CN102828054A - Method for recovering indium from waste liquid crystal panels through acid leaching-cation exchange resin adsorption technology - Google Patents
Method for recovering indium from waste liquid crystal panels through acid leaching-cation exchange resin adsorption technology Download PDFInfo
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Abstract
The invention relates to the recovery field of regeneration indium, in particular to a method for recovering indium from waste liquid crystal panels through an acid leaching-cation exchange resin adsorption technology, and solves the technical problem of low efficiency of the traditional low-level indium recovery technology has. To solve the technical problems, the technical scheme provided by the invention is to provide the method for recovering indium from waste liquid crystal panels through the acid leaching-cation exchange resin adsorption technology. The method comprises the following steps of: separating a glass substrate from a waste liquid crystal plate; crushing the glass substrate to obtain glass powder; carrying out acid leaching to the glass powder; processing the leaching liquid through countercurrent adsorption via the strong-acid cation exchange resin; and soaking the strong-acid cation exchange resin subjected to the countercurrent adsorption through inorganic acid so as to obtain the soaking liquid; adjusting the pH value of the soaking liquid through inorganic base; filtering and separating the tin hydroxide precipitation; collecting the filtrate; and replacing the indium in the filtrate through a zinc plate. The method is an effective method for recovering the indium from waste liquid crystal panels.
Description
Technical field
The recovery field of indium the present invention relates to regenerate.Specifically, the present invention relates to acidleach-cationic exchange resin adsorption technology reclaims indium from the waste liquid crystal plate method.
Background technology
Indium is rare noble metal, is widely used in high-tech areas such as robot calculator, solar cell, photoelectricity, national defense and military, aerospace, nuclear industry and modern information industry.Indium is mainly used in electronic industry, and like transparency electrode, welding material, the compound semiconductor of uses such as liquid-crystal display, indium also is used for fluor, low melting point alloy, battery material, dental alloy, bearing etc.
Along with popularizing rapidly of household electrical appliance such as mobile phone, notebook computer, LCD TV, the indium consumption of transparency electrode increases rapidly, and for the increase rapidly of liquid crystal panel demand, the quickening of indium resource exhaustion all impels the quick rise of indium price especially both at home and abroad.The price of world market indium also rises steadily since the nineties in last century, once above 10000 yuan/kilogram.The resource exhaustion of rare indium metal that more serious is has become mankind's coming crisis in Western sociology of having to.According to expert introduction, at present, still do not exist other metal can substitute phosphide element, so indium have extremely important strategic value in above-mentioned field.At present, the reserves that indium metal has been verified in the whole world are merely 1.6 ten thousand tons, are to have verified 1/6 of gold reserve.This rare, the strategic resource that faces resource exhaustion of indium, for China be like this resource exit big country be again the import big country of indium high value added product, control outlet, resources conseravtion; Accelerate indium hi-tech, high value added product industrialization process; Realizing efficient recovery, the recycle of indium as early as possible, should be the historic responsibility of country and relevant enterprise, has great strategy, society, economic implications undoubtedly.
As the recovery technology of regeneration indium, mainly be that Japan's report is more.For example; Report is arranged with after strippings such as ITO target are in acid, use sulfuration method (spy opens 2000-169991), hydroxide method (spy opens 2002-69684), remove tramp metal ion, method through solvent extration (spy opens 2000-212658) separation, recovery indium through resin (spy opens 2002-308622).But shortcomings such as indium recovery is low, foreign matter content height that these methods exist in the extraction of low-grade indium.
Domesticly be devoted to mainly from the smeltery about the patent documentation report that reclaims indium that slag, waste water etc. reclaim content at the higher-grade indium 0.5% or more, the recovery grade far below the report of 0.1% indium seldom from discarded liquid crystal panel.
CN 101368230A discloses a kind of recovery technology of low-grade indium, is characterized in technology, adopting the indium in organophosphorus extraction agent P204 or the CL-P204 resin absorption electrolytic solution, the indium that adsorbs with the hydrochloric acid desorb again.But this operation exists that operation is long, efficient is low and produce shortcoming such as organic solvent residue.
CN 101133172A (enjoying the right of priority of JP 2005-226920) discloses a kind of method and apparatus that from useless LCD, reclaims indium.The contrast experiment that the hydrochloric acid of this method application 1 %, 3% and 10% 3 different concns has carried out 24hr and 48hr stripping respectively, extraction time is oversize, and production efficiency is low.
CN 101701292A discloses and a kind ofly has been lower than the method that reclaims indium tin 0.2% the ITO waste target through oxidation style from indium grade; This method is used concentrated hydrochloric acid and is leached the indium in the ITO waste target; Leach liquor through the aluminium sheet displacement, obtains the sponge indium again after twice oxidation under the condition of different pH.But the indium that this method is not suitable on the glass baseplate extracts, and fails to solve the isolating problem of polaroid on liquid crystal display top layer.
CN 1900770A discloses a kind of liquid-crystal display recycling processing method; Mainly in order to obtain clean intact glass substrate; The subsidiary mixture of having reported nitric acid, hydrochloric acid and the nitric acid of application different concns (1:1～4), sulfuric acid etc. are removed metal coating; But there is not the recovery of play-by-play indium; Only mention and use existing technology (" the Chinese metallurgical encyclopedia-Non-ferrous Metallurgy " that metallurgical industry press publishes that volume editorial board of the metallurgical encyclopaedical editor-in-chief council of China " Non-ferrous Metallurgy " announces; 1998.11) carry out the extraction and the purifying of indium, the method that provides in " Non-ferrous Metallurgy " monograph generally is not suitable for the recovery that grade is lower than indium in 0.1% the metallurgical slag.
CN 101722169A discloses the method that a kind of liquid crystal display (LCD) harmless is handled; This method is pulverized the post-heating disaggregating treatment with the glass substrate that contains liquid crystal in the liquid-crystal display; With innoxious discharging after the at high temperature abundant burn processing of the organic gas that produces, but do not relate to the concrete grammar that reclaims indium.
Document (Nie's ear etc., environmental engineering journal, 2008; Vol2, No9, pp1251-4) desk study a kind of method that reclaims indium from the waste liquid crystal panel; It comprises, utilizes sulphuric acid soln and Manganse Dioxide to unite the leaching glass substrate, and organic efficiency is lower; The leaching rate of indium is lower, and the indium in the acid solution of leaching back reclaims the easy organic solvent residue that produces through the organic extractant extraction.
In a word, also do not have so far a kind ofly to reclaim the complete of indium and effective means from the waste liquid crystal panel.
Summary of the invention
The technical problem that the present invention will solve is that traditional low-grade indium reclaims the problem that process efficiency is low, foreign matter content is high.
The technical scheme of technical solution problem of the present invention provides a kind of acidleach-cationic exchange resin adsorption technology reclaims indium from the waste liquid crystal plate method.
Aforesaid method reclaims low-grade indium in the waste liquid crystal plate through acidleach repeatedly-cationic exchange resin adsorption process integration, may further comprise the steps:
1) separates glass substrate from the waste liquid crystal plate;
2) glass substrate is pulverized, obtained glass powder;
3) above-mentioned glass powder is carried out acidleach;
4) leach liquor of acidleach carries out adverse current absorption with strong acid cation exchange resin column;
5) soak the strongly acidic cationic exchange resin after adverse current is adsorbed with mineral acid, obtain soak solution;
6) with the pH value of this soak solution of mineral alkali adjusting, filter to isolate the stannic hydroxide deposition, collect filtrating;
7) displace the indium in the filtrating with zine plate.
Wherein, above-mentioned acidleach-cationic exchange resin adsorption technology, in the described step 1) shreds the waste liquid crystal plate to 1～4cm * 3～4cm size from the method for waste liquid crystal plate recovery indium, soaks with acetone glass substrate is separated with polaroid.
Described acetone soaks operation to carry out usually at normal temperatures.The time that said acetone soaks is 1～5h.The time that said acetone soaks is preferably 1～2h.
Wherein, the described step 2 of aforesaid method) in, the particle size range of said glass powder is 20～120 orders.The particle size range of said glass powder is preferably 40～100 orders.The particle size range of said glass powder is 60～80 orders more preferably.
Wherein, in the described step 3) of aforesaid method, the used acid of acidleach is at least a in Hydrogen chloride, rare nitric acid, the dilute sulphuric acid.
Wherein, in the described step 3) of aforesaid method, during said acidleach, glass powder is 1:8～1:3 with the mass ratio of acid.Said glass powder is preferably 1:6～1:4 with the mass ratio of acid.
Wherein, in the described step 3) of aforesaid method, the concentration of the used acid of said acidleach is 2～10mol/L.The concentration of the used acid of said acidleach is 3～8mol/L preferably.The concentration of the used acid of said acidleach is more preferably 4～7mol/L.
Wherein, in the described step 3) of aforesaid method, the temperature of reaction of said acidleach is 50～120 ℃.Preferably 60～110 ℃ of the temperature of reaction of said acidleach.The temperature of reaction of said acidleach is more preferably 70～100 ℃.
Wherein, in the described step 3) of aforesaid method, the reaction times of said acidleach is 1～12h.The reaction times of said acidleach is 3～10h preferably.The reaction times of said acidleach is more preferably 3～8h.
Wherein, in the described step 3) of aforesaid method, when the used acid of said acidleach was Hydrogen chloride, its concentration was 5～7mol/L, and the temperature of reaction that acidleach goes out is 80～100 ℃, and the reaction times is 5～8h.
Wherein, in the described step 3) of aforesaid method, when the used acid of said acidleach is the mixing acid of Hydrogen chloride and dilute sulphuric acid; Wherein, The concentration of Hydrogen chloride is 5～7mol/L, and the concentration of dilute sulphuric acid is 1～3mol/L, and the mol ratio of dilute sulphuric acid and Hydrogen chloride is 1:2 in the mixing acid; The temperature of reaction that acidleach goes out is 80～100 ℃, and the reaction times is 3～6h.
Wherein, in the described step 3) of aforesaid method, when the used acid of said acidleach was dilute sulphuric acid, its concentration was 150～300g/L, added the MnO of sulfuric acid consumption 5～15wt%
2As catalyzer, the temperature of reaction that acidleach goes out is 85～95 ℃, and the reaction times is 5～7h.
Wherein, in the described step 4) of aforesaid method, described adverse current adsorption operations is the above adverse current absorption of level Four.The preferably six stage countercurrents absorption of said adverse current adsorption operations.
Wherein, In the described step 5) of aforesaid method, above-mentioned cationic exchange resin adsorption reach saturated basically after, for example reach the 80wt% at least of resin saturated adsorption capacity; Preferred 85wt% at least; More preferably 90wt% at least then soaks 30～50h with resin with mineral acid at normal temperatures, soaks out by the metals ion of resin absorption.Described mineral acid is hydrochloric acid or sulfuric acid, wherein the hydrochloric acid best results of 6mol/L.
Wherein, in the described step 6) of aforesaid method, regulate pH value to 2.5～3.5 of soak solution with mineral alkali.Preferably, regulate pH value to 2.8～3.2 of soak solution with mineral alkali.Regulate pH value mineral alkali commonly used and comprise yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, sodium hydroxide, Pottasium Hydroxide etc.
Wherein, in the described step 6) of aforesaid method, after the adjusting soak solution pH value, soak solution is left standstill, the subsequent filtration sediment separate out is collected filtrating.Described soak solution time of repose is 6～15h.Preferred soak solution time of repose is 8～10h.
Wherein, in the described step 7) of aforesaid method, in filtrating, add 36% concentrated hydrochloric acid and regulate pH value of filtrate to 1.3～1.6, and filtrating is heated to 45～55 ℃, with the indium in the zine plate displacement filtrating, time swap is 8～20h, is preferably 8～12h.The spongy thick indium that is about 99wt% in zine plate surface deposition purity.Last bath voltage and 30～80A/m at 0.1～0.5V
2Current density under carry out electrolytic refining, obtain the pure indium that purity reaches 99.99wt%.
The inventive method has comprehensively adopted acetone immersion, pulverizing, acidleach etc. the series of process method is Promethean indium in the liquid crystal display has been leached; And according to the highly acid characteristics that contain the indium leach liquor; Select for use strong acidic ion resin that the indium in the leach liquor is carried out enrichment, realized the high efficiente callback of the indium in the liquid crystal display.
Method provided by the invention, technical process is succinct, gentleness, cleaning, environmental protection of reaction conditions, and associated materials can be recycled, and does not produce new noxious pollutant, and the thick indium foreign matter content that makes is low.
Embodiment
Acidleach provided by the invention-cationic exchange resin adsorption technology may further comprise the steps from the method for waste liquid crystal plate recovery indium:
1) separates glass substrate from the waste liquid crystal plate;
2) glass substrate is pulverized, obtained glass powder;
3) above-mentioned glass powder is carried out acidleach;
4) leach liquor of acidleach carries out adverse current absorption with strong acid cation exchange resin column;
5) soak the strongly acidic cationic exchange resin after adverse current is adsorbed with mineral acid, obtain soak solution;
6) with the pH value of this soak solution of mineral alkali adjusting, filter to isolate the stannic hydroxide deposition, collect filtrating;
7) displace the indium in the filtrating with zine plate.
The concrete operations step is following:
1) at first the waste liquid crystal plate is shredded to 1～4cm * 3～4cm size, glass substrate is separated with polaroid with the acetone immersion, and polymer substances such as liquid crystal in the dissolving liquid crystal board and tackiness agent.Acetone soaks operation to carry out usually at normal temperatures, and soak time is 1～5h, is preferably 1～2h.Acetone solution then, air distillation, the acetone recycle that steams is used, and refers again to document (for example CN 101722169A) disclosed method with resistates high temperature incineration in nitrogen atmosphere.The waste liquid crystal plate powder of remainder is dried or oven dry under 60～80 ℃.
2) glass substrate after will separating is air-dry, is crushed to the powder of certain grain size again.The particle diameter of pulverizing back gained powder is preferably 40～100 orders, more preferably 60～80 orders in 20～120 order scopes.If particle diameter is lower than 20 orders, the acid leaching efficiency that remarkably influenced is follow-up causes indium recovery to descend.But, if particle diameter is higher than 120 orders, follow-up filtering separation pickling liquor and the glass powder of being difficult for.
3) dried waste liquid crystal sheet glass powder is gone out metal wherein with acidleach, mainly comprise the iron of indium, tin and trace.At least a olefin(e) acid that can use in Hydrogen chloride, rare nitric acid, the dilute sulphuric acid leaches at a certain temperature.The mass ratio of said glass powder and diluted acid is generally 1:8～1:3, is preferably 1:6～1:4.If the mass ratio of powder and acid, leaches reaction greater than 1:3 not exclusively, the leaching efficiency of metal is lower.If the mass ratio of powder and acid is less than 1:8, the follow-up treatment time will be oversize, and the cost efficiency of indium is reclaimed in influence.
The concentration of said acid is 2～10mol/L normally, and preferably 3～8mol/L is more preferably 4～7mol/L.Temperature of reaction is 50～120 ℃, preferably 60～110 ℃, is more preferably 70～100 ℃.Reaction times is 1～12h, and preferably 3～10h is more preferably 3～8h.Wherein, if the concentration of leach liquor acid is low excessively, temperature of reaction is on the low side and/or the reaction times is too short, the leaching efficiency of metal will descend.Otherwise, higher and/or the reaction times is long like excessive concentration, the temperature of reaction of tartaric acid, though help the raising of indium organic efficiency, cause the waste of resource and the increase of cost recovery.
When said acid was Hydrogen chloride, its concentration was 5～7mol/L, and the temperature of reaction that acidleach goes out is 80～100 ℃, and the reaction times is 5～8h.
When said acid was the mixing acid of Hydrogen chloride and dilute sulphuric acid, wherein, the concentration of Hydrogen chloride was 5～7mol/L; The concentration of dilute sulphuric acid is 1～3mol/L; The mol ratio of dilute sulphuric acid and Hydrogen chloride is 1:2 in the mixing acid, and the temperature of reaction that acidleach goes out is 80～100 ℃, and the reaction times is 3～6h.
When said acid was dilute sulphuric acid, its concentration was 150～300g/L, added the MnO of sulfuric acid consumption 5～15wt%
2As catalyzer, the temperature of reaction that acidleach goes out is 85～95 ℃, and the reaction times is 5～7h.
4) after leach liquor is diluted to pH and is about 2 with deionized water,, carry out the above counter-current operation of level Four, can adsorb the indium ion in the 90wt% diluted acid leach liquor at least through having filled the adsorption column of strongly acidic cationic exchange resin; Through six stage countercurrents operations, can adsorb the indium ion in the 95wt% diluted acid leach liquor at least.
Because the content of indium ion is too low in the acid leaching liquor; Can not be through conventional hydroxide precipitation method like a lot of paper bibliographical informations; Sulphide precipitation, various SULPHOSUCCINIC ACID ESTERs (for example tributyl phosphate, P204 (di-(2-ethylhexyl)phosphoric acid ester) etc.) or other resin (for example D418 (aminomethylene phosphoric acid resin), D401 (the amino resin of N-sodium acetate) etc.) are as direct recovery indium such as the conventional extraction process of extraction agent.The present invention adopts strongly acidic cationic exchange resin, can adsorb very effectively and metals ion in the said acid leaching liquor of enrichment.
5) above-mentioned cationic exchange resin adsorption reach saturated basically after; For example reach the 80wt% at least of resin saturated adsorption capacity, preferred 85wt% at least, more preferably 90wt% at least; Then at normal temperatures resin is soaked 30～50h, soak out by the metals ion of resin absorption with mineral acid.Described mineral acid is hydrochloric acid or sulfuric acid, wherein the hydrochloric acid best results of 6mol/L.
6) with pH value to 2.5～3.5 of mineral alkali adjusting soak solution, preferably regulate soak solution pH value to 2.8～3.2, the tin in the solution is separated out with precipitation of hydroxide, and indium still is retained in the solution.Regulate soak solution pH value mineral alkali commonly used and comprise yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, sodium hydroxide, Pottasium Hydroxide etc.After the regulator solution pH value, soak solution is left standstill 6～15h, preferably leave standstill 8～10h, the subsequent filtration sediment separate out is collected filtrating.
7) in filtrating, be added on interpolation 36% concentrated hydrochloric acid adjusting pH value of filtrate to 1.3～1.6 in the filtrating, and filtrating is heated to 45～55 ℃, with the indium in the zine plate displacement filtrating, time swap is 8～20h, is preferably 8～12h.The spongy thick indium that is about 99wt% in zine plate surface deposition purity.With the spongy indium that obtains, warp is pressed group, dries and at 350～450 ℃ of following founding 1～3h, is obtained blocky thick indium, convenient preservation and refining.Last bath voltage and 30～80A/m at 0.1～0.5V
2Current density under carry out electrolytic refining, obtain the pure indium that purity reaches 99.99wt%.
Set forth in detail below in conjunction with specific embodiment.
Embodiment 1
1) weighing 100kg waste liquid crystal plate shreds the waste liquid crystal plate to 1～4cm * 3～4cm size, soaks 80min at normal temperatures with 2L acetone, glass substrate and polaroid is peeled off, again with the air-dry about 1h of the glass substrate of peeling off.
2) pulverize exsiccant glass substrate to 80 purpose powder subsequently.Filtering separation acetone soln, air distillation go out acetone and supply cycle applications, and residue high temperature incineration after centralized collection is separately handled.
3) getting the aforementioned glass substrate powder of 1kg and 4.5L concentration is that the Hydrogen chloride of 6mol/L mixes, and stirs refluxed reaction 5h at 85 ℃, promptly accomplishes an acidleach.After being cooled to room temperature, Hydrogen chloride is isolated in press filtration, and the Hydrogen chloride that replenishes 6mol/L is used for acidleach next time to 4.5L.That is, get 1kg glass substrate powder in addition,, accomplish acidleach for the second time with the time same under the aforementioned identical condition with the 4.5L Hydrogen chloride reacting phase of indium that contains last acidleach and tin.So repeat the operation of acid-leaching reaction, press filtration and additional diluted acid, finished by acidleach in batches until 100kg waste liquid crystal plate.The leaching yield that spectrophotometry (referring to document: Peng Cuihong, the research of micro-gallium, indium, germanium in the spectrophotometry cadmia, Guangdong University of Technology's master thesis, 2003) through Viola crystallina colour developing records indium is 91.5wt%.
4) after the acidleach of completion 100kg waste liquid crystal plate; Be diluted to pH with deionized water and be about 2; With use acid with diluted acid leach liquor pumping reverse flow cross placed in-line six respectively fill 100g 732 type strong acidic ion resins, internal diameter is the adsorption column of 10cm, circulates 24h.
5) after in batches repeatedly (more than 10 batches, the waste liquid crystal plate that co-processing 1000kg is above) adsorb, with the said exchange resin 48h that contains indium ion, the metals ion of wash-out resin absorption of having adsorbed of the hydrochloric acid soak at room temperature of 6mol/L.
6) with the pH value to 3 of yellow soda ash adjusting soak solution, the tin in the solution is separated out with precipitation of hydroxide, and indium still is retained in the soak solution with the chloride ion form.After regulating soak solution pH value, soak solution is left standstill 10h, the subsequent filtration sediment separate out is collected filtrating.
7) regulate pH value of filtrate to 1.5 with hydrochloric acid then, be heated to 50 ℃ (, with the indium in the zine plate displacement filtrating, time swap is 10h.The spongy indium experience that obtains is pressed group, dries and at 350 ℃ of following founding 1.5h, obtained the thick indium that content is about 99wt%.Last bath voltage and 53A/m at 0.25V
2Current density under carry out electrolytic refining and the pure indium of 99.99wt%.
Indium in the zine plate displacement filtrating and the purity of the thick indium that obtains is 99wt%, the recovery is 97.5wt% (for the indium content of leach liquor).
Embodiment 2
Elementary operation is with embodiment 1, and different is in step 3), uses rare nitric acid and replaces Hydrogen chloride to carry out acidleach, and the concentration of rare nitric acid is 3mol/L, and the temperature of reaction that acidleach goes out is 90 ℃, and the reaction times is 6h.The leaching yield that records indium is 82.1wt%.
Indium in the zine plate displacement filtrating and the purity of the thick indium that obtains is 99wt%, the recovery is 97.5wt% (for the indium content of leach liquor).
Embodiment 3
Elementary operation is with embodiment 1, and different is in step 3), and the mixing acid of using Hydrogen chloride and rare nitric acid replaces Hydrogen chloride to carry out acidleach; Wherein, The concentration of Hydrogen chloride is 5mol/L, and the concentration of rare nitric acid is 2mol/L, and the mol ratio of hydrochloric acid and nitric acid is 5:2; The temperature of reaction that acidleach goes out is 85 ℃, and the reaction times is 5h.The leaching yield that records indium is 93.2wt%.
Indium in the zine plate displacement filtrating and the purity of the thick indium that obtains is 99wt%, the recovery is 97.5wt% (for the indium content of leach liquor).
Embodiment 4
Elementary operation is with embodiment 1, and different is in step 3), uses dilute sulphuric acid and replaces Hydrogen chloride to carry out acidleach, and wherein, the concentration of dilute sulphuric acid is 200g/L, adds the MnO of sulfuric acid consumption 8wt%
2As catalyzer, the temperature of reaction that acidleach goes out is 90 ℃, and the reaction times is 4h.The leaching yield that records indium is 89.5wt%.
Indium in the zine plate displacement filtrating and the purity of the thick indium that obtains is 99wt%, the recovery is 97.5wt% (for the indium content of leach liquor).
Embodiment 5
Elementary operation is with embodiment 1, and different is in step 3), and the mixing acid of using dilute sulphuric acid and Hydrogen chloride replaces Hydrogen chloride to carry out acidleach; Wherein, The concentration of dilute sulphuric acid is 2mol/L, and the concentration of Hydrogen chloride is 5mol/L, and the mol ratio of sulfuric acid and hydrochloric acid is 1:2; The temperature of reaction that acidleach goes out is 80 ℃, and the reaction times is 4h.The leaching yield that records indium is 93.5wt%.
Indium in the zine plate displacement filtrating and the purity of the thick indium that obtains is 99wt%, the recovery is 97.5wt% (for the silver content of leach liquor).
Claims (10)
1. acidleach-cationic exchange resin adsorption technology is from the method for waste liquid crystal plate recovery indium, and it is characterized in that: this method may further comprise the steps:
1) separates glass substrate from the waste liquid crystal plate;
2) glass substrate is pulverized, obtained glass powder;
3) above-mentioned glass powder is carried out acidleach;
4) leach liquor of acidleach carries out adverse current absorption with strong acid cation exchange resin column;
5) soak the strongly acidic cationic exchange resin after adverse current is adsorbed with mineral acid, obtain soak solution;
6) with the pH value of this soak solution of mineral alkali adjusting, filter to isolate the stannic hydroxide deposition, collect filtrating;
7) displace the indium in the filtrating with zine plate.
2. acidleach according to claim 1-cationic exchange resin adsorption technology is from the method for waste liquid crystal plate recovery indium, and it is characterized in that: described step 2), the particle size range of said glass powder is 20～120 orders.
3. acidleach according to claim 2-cationic exchange resin adsorption technology is from the method for waste liquid crystal plate recovery indium, and it is characterized in that: the particle size range of said glass powder is 40～100 orders.
4. acidleach according to claim 3-cationic exchange resin adsorption technology is from the method for waste liquid crystal plate recovery indium, and it is characterized in that: the particle size range of said glass powder is 60～80 orders.
5. acidleach according to claim 1-cationic exchange resin adsorption technology reclaims the method for indium from the waste liquid crystal plate, it is characterized in that: in the described step 3), the used acid of acidleach is at least a in Hydrogen chloride, dilute sulphuric acid, the rare nitric acid.
6. acidleach according to claim 5-cationic exchange resin adsorption technology reclaims the method for indium from the waste liquid crystal plate; It is characterized in that: the used acid of said acidleach is Hydrogen chloride; Its concentration is 5～7mol/L, and the temperature of reaction that acidleach goes out is 80～100 ℃, and the reaction times is 5～8h.
7. acidleach according to claim 5-cationic exchange resin adsorption technology reclaims the method for indium from the waste liquid crystal plate; It is characterized in that: the used acid of said acidleach is the mixing acid of Hydrogen chloride and dilute sulphuric acid, and wherein, the concentration of Hydrogen chloride is 5～7mol/L; The concentration of dilute sulphuric acid is 1～3mol/L; The mol ratio of dilute sulphuric acid and Hydrogen chloride is 1:2 in the mixing acid, and the temperature of reaction that acidleach goes out is 80～100 ℃, and the reaction times is 3～6h.
8. acidleach according to claim 5-cationic exchange resin adsorption technology is from the method for waste liquid crystal plate recovery indium, and it is characterized in that: the used acid of said acidleach is dilute sulphuric acid, and its concentration is 150～300g/L, adds the MnO of sulfuric acid consumption 5～15wt%
2As catalyzer, the temperature of reaction that acidleach goes out is 85～95 ℃, and the reaction times is 5～7h.
9. acidleach according to claim 1-cationic exchange resin adsorption technology is characterized in that from the method for waste liquid crystal plate recovery indium: in the described step 4), described adverse current adsorption operations is the above adverse current absorption of level Four.
10. acidleach according to claim 8-cationic exchange resin adsorption technology is characterized in that from the method for waste liquid crystal plate recovery indium: said adverse current adsorption operations is the absorption of six stage countercurrents.
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| CN103602815A (en) * | 2013-11-06 | 2014-02-26 | 四川长虹电器股份有限公司 | Method for recycling indium from waste liquid crystal displays |
| WO2015109777A1 (en) * | 2014-01-21 | 2015-07-30 | 京东方科技集团股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment layer, preparation method therefor and liquid crystal display panel |
| CN106086481A (en) * | 2016-08-23 | 2016-11-09 | 王朋 | A kind of reclaim the method for germanium in germanic waste liquid |
| CN106734088A (en) * | 2016-12-22 | 2017-05-31 | 东莞市广信知识产权服务有限公司 | A kind of recovery and treatment method of waste mobile phone |
| CN107513619A (en) * | 2017-08-14 | 2017-12-26 | 中南大学 | A kind of method of recovery indium and tin in waste material from ito glass |
| CN109504858A (en) * | 2018-12-18 | 2019-03-22 | 广东先导稀材股份有限公司 | Method for preparing indium hydroxide by using ITO waste material |
| CN113061729A (en) * | 2021-03-19 | 2021-07-02 | 石家庄绿色再生资源有限公司 | Device and method for leaching indium from waste liquid crystal display screen in spraying manner |
| CN113234927A (en) * | 2021-03-19 | 2021-08-10 | 石家庄绿色再生资源有限公司 | Device and method for recycling indium in waste liquid crystal display |
| CN113620475A (en) * | 2021-09-02 | 2021-11-09 | 徐红艳 | Circuit board contains tin effluent treatment plant |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602815A (en) * | 2013-11-06 | 2014-02-26 | 四川长虹电器股份有限公司 | Method for recycling indium from waste liquid crystal displays |
| CN103602815B (en) * | 2013-11-06 | 2015-12-09 | 四川长虹电器股份有限公司 | The method of recovery indium from waste liquid crystal display |
| WO2015109777A1 (en) * | 2014-01-21 | 2015-07-30 | 京东方科技集团股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment layer, preparation method therefor and liquid crystal display panel |
| US9488868B2 (en) | 2014-01-21 | 2016-11-08 | Boe Technology Group Co., Ltd. | Liquid crystal aligning agent, liquid crystal aligning layer, methods of preparing the same, and liquid crystal display panel |
| CN106086481A (en) * | 2016-08-23 | 2016-11-09 | 王朋 | A kind of reclaim the method for germanium in germanic waste liquid |
| CN106734088A (en) * | 2016-12-22 | 2017-05-31 | 东莞市广信知识产权服务有限公司 | A kind of recovery and treatment method of waste mobile phone |
| CN107513619A (en) * | 2017-08-14 | 2017-12-26 | 中南大学 | A kind of method of recovery indium and tin in waste material from ito glass |
| CN107513619B (en) * | 2017-08-14 | 2019-03-05 | 中南大学 | A method of recovery indium and tin from ito glass waste material |
| CN109504858A (en) * | 2018-12-18 | 2019-03-22 | 广东先导稀材股份有限公司 | Method for preparing indium hydroxide by using ITO waste material |
| CN113061729A (en) * | 2021-03-19 | 2021-07-02 | 石家庄绿色再生资源有限公司 | Device and method for leaching indium from waste liquid crystal display screen in spraying manner |
| CN113234927A (en) * | 2021-03-19 | 2021-08-10 | 石家庄绿色再生资源有限公司 | Device and method for recycling indium in waste liquid crystal display |
| CN113234927B (en) * | 2021-03-19 | 2022-05-20 | 石家庄绿色再生资源有限公司 | Device and method for recycling indium in waste liquid crystal display |
| CN113620475A (en) * | 2021-09-02 | 2021-11-09 | 徐红艳 | Circuit board contains tin effluent treatment plant |
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