CN104630478B - Utilize the method that conducting polymer porous diffusion barrier reclaims metal from electron wastes - Google Patents
Utilize the method that conducting polymer porous diffusion barrier reclaims metal from electron wastes Download PDFInfo
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Abstract
The invention provides a kind of method reclaiming metal from electron wastes.The method by the Acid leaching liquid stream of this electron wastes through conducting polymer porous membrane so that it is in metal ion adsorbed by the conductive polymer subconstiuent in porous diffusion barrier and reduce, then carry out high melt, obtain metal simple-substance.Compared with prior art, conducting polymer composite is designed as porous, film like by the method, not only increase effectively the specific surface area of conducting polymer composite, thus improves the response rate；And, utilize this loose structure by " static adsorption ", the process of metal ion in conducting polymer composite adsorber acid leaching liquid can be improved to " dynamic adsorption ", thus eliminate the technical process being mixed mutually with this conducting polymer composite by electron wastes Acid leaching liquid and being separated, and enormously simplify processing equipment, therefore it is very suitable for processing application on a large scale, has a good application prospect.
Description
Technical field
The invention belongs to recycling of WEEE processing technology field, be specifically related to one and utilize conducting polymer porous to separate
Film reclaims the method for metal from electron wastes.
Background technology
Rich in precious metals such as gold, silver, palladium, platinum and rare in electron wastes (the most waste and old printed circuit board (PCB) etc.)
Metal, its grade is tens times of common primary ore, is called " mine, city ".The fastest accordingly, as growth,
Containing the solid refuse of the huge wealth of society and resource, the recycling treatment of electron wastes has become Now Domestic simultaneously
The rising industry of outer regenerated metal industry.
Currently for the recovery of process and the metals resources of electron wastes, applying most is Physical and chemical method phase
In conjunction with method, wherein chemical method many employings hydrometallurgical technology.This technology particularly as follows: will broken after electron wastes
Fragment by the acid or molten leaching of akaline liquid, leachate again through extracting, precipitate, replacing, ion exchanges, is electrolysed, filters
And a series of processing procedure such as distillation, final available high-grade metal.But the mistake reclaimed in precious metal reduction
Cheng Zhong, often consumes the poisonous reagents such as substantial amounts of fluoride, cyanide and produces substantial amounts of acid-base waste fluid, as appropriate in do not used
Kind way is processed, and ecological environment and human health will be caused serious pollution and harm.
How to deal carefully with electron wastes, realize environmental conservation and resource regeneration, be the important problem that faces of human society
One of.The conducting polymers such as polyaniline, polypyrrole, polythiophene have intrinsic conductivity, environmental stability, solution processing
Property and reversible redox activity etc. feature.In sour environment, the hetero atom on this type of conducting polymer main chain can be respectively
Plant and mutually convert between native oxide state and protonation state.By its reversible redox effect and electron wastes Acid leaching
In liquid, the electrochemical reducting reaction of metal ion is coupled, and can realize the spontaneous reduction of precious metal ion.Height after recovery
Molecular material is decomposed into gas discharge in metal smelting process, concentrated rear reusable containing acid waste liquid, will make environment
Pollution problem is effectively controlled.As by polyaniline, polypyrrole, polythiophene or their derivant and polyvinyl fluoride, gathered
The filmogens such as propylene, polyacrylonitrile, polyvinyl alcohol, polyimides, polysulfones, polyphenylene oxide, polybenzimidazoles are blended,
Corroded by the tape casting, poor solvent gel method, micropowder sintering process, surface-coated method, restrained stretching method, radiation chemistry
Method and hollow fiber spinning method etc. make high-molecular porous separation film, while absorption, reduction precious metal ion, and profit
With driving forces such as pressure differential, concentration difference or potential differences, elemental metals microgranule can be made to separate feed liquid one lateral enrichment of film, with
It is rapidly reached the purpose that precious metal composition separates and reclaims.This conducting polymer porous diffusion barrier is used to be favorably improved
From the Acid leaching liquid of electron wastes, reclaim the efficiency of precious metal, there is wide market prospect and far-reaching society's meaning
Justice.
Summary of the invention
It is an object of the invention to provide a kind of eco-friendly Wetting metallurgical technology recycling electron wastes, profit
Use conducting polymer porous diffusion barrier, from the Acid leaching liquid of electron wastes, reclaim precious metal composition efficiently, to take
For precipitation, solvent extraction, ion exchange, active metal displacement, electricity in current Physical and chemical method use in conjunction technology
The traditional methods such as solution, solve the problem that the severe toxicity chemical levels such as fluoride, cyanide is big, reduce chemistry further dirty
Dye, to reach the dual purpose of ecological environmental protection and resource recycling, has safe and nontoxic, efficient and environmental protection
Feature.
Technical scheme: a kind of side utilizing conducting polymer porous diffusion barrier to reclaim metal from electron wastes
Method, the method is specific as follows:
Electron wastes is broken for the granule that particle diameter is 0.05mm～5mm, then this granule is immersed in acid solution, make
Metal ion contained therein is dissolved in acid solution, obtains electron wastes Acid leaching liquid；
By this electron wastes Acid leaching liquid stream through conducting polymer porous membrane so that it is in metal ion separated by porous
Conductive polymer subconstiuent in film adsorbs and reduces, and forms metal simple-substance on porous diffusion barrier surface, is then placed on molten
High melt in furnace, makes porous diffusion barrier be decomposed into gas and reclaims, obtain metal simple-substance；
The preparation method of described conducting polymer porous diffusion barrier comprises the following steps:
(1) conducting polymer composite is mixed with filmogen, be then 1:20～1:5 by mixture by solid-to-liquid ratio
Grams per milliliter (i.e. macromolecule mixture and the mass volume ratio of solvent) joins in organic solvent, at 40 DEG C～70 DEG C
Supersound process, forms mixed solution；
Described conducting polymer is that polyaniline, polypyrrole, polythiophene and their ring substitutive derivative, hetero atom take
For the one in derivant；
Filmogen includes but not limited to Kynoar, polypropylene, polyacrylonitrile, polyvinyl alcohol, polyimides, gathers
Macromolecular material and their derivants such as sulfone, polyphenylene oxide, polybenzimidazoles；
Organic solvent include but not limited to 1-Methyl-2-Pyrrolidone, Ketohexamethylene, dimethyl acetylamide, dimethylformamide,
One in pyridine etc.；
The mass ratio of described conducting polymer composite and filmogen is preferably 1:10～10:1, and more preferably 1:
3～3:1.
(2) mixed solution obtained in step (1) is dripped in clean substrate, and makes it be laid in substrate surface,
Form liquid coating, then it is put in deionized water together with substrate, make coating quickly solidify to form conducting polymer
Thin film comes off from substrate；
Substrate includes but not limited to the one in glass plate, silicon chip, sheet metal etc..
(3) the conducting polymer separation film obtained in step (2) is dipped in Enough Dl water, therein to remove
Organic solution also forms micropore in this separation film, obtains conducting polymer porous membrane.
In order to make conducting polymer porous diffusion barrier abundant absorbing and reducing metal ion, as preferentially, first by electronic waste
Thing Acid leaching liquid and this porous diffusion barrier are fully contacted certain time, then make this electron wastes Acid leaching liquid stream many through this
Pore separation membrane.
Described acid solution does not limits, including dilute hydrochloric acid, nitric acid etc..As preferably, described electron wastes Acid leaching liquid
PH value is 1～5.
In order to improve organic efficiency, can use and conduct electricity the formation of electric high-molecular porous separation film both sides pressure differential, concentration difference
Or the driving force such as potential difference, so that metal ion is enriched with rapidly in the side of porous diffusion barrier；When using pressure differential, make
For a kind of implementation, noble gas is used to conduct electricity electric high-molecular porous separation film both sides formation pressure differential.
In order to improve the response rate of metal ion, as preferably, electron wastes Acid leaching liquid stream is through conducting polymer porous
It is recovered after separating film, again flows through this conducting polymer porous diffusion barrier, be so repeated several times.
In sum, the method reclaiming metal from electron wastes Acid leaching liquid that the present invention provides has the advantage that
(1) simple to operation
Conducting polymer composite is designed as porous, film like by the present invention, not only increase effectively this conducting polymer composite
Specific surface area, thus improve the response rate；And, utilize this loose structure to be adsorbed by conducting polymer composite dexterously
In electron wastes Acid leaching liquid, the process of metal ion is improved to " flowing through absorbing process " by former " dipping absorbing process ",
I.e. it is improved to " dynamic adsorption " by " static adsorption " of raw material, thus eliminates electron wastes Acid leaching liquid and be somebody's turn to do
The technical process that conducting polymer composite mixes mutually and is separated, and enormously simplify the processing equipment of costliness, very
It is applicable to process on a large scale application；
It addition, should " flowing through absorbing process " be that one processes technique dynamically, it is simple to utilize pressure differential, concentration difference or
The driving forces such as potential difference, make metal ion be enriched with rapidly in the side of porous diffusion barrier, thus are greatly improved organic efficiency；
(2) metal species is reclaimed various
Utilize the wide variety of the metal ion that the method for the present invention reclaimed, be generally possible to carry out electrochemical reducting reaction
Metal ion, such as Au Ag Pt Pd, hydrargyrum, copper, stannum, chromium etc. all can be by the method by efficient recovery；
(3) environmental protection
The method environmental protection of the present invention.Conducting polymer porous diffusion barrier used in the present invention is nontoxic.After process
Can be again with through concentration and recovery containing acid waste liquid, produce without any side-product.Efficiently solve existing wet treatment work
Skill uses severe toxicity chemical reagent and waste gas, waste liquid, waste sludge discharge to easily cause the problem of secondary pollution in a large number, can realize ring
Border protection and the dual purpose of resource reclaim, it is adaptable to large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is that the surface of the polyaniline-Kynoar porous diffusion barrier sample prepared in the embodiment of the present invention 1 is with transversal
Face SEM photograph；
Fig. 2 is that the polyaniline-Kynoar porous diffusion barrier prepared in the embodiment of the present invention 1 is before step (4) processes
After photo comparison；
Fig. 3 is that the polyaniline-Kynoar porous diffusion barrier prepared in the embodiment of the present invention 1 is after step (4) processes
SEM photograph；
Fig. 4 is that in the embodiment of the present invention 1-3 hydrochloric acid leaching liquid gold content in step (4) processing procedure is in time
Variation diagram.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.It should be understood that these embodiments are only used for
The present invention is described, rather than limits the scope of the present invention.
Embodiment 1:
(1) it is to mix polyaniline and Kynoar at 3: 1 according to mass ratio, is then 1: 5 by solid-to-liquid ratio
This macromolecule mixture is added in 1-Methyl-2-Pyrrolidone by (macromolecule mixture/g: solvent/ml), at 60 DEG C
Ultrasonic 1 hour, form polyaniline-Kynoar mixed solution.
(2) take polyaniline-Kynoar mixed solution that 2ml step (1) obtains and drip on clean glass plate,
And make it be laid in glass pane surface, form wide about 2cm, be about the liquid macroimolecule coating of 10cm, then by its with
Glass plate is put in deionized water together, makes polymeric coating layer quickly solidify to form separation film and come off from glass plate.
(3) solid-state polyaniline-polyvinylidene fluoride separation membrane that step (2) obtains is dipped in Enough Dl water with complete
Full removing organic solution also forms micropore in separating film, obtains polyaniline-Kynoar porous diffusion barrier, deposits in
In deionized water standby.
The surface of the above-mentioned polyaniline-Kynoar porous diffusion barrier prepared and cross section SEM photograph such as Fig. 1 institute
Show, there it can be seen that this separation membrane surface defines loose structure.
In order to verify gold (Au) ion in above-mentioned prepared polyaniline-polyvinylidene fluoride separation membrane absorbing and reducing Acid leaching liquid
Ability, carry out following steps (4)-(5).
(4) preparation gold ion concentration be 100ppm, pH value be 1.3 hydrochloric acid leaching liquid, then poured into prepackage
In the cavity of polyaniline-Kynoar porous diffusion barrier, make this hydrochloric acid leaching liquid stream through this porous diffusion barrier, wherein
Gold ion adsorbed by the polyaniline composition in porous diffusion barrier and reduce, formed on porous diffusion barrier surface gold simple substance.
During Gai, in order to improve organic efficiency, noble gas be utilized to form 6 kPas in the both sides of this porous diffusion barrier
Pressure differential, makes hydrochloric acid leaching liquid flow through to opposite side rapidly from this porous diffusion barrier side, so that metal ion is the richest
Collection is in the side of porous diffusion barrier.
Before and after processing in above-mentioned steps (4), the photo of polyaniline-Kynoar porous diffusion barrier is as in figure 2 it is shown, from figure
In it can be seen that after step (4) processes the golden simple substance of polyaniline-Kynoar porous diffusion barrier surface adsorption, table
Face is golden yellow.
After above-mentioned steps (4) processes polyaniline-Kynoar porous diffusion barrier SEM photograph as it is shown on figure 3, from
In can be seen that gold simple substance granular absorption on polyaniline-Kynoar porous diffusion barrier surface.
(5) flow through polyaniline-Kynoar porous diffusion barrier containing acid waste liquid through concentration and recovery again with；Surface
The porous diffusion barrier of ADSORPTION OF GOLD simple substance is placed in high melt in the smelting furnace of 900 DEG C, and polyaniline-Kynoar porous is divided
It is decomposed into the gases such as carbon dioxide from film and after alkali liquor absorption, directly discharges air, finally giving high-purity (>=99.9%)
Elemental gold granule.
Embodiment 2-3:
Embodiment 2,3 is the most identical with the process of embodiment 1, except that polyaniline and poly-inclined fluorine in embodiment 2
Ethylene is that 1:1 mixes according to mass ratio, and in embodiment 3, polyaniline and Kynoar are 1:3 according to mass ratio
Mix.
Observe the change in time of the gold content in step (4) processing procedure of the hydrochloric acid leaching liquid in above-described embodiment 1-3
Change, obtain the kinetics figure of golden composition as shown in Figure 4.From this figure, it can be seen that utilize polyaniline-poly-inclined fluorine
Ethylene porous diffusion barrier all can conveniently and efficiently reclaim the golden composition in Acid leaching liquid.
In like manner, find to utilize above-mentioned polyaniline-Kynoar porous diffusion barrier all can facilitate, efficiently after experiment
Ground reclaims the compositions such as the hydrargyrum in Acid leaching liquid, silver, stannum, chromium, platinum, palladium.
Embodiment 4:
(1) it is that 1:1 mix with polyimides according to mass ratio by polypyrrole, is then that 1:20(is high by solid-to-liquid ratio
This macromolecule mixture is added in 1-Methyl-2-Pyrrolidone molecule mixture/g: solvent/ml), ultrasonic at 60 DEG C
1 hour, form polypyrrole-polyimide solution；
(2) take the polypyrrole-polyimides mixed solution obtained in 2ml step (1) and drip on clean glass plate,
And use specific purpose tool to be laid in glass pane surface, form wide about 2cm, be about the liquid macroimolecule coating of 10cm,
Then it is put in deionized water together with glass plate, make polymeric coating layer quickly solidify to form separation film from glass plate
Come off；
(3) the solid-state polypyrrole-polyimide separation membrane obtained in step (2) is dipped in Enough Dl water with complete
Full removing organic solution also forms micropore in separating film, obtains polypyrrole-polyimide foraminous separation film, deposits in
In ionized water standby；
In order to verify that above-mentioned prepared polypyrrole-polyimide foraminous separation film can platinum (Au) in absorbing and reducing Acid leaching liquid
The ability of ion, carries out following steps (4)-(5).
(4) preparation platinum ion concentration be 1000ppm, pH value be 2.3 hydrochloric acid leaching liquid, then poured into prepackage
In the cavity of polypyrrole-polyimide foraminous separation film, make this hydrochloric acid leaching liquid stream through this porous diffusion barrier, therein
Platinum ion is adsorbed by the polypyrrole composition in porous diffusion barrier and reduces, and forms platinum simple substance on porous diffusion barrier surface；
During Gai, in order to improve organic efficiency, noble gas be utilized to form 5 kPas in the both sides of this porous diffusion barrier
Pressure differential, makes hydrochloric acid leaching liquid flow through to opposite side rapidly from this porous diffusion barrier side, so that platinum ion is enriched with rapidly
Side at porous diffusion barrier；
(5) flow through polypyrrole-polyimide foraminous separation film containing acid waste liquid through concentration and recovery again with；Surface is inhaled
The porous diffusion barrier of attached platinum simple substance is placed in high melt in the smelting furnace of 1000 DEG C, polypyrrole-polyimide foraminous separation film
It is decomposed into the gases such as carbon dioxide and after alkali liquor absorption, directly discharges air, finally giving the list of high-purity (>=99.9%)
Matter platinum grain.
The platinum content of the hydrochloric acid leaching liquid observed in above-described embodiment 4 in step 4 over time, obtains hydrochloric acid leaching
Liquid stream platinum content therein after this porous diffusion barrier is gradually reduced, and illustrates to utilize this polypyrrole-polyimide foraminous to separate
Film can conveniently and efficiently reclaim the platinum composition in Acid leaching liquid.
In like manner, find to utilize that above-mentioned polypyrrole-polyimide foraminous separation film all can be conveniently and efficiently after experiment
Reclaim the compositions such as the gold in Acid leaching liquid, hydrargyrum, silver, stannum, chromium, palladium.
Embodiment 5:
(1) it is that 1:3 mix with polysulfones according to mass ratio by polythiophene, is then 1:10(high score by solid-to-liquid ratio
By this macromolecule mixture it add in 1-Methyl-2-Pyrrolidone, 60 DEG C at ultrasonic sub-mixture/g: solvent/ml)
1 hour, form polythiophene-polysulfones mixed solution；
2) take the polythiophene-polysulfones mixed solution obtained in 2ml step (1) to drip on clean glass plate, use specially
It is laid in glass pane surface with instrument, forms wide about 2cm, be about the liquid macroimolecule coating of 10cm, then will
It is put in deionized water together with glass plate, makes polymeric coating layer quickly solidify to form separation film and take off from glass plate
Fall；
(3) the solid-state polythiophene obtained in step (2)-polysulfones forms separation film to be dipped in Enough Dl water with complete
The full organic solution that removes also forms micropore in separating film, obtains polythiophene-polysulfone porous separation film, after deposit in from
In sub-water standby；
In order to verify the ability of palladium ion in above-mentioned prepared polythiophene-polysulfone porous separation film absorbing and reducing Acid leaching liquid,
Carry out following steps (4)-(5).
(4) preparation palladium ion concentration be 10ppm, pH value be 3.3 electron wastes hydrochloric acid leaching liquid, then by it
Pour in the cavity having pre-installed polythiophene-polysulfone porous separation film, make this hydrochloric acid leaching liquid stream through this porous diffusion barrier, its
In palladium ion adsorbed by the polyaniline composition in porous diffusion barrier and reduce, porous diffusion barrier surface formed palladium simple substance；
During Gai, in order to improve organic efficiency, noble gas be utilized to form 4 kPas in the both sides of this porous diffusion barrier
Pressure differential, makes hydrochloric acid leaching liquid flow through to opposite side rapidly from this porous diffusion barrier side, so that palladium ion is enriched with rapidly
Side at porous diffusion barrier；
(5) flow through polythiophene-polysulfone porous separation film containing acid waste liquid through concentration and recovery again with；Surface adsorption palladium
The porous diffusion barrier of simple substance is placed in high melt in the smelting furnace of 900 DEG C, and polythiophene-polysulfone porous separation film is decomposed into dioxy
Change the gases such as carbon and after alkali liquor absorption, directly discharge air, finally giving the simple substance palladium granule of high-purity (>=99.9%).
The palladium content of the hydrochloric acid leaching liquid observed in above-described embodiment 5 in step 4 over time, obtains hydrochloric acid leaching
Liquid stream palladium content therein after this porous diffusion barrier is gradually reduced, and illustrates to utilize this polythiophene-polysulfone porous separation film energy
Palladium composition in enough conveniently and efficiently recovery Acid leaching liquid.
In like manner, find to utilize above-mentioned polythiophene-polysulfone porous separation film all can conveniently and efficiently reclaim after experiment
The compositions such as gold in Acid leaching liquid, hydrargyrum, silver, stannum, chromium, platinum.
Claims (6)
1. the method utilizing conducting polymer porous diffusion barrier to reclaim metal from electron wastes, is characterized in that:
Electron wastes is broken for the granule that particle diameter is 0.05mm～5mm, then this granule is immersed in acid solution so that it is in
Contained metal ion is dissolved in acid solution, obtains electron wastes Acid leaching liquid；By this electron wastes Acid leaching liquid stream through leading
Electricity high-molecular porous thin film so that it is in metal ion adsorbed by the conductive polymer subconstiuent in porous diffusion barrier and reduce,
Form metal simple-substance on porous diffusion barrier surface, be then placed on high melt in smelting furnace, make porous diffusion barrier decompose
Reclaim for gas, obtain metal simple-substance；
The preparation method of described conducting polymer porous diffusion barrier comprises the following steps:
(1) conducting polymer composite is mixed with filmogen, be then 1:20～1:5 by mixture by solid-to-liquid ratio
Grams per milliliter (i.e. macromolecule mixture and the mass volume ratio of solvent) joins in organic solvent, at 40 DEG C～70 DEG C
Supersound process, forms mixed solution；
Described conducting polymer is that polyaniline, polypyrrole, polythiophene and their ring substitutive derivative, hetero atom take
For the one in derivant；
Filmogen includes Kynoar, polypropylene, polyacrylonitrile, polyvinyl alcohol, polyimides, polysulfones, polyphenyl
Ether, polybenzimidazoles and their derivant；
Organic solvent includes in 1-Methyl-2-Pyrrolidone, Ketohexamethylene, dimethyl acetylamide, dimethylformamide, pyridine
One；
(2) mixed solution obtained in step (1) is dripped in clean substrate, and makes it be laid in substrate surface,
Form liquid coating, then it is put in deionized water together with substrate, make coating quickly solidify to form conducting polymer
Thin film comes off from substrate；
Substrate includes the one in glass plate, silicon chip, sheet metal；
(3) the conducting polymer separation film obtained in step (2) is dipped in Enough Dl water, therein to remove
Organic solvent also forms micropore in this separation film, obtains conducting polymer porous membrane.
Conducting polymer porous diffusion barrier is utilized to reclaim the side of metal from electron wastes the most as claimed in claim 1
Method, is characterized in that: the pH value of described electron wastes Acid leaching liquid is 1～5.
Conducting polymer porous diffusion barrier is utilized to reclaim the side of metal from electron wastes the most as claimed in claim 1
Method, is characterized in that: described conducting polymer composite is 1:10～10:1 with the mass ratio of filmogen.
Conducting polymer porous diffusion barrier is utilized to reclaim the side of metal from electron wastes the most as claimed in claim 1
Method, is characterized in that: described conducting polymer composite is 1:3～3:1 with the mass ratio of filmogen.
Conducting polymer porous diffusion barrier is utilized to reclaim the side of metal from electron wastes the most as claimed in claim 1
Method, is characterized in that: form pressure differential, concentration difference or potential difference in the described high-molecular porous separation film both sides of conduction electricity,
So that metal ion is enriched with rapidly in the side of porous diffusion barrier.
Conducting polymer porous diffusion barrier is utilized to reclaim the side of metal from electron wastes the most as claimed in claim 1
Method, is characterized in that: described electron wastes Acid leaching liquid stream is recovered after this conducting polymer porous diffusion barrier, then
Secondary flow through this conducting polymer porous diffusion barrier, be so repeated several times.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016585A (en) * | 2007-03-08 | 2007-08-15 | 同济大学 | Method of reclaiming silver from silver ion containing solution by polydiaminoanthraquinone as adsorbent |
| CN101089206A (en) * | 2007-07-09 | 2007-12-19 | 同济大学 | Methoxy-pheyl-sulfamic acid modified aniline copolymer used as silver ion absorbent |
| CN103374659A (en) * | 2012-04-25 | 2013-10-30 | 鑫广再生资源(上海)有限公司 | Method for extracting and recovering precious metal and rare metal from wastes |
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| JP5703514B2 (en) * | 2010-11-02 | 2015-04-22 | 日立化成株式会社 | Gold collector and separation and recovery method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016585A (en) * | 2007-03-08 | 2007-08-15 | 同济大学 | Method of reclaiming silver from silver ion containing solution by polydiaminoanthraquinone as adsorbent |
| CN101089206A (en) * | 2007-07-09 | 2007-12-19 | 同济大学 | Methoxy-pheyl-sulfamic acid modified aniline copolymer used as silver ion absorbent |
| CN103374659A (en) * | 2012-04-25 | 2013-10-30 | 鑫广再生资源(上海)有限公司 | Method for extracting and recovering precious metal and rare metal from wastes |
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