CN105112674B - A kind of waste printed circuit board Whote-wet method recovery process - Google Patents
A kind of waste printed circuit board Whote-wet method recovery process Download PDFInfo
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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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Abstract
The invention discloses a kind of waste printed circuit board Whote-wet method recovery process, comprise the following steps：Waste printed circuit board is crushed, obtains the more metal dusts of waste printed circuit board after gravity treatment；The more metal dusts of waste printed circuit board are leached with the acid solution that concentration is 0.1~4mol/L, leachate and leached mud are obtained after separation of solid and liquid；It is 0.5~5mol/L acid solutions displacement stripping tin that copper compound and concentration are added in leached mud, is obtained after separation of solid and liquid containing tin liquor and divides scruff；It is 0.2~6mol/L acid solutions that concentration is added in scruff is divided, then is passed through oxygen and/or air progress oxidation reaction, obtains containing copper liquid and noble metal slag after separation of solid and liquid；Containing copper liquid tough cathode is obtained through eddy flow electrodeposition.The present invention proposes Whote-wet method PROCESS FOR TREATMENT waste printed circuit board, realizes the directional separation of valuable metal, enrichment, extraction in processing step, solves the problems such as waste circuit board value metallic element trend is scattered and later separation extraction is difficult.
Description
Technical field
The present invention relates to waste resource recycling field, more particularly to a kind of waste printed circuit board Whote-wet method recovery process.
Background technology
In recent years, the production of electronic product remains stable growth.According to Chinese Ministry of Industry and Information announce as shown by data, 2013
January to November, China's scale above electronics product manufacturing industry increase by 11.2%.But the life cycle of electronic product is but with electricity
The continuous development of sub- technology and increasingly shorten.1997 so far, and computer and CPU average life span were fallen to only 2 years by 4~6 years.And
The rapid rising of the novel electronic products such as mobile phone and its update, accelerate eliminating for electronic product.According to European Union's relevant report,
The growth rate of electron wastes was maintained at 11% or so during 2008 to 2014, was 4 times of common rubbish.Electronic waste
Contain the metal of a large amount of recoverables in thing, such as aluminium, copper, lead, zinc, noble metal (gold, silver), platinum group metal and rare earth element
(samarium, europium, yttrium, gadolinium and dysprosium etc.).Also containing a large amount of different types of engineering plastics and glass fibre in electron wastes, these are non-
Metal is by can also bring considerable economic benefit after efficiently separating.
Patent publication No. is that CN101049955A Chinese patent discloses one kind using copper in waste printed circuit board for sulphur
The method of sour copper, the air oxidation of copper sulphate system is added to be carried out at room temperature to copper in waste printed circuit board using dilute sulfuric acid, sodium chloride
Leach, gained filtrate is evaporated crystallization after filtering；Sodium salt is introduced in this Leaching Systems, and only considered the element row of copper
Not study other metallic elements.Patent publication No. is US20120318681A1 United States Patent (USP), discloses one kind
Afforest without cyanogen wet processing recovery waste printed circuit board technique, the technique using Physical separation waste printed circuit board in metal with
Nonmetallic, obtained metallic copper powder is cast as electrorefining after anode, then noble metal is reclaimed from the earth of positive pole；To thing in this method
Reason separation requirement is high, and just research conditions domestic at present are seen is extremely difficult to directly cast wanting for electrolysis by physical partition method
Ask.Patent publication No. is US2013033522A1 United States Patent (USP), discloses one kind from discarded object (including discarded circuit
Plate) in recovery valuable metal method, wherein discarded printed circuit boards are without physical separation, directly after controlling Temperature Treatment,
Separation of glasses fiber and valuable metal；Clearly show that valuable metal can not be with glass when treatment temperature is less than 400 DEG C in patent
Glass fiber is separated from each other, it is therefore desirable to higher treatment temperature.Patent publication No. is that CN101049955A Chinese patent discloses
Waste printed circuit board is placed in vacuum tank, heating pyrolysis, most of pyrolysis devolatilization thing cooling liquid is liquid oil, another portion
Divide and enter gas collector；During pyrolysis, scolding tin is separated with circuit board using centrifugal separating device；Electricity after categorised collection pyrolysis
Road plate substrate and electronic component are further separated and reclaimed；This method requires high to equipment temperature control, and energy consumption is also corresponding higher.
Patent publication No. is that CN104532005A Chinese patent discloses a kind of side of discarded printed circuit boards comprehensive utilization of resources
Method, ferriferous raw material and non iron raw material are isolated by broken, magnetic separation；Metalliferous material is gone out to non iron raw material high-voltage electrostatic sorting
And non-metallic material；The metals such as copper, gold, silver are separated to metalliferous material again；The method is also concentrated mainly on physical separation and copper, expensive
Metal recovery.Meanwhile above-mentioned patent could not consider the influence of other metallic elements in waste printed circuit board, all single concentrates on
On some or several metals, this necessarily cause it to exist in industrial applications other metallic elements trend is not clear, each element
The problems such as synthetical recovery difficulty.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of cost is cheap, clean environment firendly,
A kind of strong waste printed circuit board Whote-wet method recovery process of reagent circulation usability.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of waste printed circuit board Whote-wet method recovery process, comprises the following steps：
(1) waste printed circuit board crushed, obtain the more metal dusts of waste printed circuit board after gravity treatment；
(2) the more metal dusts of waste printed circuit board are leached with the acid solution that concentration is 0.1~4mol/L, the process exists
Carried out in the reactor of design temperature, while start stirring, reacted separation of solid and liquid after a period of time, obtain leachate and leaching
Slag；Contain the active metals, the main cupric of leached mud, tin, noble metal etc. such as zinc, aluminium, iron in leachate；
(3) the acid solution displacement stripping tin of copper compound and concentration for 0.5~5mol/L, separation of solid and liquid are added in leached mud
After obtain containing tin liquor and dividing scruff；The copper compound is the one or more in copper sulphate, copper chloride, Cu oxide；It is stanniferous
It is mainly tin, the soluble-salt of copper in liquid, divides the main cupric of scruff, noble metal slag；
(4) it is 0.2~6mol/L acid solutions concentration to be added in scruff is divided, then is passed through oxygen and/or air is aoxidized
React, obtain containing copper liquid and noble metal slag after separation of solid and liquid；The temperature of the oxidation reaction is 45~90 DEG C；
(5) tough cathode is obtained through eddy flow electrodeposition containing copper liquid.
Above-mentioned technique, it is preferred that again to the more metal dusts of waste printed circuit board after acid adding in the leachate after step (2)
Leached, valuable metal is enriched to the active metal in synthetical recovery leachate of opening a way after finite concentration in liquid to be leached.
Above-mentioned technique, it is preferred that containing in tin liquor after step (3) adds oxidant, is reacted at 50~90 DEG C
Precipitated to stannic acid, stannic acid precipitation obtains tin ash through calcining, and the oxidant is in hydrogen peroxide, ozone, oxygen and air
It is one or more of；It 1~20 (is oxidant theoretical amount needed for tetravalent tin by Bivalent Tin complete oxidation that the excess coefficient of oxidant, which is,
1-20 times).
Above-mentioned technique, it is preferred that in the step (3), when hydrogen ion concentration is big in the acid solution that stripping tin process is selected
When 1mol/L, need first to carry out aoxidizing heavy tin to adding oxidant after being diluted containing tin liquor.
Above-mentioned technique, it is preferred that in the step (3), the excess coefficient (mol ratio of copper and tin) of copper compound is 1
~10.
Above-mentioned technique, it is preferred that part copper compound is replaced in the return to step containing copper liquid (3) in the step (4).
Above-mentioned technique, it is preferred that in the eddy flow electrolytic deposition process of the step (5), cathode-current density be 200~
900A/m2, sulfuric acid concentration is 0.2~1.5mol/L in electric effusion, and electrodeposition temperature is 10~40 DEG C, electrodeposition terminal copper ion concentration
Control is in more than 5g/L.
Above-mentioned technique, it is preferred that oxygen caused by eddy flow electrolytic deposition process is used for the oxygen of step (4) in the step (5)
Change reaction.
Above-mentioned technique, it is preferred that in the step (4), oxidation reaction process needs to stir, and mixing speed is not less than
200r/min, liquid-solid ratio are 3~40；The unit ratio of the liquid-solid ratio is mL/g；Gas flow (equivalent purity oxygen) is controlled with dividing
The molar ratio of copper in scruff>1.2.
Above-mentioned technique, it is preferred that in the step (2), acid solution is one or both of hydrochloric acid and sulfuric acid；It is described
Acid in step (3) and step (4) is sulfuric acid.
Above-mentioned technique, it is preferred that the granularity of the more metal dusts of waste printed circuit board is 200-50 mesh.
Acid reusable edible is in dividing tin and air oxygen caused by surplus acid and electrodeposition in above-mentioned technique after separation of solid and liquid
Change leaching copper step.
The technological process of the present invention in technique as shown in figure 1, take the lead in proposing to have reached using diluted acid leaching active metal to subtract
Light subsequent technique removal of impurities purpose, and the purpose of active metal enrichment can be reached by circulating leaching, so as to be advantageous to active metal
Further separation and recovery；The tin replaced and peeled off in waste printed circuit board using mantoquita, hydrogen peroxide, ozone, oxygen are proposed first
In one kind or its heavy tin of collocation oxidation, displaced liquid can be further used for lower step and leach, no any impurity introduces；Using sky
The more metal dusts of gas oxidation acid leaching waste printed circuit board are environment-friendly, equipment investment is low；Copper is carried using eddy flow electrodeposition in nothing to appoint
Cu-CATH-1 is made in the case of what additive.
Compared with prior art, the advantage of the invention is that：
1) conventional method relies primarily on the initial gross separation that physical separation realizes metal, and it is real that the present invention combines domestic equipment research and development
Border, the reverse proposition that takes the lead in have developed the technique under conditions of mitigating premised on physical separation burden, and technique of the invention is not
Need to carry out magnetic separation, electric separation etc., it is only necessary to carry out simply broken, roughing.
2) present invention proposes the more metal dusts of Whote-wet method PROCESS FOR TREATMENT waste printed circuit board, alleviates waste printed circuit board physics
Separation burden, realizes the directional separation of valuable metal, enrichment, extraction in processing step, how golden solves waste printed circuit board
Belong to the problems such as powder valuable metal element trend is scattered and later separation extraction is difficult.
3) present invention is replaced except active metal, mantoquita and shells tin in advance using diluted acid, molten copper, eddy flow electrodeposition system are leached in air oxidation
Cu-CATH-1 technique, simple with equipment, easy to implement, reagent circulation is good, and cost is low, and environmentally safe.And
For the present invention while valuable metal reclaim, organic matter and glass fibre in waste printed circuit board and pyrogenic process are than the destruction that is subjected to
It is low, it can be reclaimed in subsequent step.
4) present invention proposes first for waste printed circuit board selectively leaches active valuable metal such as iron, zinc with diluted acid
Deng, gained leachate concentration of metal ions can be enriched with the present invention, and open circuit can directly produce corresponding product salt after enrichment, with
Conventional physical segregation ratio has advantage.
5) present invention proposes that added regent is few, and free from admixture introduces using mantoquita displacement stripping tin first for waste printed circuit board,
Industrialization design is strong.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Fig. 2 is tough cathode product photo prepared by the embodiment of the present invention 1.
Fig. 3 is tough cathode product photo prepared by the embodiment of the present invention 2.
Fig. 4 is that the stannic acid obtained by the heavy tin of the oxidation of the embodiment of the present invention 2 precipitates photo.
Tin ash product photo of the stannic acid of Fig. 5 embodiment of the present invention 2 precipitation through calcining gained.
The XRD of tin ash product of the stannic acid of Fig. 6 embodiment of the present invention 2 precipitation through calcining gained.
Fig. 7 is tough cathode product photo prepared by the embodiment of the present invention 3.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
The more metal dust chemistry compositions of waste printed circuit board used in following embodiments, as shown in table 1.
The mixed-powder chemical composition (%, ω) of table 1
| Cu | Fe | Zn | Sn | Al | Pb | In | Au | Zr | Ag |
| 54.00 | 5.60 | 1.04 | 4.60 | 2.40 | 0.63 | 9.5μg/g | 5μg/g | 16.6μg/g | 17.6μg/g |
Embodiment 1：
A kind of waste printed circuit board Whote-wet method recovery process of the invention, comprises the following steps：
(1) waste printed circuit board use into shaking table roughing after jaw crusher is broken, much metal powder constituent such as tables 1
It is shown.
(2) the more metal dusts of waste printed circuit board in reactor are leached with 1mol/L sulfuric acid solution, sulfuric acid is molten
The liquid-solid ratio of liquid and the more metal dusts of waste printed circuit board is 20:1 (unit：mL/g)；Start stirring, mixing speed in leaching process
350r/min, 45 DEG C of extraction temperature, stirring are separated by filtration after 1.5 hours, obtain leachate and leached mud；Contain in leachate
The active metals such as zinc, aluminium, iron, the main cupric of leached mud, tin, noble metal etc..Active metal assay is removed in advance by the diluted acid
As shown in table 2.
(3) copper sulphate (excess coefficient of copper sulphate is 2) is added in leached mud and 2mol/L sulfuric acid solutions enter line replacement
Stripping tin is leached, extraction time is 2 hours, and extraction temperature is 55 DEG C, is obtained after separation of solid and liquid containing tin liquor and divides scruff；Containing in tin liquor
The predominantly soluble-salt of tin, copper, divide the main cupric of scruff, noble metal slag.
(4) 15 times of air is persistently blasted after 3 times being diluted containing tin liquor and carries out aoxidizing heavy tin and reacts 4h, after standing 2 hours
It is separated by filtration, obtains stannic acid precipitation, tin ash product is obtained through calcining.
2mol/L sulfuric acid, which is added, in scruff is divided and is stirred with 300r/min mixing speed (sulfuric acid and divides scruff
Liquid-solid ratio is 20:1, liquid-solid ratio unit is mL/g), while air is passed through with 120mL/min speed and carries out Oxidation Leaching, temperature
For 70 DEG C, extraction time is 4 hours；Obtain containing copper liquid and noble metal slag after separation of solid and liquid.
(5) through eddy flow electrodeposition carry copper containing copper liquid (wherein carrying copper bar part is：Current density 400A/m2, circular flow 300L/
H, sulfuric acid concentration 1mol/L in electric effusion, 30 DEG C of feed temperature, it is 10g/L to control terminal copper ion concentration.), tough cathode is made
Product photo is as shown in Fig. 2 tough cathode product analysis is as shown in table 5.
The diluted acid of table 2 removes active metal assay in advance
| Diluted acid removes active metal in advance | Cu | Zn | Fe | Sn | Al |
| Ion concentration/(g/L) | 1.18 | 0.51 | 2.61 | 0.06 | 1.12 |
| Leaching rate/% | 4.37 | 98.08 | 93.39 | 2.72 | 93.32 |
Mantoquita displacement stripping tin rate is 97.8% in the present embodiment, and it is 95.2% to aoxidize heavy tin rate, and air oxidation leaching copper copper carries
It is 98.2% to take rate.
Embodiment 2:
A kind of waste printed circuit board Whote-wet method recovery process of the invention, comprises the following steps：
(1) waste printed circuit board use into shaking table roughing after jaw crusher is broken, much metal powder constituent such as tables 1
It is shown.
(2) the more metal dusts of waste printed circuit board in reactor are leached with 0.8mol/L sulfuric acid solution, sulfuric acid
The liquid-solid ratio of solution and the more metal dusts of waste printed circuit board is 20:1 (liquid-solid ratio unit ratio is mL/g)；Start in leaching process
Stirring, mixing speed 300r/min, 30 DEG C of extraction temperature, stirring are separated by filtration after 1.5 hours, obtain leachate and leached mud；
Contain the active metals, the main cupric of leached mud, tin, noble metal etc. such as zinc, aluminium, iron in leachate.By the diluted acid in advance except active
Metal inspection result is as shown in table 3.
(3) copper sulphate (excess coefficient of copper sulphate is 1.5) is added in leached mud and 1mol/L sulfuric acid solutions are put
Leaching stripping tin is changed, extraction time is 2 hours, and extraction temperature is 45 DEG C, is obtained after separation of solid and liquid containing tin liquor and divides scruff；Containing tin liquor
In predominantly tin, the soluble-salt of copper, divide the main cupric of scruff, noble metal slag.
(4) by diluted containing tin liquor added after 2 times needed for 5 times of oxidant hydrogen peroxide and stir 2h and carry out aoxidizing heavy tin, it is quiet
It is separated by filtration after putting 2 hours, obtains stannic acid precipitation (product photo is as shown in Figure 4), tin ash product is obtained through calcining.
2mol/L sulfuric acid, which is added, in scruff is divided and is stirred with 400r/min mixing speed (sulfuric acid and divides scruff
Liquid-solid ratio is 15:1, liquid-solid ratio unit ratio is mL/g), while air is passed through with 120mL/min speed and carries out Oxidation Leaching,
Temperature is 70 DEG C, and extraction time is 4 hours；Obtain containing copper liquid and noble metal slag after separation of solid and liquid.
(5) through eddy flow electrodeposition carry copper containing copper liquid (carrying copper bar part is：Current density 400A/m2, circular flow 400L/h, sulphur
Acid concentration 1mol/L, 30 DEG C of feed temperature, it is 10g/L to control terminal copper ion concentration), tough cathode product photo such as Fig. 3 is made
Shown, tough cathode product analysis is as shown in table 5.
The diluted acid of table 3 removes active metal assay in advance
| Diluted acid removes active metal in advance | Cu | Zn | Fe | Sn | Al |
| Ion concentration/(g/L) | 0.83 | 0.47 | 2.67 | 0.13 | 1.13 |
| Leaching rate/% | 3.07 | 90.60 | 95.51 | 5.65 | 94.17 |
Mantoquita displacement stripping tin rate is 97.9% in the present embodiment, and it is 96.0% to aoxidize heavy tin rate, and air oxidation leaching copper copper carries
It is 96.4% to take rate, sink products therefrom photo after the calcining of tin product as shown in figure 5, after heavy tin product calcining products therefrom XRD
Analysis chart is as shown in Figure 6, the results showed that thing is mainly mutually tin ash.
Embodiment 3：
A kind of more metal dust Whote-wet method recovery process of waste printed circuit board of the invention, comprise the following steps：
(1) waste printed circuit board use shaking table roughing after jaw crusher is broken, much metal powder constituent such as institutes of table 1
Show.
(2) leachate that the step of embodiment 2 (2) obtains concentration sour after mending acid is reached into 1.21mol/L, with benefit acid
Leachate leaches to the more metal dusts of waste printed circuit board in reactor, the liquid of solution and the more metal dusts of waste printed circuit board
Gu than being 20:1 (liquid-solid ratio unit ratio is mL/g)；Start stirring, mixing speed 300r/min, extraction temperature in leaching process
30 DEG C, stirring is separated by filtration after 1 hour, obtains leachate and leached mud；Contain the active metals such as zinc, aluminium, iron, leaching in leachate
Slag tap main cupric, tin, noble metal etc..By the diluted acid in advance except active metal assay is as shown in table 4.
(3) add that the step of embodiment 2 (4) obtains in leached mud contains copper liquid, and adds the copper sulphate (excess of copper sulphate
Coefficient is 1.5) to enter line replacement to leach stripping tin, and extraction time is 1.5 hours, and extraction temperature is 45 DEG C, the speed of leaching process stirring
Spend for 300r/min, obtained after separation of solid and liquid containing tin liquor and divide scruff；Containing the soluble-salt in tin liquor being mainly tin, copper, divide tin
The main cupric of slag, noble metal slag.
(4) hydrogen peroxide that 10 times of oxidant needed for addition after 3 times is diluted containing tin liquor is stirred 2 hours, mistake after standing 2 hours
Filter separation, obtains stannic acid precipitation, and tin ash product is obtained through calcining.
2.13mol/L sulfuric acid, which is added, in scruff is divided and is stirred with 400r/min mixing speed (sulfuric acid and divides tin
The liquid-solid ratio of slag is 15:1, liquid-solid ratio unit ratio is mL/g), while air is passed through with 120mL/min speed and aoxidized
Leach, temperature is 70 DEG C, and extraction time is 4 hours；Obtain containing copper liquid and noble metal slag after separation of solid and liquid.
(5) through eddy flow electrodeposition carry copper containing copper liquid (carrying copper bar part is：Current density 400A/m2, circular flow 300L/h, sulphur
Acid concentration 1mol/L, 30 DEG C of feed temperature, it is 10g/L to control terminal copper ion concentration), obtained tough cathode product photo is as schemed
Shown in 7.
The diluted acid of table 4 removes active metal assay in advance
| Diluted acid removes active metal in advance | Cu | Zn | Fe | Sn | Al |
| Ion concentration/(g/L) | 1.34 | 0.65 | 3.42 | 0.14 | 1.49 |
| Leaching rate/% | 3.97 | 93.71 | 90.59 | 4.32 | 93.68 |
Mantoquita displacement stripping tin rate is 94.9% in the present embodiment, and it is 95.3% to aoxidize heavy tin rate, and air oxidation leaching copper copper carries
It is 97.3% to take rate.Tough cathode product analysis is as shown in table 5.
The tough cathode product analysis contrast table of table 5
| Element | Embodiment 1 | Embodiment 2 | Embodiment 3 | Standard cathode copper |
| Cu | 99.97% | 99.98% | 99.97% | >99.95% |
| Se | / | / | / | / |
| Bi | 5.9x10-4 | 4.2x10-4 | 6.3x10-4 | 6x10-3 |
| Sb | 5.2x10-4 | 5.9x10-4 | 6x10-4 | 1.5x10-3 |
| As | 70.5x10-4 | 68.2x10-4 | 70x10-4 | 1.5x10-3 |
| S | 15.1x10-4 | 10.3x10-4 | 9.1x10-4 | 2.5x10-3 |
| Mn | 1.0x10-4 | 0.9x10-4 | 0.5x10-4 | / |
| Cd | 1.6x10-4 | 1.1x10-4 | 2x10-4 | / |
| P | 11.1x10-4 | 9.9x10-4 | 7.2x10-4 | 1x10-3 |
| Ni | 6.3x10-4 | 6.9x10-4 | 5.2x10-4 | 2x10-2 |
| Si | 40.4x10-4 | 30x10-4 | 37x10-4 | / |
| Co | 6.7x10-4 | 5.1x10-4 | 4.5x10-4 | / |
| Te | / | / | / | / |
| Cr | / | / | / | / |
| Pb | 70.7x10-4 | 58.5x10-4 | 74x10-4 | 2x10-3 |
| Sn | 6.1x10-4 | 4.1x10-4 | 3.5x10-4 | 1x10-3 |
| Fe | 22.6x10-4 | 16.7x10-4 | 20.8x10-4 | 2.5x10-3 |
| Zn | 22.8x10-4 | 10.5x10-4 | 29.7x10-4 | 2x10-3 |
| Ag | 3.2x10-4 | 1.3x10-4 | 1.0x10-4 | / |
| Summation | 266.6x10-4 | 228.2x10-4 | 276x10-4 | 0.0166 |
It was found from the tough cathode product analysis contrast of table 5, tough cathode production obtained by waste printed circuit board handling process of the invention
Product meet standard cathode copper standard.
Claims (7)
1. a kind of waste printed circuit board Whote-wet method recovery process, it is characterised in that comprise the following steps：
(1) waste printed circuit board crushed, obtain the more metal dusts of waste printed circuit board after cradle roughing；
(2) the more metal dusts of the waste printed circuit board are leached with the acid solution that concentration is 0.1~4mol/L, separation of solid and liquid
After obtain leachate and leached mud；Wherein, the liquid-solid ratio of acid solution and the more metal dusts of waste printed circuit board is 20:1, liquid-solid ratio list
Position ratio is mL/g；Start stirring, mixing speed 300r/min, 30 DEG C of extraction temperature, mistake after stirring 1.5 hours in leaching process
Filter separation；Acid is sulfuric acid；
(3) it is 0.5~5mol/L acid solutions displacement stripping tin that copper compound and concentration are added in leached mud, is obtained after separation of solid and liquid
Containing tin liquor and divide scruff；The copper compound is the one or more in copper sulphate, copper chloride, Cu oxide；The acid is sulphur
Acid；
(4) concentration is added in scruff is divided and is 0.2~6mol/L acid solution, then be passed through oxygen and/or air aoxidize it is anti-
Should, obtain containing copper liquid and noble metal slag after separation of solid and liquid；The temperature of the oxidation reaction is 45~90 DEG C；The acid is sulfuric acid；
Need to stir in oxidation reaction process, and mixing speed is not less than 200r/min, liquid-solid ratio is 3~40, the unit of the liquid-solid ratio
Than for mL/g；
(5) it is described to obtain tough cathode through eddy flow electrodeposition containing copper liquid；Oxygen caused by eddy flow electrolytic deposition process is used to walk in the step (5)
Suddenly the oxidation reaction of (4).
2. technique as claimed in claim 1, it is characterised in that again to discarded electricity after acid adding in the leachate after step (2)
Plate more metal dusts in road are leached.
3. technique as claimed in claim 1, it is characterised in that oxidant is added in step (3) is containing tin liquor, 50~90
Reaction obtains stannic acid precipitation at DEG C, and stannic acid precipitation obtains tin ash through calcining, and the oxidant is hydrogen peroxide, ozone, oxygen
With the one or more in air；The excess coefficient of oxidant is 1~20.
4. technique as claimed in claim 3, it is characterised in that in the step (3), when in the acid solution that stripping tin process is selected
When hydrogen ion concentration is more than 1mol/L, need first to carry out aoxidizing heavy tin to adding oxidant after being diluted containing tin liquor.
5. the technique as described in any one of Claims 1 to 4, it is characterised in that in the step (3), the excess of copper compound
Coefficient is 1~10.
6. the technique as described in any one of Claims 1 to 4, it is characterised in that the return to step containing copper liquid in the step (4)
(3) part copper compound is replaced in.
7. the technique as described in any one of Claims 1 to 4, it is characterised in that in the eddy flow electrolytic deposition process of the step (5),
Cathode-current density is 200~900A/m2, sulfuric acid concentration is 0.2~1.5mol/L in electric effusion, and electrodeposition temperature is 10~40
DEG C, electrodeposition terminal copper ion concentration is controlled in more than 5g/L.
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| CN201510598245.3A CN105112674B (en) | 2015-09-18 | 2015-09-18 | A kind of waste printed circuit board Whote-wet method recovery process |
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| CN105112674B true CN105112674B (en) | 2017-11-21 |
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| CN105297077A (en) * | 2015-12-03 | 2016-02-03 | 陈梦君 | Recovery method for metals in waste printed circuit boards |
| CN105779770B (en) * | 2016-03-10 | 2017-04-12 | 中南大学 | Method for recycling valuable metal in waste circuit board |
| CN105624681B (en) * | 2016-03-11 | 2018-07-13 | 中南大学 | The method of electronic component and a kind of etching agent in a kind of wet separation waste printed circuit board |
| CN106468630A (en) * | 2016-09-30 | 2017-03-01 | 珠海格力电器股份有限公司 | Metal ingredient analysis method in a kind of wiring board |
| CN107502920A (en) * | 2017-08-10 | 2017-12-22 | 云南龙蕴科技环保股份有限公司 | A kind of method of the hydrometallurgic recovery copper from circuit board |
| CN107574310A (en) * | 2017-09-19 | 2018-01-12 | 南京工业大学 | A kind of method for efficiently leaching copper in waste printed circuit board |
| CN108160683A (en) * | 2018-02-06 | 2018-06-15 | 湖南科技大学 | A kind of method that waste and old tin plating copper-clad plate resource utilization utilizes |
| CN108346715A (en) * | 2018-02-09 | 2018-07-31 | 中南大学 | The recovery method of silicon solar cell |
| CN109825716A (en) * | 2019-03-28 | 2019-05-31 | 湖南科技大学 | A method of recycling copper and tin in waste and old tin plating copper-clad plate |
| CN111172398A (en) * | 2020-01-17 | 2020-05-19 | 广东华越环保科技有限公司 | Wet harmless extraction process for metal in waste mobile phone circuit board |
| CN111139360B (en) * | 2020-01-17 | 2021-10-26 | 广东华越环保科技有限公司 | Method for recovering metals in IC (integrated circuit) chip and component in waste mobile phone circuit board |
| CN111154979A (en) * | 2020-01-17 | 2020-05-15 | 广东华越环保科技有限公司 | Cyanide-free recovery process for gold and palladium in IC (integrated circuit) chip and component in waste mobile phone circuit board |
| CN111663045B (en) * | 2020-06-16 | 2021-05-14 | 中南大学 | Comprehensive waste circuit board resource recovery process |
| CN112143899B (en) * | 2020-09-16 | 2022-07-01 | 励福(江门)环保科技股份有限公司 | Method for recovering copper and enriching precious metals from waste circuit boards |
| CN112921356B (en) * | 2021-01-22 | 2022-05-27 | 西南科技大学 | Method for recovering copper from waste printed circuit board |
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| CN86101938B (en) * | 1986-03-21 | 1987-05-20 | 个旧市化工研究所 | Preparation of stannic oxide from medium grade tin ore by liquid phasing oxidization |
| ZA987217B (en) * | 1997-08-15 | 2000-02-14 | Cominco Eng Services | Chloride assisted hydrometallurgical extraction of metal from sulphide or laterite ores. |
| CN101864519A (en) * | 2009-04-17 | 2010-10-20 | 中国科学院过程工程研究所 | Method for selectively leaching and separating tin, lead and copper from waste circuit board |
| CN101643852B (en) * | 2009-09-02 | 2011-10-12 | 北京科技大学 | Heap-leaching method for separating copper and tin from tin-plated copper wires |
| CN101787547B (en) * | 2010-02-09 | 2011-06-15 | 中南大学 | Method for recovering valuable metals from waste printed circuit board |
| CN103725879A (en) * | 2013-12-24 | 2014-04-16 | 戴元宁 | Method for producing tungsten and tin chemical products through chemical metallurgical separation of tungsten-tin paragenic ore |
| CN104843770B (en) * | 2015-03-30 | 2017-09-26 | 中国钢研科技集团有限公司 | A kind of method that tin mud resource is utilized |
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