is heated to, stops 20min, until metal
Warpage occurs for layer, and heating process carries out under helium protection, the waste and old circuit board after being pyrolyzed；
(b) waste and old circuit board after the pyrolysis for obtaining step (a) is cooling, removes glass fabric and metal layer, will be golden
After category layer heats 15min at 1500 DEG C, it is cooled to room temperature and obtains pole plate.
Other than above-mentioned condition, other conditions are same as Example 4.
The dissolution rate of above method copper is 95%, and the purity for the copper being prepared is 99%.
Embodiment 9
A method of recycling copper, step (1) metal layer by waste and old circuit board point from waste and old circuit board
From, and the method for preparing pole plate are as follows:
(a) by sample since room temperature, with 20 DEG C/min heating rate, 600 DEG C is heated to, stops 40min, until metal
Warpage occurs for layer, and heating process carries out under protection of argon gas, the waste and old circuit board after being pyrolyzed；
(b) waste and old circuit board after the pyrolysis for obtaining step (a) is cooling, removes glass fabric and metal layer, will be golden
After category layer heats 20min at 1300 DEG C, it is cooled to room temperature and obtains pole plate.
Other than above-mentioned condition, other conditions are same as Example 4.
The dissolution rate of above method copper is 95%, and the purity for the copper being prepared is 99%.
Embodiment 10
A method of from waste and old circuit board recycle copper, in addition in step (3) voltage be 0.1V other than, other conditions with
Embodiment 4 is identical.
The dissolution rate of above method copper is 76%, and the purity for the copper being prepared is 99%.
Embodiment 11
A method of from waste and old circuit board recycle copper, in addition in step (3) voltage be 2V other than, other conditions with reality
It is identical to apply example 4.
The dissolution rate of above method copper is 90%, and the purity for the copper being prepared is 83%.
Embodiment 12
A method of recycling copper from waste and old circuit board, other than the temperature being electrolysed in step (3) is 10 DEG C, other
Part is same as Example 4.
The dissolution rate of above method copper is 85%, and the purity for the copper being prepared is 99%.
Embodiment 13
A method of recycling copper from waste and old circuit board, other than the temperature being electrolysed in step (3) is 75 DEG C, other
Part is same as Example 4.
The dissolution rate of above method copper is 88%, and the purity for the copper being prepared is 99%.
Comparative example 1
A method of recycling copper from waste and old circuit board, other than high pure oxygen is not passed through into electrolyte in step (3),
Other conditions are same as Example 4.
The dissolution rate of above method copper is 81%, and the purity for the copper being prepared is 99%.
From embodiment 1-9 can be seen that it is provided by the invention it is a kind of from waste and old circuit board recycle copper method, copper it is molten
Extracting rate is greater than 90%, reaches as high as 95%, and the voltage being electrolysed in embodiment 10 is 0.1V, since voltage is too small, in 90min,
Copper dissolution rate only has 76%, and the voltage being electrolysed in embodiment 11 is 2V, causes other metals such as Cr, Ag and analyses together with copper
Out, preparation to the purity of copper there was only 83%, the temperature of cell reaction is too low in embodiment 12, leads to the molten of copper in 90min
Extracting rate drops to 85%, and the excessively high dissolution rate for also resulting in copper totality of electrolysis temperature drops to 88% in embodiment 13, and compares
It is not passed through oxidizing gas in example 1, results in the dissolution rate decline of copper, dissolution rate 81%.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (11)
1. a kind of method for recycling copper from waste and old circuit board, which is characterized in that the described method comprises the following steps:
(1) metal layer of waste and old circuit board is separated, is prepared into pole plate；
(2) pole plate that step (1) is prepared forms electricity with to electrode, reference electrode and electrolyte as working electrode
Device is solved, the electrolyte is sulfuric acid；
(3) it is powered to the electrolysis unit of step (2) composition, connects circuit and is passed through oxidizing gas progress electricity into electrolyte
Solution, obtains copper simple substance in cathode；
Step (3) described oxidizing gas includes the combination of any one in air, industrial oxygen and high pure oxygen or at least two；
The flow of step (3) described oxidizing gas is 20~100mL/min.
2. the method according to claim 1, wherein it includes stainless steel electrode, carbon-point to electrode that step (2) is described
Any one in electrode and carbon felt electrode.
3. the method according to claim 1, wherein step (2) described reference electrode includes Ag/AgCl electrode
And/or Hg/Hg2Cl2Electrode.
4. the method according to claim 1, wherein the concentration of the sulfuric acid is 0.01~1.2mol/L.
5. according to the method described in claim 4, it is characterized in that, the concentration of the sulfuric acid is 0.01~0.5mol/L.
6. the method according to claim 1, wherein the voltage of step (3) described energization is 0.3~1.2V.
7. according to the method described in claim 6, it is characterized in that, the voltage of step (3) described energization is 0.3~1V.
8. the method according to claim 1, wherein the flow of step (3) described oxidizing gas be 30~
90mL/min。
9. the method according to claim 1, wherein the temperature of step (3) described electrolysis is 20~50 DEG C.
10. the method according to claim 1, wherein electrolysis time described in step (3) is 30~90min.
11. according to the method described in claim 10, it is characterized in that, electrolysis time described in step (3) is 60~90min.
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| CN104947155A (en) * | 2015-05-28 | 2015-09-30 | 中南大学 | Process for recovering copper from waste circuit board to prepare high purity and high strength copper foil based on electrochemical method |
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| JP2009074140A (en) * | 2007-09-21 | 2009-04-09 | Sumitomo Metal Mining Co Ltd | Wet copper refining method for copper raw material comprising copper sulfide mineral |
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| CN104878205A (en) * | 2015-04-21 | 2015-09-02 | 昆明理工大学 | Method for recovering valuable metals in waste circuit boards |
| CN104947155A (en) * | 2015-05-28 | 2015-09-30 | 中南大学 | Process for recovering copper from waste circuit board to prepare high purity and high strength copper foil based on electrochemical method |
| CN105132691A (en) * | 2015-09-23 | 2015-12-09 | 宁波恒创环保科技有限公司 | Method for refining metallic copper from used printed circuit board |
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