CN104630479B - A kind of method reclaiming various metals from electron wastes - Google Patents
A kind of method reclaiming various metals from electron wastes Download PDFInfo
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Abstract
The invention provides a kind of method reclaiming various metals from electron wastes.The method is: electron wastes after crushed, dissolves various metals composition by nitric acid liquid leaching and enters solution；Utilizing Polyviologen functional high molecule material to process gained solution, the non-ferrous metal such as copper, lead, nickel is enriched with and separates；Residue after hydrochloric acid, chloroazotic acid leaching, filters and is directly separated plastic fraction respectively；Solution obtained by utilizing the composite containing heteroatomic conducting function macromolecular material or this conducting function macromolecule with Graphene to process, is enriched with and reduces precious metal ion, then obtains highly purified precious metal after high melt.Compared with prior art, the method is capable of multiple non-ferrous metal, such as copper, lead, nickel, stannum etc., and precious metal Au Ag Pt Pd, hydrargyrum etc. gradually, orderly recovery, substantially increase the number reclaiming metal and recycle efficiency, adequately achieving effective recycling of electron wastes.
Description
Technical field
The invention belongs to recycling of WEEE processing technology field, be specifically related to one and reclaim many from electron wastes
Plant the coloured and method of precious metal.
Background technology
In recent years, China has been enter into the peak period that electronic product is eliminated, and the most at least to scrap and include 20,000,000 computers
With 60,000,000 mobile phones at 2,300,000 tons of interior solid electronic rubbish, it it is the second-biggest-in-the-world electron wastes life being only second to the U.S.
Produce state.Electron wastes (especially waste and old printed circuit board) contains substantial amounts of non-ferrous metal and gold, silver, palladium, platinum etc. expensive
Heavy metal and rare metal, its grade is tens times of common primary ore, thus the recovery of electron wastes becomes current state
The rising industry of inside and outside regenerated metal industry, contains huge economic worth.
The method of recycling electron wastes mainly includes Physical, chemical method and microbial method etc..Physical uses
Between each component, the difference of physical property sorts, as utilized the method for broken, screening, electric separation and magnetic separation can realize discarded print
In printed circuit board, gold, silver separate with ferrum, aluminum, zinc and stannum.Material after sorting need to could obtain metal through subsequent treatment, mould
The regenerative raw materials such as material, glass, thus mainly as the auxiliary preprocessing means of additive method.Chemical method be divided into again pyrometallurgy and
The techniques such as hydrometallurgy, are mainly used in purifying precious metal such as gold, ruthenium etc..Pyrometallurgy technology by burning, melting, sintering,
The mode such as melted removes the plastics in electron wastes and other organic principles to carry out metal enrichment, can cause environment seriously
Harm.Electronic waste composition granule after hydrometallurgical processes will crush is put in acidity or akaline liquid, then through extracting, sinking
Form sediment, displacement, ion exchange, filter and a series of process such as distillation finally gives highly purified metal, but in removal process
Waste liquid, waste gas and reclaim after waste residue the most serious to the pollution of environment.Biological technique method mainly utilizes certain micro-organisms
The adsorption of the surface of solids and the Oxidation of microorganism make active metal become soluble substance enter solution, and then exposed also
Extract the low content precious metal in electron wastes, there is the advantage that technique is simple, expense is low, easy to operate, but due to leaching
The time that takes is longer, extraction rate is low, now still in research, the most really comes into operation.
It addition, metal species contained in most of electron wastes is various, such as include various non-ferrous metal (copper, lead,
Nickel, stannum etc.) and precious metal (Au Ag Pt Pd, hydrargyrum, copper, stannum etc.), and current research focuses mostly on to single or few
The recovery of several metals of number, carries out green reclaim gradually, in an orderly manner to various metals, returns improving the metal in electron wastes
Research in terms of sowing class and organic efficiency is still rarely reported.
Summary of the invention
For the deficiency of above-mentioned existing recycling of WEEE technology, the present inventor explores through long term test, it is provided that
A kind of method reclaiming various metals from electron wastes, utilizes the method to be capable of multiple non-ferrous metal, as copper,
Lead, nickel, stannum etc., and precious metal Au Ag Pt Pd, chromium, hydrargyrum etc. gradually, green reclaim in an orderly manner, substantially increase institute
Reclaim the number of metal, and substantially increase recycling efficiency, it is achieved that the abundant recycling of electron wastes.
The technical scheme is that a kind of method reclaiming various metals from electron wastes, as it is shown in figure 1, adopt
With hydrometallurgical technology, leached by acid solution and separate various metal ingredient step by step, specifically comprise the following steps that
(1) Mechanical Crushing: electron wastes is crushed, it is thus achieved that particle diameter electronic waste between 0.05mm～5mm
Composition granule；
(2) electronic waste composition granule is immersed in the aqueous solution of nitric acid that mass concentration is 3%～50% so that it is the gold contained by
Belong to the reaction of one or more compositions in copper, nickel, lead, silver to be dissolved in aqueous solution of nitric acid, and metallic tin and nitric acid reaction generate solid
State α stannic acid, filters and separates, and obtains the solution A of the metal ions such as solid slag X and cupric, nickel, lead, silver；
(3) solution A is carried out following process respectively with solid slag；
Solution A is handled as follows step (3-1) and (3-2):
(3-1) in solution A stirring add metal chloride inorganic salt so that it is in silver ion formed silver nitride precipitation analysis
Go out；Filter and separate, obtain silver nitride precipitation and solution B；
(3-2) silver nitride precipitation recycling is obtained silver ion；In solution B, stirring adds Polyviologen family macromolecule
Material so that it is in copper, lead, one or more in nickel ion form Precipitation with macromolecule complexation；Filter and separate, obtain
Gu slag and solution C, Gu slag recycling obtains copper, lead, nickel ion, solution C recycling；
Gu slag X is handled as follows step (3-1 ') and (3-5 '):
(3-1 ') adds in the first aqueous hydrochloric acid solution in solid slag X so that it is in solid-state α stannic acid dissolve in the solution, mistake
Filter separates, and obtains solid slag Y and solution D；
(3-2 ') is adding the second aqueous hydrochloric acid solution after solution D being concentrated, and separates out Tin tetrachloride pentahydrate, gained solution warp
Recycling after concentration；Solid slag Y is immersed in wang aqueous solution so that it is the metallic element gold contained by, platinum, palladium, hydrargyrum, chromium are dissolved in
Solution, filters and separates, and obtains solid slag Z and a kind of ion contained in gold, platinum, palladium, hydrargyrum, chromium ion or the solution E of several ion；
(3-3 ') adds carbamide in solution E, makes the nitric acid in solution E form urea nitrate precipitation, filters and separate, consolidate
Slag urea nitrate and a kind of ion contained in gold, platinum, palladium, hydrargyrum, chromium ion or the solution F of several ion；Urea nitrate is reclaimed again
Utilizing, added water or hydrochloric acid by solution F, make the pH value of this solution F be adjusted to 1～3, gold, platinum, palladium, hydrargyrum, the ion concentration of chromium are adjusted
To 10～1000ppm；
Functional high molecule material is immersed in solution F by (3-4 ') so that it is in gold, platinum, palladium, hydrargyrum, one in chromium ion
Ion or several ion are selectively adsorbed according to reduction potential from low to high on this functional polymer surface, and are reduced
Adsorb on this functional polymer surface for elemental metals；Filter and separate, obtain the functional polymer of surface adsorption elemental metals with
Solution F after process, repeats this step (3-4 ') for several times；Described functional polymer include but not limited to polyaniline, polypyrrole,
Polythiophenes etc. are containing the one in heteroatomic macromolecular material and their ring substitutive derivative, heterosubstituted derivatives
Or two or more compositionss；
The solution F that (3-5 ') obtains after step (3-4 ') processes carries out chlorine treatment and concentration, obtains chloroazotic acid
Recycling, the functional polymer of surface adsorption elemental metals is placed in high melt in smelting furnace, obtain gold, platinum, palladium, hydrargyrum,
One or several in chromium elemental metals.
Described electron wastes is the electron wastes after the useful components and parts such as battery, electric capacity, resistance are removed in dismounting, its
Kind does not limits, the printed circuit board (PCB) such as including computer main board, computer memory bar, cell phone mainboard, bank card, public transport card, gate inhibition
In the rfid card sheets such as card, the IC-card sheet such as SIM cards of mobile phones, IC phonecard and the leftover bits that produce when producing the said goods one
Kind or two or more compositionss.
As preferably, in described step (2), electronic waste composition granule is 1 with the ratio of the quality volume of aqueous solution of nitric acid:
1～1:10 grams per milliliter；Reaction temperature is 50～70 DEG C, and the response time is 1～3 hour.
In described step (3-1), metal chloride inorganic salt includes but not limited to sodium chloride, potassium chloride, magnesium chloride, chlorine
Change one or more the compositions in calcium, zinc chloride, copper chloride etc..As preferably, described metal chloride is inorganic
Salt is 1:10～1:100 grams per milliliter with the ratio of the quality volume of nitrate solution A；Response time is 10～30 minutes.
In described step (3-2), Polyviologen macromolecule includes but not limited to that side chain contains the poly-of bipyridyl functional group
Vinyl non-conjugate high molecular, polymethacrylic acid non-conjugate high molecular, polyimide non-conjugate high molecular and main chain
In polysulfones non-conjugate high molecular containing bipyridyl functional group, polyfluorene class conjugated polymer one or more kinds of groups
Compound.As preferably, the ratio of described Polyviologen family macromolecule material and the quality volume of solution B be 1:10～1:100 gram/
Milliliter；Response time is 10～30 minutes.
As preferably, in described step (3-1 '), in the first aqueous hydrochloric acid solution, the mass percent concentration of hydrochloric acid is 1%
～5%；Gu the ratio of the quality volume of slag X and the first aqueous hydrochloric acid solution is 1:1～1:10 grams per milliliter；Reaction temperature is 50～70
DEG C, the response time is 10～30 minutes；In second aqueous hydrochloric acid solution, the mass percent concentration of hydrochloric acid is preferably 5%～10%.
As preferably, in described step (3-2 '), in wang aqueous solution, chloroazotic acid is 1:1～1:10 with the volume ratio of water；Gu
Slag Y is 1:1～1:10 grams per milliliter with the ratio of the quality volume of wang aqueous solution；Reaction temperature is 70～100 DEG C, and the response time is
30 minutes～3 hours.
In described step (3-2), Polyviologen family macromolecule material includes but not limited to duplex pyridine or terpyridyl
One or more kinds of compositionss in the copolymer formed with the monomer such as fluorenes, acid imide, polyacrylic acid.Its form is not
Limit, can be powder, thin film and cotton thread complex etc..
In described step (3-4 '), the form of functional high molecule material does not limits, and can be that powder, thin film and cotton thread are multiple
Compound etc..Its chemical structural formula includes but not limited to following structural formula:
As preferably, in described step (3-4 '), functional polymer is 1:1～1 with the ratio of the quality volume of solution F:
100 grams per milliliters；Reaction temperature is 20～50 DEG C, and the response time is 30 minutes～6 hours.、
As preferably, the gas produced in described each step is by outlet pipe recycling.Such as, in step
(2), in (3-2 ') and (8), the nitrogenous gas produced in course of reaction utilize after leading to chlorine treatment aqueous solution absorb prepare nitric acid,
Nitrous acid recycles with hydrochloric acid weak solution.
The chemical reaction that in described step (2) to (3), acid solutions at different levels leaching relates to includes but not limited to:
3Ag+4HNO3→3Ag(NO3)+NO+2H2O (1)
3Cu+8HNO3→3Cu(NO3)2+4H2O+2NO (2)
Pb+2HNO3→Pb(NO3)2+H2 (3)
Ni+4HNO3→Ni(NO3)2+2H2O+2NO2 (4)
Sn+4HNO3→H2SnO3+H2O+4NO2 (5)
H2SnO3+6HCl→H2SnCl6+3H2O (6)
2HNO3+6HCl→2NO+4H2O+3Cl2 (7)
2Au+11HCl+3HNO3→2HAuCl4+3NOCl+6H2O (8)
3Pt+12HCl+2HNO3→3H2PtCl4+2NO+4H2O (9)
3Pd+6HCl+2HNO3→3PdCl2+2NO+4H2O (10)
2NO+Cl2→2NOCl (12)
2NO2+H2O→HNO2+HNO3 (13)
AuCl4 -+3e→Au+4Cl- (14)
PtCl4 2-+2e→Pt+4Cl- (15)
Pd2++2e→Pd (16)
The precious metal related in described step (3-1 ') to (3-5 ') and other gold that can be reduced by functional polymer
Belonging to and include but not limited to Cr VI, gold, palladium, platinum, hydrargyrum, their reduction potential is: and chromium (+1.330 volts, Cr2O7 2-→Cr3+),
Gold (+0.930 volt, AuCl4 -→Au 0), palladium (+0.915 volt, Pd2+→Pd0), platinum (+0.758 volt, PtCl4 2-→Pt0),
Hydrargyrum (+0.850 volt, Hg2+→Hg0(liquid)), chromium (+0.300 volt, Cr6+→Cr3+).
The reversible electrochemical oxygen of the functional polymer including polyaniline etc. related in described step (3-1 ') to (3-5 ')
Change reduction reaction to include but not limited to:
In described step (3-4 '), in order to improve further described functional high molecule material to gold, platinum, palladium, hydrargyrum,
The absorbing and reducing ability of the elemental metals such as chromium, the inventors discovered that, can after being combined with Graphene by this functional high molecule material
It is effectively improved its absorbing and reducing ability.This composite is specifically by polymer, i.e. this functional high molecule material is constituted with Graphene,
Described polymer, with Graphene as carrier, is dispersed in graphene sheet layer body structure surface, therefore effectively prevent this conductive polymer
The problems such as the reunion of sub-material, adhesion, increase the specific surface area of this conducting polymer composite；On the other hand, due to Graphene
Having good electric conductivity, the composite therefore obtained after compound with Graphene also improves leading of this macromolecular material simultaneously
Electrical property.Described polymer is polyaniline, polypyrrole, polythiophene, and the replacement of their ring substitutive derivative, hetero atom is spread out
It is biological that (i.e. the ring substitutive derivative of polyaniline, heterosubstituted derivatives, the ring substitutive derivative of polypyrrole, hetero atom replace
Derivant, the ring substitutive derivative of polythiophene, heterosubstituted derivatives) in one.
As further preferably, described functional polymer monomer is 1:100～1:10 with the mass ratio of Graphene.
Present invention also offers a kind of method preparing this functional polymer-graphene nanocomposite material, use Fig. 2 institute
The route shown prepares, specific as follows:
(1) by polyaniline, polypyrrole, polythiophene and their ring substitutive derivative, heterosubstituted derivatives
A kind of corresponding monomer is dissolved in alkene hydrochloric acid, obtains solution A；Graphene oxide powder or graphene oxide fiber are disperseed
In deionized water, obtain solution B；Stirring mixed solution A and solution B, makes the two react, then filter or at a high speed from
The heart, obtains the functional polymer-Graphene solid product of protonation；
On the one hand in above-mentioned course of reaction, due to graphene oxide there is oxidability, trigger monomer generation polyreaction,
It is polymerized to phase emergencing copolymer；Meanwhile, under sour environment, graphene oxide is reduced to Graphene；Therefore, the two stirring mixing
After this polymer be dispersed in graphene film Rotating fields.
In above-mentioned course of reaction, the preparation technology of optimization is as follows:
Described monomer is preferably 1:100～1:10 with the mass ratio of Graphene；
The molar concentration of described dilute hydrochloric acid is preferably 0.1M～1M；
In described solution A, monomer is preferably 1:10～1:100 with the volume ratio of dilute hydrochloric acid；
In described solution B, solid-to-liquid ratio is preferably 1:1～1:10；
Described reaction is preferably carried out at 60 DEG C～80 DEG C, reacts 6 hours～24 hours；
(2) functional polymer of protonation-Graphene solid product is utilized ammonia weak solution deprotonation, remained ammonia
Remove with deionized water rinsing, be then vacuum dried, then through broken, screening, obtain functional polymer-graphene nano composite wood
Material.
The concentration of described ammonia weak solution is preferably 0.1M～1M.
Described baking temperature is preferably 60 DEG C～100 DEG C.
It is experimentally confirmed that utilize the gold in this functional polymer-graphene nanocomposite material absorbing and reducing solution F, platinum,
When palladium, hydrargyrum, chromium plasma, its organic efficiency is higher.Method particularly includes: by this functional polymer-graphene nanocomposite material
Immerse in solution F so that it is in gold, platinum, palladium, hydrargyrum, a kind of ion in chromium ion or several ion according to reduction potential by
Low paramount it is selectively adsorbed at this composite material surface, and is reduced to elemental metals and adsorbs at this composite material surface.
In sum, the invention provides a kind of eco-friendly process electron wastes optionally reclaiming various to have
Color and the hydrometallurgical processes route of precious metal.This process route is: electron wastes after crushed, by multiple acid solution by
Level leaching, effectively dissolves various metal ingredient and enters solution；Polyviologen functional high molecule material is utilized to process nitrate leaching
The acid solution obtained, by with metalloform-selective ground complexation form coordination compound Precipitation, it is achieved copper, lead, nickel etc.
The enrichment of non-ferrous metal with separate；Residue after hydrochloric acid, chloroazotic acid leaching, is directly separated plastic fraction by filtration respectively, thus
Eliminate the conventional metals/nonmetallic ingredient sorting step such as magnetic separation, electric separation, selecting crude drugs with winnower；Then utilize containing heteroatomic conduction merit
Solution obtained by the composite process of energy macromolecular material or this conducting function macromolecule and Graphene, it is possible to efficient, high
The enrichment of selectivity, Non-energy-consumption ground the precious metal ion that reduces；Adsorb the macromolecular material of elemental metals after high melt
Obtain the precious metal of high-purity (>=99.9%), and macromolecular material Direct Resolution when melting is that gas is discharged, without any
Side-product produces.Compared with prior art, this process route is capable of multiple non-ferrous metal, such as copper, lead, nickel, stannum etc., with
And precious metal Au Ag Pt Pd, hydrargyrum etc. gradually, orderly recovery, substantially increase the number of reclaimed metal, and greatly
Improve greatly recycling efficiency, adequately achieve effective recycling of electron wastes, be therefore that a kind of electron wastes closes
Reason, efficient recovery process route.
It addition, the method low cost, simple and environmental protection, it is embodied in: acid solution leaching is produced useless
Liquid can be again with through concentration and recovery；Nitrogenous waste gas can obtain nitric acid, nitrous acid and hydrochloric acid weak solution after aqueous solution processes,
Concentrated recovery can be again with；The organic polymer functional material used is nontoxic, and polyaniline, polypyrrole, poly-thiophene
The conducting polymers such as fen can regenerate to reuse in containing auric acid liquid certainly, until complete failure；Waste gas and waste liquid can realize zero-emission
Put, metal recovery rate and selectivity high, can effectively solve existing wet processing process use in a large number severe toxicity chemical reagent and waste gas,
The problem that waste liquid, waste sludge discharge easily cause secondary pollution.
Therefore, the method for recovery electron wastes provided by the present invention is a kind of reasonable, efficient, method of environmental protection, real
Show the dual purpose of environmental conservation and resource reclaim, it is adaptable to large-scale industry utilizes, and has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the flow chart that the present invention reclaims various metals from electron wastes；
Fig. 2 is the synthetic route schematic diagram of conducting polymer-graphene nanocomposite material of the present invention；
Fig. 3 is the conducting function macromolecule used in embodiment of the present invention 1-3: polyaniline film, polypyrrole powder, and
Polythiophene-cotton cord complex；
Fig. 4 is in the embodiment of the present invention 1 before the noble metal in polyaniline film absorbing and reducing electron wastes Acid leaching liquid
After outside drawing；
Fig. 5 is the x-ray photoelectron energy spectrogram reclaiming the golden simple substance-polyaniline film obtained in the embodiment of the present invention 1；
Fig. 6 is the kinetics result of gold ion in solution F in the embodiment of the present invention 1 step (3-3 ') to (3-4 ')；
Fig. 7 is the graphene oxide in the embodiment of the present invention 1, polyaniline and polyaniline-graphite alkene nano composite material
X-ray photoelectron energy spectrogram；
Fig. 8 is the graphene oxide in the embodiment of the present invention 2, polypyrrole and polypyrrole-graphene nanocomposite material
X-ray photoelectron energy spectrogram；
Fig. 9 is the graphene oxide in the embodiment of the present invention 3, polythiophene-graphene nanocomposite material and removes
The x-ray photoelectron energy spectrogram of the reduced graphene of polythiophene component.
Detailed description of the invention
The present invention is described in further detail with embodiment below in conjunction with accompanying drawing.Only it should be understood that these embodiments
For the present invention is described, rather than limit the scope of the present invention.
Embodiment 1:
In the present embodiment, electron wastes is Nokia 2100 circuit board of mobile phone, reclaims multiple from this electron wastes
The method of metal is as follows:
(1) single discarded Nokia 2100 circuit board of mobile phone, weighs 22 grams, clipped broken particle diameter be 0.1mm～
The electronic waste composition granule of 0.5mm.
(2), after electronic waste composition granule being loaded eluting post, immersing mass percent concentration at 70 DEG C is the nitric acid of 30%
In aqueous solution, solid-to-liquid ratio is 1:3 so that it is the metallic element copper contained by, nickel, lead, silver reaction are dissolved in aqueous solution of nitric acid, and its
Metallic tin contained by generates solid-state α stannic acid with nitric acid reaction, filters and separates, obtain rich in metal ion after leaching 1 hour
Nitrate solution A and solid slag X.
(3) nitrate solution A is handled as follows step (3-1) and (3-2):
(3-1) by solid-to-liquid ratio be 1:100 stir in nitrate solution addition sodium chloride so that it is in silver ion formed chlorine
Change silver Precipitation, filter after stirring 10 minutes and separate, obtain silver nitride precipitation and solution B, silver nitride precipitation is recycled.
(3-2) it is that 1:100 adds polyacrylic acid-bipyridyl polymeric powder in solution B and stirs rapidly by solid-to-liquid ratio
Dissolve, stir 30 minutes so that it is in one or more and macromolecule complexation in contained metallic element copper, lead, nickel plasma
Form Precipitation, obtain solid slag and solution C, Gu slag recycling obtains copper, lead, nickel plasma, solution C recycling.
Gu slag is handled as follows step (3-1 ') and (3-5 '):
(3-1 ') in eluting post by solid-to-liquid ratio be 1:5 add quality mass percent concentration be 3.7% hydrochloric acid water-soluble
Liquid, leaches 15 minutes at 60 DEG C, dissolves α stannic acid, filters and separates, obtains solid slag Y and solution D.
Solution D is concentrated and adds a large amount of aqueous hydrochloric acid solution by (3-2 '), forms Tin tetrachloride pentahydrate precipitation and from solution
Middle precipitation, the concentrated rear recycling of gained solution.Eluting post is that 1:4 soaks at 90 DEG C with newly joining chloroazotic acid by solid-to-liquid ratio
Take solid slag 1 hour so that it is in contained precious metal gold, platinum, palladium, hydrargyrum etc. be completely dissolved entrance solution, obtain solid slag Z and solution E.
(3-3 ') is that 1:5 adds carbamide in solution E by solid-to-liquid ratio, makes nitric acid and carbamide form urea nitrate precipitation and from molten
Liquid separates out.Filtering and obtain solid slag urea nitrate and solution F after separating, dilute this solution F with dilute hydrochloric acid, regulation pH value, will to 1.3
The ion concentration of contained noble metal is adjusted to about 100ppm.
The solution that (3-4 ') obtains in 50 milliliters above-mentioned (3-3 ') adds be heavily the polyaniline film of 10 milligrams not
Disconnected stirring, reacts 5 hours under room temperature, makes the absorption of precious metal composition at this film surface and be reduced.Filter and separate, obtain table
Solution F after the polyaniline film of face adsorbing metal simple substance and process, repeats this step (3-4 '), will this surface adsorption simple substance
The functional polymer of metal is again dipped in the solution F after processing, and makes the precious metal composition in solution adsorb at this thin film table
Face is also reduced, and so repeats 3 to 5 times；
Comparison diagram before and after this polyaniline film adsorbing metal simple substance is as shown in Figure 4, it can be seen that after adsorbing metal simple substance
This thin film presents metallic luster.Learn through X-ray photoelectron spectroscopic analysis, be adsorbed in the metal ingredient of this polymer surface
Including gold, platinum, palladium, all simple substance of these metal ingredients, such as it is illustrated in figure 5 the X-ray light reclaiming the golden simple substance obtained
Electronic energy spectrum.
The functional polymer of surface adsorption elemental metals is placed in high melt in smelting furnace by (3-5 '), and organic component is complete
Being decomposed into gas to discharge, precious metal forms microparticle retention in crucible.After processing the solution F that obtains carry out chlorine treatment with
And concentration, obtain chloroazotic acid recycling.
During Fig. 6 is step (3-3 ') to (3-4 '), the precious metal composition in solution adsorbs at this film surface also
It is reduced the kinetics interpretation of result figure of the gold ion of 1 time.It can be seen that GOLD FROM PLATING SOLUTION ion concentration dropped in 5 hours
To below 2ppm, the response rate is close to 100%.
Above-mentioned reclaimed non-ferrous metal and precious metal are analyzed further and learns, above-mentioned each Nokia 2100 mobile phone
Circuit board reclaims about 15 milligrams of gold, 0.5 milligram of platinum, 2 milligrams of palladiums, 37.5 milligrams of silver, 0.75 gram of stannum and 3 grams of copper.
In above-mentioned recovery method, the gas produced in each step is by outlet pipe recycling.Such as, in step
(2), in (3-2 ') and (8), the nitrogenous gas produced in course of reaction utilize after leading to chlorine treatment aqueous solution absorb prepare nitric acid,
Nitrous acid recycles with hydrochloric acid weak solution.Reuse after the concentrated recovery of nitric acid waste.Containing acid waste liquid through chlorine treatment with
And reuse after concentration regeneration chloroazotic acid.
In order to improve the functional high molecule material absorbing and reducing to precious metal composition in above-mentioned steps (3-4 ') further
Ability, in the present embodiment step (3-4 '), it is also possible to the composite preferably employing polyaniline and Graphene carries out absorbing and reducing.
Composite is made up of with Graphene polyaniline, and polyaniline, with Graphene as carrier, is dispersed in graphene sheet layer body structure surface, structure
Become polyaniline-graphite alkene nano composite material.As preferably, this functional polymer monomer is 1:100 with the mass ratio of Graphene
～1:10.
The preparation method of this polyaniline-graphite alkene nano composite material is as follows:
(1) 1ml aniline monomer is sufficiently mixed with the hydrochloric acid weak solution that 10ml concentration is 1M, obtains aniline hydrochloric acid dilute molten
Liquid；100mg graphene oxide powder or fiber are scattered in 100ml deionized water, then aniline hydrochloric acid weak solution are added
Wherein stir, then high degree of agitation at 70 DEG C, react 12 hours, at a high speed by mixture with the rotating speed of 12000rpm finally
Centrifugal 10 minutes, obtain the polyaniline-graphite alkene complex precipitate of protonation；
(2) the ammonia weak solution that 200ml concentration is 0.5M is utilized to go the polyaniline-graphite alkene complex precipitate of protonation
Protonation, then removes excessive ammonia with a large amount of deionized water rinsings, is then vacuum dried at 60 DEG C, then through broken, screening,
I.e. obtain polyaniline-graphite alkene nano composite material.
Above-mentioned graphene oxide, polyaniline and the x-ray photoelectron of prepared polyaniline-graphite alkene nano composite material
Can spectrogram as it is shown in fig. 7, there it can be seen that obtained by Graphene has been reduced to low-oxidation-state, and polyaniline exists in
Nano composite material in.
In above-mentioned steps (3-4 '), this polyaniline is used to replace polyaniline film to carry out reality with the composite of Graphene
Test, and the response time is 2 hours, particularly as follows:
Adding in the solution obtained in 50 milliliters above-mentioned (3-3 ') is heavily the answering of this polyaniline and Graphene of 10 milligrams
Condensation material is also stirred continuously, and reacts 5 hours under room temperature, makes the absorption of precious metal composition at this film surface and be reduced.Filter
Separate, the solution F after obtaining the polyaniline film of surface adsorption metal simple-substance and processing, repeat this step (3-4 ') 3 to 5 times,
The functional polymer of this surface adsorption elemental metals will be again dipped in the solution F after processing, make the precious metal in solution
Composition absorption at this film surface and is reduced.
Comparison diagram before and after this polyaniline composite material film adsorbing metal simple substance with Graphene is it can be seen that adsorb
After metal simple-substance, this thin film presents metallic luster.Learn through X-ray photoelectron spectroscopic analysis, be adsorbed in this polymer surface
Metal ingredient include gold, platinum, palladium, all simple substance of these metal ingredients.Step (3-3 ') to (3-4 ') is obtained through mensuration
During, the absorption of precious metal composition in solution can in the kinetics of this film surface the gold ion that is reduced 1 time
Knowing, GOLD FROM PLATING SOLUTION ion concentration was down to below 2ppm in 2 hours, and the response rate is close to 100%.That is, polyaniline-graphite alkene is utilized
Nano composite material is higher than the response rate utilizing polyaniline material to the response rate of gold ion.In like manner, mensuration is obtained by gathering
Aniline-graphene nanocomposite material is higher than the response rate utilizing polyaniline material to the response rate of platinum, palladium ion.
Embodiment 2:
In the present embodiment, electron wastes is certain discarded bank IC card, reclaims various metals from this electron wastes
Method is as follows:
(1) certain discarded bank IC card, clipped broken to obtain the electronic waste composition granule that particle diameter is 0.5mm～1mm.
(2), after electronic waste composition granule being loaded eluting post, immersing mass percent concentration at 70 DEG C is the nitric acid of 3%
In aqueous solution, solid-to-liquid ratio is 1:1 so that it is the metallic element copper contained by, nickel, lead, silver reaction are dissolved in aqueous solution of nitric acid, and its
Metallic tin contained by generates solid-state α stannic acid with nitric acid reaction, filters and separates, obtain rich in metal ion after leaching 3 hours
Nitrate solution A and solid slag X.
(3) nitrate solution A is handled as follows step (3-1) and (3-2):
(3-1) by solid-to-liquid ratio be 1:100 stir in nitrate solution addition sodium chloride so that it is in silver ion formed chlorine
Change silver Precipitation, filter after stirring 10 minutes and separate, obtain silver chloride and solution B, silver nitride precipitation is recycled.
(3-2) it is that 1:100 adds polyimides-bipyridyl polymeric particles in solution B by solid-to-liquid ratio, stirs 10 points
Clock so that it is in one or more in contained metallic element copper, lead, nickel plasma form Precipitation with macromolecule complexation,
Obtain solid slag and solution C, Gu slag recycling obtains copper, lead, nickel plasma, solution C recycling.
Gu slag is handled as follows step (3-1 ') and (3-5 '):
(3-1 ') in eluting post by solid-to-liquid ratio be 1:1 add mass percent fraction concentration be 3.7% hydrochloric acid water-soluble
Liquid, leaches 30 minutes at 70 DEG C, dissolves α stannic acid, filters and separates, obtains solid slag Y and solution D.
Solution D is concentrated and adds a large amount of aqueous hydrochloric acid solution by (3-2 '), forms Tin tetrachloride pentahydrate precipitation and from solution
Middle precipitation, the concentrated rear recycling of gained solution.In eluting post by chloroazotic acid by solid-to-liquid ratio be 1:1 close to 100 DEG C (or
Close to boiling) at a temperature of the solid slag of leaching 3 hours, acid in chloroazotic acid: water ratio is for 1:10 so that it is in contained precious metal gold, platinum,
Palladium, hydrargyrum etc. are completely dissolved entrance solution, obtain solid slag Z and solution E.
(3-3 ') is that 1:1 adds carbamide in solution E by solid-to-liquid ratio, makes nitric acid and carbamide form urea nitrate precipitation and from molten
Liquid separates out.Filtering and obtain solid slag urea nitrate and solution F after separating, dilute this solution F with dilute hydrochloric acid, regulation pH value is to 1, by institute
The ion concentration of the noble metal contained is adjusted to about 100ppm.
Adding in the solution that (3-4 ') obtains in 50 milliliters of above-mentioned steps (3-3 ') solution is heavily the polypyrrole of 10 milligrams
Powder is also stirred continuously, and reacts 1 hour, make precious metal composition all adsorb at powder particle surface and be reduced under room temperature.
Filter and separate, the solution F after obtaining the polypyrrole powder of surface adsorption metal simple-substance and processing, repeats this step (3-4 '), i.e.
The functional polymer of this surface adsorption elemental metals is again dipped in the solution F after processing, makes the precious metal in solution become
Divide absorption on this polypyrrole powder surface and to be reduced, so repeat 3 to 5 times；
The polypyrrole powder of surface adsorption elemental metals is placed in high melt in smelting furnace by (3-5 '), and organic component is complete
Being decomposed into gas to discharge, precious metal forms microparticle retention in crucible.After processing the solution F that obtains carry out chlorine treatment with
And concentration, obtain chloroazotic acid recycling.
Above-mentioned reclaimed non-ferrous metal and precious metal are learnt through analyzing further, above-mentioned each IC-card reclaims about
2 milligrams of gold, 0.2 gram of stannum and 0.5 gram of copper.
In above-mentioned recovery method, the gas produced in each step is by outlet pipe recycling.Such as, in step
(2), in (3-2 ') and (8), the nitrogenous gas produced in course of reaction utilize after leading to chlorine treatment aqueous solution absorb prepare nitric acid,
Nitrous acid recycles with hydrochloric acid weak solution.Reuse after the concentrated recovery of nitric acid waste.Containing acid waste liquid through chlorine treatment with
And concentration regenerates chloroazotic acid and reuses.
In order to improve the functional high molecule material absorbing and reducing to precious metal composition in above-mentioned steps (3-4 ') further
Ability, in the present embodiment step (3-4 '), it is also possible to the composite preferably employing polypyrrole and Graphene carries out absorbing and reducing.
Composite is made up of with Graphene polyaniline, and polyaniline, with Graphene as carrier, is dispersed in graphene sheet layer body structure surface, structure
Become polyaniline-graphite alkene nano composite material.As preferably, this functional polymer monomer is 1:100 with the mass ratio of Graphene
～1:10.
The preparation method of this polyaniline-graphite alkene nano composite material is as follows:
(1) 1ml pyrrole monomer is sufficiently mixed with the hydrochloric acid weak solution that 50ml concentration is 1M, obtains pyrroles's hydrochloric acid dilute molten
Liquid；100mg graphene oxide powder or fiber are scattered in 500ml deionized water, then pyrroles's hydrochloric acid weak solution are added
Wherein stir, then high degree of agitation at 80 DEG C, react 6 hours, finally mixture is separated with filter type, obtain matter
The polypyrrole of sonization-graphene complex precipitation；
(2) the ammonia weak solution that 200ml concentration is 0.5M is utilized to go the polypyrrole of protonation-graphene complex precipitation
Protonation, then removes excessive ammonia with a large amount of deionized water rinsings, is then vacuum dried at 70 DEG C, then through broken, screening,
I.e. obtain polypyrrole-graphene nanocomposite material.
Above-mentioned graphene oxide, polypyrrole and the x-ray photoelectron of prepared polypyrrole-graphene nanocomposite material
As shown in Figure 8, there it can be seen that Graphene has been reduced to low-oxidation-state, and polypyrrole exists in obtained energy spectrogram
Nano composite material in.
In above-mentioned steps (3-4 '), this polypyrrole is used to replace film of poly pyrrole to carry out reality with the composite of Graphene
Test, and the response time is 0.5 hour, particularly as follows:
Adding in the solution obtained in 50 milliliters of above-mentioned steps (3-3 ') solution is heavily polypyrrole and the graphite of 10 milligrams
The composite of alkene is also stirred continuously, and reacts 0.5 hour, make precious metal composition all adsorb at powder particle surface under room temperature
And be reduced.Filter and separate, the solution F after obtaining the polypyrrole powder of surface adsorption metal simple-substance and processing, repeats this step
(3-4 '), will the functional polymer of this surface adsorption elemental metals be again dipped in the solution F after processing, and make in solution is expensive
Heavy metal component absorption on this polypyrrole powder surface and is reduced, and so repeats 3 to 5 times；
Comparison diagram before and after this polypyrrole composite material film adsorbing metal simple substance with Graphene is it can be seen that adsorb
After metal simple-substance, this thin film presents metallic luster.Learn through X-ray photoelectron spectroscopic analysis, be adsorbed in this polymer surface
Metal ingredient be modern, all simple substance of this metal ingredient.During mensuration obtains step (3-3 ') to (3-4 '), solution
In precious metal composition absorption this film surface and be reduced 1 time gold ion kinetics understand, utilize polyphenyl
Amine-graphene nanocomposite material is higher than the response rate utilizing polyaniline material to the response rate of gold ion.
Embodiment 3:
In the present embodiment, electron wastes is to give up in the corner producing printed circuit board (PCB), rfid card sheet and the generation of IC-card sheet
Material, the process reclaiming various metals from this electron wastes is as follows:
(1) leftover bits that produce when producing printed circuit board (PCB), rfid card sheet and IC-card sheet etc. are clipped broken to obtain grain
Footpath is the electronic waste composition granule of 1mm～5mm.
(2), after electronic waste composition granule being loaded eluting post, immersing mass percent concentration at 50 DEG C is the nitric acid of 50%
In aqueous solution, solid-to-liquid ratio is 1:10 so that it is the metallic element copper contained by, nickel, lead, silver reaction are dissolved in aqueous solution of nitric acid, and
Metallic tin contained therein generates solid-state α stannic acid with nitric acid reaction, filters and separates, obtain rich in metal ion after leaching 1 hour
Nitrate solution A and solid slag X.
(3) nitrate solution A is handled as follows step (3-1) and (3-2):
(3-1) by solid-to-liquid ratio be 1:100 stir in nitrate solution addition sodium chloride so that it is in silver ion formed chlorine
Change silver Precipitation, filter after stirring 30 minutes and separate, obtain silver nitride precipitation and solution B, silver nitride precipitation is recycled.
(3-2) it is that 1:100 adds chitin-bipyridyl powder rapidly stirring and dissolving, stirring in solution B by solid-to-liquid ratio
30 minutes so that it is in one or more in contained metallic element copper, lead, nickel plasma form precipitation analysis with macromolecule complexation
Go out rear copper ion all with macromolecule complexation form Precipitation, obtain solid slag and solution C, Gu slag recycling obtain copper,
Lead, nickel plasma, solution C recycling.
Gu slag is handled as follows step (3-1 ') and (3-5 '):
(3-1 ') in eluting post by solid-to-liquid ratio be 1:10 add mass percent concentration be the aqueous hydrochloric acid solution of 3.7%,
Leach 15 minutes at 50 DEG C, dissolve α stannic acid, filter and separate, obtain solid slag Y and solution D.
Solution D is concentrated and adds a large amount of aqueous hydrochloric acid solution by (3-2 '), forms Tin tetrachloride pentahydrate precipitation and from solution
Middle precipitation, the concentrated rear recycling of gained solution.Chloroazotic acid diluent is that 1:10 is at 70 DEG C by solid-to-liquid ratio by eluting post
The solid slag of lower leaching 30 minutes, acid in chloroazotic acid diluent: water ratio is for 1:1 so that it is in contained precious metal gold, platinum, palladium, hydrargyrum etc. complete
CL, obtains solid slag Z and solution E.
(3-3 ') is that 1:10 adds carbamide in E solution by solid-to-liquid ratio, make nitric acid and carbamide formed urea nitrate precipitation and from
Solution separates out.Filtering and obtain solid slag urea nitrate and solution F, dilute with water this solution F after separating, regulation pH value is to 3, by contained
The ion concentration of noble metal be adjusted to about 1000ppm.
Adding in the solution that (3-4 ') obtains in 50 milliliters of above-mentioned steps (3-3 ') is heavily the polythiophene-cotton cord of 50 milligrams
Complex is also stirred continuously, and reacts 30 minutes, make precious metal composition all adsorb at this polythiophene-cotton cord complex under room temperature
Surface is also reduced.Filter and separate, the solution F after obtaining the polyaniline film of surface adsorption metal simple-substance and processing, repeats this
Step (3-4 '), the functional polymer of this surface adsorption elemental metals will be again dipped in the solution F after processing, makes in solution
The absorption of precious metal composition in this polythiophene-cotton cord composite surface and be reduced, so repeat 3 to 5 times；
The polythiophene of surface adsorption elemental metals-cotton cord complex is placed in high melt in smelting furnace by (3-5 '), organic
Component is completely decomposed into gas and discharges, and precious metal forms microparticle retention in crucible.The solution F obtained after processing carries out chlorine
Gas disposal and concentration, obtain chloroazotic acid recycling.
Above-mentioned reclaimed non-ferrous metal and precious metal are analyzed further and learns, above-mentioned per kilogram leftover bits return
Receive about 80 milligrams of palladiums, 0.45 gram of gold, 2 grams of silver, 20 grams of stannum and 130 grams of copper.
In above-mentioned removal process, the gas produced in each step is by outlet pipe recycling.Such as, in step
(2), in (3-2 ') and (8), the nitrogenous gas produced in course of reaction utilize after leading to chlorine treatment aqueous solution absorb prepare nitric acid,
Nitrous acid recycles with hydrochloric acid weak solution.Reuse after the concentrated recovery of nitric acid waste.Containing acid waste liquid through chlorine treatment with
And reuse after concentration regeneration chloroazotic acid.
In order to improve the functional high molecule material absorbing and reducing to precious metal composition in above-mentioned steps (3-4 ') further
Ability, in the present embodiment step (3-4 '), it is also possible to the composite preferably employing polythiophene and Graphene carries out absorbing and reducing.
Composite is made up of with Graphene polythiophene, and polythiophene, with Graphene as carrier, is dispersed in graphene sheet layer body structure surface, structure
Become polythiophene-graphene nanocomposite material.As preferably, this functional polymer monomer is 1:100 with the mass ratio of Graphene
～1:10.
The preparation method of this polythiophene-graphene nanocomposite material is as follows:
(1) 1g thiophene monomer is sufficiently mixed with the hydrochloric acid weak solution that 100ml concentration is 1M, obtains thiophene hydrochloric acid dilute molten
Liquid；100mg graphene oxide powder or fiber are scattered in 1000ml deionized water, then thiophene hydrochloric acid weak solution are added
Wherein stirring, then high degree of agitation at 90 DEG C, mixture, after 24 hours, is finally separated by question response with filter type,
Obtain the polythiophene-graphene complex precipitation of protonation；
(2) the ammonia weak solution that 200ml concentration is 0.5M is utilized to go the polythiophene of protonation-graphene complex precipitation
Protonation, then removes excessive ammonia with a large amount of deionized water rinsings, is then vacuum dried at 80 DEG C, then through broken, screening,
I.e. can get polypyrrole-graphene nanocomposite material.
Above-mentioned graphene oxide, prepared polythiophene-graphene nanocomposite material, and use organic solvent this to be gathered
Polythiophene in thiophene-graphene nanocomposite material passes through the x-ray photoelectron of the reduced graphene being dried to obtain after removing
Can spectrogram as it is shown in figure 9, there it can be seen that obtained by Graphene has been reduced to low-oxidation-state, and polythiophene exists in
Nano composite material in.
In above-mentioned steps (3-4 '), this polythiophene is used to replace polythiophene film to carry out reality with the composite of Graphene
Test, and the response time is 10 minutes, particularly as follows:
Adding in the solution obtained in 50 milliliters of above-mentioned steps (3-3 ') solution is heavily polythiophene and the graphite of 10 milligrams
The composite of alkene is also stirred continuously, and reacts 0.5 hour, make precious metal composition all adsorb at powder particle surface under room temperature
And be reduced.Filter and separate, the solution F after obtaining the polythiophene powder of surface adsorption metal simple-substance and processing, repeats this step
(3-4 '), will the functional polymer of this surface adsorption elemental metals be again dipped in the solution F after processing, and make in solution is expensive
Heavy metal component absorption on this polythiophene powder surface and is reduced, and so repeats 3 to 5 times；
Comparison diagram before and after this polythiophene composite material film adsorbing metal simple substance with Graphene is it can be seen that adsorb
After metal simple-substance, this thin film presents metallic luster.Learn through X-ray photoelectron spectroscopic analysis, be adsorbed in this polymer surface
Metal ingredient include gold, palladium, all simple substance of these metal ingredients.Step (3-3 ') to (3-4 ') process is obtained through mensuration
In, the absorption of precious metal composition in solution understands in the kinetics of this film surface the gold ion that is reduced 1 time, profit
With polythiophene-graphene nanocomposite material the response rate of gold ion is higher than the response rate utilizing polythiophene material.
Technical scheme has been described in detail by embodiment described above, it should be understood that the above is only
For the specific embodiment of the present invention, be not limited to the present invention, all made in the spirit of the present invention any amendment,
Supplement or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (10)
1. the method reclaiming various metals from electron wastes, described various metals include copper, lead, nickel, stannum, gold,
At least one in silver, platinum, palladium, chromium, hydrargyrum, is characterized in that: specifically comprise the following steps that
(1) Mechanical Crushing: electron wastes is crushed, it is thus achieved that particle diameter is the electronic waste composition granule of 0.05mm～5mm；
(2) electronic waste composition granule is immersed in the aqueous solution of nitric acid that mass concentration is 3%～50% so that it is the metal contained by
Copper, nickel, lead, silver composition reaction are dissolved in aqueous solution of nitric acid, and metallic tin and nitric acid reaction generate solid-state α stannic acid, then filtration point
From, obtain solid slag X and cupric, nickel, lead, the solution A of silver ion；
(3) solution A is handled as follows step (3-1) and (3-2):
(3-1) in solution A stirring add metal chloride inorganic salt so that it is in silver ion formed silver nitride precipitation separate out；
Filter and separate, obtain silver nitride precipitation and solution B；
(3-2) silver nitride precipitation recycling is obtained silver ion；In solution B, stirring adds Polyviologen family macromolecule material
Material so that it is the copper contained by, lead, nickel ion form Precipitation with macromolecule complexation；Filter and separate, obtain solid slag and solution C,
Gu slag recycling obtains copper, lead, nickel ion, solution C recycling；
Gu slag X is handled as follows step (3-1 ') to (3-5 '):
(3-1 ') adds the first aqueous hydrochloric acid solution in solid slag X so that it is in solid-state α stannic acid dissolve in the solution, filter separate,
Obtain solid slag Y and solution D；
(3-2 ') adds the second aqueous hydrochloric acid solution after solution D being concentrated, separate out Tin tetrachloride pentahydrate, after gained solution is concentrated
Recycling；Solid slag Y is immersed in wang aqueous solution so that it is in one in contained metallic element gold, platinum, palladium, chromium, hydrargyrum or
Several solution that is dissolved in of person, filters and separates, and obtains solid slag Z and contains gold, platinum, palladium, chromium, the solution E of mercury ion；
(3-3 ') adds carbamide in solution E, makes the nitric acid in solution E form urea nitrate precipitation, filters and separate, obtain solid slag nitre
Acid urea with containing gold, platinum, palladium, chromium, the solution F of mercury ion；By urea nitrate recycling, solution F is added water or hydrochloric acid, makes
The pH value of this solution F is adjusted to 1～3, and gold, platinum, palladium, chromium, the ion concentration of hydrargyrum are adjusted to 10～1000ppm；
Functional high molecule material is immersed in solution F by (3-4 ') so that it is in gold, platinum, palladium, chromium, mercury ion is according to reduction potential
It is selectively adsorbed from low to high on this functional polymer surface, and is reduced to elemental metals absorption at this functional polymer
Surface；Filter and separate, the solution F after obtaining the functional polymer of surface adsorption elemental metals and processing, repeats this step (3-
4 ') for several times；Described functional high molecule material is polyaniline, polypyrrole, polythiophene and their ring substitutive derivative, miscellaneous former
One or more kinds of compositionss in sub-substitutive derivative, or, described functional high molecule material be polymer with
The composite that Graphene is constituted, wherein Graphene is carrier, and polymer is dispersed in graphene sheet layer body structure surface, this polymer
For polyaniline, polypyrrole, polythiophene, and their ring substitutive derivative, heterosubstituted derivatives (i.e. the ring of polyaniline takes
For derivant, heterosubstituted derivatives, the ring substitutive derivative of polypyrrole, heterosubstituted derivatives, the ring of polythiophene takes
For derivant, heterosubstituted derivatives) in one；
The solution F that (3-5 ') obtains after step (3-4 ') processes carries out chlorine treatment and concentration, obtains chloroazotic acid and reclaims
Recycling, the functional polymer of surface adsorption elemental metals is placed in high melt in smelting furnace, obtains gold, platinum, palladium, chromium, hydrargyrum list
Matter metal.
2. the method reclaiming various metals from electron wastes as claimed in claim 1, is characterized in that: described each step
The gas of middle generation passes through outlet pipe recycling.
3. the method reclaiming various metals from electron wastes as claimed in claim 1, is characterized in that: described step
(3-1), in, metal chloride inorganic salt includes the one in sodium chloride, potassium chloride, magnesium chloride, calcium chloride, zinc chloride, copper chloride
Or two or more compositionss.
4. the method reclaiming various metals from electron wastes as claimed in claim 1, is characterized in that: described step
(3-2), in, Polyviologen family macromolecule includes the polyethylene kind non-conjugate high molecular that side chain contains bipyridyl functional group, poly-methyl
The polysulfones that acrylic compounds non-conjugate high molecular, polyimide non-conjugate high molecular and main chain contain bipyridyl functional group is non-
One or more kinds of compositionss in conjugated polymer, polyfluorene class conjugated polymer.
5. the method reclaiming various metals from electron wastes as described in any claim in Claims 1-4, it is special
Levying and be: in described step (2), the ratio of electronic waste composition granule and the quality volume of aqueous solution of nitric acid is 1:1～1:10 gram/in the least
Rise；Reaction temperature is 50～70 DEG C.
6. the method reclaiming various metals from electron wastes as described in any claim in Claims 1-4, it is special
Levying and be: in described step (3-1), metal chloride inorganic salt is 1:10～1 with the ratio of the quality volume of nitrate solution A:
100 grams per milliliters.
7. the method reclaiming various metals from electron wastes as described in any claim in Claims 1-4, it is special
Levying and be: in described step (3-2), described Polyviologen family macromolecule material is 1:10 with the ratio of the quality volume of solution B
～1:100 grams per milliliter.
8. the method reclaiming various metals from electron wastes as described in any claim in Claims 1-4, it is special
Levying and be: in described step (3-1 '), in the first aqueous hydrochloric acid solution, the mass percent concentration of hydrochloric acid is 1%～5%；Gu slag X
It is 1:1～1:10 grams per milliliter with the ratio of the quality volume of the first aqueous hydrochloric acid solution；Reaction temperature is 50～70 DEG C；Second hydrochloric acid
In aqueous solution, the mass percent concentration of hydrochloric acid is preferably 5%～10%.
9. the method reclaiming various metals from electron wastes as described in any claim in Claims 1-4, it is special
Levying and be: in described step (3-2 '), in wang aqueous solution, chloroazotic acid is 1:1～1:10 with the volume ratio of water；Gu slag Y and wang aqueous solution
The ratio of quality volume be 1:1～1:10 grams per milliliter；Reaction temperature is 70～100 DEG C.
10. the method reclaiming various metals from electron wastes as described in any claim in Claims 1-4, its
Feature is: in described step (3-4 '), and functional polymer is 1:1～1:100 grams per milliliter with the ratio of the quality volume of solution F；
Reaction temperature is 20～50 DEG C.
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| CN108346715A (en) * | 2018-02-09 | 2018-07-31 | 中南大学 | The recovery method of silicon solar cell |
| US20210071284A1 (en) * | 2018-02-09 | 2021-03-11 | Heraeus Deutschland GmbH & Co. KG | Method for hydrometallurgical processing of a noble metal-tin alloy |
| CN113355515A (en) * | 2021-05-26 | 2021-09-07 | 昆明理工大学 | Method for separating tin-silver alloy by chlorination |
| CN113403478B (en) * | 2021-06-15 | 2024-01-26 | 苏州市富荣环保科技有限公司 | Method for separating metal from electronic waste based on nano carbon material |
| WO2023087114A1 (en) * | 2021-11-22 | 2023-05-25 | Pyrocycle Inc. | A process for recovering a metallic fraction from electronic waste and producing value-added products |
| CN115282945B (en) * | 2022-07-15 | 2023-12-08 | 宁波新材料测试评价中心有限公司 | Application of polyimide resin powder containing sulfonic acid group as solid phase extraction material |
| CN115181327A (en) * | 2022-08-30 | 2022-10-14 | 湖北恒驰电子科技有限公司 | Method for recycling waste multiphase flexible copper clad laminate by subcritical technology |
| TWI841095B (en) * | 2022-12-06 | 2024-05-01 | 泓泰環保科技股份有限公司 | Method for recovering metal-containing substances from silver-copper tin mud, method for recovering metal, and metal composite material and preparation method thereof |
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