CN105112674A - All-wet recovery process for waste circuit boards - Google Patents
All-wet recovery process for waste circuit boards Download PDFInfo
- Publication number
- CN105112674A CN105112674A CN201510598245.3A CN201510598245A CN105112674A CN 105112674 A CN105112674 A CN 105112674A CN 201510598245 A CN201510598245 A CN 201510598245A CN 105112674 A CN105112674 A CN 105112674A
- Authority
- CN
- China
- Prior art keywords
- copper
- tin
- liquid
- acid
- technique
- 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.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses an all-wet recovery process for waste circuit boards. The all-wet recovery process comprises the following steps of crushing and reselecting the waste circuit boards to obtain multi-metal powder of the waste circuit boards; performing leaching on the multi-metal powder of the waste circuit boards with an acid solution with the concentration of 0.1-4 mol/L, and obtaining leach liquid and leach residues after solid-liquid separation; adding copper compounds and an acid solution with the concentration of 0.5-5 mol/L into the leach residues to replace and strip tin, and obtaining tin-bearing liquid and tin-separated residues after solid-liquid separation; adding an acid solution with the concentration of 0.2-6 mol/L into the tin-separated residues, leading oxygen and/or air into the mixture for an oxidation reaction, and obtaining copper-bearing liquid and precious metal residues after solid-liquid separation; and performing vortex electrodeposition on the copper-bearing liquid to obtain cathode copper. According to the all-wet recovery process for the waste circuit boards, the all-wet recovery process is provided for treating the waste circuit boards, so that directional separation, gathering and extraction of valuable metal in the process steps are achieved, and the problems of the dispersed moving of valuable metal elements of the waste circuit boards, the difficulty in subsequent separation and extraction and the like are solved.
Description
Technical field
The present invention relates to waste resource and reclaim field, particularly relate 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.Show according to Chinese Ministry of Industry and Information publish data, in January, 2013, the above electronics product manufacturing industry of China's scale increased by 11.2% to November.But the life cycle of electronic product but shortens day by day along with the development of electronic technology.1997 so far, and the mean lifetime of computer and CPU fell to only 2 years by 4 ~ 6 years.And the rapid rising of the Novel electronic products such as mobile phone and update thereof, accelerate eliminating of electronic product.According to European Union's relevant report, the rate of increase of electron wastes remained on about 11% in 2008 during 2014, was 4 times of common rubbish.Metal containing a large amount of recoverable in electron wastes, as aluminium, copper, lead, zinc, precious metal (gold and silver), platinum metals 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 nonmetal by also bringing considerable economic benefit after effective separation.
Patent publication No. is that the Chinese patent of CN101049955A discloses a kind of copper that to utilize in waste printed circuit board for the method for copper sulfate, employing dilute sulphuric acid, sodium-chlor add the atmospheric oxidation of copper sulfate system and at room temperature leach copper in waste printed circuit board, and after filtering, gained filtrate carries out evaporative crystallization; Introduce sodium salt in this Leaching Systems, and only considered the element behavior of copper, other metallic elements are not studied.Patent publication No. is the United States Patent (USP) of US20120318681A1, disclose a kind of technique of afforesting without cyanogen wet processing recovery waste printed circuit board, this technique adopts Physical to be separated metal in waste printed circuit board and nonmetal, the metallic copper powder obtained is cast as refining after anode, then reclaims precious metal from the anode sludge; Require high to physical sepn in this method, just research conditions domestic is at present seen and is difficult to reach the requirement directly can casting electrolysis by physical partition method.Patent publication No. is the United States Patent (USP) of US2013033522A1, disclose a kind of method reclaiming valuable metal from waste (comprising waste printed circuit board), wherein discarded printed circuit boards is without physical sepn, directly after control temperature process, separation of glasses fiber and valuable metal; Clearly in patent show that valuable metal can not be separated from each other with glass fibre, therefore needs higher treatment temp when treatment temp is lower than 400 DEG C.Patent publication No. is that the Chinese patent of CN101049955A discloses and waste printed circuit board is placed in vacuum vessel, intensification pyrolysis, and the cooling liquid of most of pyrolysis devolatilization thing is liquid oils, and another part enters gas trap; During pyrolysis, centrifugal separating device is utilized to be separated with circuit card by scolding tin; Circuit board substrate after categorised collection pyrolysis and electronic component further separate and recovery; This method requires high to equipment temperature control, and energy consumption is also corresponding higher.Patent publication No. is a kind of method that the Chinese patent of CN104532005A discloses discarded printed circuit boards comprehensive utilization of resources, by fragmentation, magnetic separation separating ferrum raw material and non iron raw material; Metalliferous material and non-metallic material are gone out to non iron raw material high-voltage electrostatic sorting; Again the metal such as copper, gold and silver is separated to metalliferous material; This method also mainly concentrates on physical sepn and copper, precious metal reclaim.Simultaneously, above-mentioned patent all could not consider the impact of other metallic elements in waste printed circuit board, all single concentrates on some or several metal, and this must cause it to there is the problems such as not clear, each element synthetical recovery difficulty of other metallic elements trend when industrial applications.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of with low cost, a kind of waste printed circuit board Whote-wet method recovery process that clean environment firendly, reagent circulation usability are strong.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A kind of waste printed circuit board Whote-wet method recovery process, comprises the following steps:
(1) the many metal-powders of waste printed circuit board are obtained by after described waste printed circuit board fragmentation, gravity treatment;
(2) be that the acid solution of 0.1 ~ 4mol/L leaches the many metal-powders of waste printed circuit board by concentration, this process is carried out in the reactor of design temperature, starts stirring simultaneously, and solid-liquid separation after reaction for some time, obtains leach liquor and leached mud; Containing active metals such as zinc, aluminium, iron in leach liquor, the main cupric of leached mud, tin, precious metal etc.;
(3) in leached mud, add the acid solution displacement stripping tin that copper compound and concentration are 0.5 ~ 5mol/L, obtain containing tin liquor and a point scruff after solid-liquid separation; Described copper compound is one or more in copper sulfate, cupric chloride, copper oxide; Containing the soluble salt being mainly tin, copper in tin liquor, point main cupric of scruff, precious metal slag;
(4) in point scruff, adding concentration is 0.2 ~ 6mol/L acid solution, then passes into oxygen and/or air carries out oxidizing reaction, obtains cupric liquid and precious metal slag after solid-liquid separation; The temperature of described oxidizing reaction is 45 ~ 90 DEG C;
(5) cupric liquid obtains cathode copper through eddy flow electrodeposition.
Above-mentioned technique, preferably, leaches the many metal-powders of waste printed circuit board after acid adding in the leach liquor after step (2), the active metal that in liquid to be leached, valuable metal is opened a way in synthetical recovery leach liquor after being enriched to finite concentration again.
Above-mentioned technique, preferably, containing in tin liquor after step (3) adds oxygenant, is obtained by reacting stannic acid precipitation at 50 ~ 90 DEG C, stannic acid precipitation obtains tindioxide through calcining, and described oxygenant is one or more in hydrogen peroxide, ozone, oxygen and air; The excess coefficient of oxygenant is 1 ~ 20 (being 1-20 times of tetravalent tin requisite oxygen agent theoretical amount by Bivalent Tin complete oxidation).
Above-mentioned technique, preferably, in described step (3), when shelling that in the acid solution that tin process selects, hydrogen ion concentration is greater than 1mol/L, needs first to be oxidized heavy tin to adding oxygenant again after diluting containing tin liquor.
Above-mentioned technique, preferably, in described step (3), the excess coefficient (mol ratio of copper and tin) of copper compound is 1 ~ 10.
Above-mentioned technique, preferably, the cupric liquid in described step (4) returns in step (3) and replaces part copper compound.
Above-mentioned technique, preferably, in the eddy flow electrolytic deposition process of described step (5), cathode current density is 200 ~ 900A/m
2, in electric effusion, sulfuric acid concentration is 0.2 ~ 1.5mol/L, and electrodeposition temperature is 10 ~ 40 DEG C, and electrodeposition terminal copper ion concentration controls at more than 5g/L.
Above-mentioned technique, preferably, the oxygen that in described step (5), eddy flow electrolytic deposition process produces is used for the oxidizing reaction of step (4).
Above-mentioned technique, preferably, in described step (4), oxidation reaction process needs to stir, and stirring velocity is not less than 200r/min, and liquid-solid ratio is 3 ~ 40; The unit of described liquid-solid ratio is than being mL/g; Control gas flow (amounting to purity oxygen) and the molar ratio >1.2 dividing copper in scruff.
Above-mentioned technique, preferably, in described step (2), acid solution is one or both in hydrochloric acid and sulfuric acid; Acid in described step (3) and step (4) is sulfuric acid.
Above-mentioned technique, preferably, the granularity of the many metal-powders of described waste printed circuit board is 200-50 order.
The equal reusable edible of acid that surplus acid in above-mentioned technique after solid-liquid separation and electrodeposition produce is in point tin and atmospheric oxidation leaching copper step.
Technical process of the present invention as shown in Figure 1, take the lead in proposing to adopt diluted acid leaching active metal to reach in technique and alleviate subsequent technique removal of impurities object, and reach the object of active metal enrichment by circulating leaching, thus be conducive to the further Separation and Recovery of active metal; Propose the tin adopted in mantoquita displacement stripping waste printed circuit board first, the one in hydrogen peroxide, ozone, oxygen or the heavy tin of its collocation oxidation, displaced liquid can be further used for lower step and leach, and introduces without any impurity; Adopt atmospheric oxidation acidleach waste printed circuit board many metal-powders environmental friendliness, facility investment low; Adopting eddy flow electrodeposition to carry copper can when without Cu-CATH-1 obtained when any additive.
Compared with prior art, the invention has the advantages that:
1) traditional method mainly relies on physical sepn to realize the initial gross separation of metal, the present invention is actual in conjunction with domestic equipment research and development, the reverse proposition that takes the lead in have developed this technique alleviating under the condition premised on physical sepn burden, technique of the present invention does not need to carry out magnetic separation, electric separation etc., only needs to carry out simple fragmentation, roughly select.
2) the present invention proposes the many metal-powders of Whote-wet method art breading waste printed circuit board, alleviate waste printed circuit board physical sepn burden, achieve the directional separation of valuable metal in processing step, enrichment, extraction, solve waste printed circuit board many metal-powders valuable metal element and move towards the problem such as dispersion and later separation extraction difficulty.
3) the present invention adopts diluted acid in advance except molten copper, eddy flow electrodeposition Cu-CATH-1 technique are leached in active metal, mantoquita displacement stripping tin, atmospheric oxidation, and have equipment simple, easy to implement, reagent circulation is good, and cost is low, and environmentally safe.And the present invention recovery valuable metal while, the organism in waste printed circuit board and glass fibre lower than the destruction suffered with pyrogenic process, can reclaim in subsequent step.
4) the present invention is directed to waste printed circuit board to propose first and leach active valuable metal as iron, zinc etc. with diluted acid selectivity, gained leach liquor concentration of metal ions can enrichment in the present invention, after enrichment, open circuit can directly produce corresponding product salt, has advantage with conventional physical segregation ratio.
5) the present invention is directed to waste printed circuit board to propose first to adopt mantoquita displacement stripping tin, added regent is few, and inclusion-free is introduced, and industrialization design is strong.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is cathode copper product photo prepared by the embodiment of the present invention 1.
Fig. 3 is cathode copper product photo prepared by the embodiment of the present invention 2.
Fig. 4 is the stannic acid precipitation photo that the embodiment of the present invention 2 is oxidized heavy tin gained.
Fig. 5 embodiment of the present invention 2 stannic acid precipitation is through calcining the tindioxide product photo of gained.
Fig. 6 embodiment of the present invention 2 stannic acid precipitation is through calcining the XRD figure of the tindioxide product of gained.
Fig. 7 is cathode copper product photo prepared by the embodiment of the present invention 3.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Apart from special instruction, all ingredients used in the present invention, raw material are can commodity commercially or can by the obtained product of known method.
In following embodiment, waste printed circuit board used many metal-powder chemistry composition, as shown in table 1.
Table 1 mixed powder chemical constitution (%, ω)
| 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 present invention, comprises the following steps:
(1) after jaw crusher fragmentation, adopt shaking table to roughly select waste printed circuit board, the many metal powder constituent of gained are as shown in table 1.
(2) leach the many metal-powders of the waste printed circuit board in reactor with the sulphuric acid soln of 1mol/L, the liquid-solid ratio of sulphuric acid soln and the many metal-powders of waste printed circuit board is 20:1 (unit: mL/g); Start in leaching process and stir, stirring velocity 350r/min, extraction temperature 45 DEG C, stirs filtering separation after 1.5 hours, obtains leach liquor and leached mud; Containing active metals such as zinc, aluminium, iron in leach liquor, the main cupric of leached mud, tin, precious metal etc.Through this diluted acid in advance except active metal assay is as shown in table 2.
(3) in leached mud, add copper sulfate (excess coefficient of copper sulfate is 2) and 2mol/L sulphuric acid soln carry out displacement and leach stripping tin, extraction time is 2 hours, and extraction temperature is 55 DEG C, obtains containing tin liquor and a point scruff after solid-liquid separation; Containing the soluble salt being mainly tin, copper in tin liquor, point main cupric of scruff, precious metal slag.
(4) undertaken being oxidized heavy tin reaction 4h by diluting 3 times of air continuing to blast 15 times afterwards containing tin liquor, leave standstill filtering separation after 2 hours, obtain stannic acid precipitation, obtain tindioxide product through calcining.
In point scruff, add 2mol/L sulfuric acid and carry out stirring that (liquid-solid ratio of sulfuric acid and point scruff is for 20:1 with the stirring velocity of 300r/min, liquid-solid ratio unit is mL/g), passing into air with the speed of 120mL/min carries out Oxidation Leaching simultaneously, and temperature is 70 DEG C, and extraction time is 4 hours; Cupric liquid and precious metal slag is obtained after solid-liquid separation.
(5) cupric liquid is carried copper through eddy flow electrodeposition (wherein carrying copper bar part is: current density 400A/m
2, circular flow 300L/h, sulfuric acid concentration 1mol/L in electric effusion, feed temperature 30 DEG C, controlling terminal copper ion concentration is 10g/L.), as shown in Figure 2, cathode copper product analysis is as shown in table 5 for obtained cathode copper product photo.
Table 2 diluted acid is in advance except active metal assay
| Diluted acid is in advance except active metal | Cu | Zn | Fe | Sn | Al |
| Ionic concn/(g/L) | 1.18 | 0.51 | 2.61 | 0.06 | 1.12 |
| Leaching yield/% | 4.37 | 98.08 | 93.39 | 2.72 | 93.32 |
In the present embodiment, mantoquita displacement stripping tin rate is 97.8%, and the heavy tin rate of oxidation is 95.2%, and atmospheric oxidation leaching copper copper extraction yield is 98.2%.
Embodiment 2:
A kind of waste printed circuit board Whote-wet method recovery process of the present invention, comprises the following steps:
(1) after jaw crusher fragmentation, adopt shaking table to roughly select waste printed circuit board, the many metal powder constituent of gained are as shown in table 1.
(2) leach the many metal-powders of the waste printed circuit board in reactor with the sulphuric acid soln of 0.8mol/L, the liquid-solid ratio of sulphuric acid soln and the many metal-powders of waste printed circuit board is 20:1 (liquid-solid ratio unit ratio is mL/g); Start in leaching process and stir, stirring velocity 300r/min, extraction temperature 30 DEG C, stirs filtering separation after 1.5 hours, obtains leach liquor and leached mud; Containing active metals such as zinc, aluminium, iron in leach liquor, the main cupric of leached mud, tin, precious metal etc.Through this diluted acid in advance except active metal assay is as shown in table 3.
(3) in leached mud, add copper sulfate (excess coefficient of copper sulfate is 1.5) and 1mol/L sulphuric acid soln carry out displacement and leach stripping tin, extraction time is 2 hours, and extraction temperature is 45 DEG C, obtains containing tin liquor and a point scruff after solid-liquid separation; Containing the soluble salt being mainly tin, copper in tin liquor, point main cupric of scruff, precious metal slag.
(4) add the hydrogen peroxide of requisite oxygen agent 5 times after 2 times being diluted containing tin liquor and stir 2h and carry out being oxidized heavy tin, leaving standstill filtering separation after 2 hours, obtaining stannic acid precipitation (product photo as shown in Figure 4), obtaining tindioxide product through calcining.
In point scruff, add 2mol/L sulfuric acid and carry out stirring that (liquid-solid ratio of sulfuric acid and point scruff is for 15:1 with the stirring velocity of 400r/min, liquid-solid ratio unit ratio is mL/g), passing into air with the speed of 120mL/min carries out Oxidation Leaching simultaneously, temperature is 70 DEG C, and extraction time is 4 hours; Cupric liquid and precious metal slag is obtained after solid-liquid separation.
(5) cupric liquid is carried copper through eddy flow electrodeposition (carrying copper bar part is: current density 400A/m
2, circular flow 400L/h, sulfuric acid concentration 1mol/L, feed temperature 30 DEG C, controlling terminal copper ion concentration is 10g/L), as shown in Figure 3, cathode copper product analysis is as shown in table 5 for obtained cathode copper product photo.
Table 3 diluted acid is in advance except active metal assay
| Diluted acid is in advance except active metal | Cu | Zn | Fe | Sn | Al |
| Ionic concn/(g/L) | 0.83 | 0.47 | 2.67 | 0.13 | 1.13 |
| Leaching yield/% | 3.07 | 90.60 | 95.51 | 5.65 | 94.17 |
In the present embodiment, mantoquita displacement stripping tin rate is 97.9%, the heavy tin rate of oxidation is 96.0%, atmospheric oxidation leaching copper copper extraction yield is 96.4%, after heavy tin product calcining, products therefrom photo as shown in Figure 5, after heavy tin product calcining, as shown in Figure 6, result shows that thing is mainly tindioxide mutually to the XRD analysis figure of products therefrom.
Embodiment 3:
A kind of waste printed circuit board many metal-powders Whote-wet method recovery process of the present invention, comprises the following steps:
(1) waste printed circuit board adopts shaking table to roughly select after jaw crusher fragmentation, and the many metal powder constituent of gained are as shown in table 1.
(2) concentration of leach liquor embodiment 2 step (2) obtained acid after mending acid reaches 1.21mol/L, leach the many metal-powders of the waste printed circuit board in reactor with this benefit acid leaching liquor, the liquid-solid ratio of solution and the many metal-powders of waste printed circuit board is 20:1 (liquid-solid ratio unit ratio is mL/g); Start in leaching process and stir, stirring velocity 300r/min, extraction temperature 30 DEG C, stirs filtering separation after 1 hour, obtains leach liquor and leached mud; Containing active metals such as zinc, aluminium, iron in leach liquor, the main cupric of leached mud, tin, precious metal etc.Through this diluted acid in advance except active metal assay is as shown in table 4.
(3) in leached mud, add the cupric liquid that embodiment 2 step (4) obtains, and add copper sulfate (excess coefficient of copper sulfate is 1.5) carry out displacement leach stripping tin, extraction time is 1.5 hours, extraction temperature is 45 DEG C, the speed that leaching process stirs is 300r/min, obtains containing tin liquor and point scruff after solid-liquid separation; Containing the soluble salt being mainly tin, copper in tin liquor, point main cupric of scruff, precious metal slag.
(4) stirring 2 hours by containing the hydrogen peroxide adding requisite oxygen agent 10 times after tin liquor dilutes 3 times, leaving standstill filtering separation after 2 hours, obtaining stannic acid precipitation, obtain tindioxide product through calcining.
In point scruff, add 2.13mol/L sulfuric acid and carry out stirring that (liquid-solid ratio of sulfuric acid and point scruff is for 15:1 with the stirring velocity of 400r/min, liquid-solid ratio unit ratio is mL/g), passing into air with the speed of 120mL/min carries out Oxidation Leaching simultaneously, temperature is 70 DEG C, and extraction time is 4 hours; Cupric liquid and precious metal slag is obtained after solid-liquid separation.
(5) cupric liquid is carried copper through eddy flow electrodeposition (carrying copper bar part is: current density 400A/m
2, circular flow 300L/h, sulfuric acid concentration 1mol/L, feed temperature 30 DEG C, controlling terminal copper ion concentration is 10g/L), obtained cathode copper product photo is as shown in Figure 7.
Table 4 diluted acid is in advance except active metal assay
| Diluted acid is in advance except active metal | Cu | Zn | Fe | Sn | Al |
| Ionic concn/(g/L) | 1.34 | 0.65 | 3.42 | 0.14 | 1.49 |
| Leaching yield/% | 3.97 | 93.71 | 90.59 | 4.32 | 93.68 |
In the present embodiment, mantoquita displacement stripping tin rate is 94.9%, and the heavy tin rate of oxidation is 95.3%, and atmospheric oxidation leaching copper copper extraction yield is 97.3%.Cathode copper product analysis is as shown in table 5.
Table 5 cathode copper product analysis contrast table
| 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 |
Contrast from the cathode copper product analysis of table 5, waste printed circuit board treatment process gained cathode copper product conformance with standard cathode copper standard of the present invention.
Claims (10)
1. a waste printed circuit board Whote-wet method recovery process, is characterized in that, comprises the following steps:
(1) the many metal-powders of waste printed circuit board are obtained by after described waste printed circuit board fragmentation, gravity treatment;
(2) be that the acid solution of 0.1 ~ 4mol/L leaches the many metal-powders of described waste printed circuit board by concentration, after solid-liquid separation, obtain leach liquor and leached mud;
(3) in leached mud, add copper compound and concentration is 0.5 ~ 5mol/L acid solution displacement stripping tin, obtains containing tin liquor and a point scruff after solid-liquid separation; Described copper compound is one or more in copper sulfate, cupric chloride, copper oxide;
(4) in point scruff, add the acid solution that concentration is 0.2 ~ 6mol/L, then pass into oxygen and/or air carries out oxidizing reaction, after solid-liquid separation, obtain cupric liquid and precious metal slag; The temperature of described oxidizing reaction is 45 ~ 90 DEG C;
(5) described cupric liquid obtains cathode copper through eddy flow electrodeposition.
2. technique as claimed in claim 1, is characterized in that, leach in the leach liquor after step (2) after acid adding to the many metal-powders of waste printed circuit board again.
3. technique as claimed in claim 1, it is characterized in that, oxygenant is added in containing in tin liquor of step (3), stannic acid precipitation is obtained by reacting at 50 ~ 90 DEG C, stannic acid precipitation obtains tindioxide through calcining, and described oxygenant is one or more in hydrogen peroxide, ozone, oxygen and air; The excess coefficient of oxygenant is 1 ~ 20.
4. technique as claimed in claim 3, is characterized in that, in described step (3), when shelling that in the acid solution that tin process selects, hydrogen ion concentration is greater than 1mol/L, needs first to be oxidized heavy tin to adding oxygenant again after diluting containing tin liquor.
5. the technique as described in any one of Claims 1 to 4, is characterized in that, in described step (3), the excess coefficient of copper compound is 1 ~ 10.
6. the technique as described in any one of Claims 1 to 4, is characterized in that, the cupric liquid in described step (4) returns in step (3) and replaces part copper compound.
7. the technique as described in any one of Claims 1 to 4, is characterized in that, in the eddy flow electrolytic deposition process of described step (5), cathode current density is 200 ~ 900A/m
2, in electric effusion, sulfuric acid concentration is 0.2 ~ 1.5mol/L, and electrodeposition temperature is 10 ~ 40 DEG C, and electrodeposition terminal copper ion concentration controls at more than 5g/L.
8. the technique as described in any one of Claims 1 to 4, is characterized in that, the oxygen that in described step (5), eddy flow electrolytic deposition process produces is used for the oxidizing reaction of step (4).
9. the technique as described in any one of Claims 1 to 4, is characterized in that, in described step (4), need in oxidation reaction process to stir, and stirring velocity is not less than 200r/min, liquid-solid ratio is 3 ~ 40, and the unit of described liquid-solid ratio is than being mL/g.
10. the technique as described in any one of Claims 1 to 4, is characterized in that, in described step (2), acid is one or both in hydrochloric acid and sulfuric acid; Acid in described step (3) and step (4) is sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510598245.3A CN105112674B (en) | 2015-09-18 | 2015-09-18 | A kind of waste printed circuit board Whote-wet method recovery process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510598245.3A CN105112674B (en) | 2015-09-18 | 2015-09-18 | A kind of waste printed circuit board Whote-wet method recovery process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105112674A true CN105112674A (en) | 2015-12-02 |
| CN105112674B CN105112674B (en) | 2017-11-21 |
Family
ID=54660775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510598245.3A Active CN105112674B (en) | 2015-09-18 | 2015-09-18 | A kind of waste printed circuit board Whote-wet method recovery process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105112674B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105297077A (en) * | 2015-12-03 | 2016-02-03 | 陈梦君 | Recovery method for metals in waste printed circuit boards |
| CN105624681A (en) * | 2016-03-11 | 2016-06-01 | 中南大学 | Method for wet separation of electronic components in discarded printed circuit board and tin stripping agent |
| CN105779770A (en) * | 2016-03-10 | 2016-07-20 | 中南大学 | Method for recycling valuable metal in waste 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 |
| CN111139360A (en) * | 2020-01-17 | 2020-05-12 | 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 |
| 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 |
| CN111663045A (en) * | 2020-06-16 | 2020-09-15 | 中南大学 | Comprehensive waste circuit board resource recovery process |
| CN112143899A (en) * | 2020-09-16 | 2020-12-29 | 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 |
| CN112921356A (en) * | 2021-01-22 | 2021-06-08 | 西南科技大学 | Method for recovering copper from waste printed circuit board |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101938A (en) * | 1986-03-21 | 1987-05-20 | 个旧市化工研究所 | The medium tin ore liquid phase oxidation is produced tindioxide |
| US6455019B2 (en) * | 1997-08-15 | 2002-09-24 | Cominco Engineering Services Ltd. | Process for the extraction of copper from a sulphide copper ore or concentrate |
| CN101643852A (en) * | 2009-09-02 | 2010-02-10 | 北京科技大学 | Heap-leaching method for separating copper and tin from tin-plated copper wires |
| CN101787547A (en) * | 2010-02-09 | 2010-07-28 | 中南大学 | Method for recovering valuable metals from waste printed circuit board |
| 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 |
| 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 |
| CN104843770A (en) * | 2015-03-30 | 2015-08-19 | 中国钢研科技集团有限公司 | Method of resource utilization of tin sludge |
-
2015
- 2015-09-18 CN CN201510598245.3A patent/CN105112674B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101938A (en) * | 1986-03-21 | 1987-05-20 | 个旧市化工研究所 | The medium tin ore liquid phase oxidation is produced tindioxide |
| US6455019B2 (en) * | 1997-08-15 | 2002-09-24 | Cominco Engineering Services Ltd. | Process for the extraction of copper from a sulphide copper ore or concentrate |
| 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 |
| CN101643852A (en) * | 2009-09-02 | 2010-02-10 | 北京科技大学 | Heap-leaching method for separating copper and tin from tin-plated copper wires |
| CN101787547A (en) * | 2010-02-09 | 2010-07-28 | 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 |
| CN104843770A (en) * | 2015-03-30 | 2015-08-19 | 中国钢研科技集团有限公司 | Method of resource utilization of tin sludge |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105297077A (en) * | 2015-12-03 | 2016-02-03 | 陈梦君 | Recovery method for metals in waste printed circuit boards |
| CN105779770A (en) * | 2016-03-10 | 2016-07-20 | 中南大学 | Method for recycling valuable metal in waste circuit board |
| CN105779770B (en) * | 2016-03-10 | 2017-04-12 | 中南大学 | Method for recycling valuable metal in waste circuit board |
| CN105624681A (en) * | 2016-03-11 | 2016-06-01 | 中南大学 | Method for wet separation of electronic components in discarded printed circuit board and tin stripping agent |
| 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 |
| CN111139360A (en) * | 2020-01-17 | 2020-05-12 | 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 |
| 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 |
| CN111663045A (en) * | 2020-06-16 | 2020-09-15 | 中南大学 | Comprehensive waste circuit board resource recovery process |
| CN112143899A (en) * | 2020-09-16 | 2020-12-29 | 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105112674B (en) | 2017-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105112674B (en) | A kind of waste printed circuit board Whote-wet method recovery process | |
| US8834818B2 (en) | Treatment of indium gallium alloys and recovery of indium and gallium | |
| Xiao et al. | Hydrometallurgical recovery of copper from complex mixtures of end-of-life shredded ICT products | |
| Zhu et al. | Selective recovery of zinc from zinc oxide dust using choline chloride based deep eutectic solvents | |
| CN102051478B (en) | Wet process for treating lead copper matte | |
| Ekmekyapar et al. | Leaching of malachite ore in ammonium sulfate solutions and production of copper oxide | |
| CN102491287A (en) | Process for separating and recovering selenium from selenium-containing material | |
| AU2020259139A1 (en) | Process for the recovery of metals from a Li-containing starting material | |
| Haghighi et al. | Production of copper cathode from oxidized copper ores by acidic leaching and two-step precipitation followed by electrowinning | |
| CN101109043A (en) | Method for processing cunico | |
| Fan et al. | Extraction of tellurium and high purity bismuth from processing residue of zinc anode slime by sulfation roasting-leaching-electrodeposition process | |
| Alam et al. | Electrolyte purification in energy-saving monovalent copper electrowinning processes | |
| CN102747229B (en) | Method for separating and recycling valuable metals in powder rich in multiple metals of waste circuit board | |
| CN102888515A (en) | Comprehensive utilization method of amarillite slag | |
| CN105886768A (en) | Method for efficiently enriching precious metal from electronic waste | |
| CN103882236A (en) | Method for processing high-sulfur copper dust and recovering copper by employing a wet process | |
| CN107502743A (en) | A kind of processing method of cathode copper waste liquid | |
| Hao et al. | Study of gold leaching from pre-treated waste printed circuit boards by thiosulfate‑cobalt-glycine system and separation by solvent extraction | |
| CN104004907A (en) | Method for separating copper from lead matte and comprehensively utilizing lead matte | |
| Kumar et al. | Recovery of cadmium from hydrometallurgical zinc smelter by selective leaching | |
| JP6744981B2 (en) | How to concentrate and recover precious metals | |
| CN101525696A (en) | Method for leaching indium from leaching residue containing indium | |
| Bo et al. | Selective separation of copper and cadmium from zinc solutions by low current density electrolysis | |
| JP2015086436A (en) | Method for recovering valuable material | |
| TW202407160A (en) | Method of manufacturing copper sulfate electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |