CN100554454C - The recovery method of the indium from waste liquid crystal display and device thereof - Google Patents
The recovery method of the indium from waste liquid crystal display and device thereof Download PDFInfo
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- CN100554454C CN100554454C CNB2006800070686A CN200680007068A CN100554454C CN 100554454 C CN100554454 C CN 100554454C CN B2006800070686 A CNB2006800070686 A CN B2006800070686A CN 200680007068 A CN200680007068 A CN 200680007068A CN 100554454 C CN100554454 C CN 100554454C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to from useless LCD, will belong to method and the device thereof of the In of valuable thing as alloy or metal MONOMER RECOVERY.Recovery method and the device of following In can be provided, promptly, owing to can not need reclaim with the state of indium hydroxide, and In is reclaimed as precious metals, therefore the processing as the situation of indium hydroxide bad not when reclaiming, can easily reclaim with strainer etc., and the rate of recovery obviously becomes good.It is characterized in that, the useless LCD that will contain tin indium oxide pulverizes, from chippy useless LCD, use acid that tin indium oxide is dissolved, obtain containing indium compound solution, flow into and reclaim with in the reactor, and add by compare the metallics that the bigger metal of ionization tendency constitutes with In in reactor to this recovery, this metallics is flowed, the described In or the In alloy that are contained in the indium compound solution of containing separated out to the surface of described metallics, thereafter, utilize the mechanism for stripping from described metallics, to peel off described In that separates out or In alloy, the In of the solid shape peeled off or In alloy are separated from liquid portion and reclaim.
Description
Technical field
The present invention relates to the recovery method and the device thereof of the indium from waste liquid crystal display, more particularly, relate to from outmoded LCD TV, portable phone, carry game machine etc. or the liquid-crystal display of discharging as substandard products in process of production (below be also referred to as useless LCD) will belong to method and the device thereof of the indium (In) of valuable thing as alloy or metal MONOMER RECOVERY.
Background technology
In liquid-crystal display (below be also referred to as LCD), use tin indium oxide (ITO) film as transparency electrode.The ITO film mainly is to utilize sputter to come film forming, and uses In in its target.In is the rare metal that obtains in the zinc treating process, worrying in recent years its might be exhausted.In useless LCD, contain the In about 300mg/L, be accompanied by the exhaustionization of In, be desirably in the recycle process In is reclaimed.
In order to respond this kind requirement, attempted reclaiming the In among the useless LCD, as this kind technology, the invention of record in the following non-patent literature 1 is for example arranged.This invention is the technology about fluidized-bed LCD treatment system, this fluidized-bed LCD treatment system is made of fluidized layer handling part, cyclonic separator, water cooler, house-bag duster for high temperature, catalyst fluidized bed and water cleaning tower, and the In that utilizes the silica sand of flow media mechanically to peel off in the fluidized layer handling part is accumulated in flow media.But, use in the method for this treatment system, because about 60% among the useless LCD accumulate in flow media, remainingly collected, so indium recovery is about 60% on the whole by the pocket type fly-ash separator, its rate of recovery is low to be reached about 60%.
Non-patent literature 1: monthly magazine Display in April, 2002 P36～46
In order to improve the lower rate of recovery of aforesaid dry process, also develop the method for utilizing wet processed.For example following patent documentation 1 is ITO to be dissolved in the acid such as nitric acid or hydrochloric acid, after contamination precipitations such as Sn are removed, adds ammonia and neutralizes, the method that reclaims as indium hydroxide.
Patent documentation 1: the spy of Japan opens the 2000-128531 communique
But, according to the method for aforesaid wet processed, utilize the filterableness of handling the indium hydroxide that obtains poor, need for a long time the problem that also has the neutralization of utilizing to wait the character of the indium hydroxide that obtains to change in addition in operation.
Summary of the invention
The present invention finishes in order to solve this kind problem, purpose is, recovery method and the device of following In are provided, promptly, owing to do not need as in the past to reclaim with the state of indium hydroxide, In can be reclaimed as precious metals, so when recovery the processing as the situation of indium hydroxide bad not, can easily reclaim with strainer etc., and the rate of recovery of In becomes good significantly.
The present invention finishes in order to solve this kind problem, the feature of the invention of being put down in writing about the technical scheme 1 of the recovery method of the In from useless LCD is, the waste liquid crystal display that will contain tin indium oxide is pulverized, from chippy waste liquid crystal display, use acid that tin indium oxide is dissolved, obtain containing indium compound solution, make this contain indium compound solution and flow into recovery with in the reactor, and add by compare the metallics that the bigger metal of ionization tendency constitutes with indium in reactor to this recovery, this metallics is flowed, the described indium or the indium alloy that are contained in the indium compound solution of containing separated out to the surface of described metallics, thereafter, utilize the mechanism for stripping from described metallics, to peel off described indium of separating out or indium alloy, the indium of the solid shape peeled off or indium alloy are separated from liquid portion and reclaim.
In addition, the invention that technical scheme 2 is put down in writing has following feature in the recovery method of the indium from waste liquid crystal display that technical scheme 1 is put down in writing, and is zinc particles or aluminum particulate by compare the metallics that the bigger metal of ionization tendency constitutes with indium.In addition, the invention that technical scheme 3 is put down in writing has following feature in the recovery method of the indium from waste liquid crystal display that technical scheme 1 or 2 is put down in writing, the indium that will separate out in metallics or indium alloy are the mechanism that utilizes the ultra-sonic oscillation metallics from the mechanism that described metallics is peeled off; Or utilize electro-magnet to stir metallics and make it the mechanism of collision mutually.
In addition, has following feature in the recovery method of invention any indium from waste liquid crystal display of being put down in writing in technical scheme 1 to 3 that technical scheme 4 is put down in writing, flow into to reclaim with before in the reactor at the indium compound solution that contains that will from waste liquid crystal display, dissolve tin indium oxide, making this contain indium compound solution inflow impurity removes with in the reactor, add described impurity to and remove compare metallics that the bigger metal of ionization tendency constitutes by the foreign metal beyond containing indium in the indium compound solution with this with in the reactor, this metallics is flowed, described foreign metal is separated out to the surface of described metallics, utilize mechanism for stripping from described metallics described foreign metal of separating out peeled off and remove thereafter.
In addition, the invention that technical scheme 5 is put down in writing has following feature in the recovery method of the indium from waste liquid crystal display that technical scheme 4 is put down in writing, be the mechanism that utilizes the ultra-sonic oscillation metallics from the mechanism that described metallics is peeled off with the foreign metal that precipitate on the metallics; Or utilize electro-magnet to stir metallics and make it the mechanism of collision mutually.In addition, the invention that technical scheme 6 is put down in writing has following feature in the recovery method of the indium from waste liquid crystal display that technical scheme 4 or 5 is put down in writing, and foreign metal is a tin.In addition, having following feature in the recovery method of the indium from waste liquid crystal display that the invention that technical scheme 7 is put down in writing is put down in writing in technical scheme 4 to 6, is iron particle by compare the metallics that the bigger metal of ionization tendency constitutes with foreign metal.In addition, the invention that technical scheme 8 is put down in writing has following feature in the recovery method of the indium from waste liquid crystal display that technical scheme 7 is put down in writing, add alkali containing in the indium compound solution behind the foreign metal to having removed, iron is removed as precipitation of hydroxide.
In addition, the feature of the invention that technical scheme 9 is put down in writing is, under the state that waste liquid crystal display is contained in always in the bag, from this waste liquid crystal display, use sour dissolved oxygen indium tin, obtain containing indium compound solution, on the other hand, the waste liquid crystal display of being accommodated in the described bag is cleaned neutralizing treatment, carry out drying treatment thereafter.
In addition, the feature of the invention of being put down in writing about the technical scheme 10 of the retrieving arrangement of the indium from waste liquid crystal display is to comprise: will contain the pulverizer that the waste liquid crystal display of tin indium oxide is pulverized; Use acid the tin indium oxide dissolving to be obtained containing the indium dissolver of indium compound solution to chippy waste liquid crystal display; Inflow utilizes that this indium dissolver obtains contains indium compound solution, and add by compare the metallics that the bigger metal of ionization tendency constitutes, the recovery reactor that the metal evolution reaction that indium or indium alloy are separated out to the surface of described metallics is used with described indium; In order to reclaim described indium of separating out or indium alloy, and it is peeled off the mechanism for stripping of usefulness from described metallics; Indium or indium alloy isolating separation mechanism from liquid portion with the solid state peeled off.
In addition, the invention that technical scheme 11 is put down in writing has following feature in the retrieving arrangement of the indium from waste liquid crystal display that technical scheme 10 is put down in writing, and is zinc particles or aluminum particulate by compare the metallics that the bigger metal of ionization tendency constitutes with indium.The invention that technical scheme 12 is put down in writing has following feature in the retrieving arrangement of the indium from waste liquid crystal display that technical scheme 10 or 11 is put down in writing, be the mechanism that utilizes the ultra-sonic oscillation metallics from the mechanism that described metallics is peeled off with indium or the indium alloy that precipitate on the metallics; Or utilize electro-magnet to stir metallics and make it the mechanism of collision mutually.
Has following feature in the retrieving arrangement of invention any indium from waste liquid crystal display of being put down in writing in technical scheme 10 to 12 that technical scheme 13 is put down in writing, be provided with impurity and remove and use reactor reclaiming leading portion side with reactor, this impurity is removed with reactor and is comprised following mechanism, promptly, the indium compound solution that contains that utilizes the indium dissolver to obtain is flowed into, interpolation is by comparing the metallics that the bigger metal of ionization tendency constitutes with this indium foreign metal in addition that contains in the indium compound solution, this metallics is flowed, described foreign metal is separated out to the surface of described metallics, described foreign metal of separating out is peeled off and removed from described metallics.
In addition, the invention that technical scheme 14 is put down in writing has following feature in the retrieving arrangement of the indium from waste liquid crystal display that technical scheme 13 is put down in writing, be the mechanism that utilizes the ultra-sonic oscillation metallics from the mechanism that described metallics is peeled off with the foreign metal that precipitate on the metallics; Or utilize electro-magnet to stir metallics and make it the mechanism of collision mutually.In addition, the invention that technical scheme 15 is put down in writing has following feature in the retrieving arrangement of the indium from waste liquid crystal display that technical scheme 13 or 14 is put down in writing, and foreign metal is a tin.
In addition, the invention that technical scheme 16 is put down in writing has following feature in the retrieving arrangement of the indium from waste liquid crystal display that technical scheme 13 to 15 is put down in writing, be iron particle by compare the metallics that the bigger metal of ionization tendency constitutes with foreign metal.In addition, the invention that technical scheme 17 is put down in writing has following feature in the retrieving arrangement of the indium from waste liquid crystal display that technical scheme 16 is put down in writing, add alkali containing in the indium compound solution behind the foreign metal to having removed, iron is removed as precipitation of hydroxide.
The present invention as mentioned above, owing to be following method, promptly, the waste liquid crystal display (useless LCD) that will contain tin indium oxide is pulverized, from chippy useless LCD, use acid that tin indium oxide is dissolved, obtain containing indium compound solution, flow into and reclaim with in the reactor, and add by compare the metallics that the bigger metal of ionization tendency constitutes with indium (In) in reactor to this recovery, this metallics is flowed, the described In or the In alloy that are contained in the indium compound solution of containing separated out to the surface of described metallics, thereafter, utilize mechanism for stripping from described metallics, to peel off described In that separates out or In alloy, the In of the solid shape peeled off or In alloy are separated from liquid portion and reclaim, therefore can from useless LCD, dissolve ITO easily and effectively, because by displacement (cementation) reaction and the lift-off technology combination that in the recovery of the In from the liquid that has dissolved In, will utilize ionization tendency, promptly, by using metallics, the total surface area that is used for the metal of metal evolution reaction increases, evolution reaction speed improves, utilize mechanism for stripping to peel off by the precipitating metal to a certain degree of will having grown in addition, just can keep the speed of response of always exposing new metallic surface, therefore compare with in the past dry type and any method of wet type, the effect of the rate of recovery that can obviously improve the In from useless LCD is all arranged.That is, among the present invention, the In rate of recovery for from waste liquid can obtain the high-recovery more than 80%.
In addition, state with indium hydroxide reclaims as damp process in the past owing to not needing, and In can be reclaimed as precious metals, therefore when reclaiming, do not have the bad of processing as the situation of indium hydroxide, having can be with the effect of recovery easily such as strainer.
In addition, in the leading portion side that reclaims with reactor, be provided with to produce and remove with under the situation of reactor with the impurity of the identical metal evolution reaction of reactor with this recovery, by adding and the metal beyond the In contained in the indium compound solution of containing that from useless LCD, has dissolved tin indium oxide, for example the foreign metal of tin (Sn) and so on is compared the bigger metal of ionization tendency, iron metallicss such as (Fe) and make it mobile for example, foreign metals such as Sn contained in the described waste liquid are separated out to the surface of metallicss such as described iron, thereafter, utilize mechanism for stripping described foreign metal of separating out to be peeled off, just can will remove well as Sn of foreign metal etc. from described metallics.
So,, therefore have the effect that further improves by the purity that reclaims the In that reclaims with reactor owing to can under the state of the foreign metal beyond from waste liquid, having removed In such as Sn in advance, this waste liquid be supplied with to reclaiming with reactor.That is, be located at the leading portion side that reclaims with reactor, just can reclaim the highly purified In more than 95% by this kind impurity being removed with reactor.
In addition, though remove under the situation of having removed foreign metal with reactor at this kind of use impurity, the ion of the metal that described iron etc. added will stripping, yet by remove in the precipitation of its back segment in the device add alkali and with metals such as iron as precipitation of hydroxide, just can to reclaim supply with waste liquid with reactor before, remove the oxyhydroxide of de-iron etc. in advance.Under this situation, though when pH uprises, indium hydroxide might generate as precipitation, yet because for the throw out formation speed, ironic hydroxide one side is far faster than it, therefore the residence time of utilizing precipitation to remove in the device is controlled, and just can not generate indium hydroxide, and In is not supplied with reactor to following recovery basically with losing.In addition, even because the part of In exists in solution as indium hydroxide, and the recovery by below is with adjusting pH in the reactor, indium hydroxide is solution once more, does not therefore have the situation of the rate of recovery of reduction In.
In addition, under the LCD that will give up is contained in state in the bag always, utilize the In stripping of acid to handle, clean under the situation of neutralizing treatment, drying treatment, chippy fine useless LCD in useless LCD pulverizing process can be contained in the bag always always handle, have the effect that to simplify processing as a whole.In addition, owing to do not need the fine useless LCD sheet that receives from useless LCD pulverizing process is disposed as powder, therefore have and do not have the property the handled situation of difficult that becomes.
As mentioned above, owing to utilize the present invention, can provide the rate of recovery high In recovery method, therefore even in household electrical appliances recycle method in the future, under the situation of the obligated recycle and reuse of carrying out LCD of regulation, just have the practical advantages that the present invention can be used as the In recovery method of the recycle process in the recycle factory of LCD TV.
Description of drawings
Fig. 1 is the general block diagram as the In retrieving arrangement from useless LCD of an embodiment.
Fig. 2 is that the impurity of identical In retrieving arrangement is removed with reactor or reclaimed diagrammatic elevational view with reactor.
Fig. 3 is that the impurity of other embodiments is removed the general principal view of using reactor with reactor or recovery.
Fig. 4 is that the impurity of other embodiments is removed the general principal view of using reactor with reactor or recovery.
Fig. 5 is the approximate vertical view of the slide plate that has possessed electro-magnet used in the embodiment of Fig. 4.
Fig. 6 is the general block diagram of the In retrieving arrangement of other embodiments of expression.
Fig. 7 is the summary section of the stripping treatment unit of same apparatus.
Fig. 8 is the diagrammatic illustration figure of device used among the embodiment.
Wherein, 2 ... impurity is removed and is used reactor, 3 ... precipitation is removed device, 4 ... the recovery reactor
Embodiment
Below with reference to accompanying drawings embodiments of the present invention are described.
(embodiment 1)
The retrieving arrangement of the indium from useless LCD of present embodiment comprises as shown in Figure 1: use hydrochloric acid with ITO dissolved indium dissolver (below be also referred to as the In dissolver) 1 from useless LCD; Remove with reactor 2 to remove the impurity that the foreign metal beyond the In uses with adding iron particle (Fe particle) in the indium compound solution containing of this In dissolver 1 lysed In of containing; To remove with this impurity and remove the precipitation that the described Fe particle in the waste liquid of foreign metal removes as the precipitation of hydroxide of iron (Fe) with reactor 2 and remove device 3; From the waste liquid of removing the oxyhydroxide that device 3 precipitation removed Fe with this precipitation, reclaim recovery that In uses with reactor 4.And, at the leading portion of In dissolver 1, though not shown, be provided with the pulverizer that useless LCD is pulverized.And so-called pulverizer is meant useless LCD is broken into pieces among the present invention, no matter the size of the fragment that this quilt has been broken into pieces for example also comprises being considered in general be meant such pulverizing state of breaking into pieces to broken end finely.
In dissolver 1 is from being utilized hydrochloric acid (aqueous hydrochloric acid) with the In dissolving the chippy useless LCD, being used to obtain to contain the device of indium compound solution.Containing indium compound solution is modulated to In content and reaches 100～300mg/L.In addition, this contains the concentration that indium compound solution is modulated to hydrochloric acid and reaches 20%, and the pH of hydrochloric acid reaches 1.5.
It is to be used for removing device as the Sn of impurity from the described indium compound solution that contains that impurity is removed with reactor 2, as shown in Figure 2, comprises vertically long reactor body 5.This reactor body 5 is made of reactor top 6, reactor pars intermedia 7 and reactor lower part 8 as shown in the figure, is connected by the portion of being connected with 9,10 respectively to be provided with.Though reactor top 6, reactor pars intermedia 7 and reactor lower part 8 are made into same widths respectively, but the sectional area on reactor top 6 is made into the sectional area greater than reactor pars intermedia 7, and the sectional area of reactor pars intermedia 7 is made into the sectional area greater than reactor lower part 8.Consequently, be constituted as a whole, the sectional area of reactor body 5 increases discontinuously towards the top.And, be connected with the taper that portion 9,10 is made into upwards to broaden.
At the downside of reactor lower part 8, be provided with the approximate conical inflow cell 11 that contains indium compound solution that is used to flow into as process object, be provided with inflow pipe 12 in addition in its underpart.On inflow pipe 12, though not shown, be provided with vacuum breaker.In addition, the upside on reactor top 6 is provided with top cell 13, at its sidepiece, is provided with that the Sn that is used to make as foreign metal separates out and the vent pipe 14 of discharging on metallics (Fe particle).Top cell 13 is to be used to the part of utilizing this kind vent pipe 14 that Sn is discharged with the Fe particle, and also is the part that drops into based on produce the Fe particle of so-called replacement(metathesis)reaction (metal evolution reaction) usefulness with the difference of the ionization tendency of the Sn that removes as impurity.In fact, the replacement(metathesis)reaction of Fe and Sn is to produce in the integral body of described reactor 1.
In addition, also by following formation, that is, and flow into from inflow pipe 12 contain indium compound solution and arrive vent pipe 14 during, this waste liquid forms the fluidized-bed of Fe particle when vertically rising.In addition, on reactor top 6, reactor pars intermedia 7 and reactor lower part 8 be respectively equipped with ultra-sonic oscillation body 15a, 15b, 15c as mechanism for stripping, they will be peeled off as contain the Sn that the described replacement(metathesis)reaction of utilizing of foreign metal contained in the indium compound solution separates out on described Fe.
In the present embodiment,, use the Fe particle as mentioned above as input metallics.Though the median size of Fe particle is preferably used the metallics of 0.1～8mm, yet in the present embodiment, can use median size to be about 3mm's.And median size can be utilized image analysis method or JIS Z 8801 size analysis methods to wait and measure.
It is to be used for device that described Fe particle is removed as precipitation of hydroxide that precipitation is removed device 3.The precipitation of oxyhydroxide is removed and can be undertaken by adding alkali (alkaline solution) such as sodium hydroxide.The pH that this precipitation is removed the waste liquid in the device 3 is adjusted to 8～9.
Reclaiming with reactor 4 is to be used for from having removed the Sn as impurity as described above, and the device that contains recovery In in the indium compound solution after Fe is removed as precipitation of hydroxide forms by removing with reactor 2 identical constituting with described impurity.That is as shown in Figure 2, be to comprise the device that reactor top 6, reactor pars intermedia 7, reactor lower part 8 is connected the reactor body 5 that is provided with and constitutes by the portion of being connected with 9,10.This reclaims with in the reactor 4, and pH is adjusted to below 1.5.
Be provided with inflow aspect cell 11, inflow pipe 12, top cell 13, vent pipe 14, and be respectively equipped with aspect ultrasonic oscillator 15a, 15b, the 15c at reactor top 6, reactor pars intermedia 7 and reactor lower part 8, all remove with reactor 2 identical with impurity.
In addition, if the method for utilizing the In retrieving arrangement from useless LCD of planting formation formation thus to reclaim In from useless LCD is described, the LCD that then at first will give up pulverizer (not shown) pulverizing is supplied with chippy useless LCD to In dissolver 1.Add hydrochloric acid (aqueous hydrochloric acid) in this In dissolver 1, utilize this hydrochloric acid stripping In from useless LCD, what obtain In content and be 100～300mg/L in described In dissolver 1 contains indium compound solution.
Then, this being contained indium compound solution removes with reactor 2 supplies to impurity.Remove the indium compound solution of supplying with reactor 2 that contains to impurity and remove the inflow pipe 12 of usefulness reactor 2 from impurity via in flowing into cell 11 inflow reactor main bodys 5.On the other hand, drop into the metallics (Fe particle) that is used to produce replacement(metathesis)reaction from top cell 13.In reactor body 5, the indium compound solution that contains that is flowed into vertically rises, and on the other hand, this contains indium compound solution becomes flow state with the Fe particle that drops into from top cell 13 in the mode that forms fluidized-bed.
In addition, be Sn based on the foreign metal that contains beyond the In contained in the indium compound solution, the difference with as the ionization tendency of the Fe of input metallics produces so-called replacement(metathesis)reaction.If it is described in more detail, then each reduction of metal ion reaction is shown below, and expression has the standard potential (E of each metal ion respectively
0).
Fe
2++2e→Fe…(1)-0.44V
Sn
2++2e→Sn…(2)-0.14V
From described (1), (2), can see, with Sn
2+Compare Fe
2+Standard potential littler.In other words, compare with Sn, the ionization tendency of Fe is bigger.Thus, under the state that has become aforesaid flow state, the Fe that ionization tendency is big becomes Fe
2+(with the opposite reaction of described (1) formula) and stripping in containing indium compound solution meanwhile, contains Sn contained in the indium compound solution
2+Become Sn, on the surface of the particle of Fe, separate out.
After this, utilizing this kind replacement(metathesis)reaction to make Sn after separating out on the surface of Fe particle, making ultra-sonic oscillation body 15a, 15b, 15c action.By making this ultra-sonic oscillation body 15a, 15b, 15c action, will give oscillation force and whipping force to described Fe particle of having separated out Sn by the ultrasonic wave that produces among this ultra-sonic oscillation body 15a, 15b, the 15c, the Sn that is separated out forcibly will be peeled off from the Fe particle thus.
The Sn that has so been peeled off discharges to the outside of reactor body 5 through vent pipe 14 from top cell 13, and the result just removed from contain indium compound solution.Under this situation, in the present embodiment, owing to as using emboliform material in order to remove the metal (Fe) that foreign metal drops into, therefore for example compare with such situation such as the bulk that drops into iron, the surface-area that is used to produce the metal (Fe) of replacement(metathesis)reaction increases, and the speed of the evolution reaction of Sn improves.In addition, after having seen the separating out of the metal to a certain degree of having grown, utilize aforesaidly, just can always expose new metallic surface (surface of Fe particle), keep speed of response by enforceable the peeling off that hyperacoustic vibration caused.
In addition, because the metallics that is made of Fe flows in reactor body 5, utilize aforesaid replacement(metathesis)reaction to make Fe
2+Stripping, the particle diameter of input during the initial stage that has therefore been dropped into the metallics of top cell 13 just must reduce along with the process of time.Consequently, because original words waste liquid is to rise reactor body 5 in the roughly the same speed to the upper reaches, so flow to more that the top particle diameter reduces more and the just overflow from reactor body 5 absent-mindedly of metallics that diminishes.
But, in the present embodiment, because the sectional area of reactor body 5 is made, more towards the top, then become big discontinuously, so the speed to the upper reaches of the waste liquid in the reactant main body 5 reduces at leisure, so make the top of the reactor body 5 that metallics that particle diameter reduced increases in the sectional area trend as mentioned above because of replacement(metathesis)reaction etc., the situation of overflow absent-mindedly can not take place, and the possibility that is held in the reactor body 5 improves.
In addition, containing of the lower side inflow of indium compound solution from reactor body 5, in in the reactor body 5, owing to utilize replacement(metathesis)reaction on the metallics that constitutes by Fe, to separate out the metals such as Sn that become object, therefore the top of orientating reaction device main body 5, the concentration that then contains the foreign metal in the indium compound solution is just more for reducing.
But, in the present embodiment, because on the top of reactor body 5, then exist and be fine metallics more, in addition, the speed to the upper reaches that contains indium compound solution reduces at leisure, thereby the number that can confirm metallics increases, therefore on the top of reactor body 5, then the total surface area of metallics is just big more.Consequently, because the speed of response (efficient that foreign metal is separated out) of replacement(metathesis)reaction improves, even therefore reach the top of the reactor body 5 of lower concentration, also Ni, the Sn as foreign metal can be removed from waste liquid effectively in the concentration of foreign metal.
Then, the indium compound solution that contains of having removed Sn is removed device 3 supplies to precipitation.Remove in the device 3 in this precipitation, be added with alkali such as sodium hydroxide (alkaline solution).Like this, will generate the oxyhydroxide of Fe and the solid substance of indium hydroxide.That is, remove with in the reactor 2 at described impurity, Sn separates out on the particle of Fe because of replacement(metathesis)reaction and is removed, on the other hand ion (the Fe of Fe
2+) stripping in containing indium compound solution.So, this Fe
2+Before the recovery to back segment contains indium compound solution with reactor 4 supplies, also need from contain indium compound solution, to remove in advance.So, though can generate the oxyhydroxide of Fe and the solid substance of indium hydroxide by adding aforesaid alkali, yet because the throw out formation speed of the oxyhydroxide of Fe is far faster than indium hydroxide, therefore remove residence time etc. of the processed liquid in the device 3 by being controlled at precipitation as the coagulative precipitation groove, just can remove device 3 oxyhydroxide of this Fe is easily removed with precipitation.
Then, after containing indium compound solution to be adjusted into pH be to dissolve once more below 1.5 and with indium hydroxide behind the oxyhydroxide of precipitation having been removed Fe, supply with to reclaiming with reactor 4.Remove with the situation of reactor 2 identically to reclaiming contain indium compound solution and the impurity supplied with reactor 4, use cell 11 via inflow and in the inflow reactor main body 5 from inflow pipe 12.On the other hand, drop into the metallics (Zn particle or Al particle) that is used to produce replacement(metathesis)reaction from top cell 13.The situation of removing with reactor 2 with impurity is identical, and in reactor body 5, containing of being flowed into, indium compound solution rose and the metallics that drops into from top cell 13 becomes flow state.
After this, the In and difference as the ionization tendency of the Zn of input metallics or Al in the indium compound solution of containing based on as the object that reclaims produces so-called replacement(metathesis)reaction.Each reduction of metal ion reaction is shown below, and expression has the standard potential (E of each metal ion respectively
0).
In
3++3e→In…(3)-0.34V
Zn
2++2e→Zn…(4)-0.76V
Al
3++3e→Al…(5)-1.66V
From described (3)～(5), can see, with In
3+Compare Zn
2+Or Al
3+Standard potential littler.In other words, compare with In, the ionization tendency of Zn or Al is bigger.Thus, under the state that has become aforesaid flow state, Zn or Al that ionization tendency is big become Zn
2+Or Al
3+(with described (4), the opposite reaction of (5) formula) and stripping in containing indium compound solution meanwhile, contains In contained in the indium compound solution
3+Become In, on the surface of the particle of Zn or Al, separate out.
After this, utilizing this kind replacement(metathesis)reaction to make In after separating out on the surface of Zn or Al particle, making ultra-sonic oscillation body 15a, 15b, 15c action.By making this ultra-sonic oscillation body 15a, 15b, 15c action, will give oscillation force and whipping force to described Zn or Al particle of having separated out In by the ultrasonic wave that produces among this ultra-sonic oscillation body 15a, 15b, the 15c, the In that is separated out forcibly will be peeled off on Zn or Al particle thus.
The In that has so been peeled off discharges to the outside of reactor body 5 through vent pipe 14 from top cell 13, In will be reclaimed as precious metals like this.Under this situation, in the present embodiment, owing to remove with the situation of the iron of reactor 2 as input Zn or Al and described impurity and to use emboliform material in the same manner, therefore be used to produce the long-pending increase of metallic surface of replacement(metathesis)reaction, the speed raising of the evolution reaction of In.
In addition, after having seen the separating out of the metal to a certain degree of having grown, utilize aforesaidly by enforceable the peeling off that hyperacoustic vibration caused, speed of response is kept on the surface that just can always expose the particle of new Zn or Al.
In addition, owing to utilize replacement(metathesis)reaction stripping Zn from the particle of Zn or Al
2+Or Al
3+, the particle diameter of input during the initial stage that has therefore been dropped into the particle of the Zn of top cell 13 or Al just must reduce along with the process of time.Consequently, because to contain indium compound solution is to rise reactor body 5 in the roughly the same speed to the upper reaches to original words, so flow to more that the top particle diameter reduces more and the Zn that diminishes or the just overflow from reactor body 5 absent-mindedly of particle of Al.
But, in the present embodiment, because the sectional area of reactor body 5 is made, more towards the top, then become big discontinuously, so the speed to the upper reaches that contain indium compound solution in the reactant main body 5 reduce at leisure, so make the top of the reactor body 5 that metallics that particle diameter reduced increases in the sectional area trend as mentioned above because of replacement(metathesis)reaction etc., overflow carefully, the possibility that is held in the reactor body 5 improves.
In addition, containing of the lower side inflow of indium compound solution from reactor body 5, in in the reactor body 5, owing to utilize replacement(metathesis)reaction on the particle of Zn or Al, to separate out the In that becomes object, therefore the top of orientating reaction device main body 5, the concentration that then contains the In in the indium compound solution is just more for reducing.
But, in the present embodiment, because on the top of reactor body 5, then exist and be fine Zn or the particle of Al more, in addition, the speed to the upper reaches that contains indium compound solution reduces at leisure, thereby the number that can confirm Zn or Al particle increases, therefore on the top of reactor body 5, then the total surface area of Zn or Al particle is just big more.Consequently, because the speed of response (efficient that In separates out) of replacement(metathesis)reaction improves,, also the In as recycle object can be reclaimed from contain indium compound solution effectively even therefore reach the top of the reactor body 5 of lower concentration in the concentration of In.
(embodiment 2)
The impurity of present embodiment is removed with reactor 2 and is reclaimed with the structure of the reactor body 5 of reactor 4 different with described embodiment 1.That is, in the present embodiment, constitute as shown in Figure 3, the side face integral body of reactor body 5 is made up become taper, the sectional area of reactor body 5 increases towards the top continuously.In this, the situation of the embodiment 1 that increases upward discontinuously with the sectional area of reactor body 5 is different.
Owing to be not discontinuously, constitute but make sectional area increase ground continuously towards the top, so be not in the present embodiment as embodiment 1, divide into reactor top 6, reactor pars intermedia 7, reactor lower part 8 and constitute.
But, be provided with on ultra-sonic oscillation body 15a, 15b, the 15c this point up to 3 positions of bottom on top from reactor body 5, with embodiment 1 be common.So, in the present embodiment, also identical with embodiment 1, can obtain following effect, promptly, can utilize the ultrasonic wave that produces by ultra-sonic oscillation body 15a, 15b, 15c, the Sn of the foreign metal that the conduct that will separate out should be removed or forcibly peel off as the In of recycle object metal on metallics.
In addition, though owing to have is discontinuous or successive difference, yet sectional area by towards above with increasing formation on this point be and embodiment 1 common, therefore in the present embodiment, also can produce following effect, that is, the fine metallics that particle diameter can have been reduced remains on the top of reactor body 5, prevents overflow absent-mindedly; And can be that the top of the reactor body 5 of lower concentration is removed effectively or recycled the object metal in the object concentration of metal.
(embodiment 3)
In the present embodiment, as with precipitating metal from the mechanism that metallics is peeled off, replace the mechanism that the ultrasonic wave of utilizing the ultra-sonic oscillation body to produce of described embodiment 1 and 2 is vibrated, and adopted the mechanism that uses electro-magnet to stir.That is, in the present embodiment,, the slide plate 17 that has possessed electro-magnet 16 as shown in Figure 5 is installed free lifting being located at as shown in Figure 4 on the guide rail 18 of side that the horizontal section is rectangular reactor body 5.Slide plate 17 has spatial portion 19 in central authorities as shown in Figure 5, is set to insert reactor body 5 in this spatial portion 19 this reactor body 5 is surrounded.And used metallics is iron as magnetic substance etc. in the present embodiment.
In addition, shown in the arrow 20 of Fig. 4, by mobile alternately up and down, and the metallics in the stirred reactor 5, and a plurality of metallicss are collided mutually, thus precipitating metal is forcibly peeled off from metallics.Though mechanism's difference of precipitating metal being peeled off from the metallics, in the present embodiment, also precipitating metal can be peeled off from the metallics well and carry out well foreign metal remove or as the recovery of the In of precious metals.
(embodiment 4)
In the present embodiment, to be contained at the LCD that will give up under the state in the bag always, the situation of utilizing sour In stripping to handle, clean neutralizing treatment, drying treatment describes.In the retrieving arrangement of the indium from useless LCD of present embodiment, as shown in Figure 6, possess stripping treatment unit 25, clean neutralizing treatment device 26 and drying treatment 27.Stripping treatment unit 25 possesses stripping processing vessels 22 such as FRP system jar as shown in Figure 7.This stripping processing vessel 22 is made into to be housed in the size of having accommodated the object of useless LCD in the resin system of flexible container and so on, the fabric bag 21.In addition, in the bottom of described stripping processing vessel 22, be provided with porous plate 23 and porous plate supporting mass 24.In addition, described bag 21 is maintained on this porous plate 23.
After this, under the state of the chippy useless LCD of pulverizer in being contained in described bag 21, the hydrochloric acid soln of usefulness is leached in circular treatment In dissolving,, from useless LCD the In dissolving is leached in useless LCD layer 28 at hydrochloric acid soln.That is to say, from useless LCD, use dissolving with hydrochloric acid silver suboxide tin, obtain containing indium compound solution.
On the other hand, under the state of useless LCD in still being contained in bag 21 after dissolving leach to be handled, move with treatment unit 26, be contained in this cleaning and neutralize interior and clean neutralizing treatment with treatment unit 26 to following cleaning neutralization.Describedly carry out to the mobile lift etc. of utilizing that cleans neutralizing treatment device 26 from stripping treatment unit 25.Identical with the In dissolution process, water carries out circular treatment during clean, carries out circular treatment with basic solution during neutralizing treatment.The logical liquid direction of the circular treatment under this situation both can also can be carried out to ground, upper reaches to scurrilously carrying out.The useless LCD of the cleaning neutralizing treatment that is through with moves to drying process device 27 under still taking in the state that remains in the bag.Though this drying process device 27 for example can utilize air stream drying to carry out drying treatment, also can not use this kind drying process device 27, for example utilize drying meanss such as solar drying to carry out drying treatment.Under the state of useless LCD in still remaining in bag 21 after drying treatment finishes, be used as the recycle raw material and transport to Bricks and Tiles Plant, glass works etc.
In the present embodiment, can simplify processing by will be in useless LCD pulverizing process be contained in always to handle in the aforesaid bag 21 always by chippy fine useless LCD.In addition, owing to do not need and to dispose as powder from the fine useless LCD sheet that useless LCD pulverizing process receives, therefore do not have the property the handled situation of difficult that becomes yet.
And, as long as bag 21 has the mesh (porousness) that can not make the degree that useless LCD comes off, with fabric and so on bag with regard to enough.Both can be the whole porousness of bag, and also can only the bottom surface sections of bag 21 have been made in addition and have porousness with degree that hydrochloric acid soln can pass through.No matter under which kind of situation, because by bag 21 is set on the porous plate in stripping treatment unit 22 23, deadweight with the useless LCD in the bag 21 is connected airtight the bag and the wall of stripping processing vessel 22, hydrochloric acid soln passes useless LCD layer and moves to the bottom of stripping processing vessel 22 through porous plate 23 from the bottom surface sections of bag 21, therefore just can utilize circular treatment from useless LCD In to be dissolved and leach processing.
(other embodiment)
And, in the described embodiment, though to as from useless LCD, using dissolving with hydrochloric acid ITO contain foreign metal beyond the In contained in the indium compound solution, the situation of removing Sn is illustrated, yet also can remove the metal beyond the Sn.Under this situation, also can add Fe metallics in addition.
In addition, in this embodiment, though to In is precipitate on the metallics, the situation that this In that separates out is peeled off from metallics is illustrated, yet be not limited to as the monomeric In of metal, at the alloy that makes In and other metal, promptly the In alloy is separated out on metallics, under the situation that this In alloy of separating out is peeled off from metallics, also can use the present invention.
In addition, in the described embodiment, though used hydrochloric acid as the acid of dissolving ITO from useless LCD, kind that should acid is not limited to hydrochloric acid, for example also can use sulfuric acid, nitric acid etc., perhaps also can use mixing acid etc.
In addition, in the described embodiment,, this kind impurity is set removes with the also nonessential in the present invention condition of reactor 2 though remove with reactor 2 and can obtain aforesaid ideal effect by aforesaid impurity is set.In addition, in the described embodiment, though the situation that the particle that adds Zn or Al is reclaimed In is illustrated, but add to reclaim and be not limited to the Zn of this embodiment or the particle of Al with the metallics in the reactor, in brief, as long as the bigger metal of ionization tendency is compared in use with In.
In addition, in this embodiment, though the particle diameter of metallics is made as about 3mm, the particle diameter of metallics is not limited to this embodiment, preferred 0.1～8mm.This be because, when less than 0.1mm, not only not necessarily can carry out replacement(metathesis)reaction well, and might easily carry out the recovery of the precipitating metal peeled off from metallics, in addition when surpassing 8mm, the reduced number of the metallics that can in reactor body, keep then, the total surface area of metallics reduces and the efficient of evolution reaction is reduced as a result, might separate out on metallics as the metal beyond precious metals that reclaims purpose or the foreign metal in addition.
In addition, then big more towards top more in the described embodiment 1,2 owing to the sectional area of reactor body 5 is made, therefore can obtain aforesaid ideal effect, but form the also nonessential in the present invention condition of reactor body 5 like this.In addition, also be not limited to the mechanism that utilizes electro-magnet that utilizes hyperacoustic mechanism or embodiment 3 of described embodiment 1,2, mechanism that also can be in addition from the mechanism that metallics is peeled off precipitating metal.
Embodiment
The hydrochloric acid soln of use 1%, 3%, 10% has carried out being used for the In dissolving leaching processing of In recycling with device as shown in Figure 8.Among Fig. 8,28 are illustrated in the useless LCD layer that also illustrated among Fig. 7,29 expression in-line pumps, 30 expression hydrochloric acid, 31 expression resin containers, 32 expression mesh cages.According to analysis, useless LCD contains the In of 400mg/kg.It is that useless LCD24kg is remained in the cotton bag that stripping is handled, this is packedly gone into offering in the resin container 31 in a plurality of holes in the bottom surface of being placed on the mesh cage 32 in being located at the 100L resin container as shown in Figure 8, drop into hydrochloric acid 14L, use in-line pump (tube pump) 29 at room temperature to carry out circular treatment.In order not change during handling in stripping because of moisture evaporation makes concentration of hydrochloric acid, amount, on the lid of 100L resin container, possesses liner, the insertion taking-up portion of the in-line pump 29 of the lid that seals between 100L resin container and the lid can have been used with the hermetically sealed member of spackling.
Test-results is shown in the table 1.
Table 1
| 1% |
3% |
10% hydrochloric acid soln | |
| Dissolution time 24Hr | In concentration 670ppm | In concentration 680ppm | In concentration 680ppm |
| Dissolution time 48Hr | In concentration 680ppm | In concentration 685ppm | In concentration 685ppm |
| The In rate of recovery | More than 99% | More than 99% | More than 99% |
From table 1, can see, in handling arbitrarily, utilize 24 hours stripping to handle, can obtain the In rate of recovery enough more than 98%.And the rate of recovery is according to useless LCD weight and In oil length and In concentration, hydrochloric acid content in the hydrochloric acid after handling are calculated.
Claims (17)
1. the recovery method of the indium from waste liquid crystal display, it is characterized in that, the waste liquid crystal display that will contain tin indium oxide is pulverized, from chippy waste liquid crystal display, use acid that tin indium oxide is dissolved, obtain containing indium compound solution, make this contain indium compound solution and flow into recovery with in the reactor, and add by compare the metallics that the bigger metal of ionization tendency constitutes with indium in reactor to this recovery, this metallics is flowed, the described indium or the indium alloy that are contained in the indium compound solution of containing separated out to the surface of described metallics, thereafter, utilize the mechanism for stripping from described metallics, to peel off described indium of separating out or indium alloy, the indium of the solid shape peeled off or indium alloy are separated from liquid portion and reclaim.
2. the recovery method of the indium from waste liquid crystal display according to claim 1 wherein, is zinc particles or aluminum particulate by compare the metallics that the bigger metal of ionization tendency constitutes with indium.
3. the recovery method of the indium from waste liquid crystal display according to claim 1 and 2 wherein, is the mechanism that utilizes the ultra-sonic oscillation metallics from the mechanism that described metallics is peeled off with indium or the indium alloy that precipitate on the metallics; Or utilize electro-magnet to stir metallics and make it the mechanism of collision mutually.
4. according to the recovery method of any described indium from waste liquid crystal display in the claim 1 to 3, wherein, flow into to reclaim with before in the reactor at the indium compound solution that contains that will from waste liquid crystal display, dissolve tin indium oxide, making this contain indium compound solution inflow impurity removes with in the reactor, add described impurity to and remove compare metallics that the bigger metal of ionization tendency constitutes by the foreign metal beyond containing indium in the indium compound solution with this with in the reactor, this metallics is flowed, described foreign metal is separated out to the surface of described metallics, utilize mechanism for stripping from described metallics described foreign metal of separating out peeled off and remove thereafter.
5. the recovery method of the indium from waste liquid crystal display according to claim 4 wherein, is the mechanism that utilizes the ultra-sonic oscillation metallics from the mechanism that described metallics is peeled off with the foreign metal that precipitate on the metallics; Or utilize electro-magnet to stir metallics and make it the mechanism of collision mutually.
6. according to the recovery method of claim 4 or 5 described indiums from waste liquid crystal display, wherein, foreign metal is a tin.
7. according to the recovery method of any described indium from waste liquid crystal display in the claim 4 to 6, wherein, be iron particle by compare the metallics that the bigger metal of ionization tendency constitutes with foreign metal.
8. the recovery method of the indium from waste liquid crystal display according to claim 7 wherein, adds alkali to having removed containing in the indium compound solution behind the foreign metal, and iron is removed as precipitation of hydroxide.
9. the recovery method of the indium from waste liquid crystal display, it is characterized in that, the waste liquid crystal display that will contain tin indium oxide is pulverized, under the state that chippy waste liquid crystal display is contained in the bag, from this waste liquid crystal display, use sour dissolved oxygen indium tin, obtain containing indium compound solution, on the other hand, the waste liquid crystal display of being accommodated in the described bag is cleaned neutralizing treatment, carry out drying treatment thereafter.
10. the retrieving arrangement of the indium from waste liquid crystal display is characterized in that, comprising:
The pulverizer that will contain the waste liquid crystal display pulverizing of tin indium oxide;
Use acid the tin indium oxide dissolving to be obtained containing the indium dissolver of indium compound solution to chippy waste liquid crystal display;
Inflow utilizes that this indium dissolver obtains contains indium compound solution, and add by compare the metallics that the bigger metal of ionization tendency constitutes, the recovery reactor that the metal evolution reaction that indium or indium alloy are separated out to the surface of described metallics is used with described indium;
For reclaiming described indium of separating out or indium alloy, and it is peeled off the mechanism for stripping of usefulness from described metallics;
Indium or indium alloy isolating separation mechanism from liquid portion with the solid state peeled off.
11. the retrieving arrangement of the indium from waste liquid crystal display according to claim 10 wherein, is zinc particles or aluminum particulate by compare the metallics that the bigger metal of ionization tendency constitutes with indium.
12., wherein, be the mechanism that utilizes the ultra-sonic oscillation metallics from the mechanism that described metallics is peeled off with indium or the indium alloy that precipitate on the metallics according to the retrieving arrangement of claim 10 or 11 described indiums from waste liquid crystal display; Or utilize electro-magnet to stir metallics and make it the mechanism of collision mutually.
13. retrieving arrangement according to any described indium from waste liquid crystal display in the claim 10 to 12, wherein, be provided with impurity and remove and use reactor reclaiming leading portion side with reactor, this impurity is removed with reactor and is comprised following mechanism, promptly, the indium compound solution that contains that utilizes the indium dissolver to obtain is flowed into, interpolation is by comparing the metallics that the bigger metal of ionization tendency constitutes with this indium foreign metal in addition that contains in the indium compound solution, this metallics is flowed, described foreign metal is separated out to the surface of described metallics, described foreign metal of separating out is peeled off and removed from described metallics.
14. the retrieving arrangement of the indium from waste liquid crystal display according to claim 13, wherein, be to utilize the mechanism of ultra-sonic oscillation metallics or utilize electro-magnet to stir metallics and make it the mechanism of collision mutually the foreign metal that precipitate on the metallics from the mechanism that described metallics is peeled off.
15. according to the retrieving arrangement of claim 13 or 14 described indiums from waste liquid crystal display, wherein, foreign metal is a tin.
16., wherein, be iron particle by compare the metallics that the bigger metal of ionization tendency constitutes with foreign metal according to the retrieving arrangement of any described indium from waste liquid crystal display in the claim 13 to 15.
17. the retrieving arrangement of the indium from waste liquid crystal display according to claim 16, it comprises to having removed and adds alkali containing in the indium compound solution behind the foreign metal, and the precipitation that iron is removed as precipitation of hydroxide is removed device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011481A (en) * | 2016-06-30 | 2016-10-12 | 华南理工大学 | Method for recovering indium (In) from waste liquid crystal displays |
| DE102020100243A1 (en) | 2020-01-08 | 2021-07-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Process for reconditioning glass-plastic-metal composite materials |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5016895B2 (en) * | 2006-03-06 | 2012-09-05 | 株式会社神鋼環境ソリューション | Indium recovery method and apparatus |
| JP5068772B2 (en) * | 2007-01-23 | 2012-11-07 | シャープ株式会社 | Method for recovering indium from an etching waste solution containing indium and ferric chloride |
| JP2008208396A (en) * | 2007-02-23 | 2008-09-11 | Kobelco Eco-Solutions Co Ltd | Method for collecting indium, and apparatus therefor |
| JP2009155717A (en) * | 2007-12-28 | 2009-07-16 | Dowa Eco-System Co Ltd | Method for recovering indium |
| JP5217480B2 (en) * | 2008-02-14 | 2013-06-19 | 住友金属鉱山株式会社 | Recovery method of crude indium |
| CN101690936B (en) * | 2009-10-16 | 2011-06-15 | 清华大学 | Resourceful treatment method of waste thin film transistor liquid crystal monitor |
| FI122676B (en) * | 2010-10-12 | 2012-05-15 | Outotec Oyj | Method for treating a solution containing zinc sulphate |
| KR101308972B1 (en) * | 2011-05-31 | 2013-09-16 | 강릉원주대학교산학협력단 | Adsorbent having selective adsorption and preparing method of the same and recovery method of indium from wasted portabel device using the adsorbent |
| KR101289987B1 (en) * | 2011-06-29 | 2013-07-26 | 엘지디스플레이 주식회사 | Method for recovering valuable metal in lcd waste glass |
| CN103157646B (en) * | 2011-12-14 | 2015-08-19 | 格林美股份有限公司 | A kind of integrated conduct method of waste liquid crystal display |
| AP2014007781A0 (en) * | 2011-12-15 | 2014-07-31 | Advanced Tech Materials | Apparatus and method for stripping solder metals during the recycling of waste electrical and electronic equipment |
| JP5713946B2 (en) * | 2012-03-27 | 2015-05-07 | 三菱電機株式会社 | Method for recovering metal component in oxide semiconductor |
| CN103331295B (en) * | 2012-04-24 | 2015-05-20 | 合肥工业大学 | Industrialized recovery method and apparatus of waste liquid crystal display glass panel |
| JP5971521B2 (en) * | 2012-08-23 | 2016-08-17 | 住友電気工業株式会社 | Metal manufacturing method |
| CN102925696B (en) * | 2012-10-29 | 2014-04-02 | 四川长虹电器股份有限公司 | Comprehensive recycling method of waste plasma screen |
| CN103103356B (en) * | 2012-11-09 | 2014-12-10 | 柳州百韧特先进材料有限公司 | Process for recovering crude indium and tin from ITO (indium tin oxide) waste target |
| HK1177382A2 (en) * | 2012-12-21 | 2013-08-23 | Li Tong H K Telecom Company Ltd | A system and method for processing objects having chemical contaminates |
| CN103436692B (en) * | 2013-09-02 | 2016-01-20 | 沈阳隆基电磁科技股份有限公司 | A kind of electromagnetic oscillation treatment unit and method |
| 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 |
| FR3017883A1 (en) | 2014-02-27 | 2015-08-28 | Centre Nat Rech Scient | METHOD FOR TREATING AN ELEMENT COMPRISING AT LEAST ONE FIRST MEDIUM WHOSE FACE IS AT LEAST PARTIALLY COVERED WITH A LAYER OF INDIUM OXIDES AND TIN (ITO) |
| FR3025806B1 (en) * | 2014-09-15 | 2019-09-06 | Bigarren Bizi | PROCESS FOR PROCESSING AND EXTRACTING ELECTRONIC WASTE FOR RECOVERING COMPONENTS INCLUDED IN SUCH WASTE |
| CN104498721A (en) * | 2015-01-08 | 2015-04-08 | 中国科学院城市环境研究所 | Innocent treatment method and system for liquid crystal panel |
| TWI748686B (en) * | 2020-10-14 | 2021-12-01 | 遠東科技大學 | Method and device for separating oxide film from surface of indium-bismuth alloy |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054513A (en) * | 1973-07-10 | 1977-10-18 | English Clays Lovering Pochin & Company Limited | Magnetic separation, method and apparatus |
| JPS55141530A (en) * | 1979-04-21 | 1980-11-05 | Fujisash Co | Reducing method of heavy metal ion |
| JPS5831049A (en) * | 1981-08-18 | 1983-02-23 | Sumitomo Metal Mining Co Ltd | Collecting method of high purity indium from sulfuric acid acidic solution containing indium |
| JPS6056031A (en) * | 1983-09-05 | 1985-04-01 | Dowa Mining Co Ltd | Method for recovering ge, ga and in from substance containing trace of ge, ga and in |
| JP2649148B2 (en) * | 1995-01-27 | 1997-09-03 | 小島プレス工業株式会社 | Vehicle outside handle |
| JPH09268334A (en) * | 1996-04-04 | 1997-10-14 | Mitsui Mining & Smelting Co Ltd | Method for recovering indium |
| JP3173404B2 (en) * | 1997-01-22 | 2001-06-04 | 三菱マテリアル株式会社 | How to recover indium |
| WO1998050304A1 (en) * | 1997-05-08 | 1998-11-12 | Mitsubishi Chemical Corporation | Method for treating selenium-containing solution |
| JP3602329B2 (en) * | 1998-03-20 | 2004-12-15 | 同和鉱業株式会社 | Method for recovering indium from indium-containing material |
| JP3428931B2 (en) * | 1998-09-09 | 2003-07-22 | キヤノン株式会社 | Flat panel display dismantling method |
| JP4598921B2 (en) * | 2000-06-09 | 2010-12-15 | 出光興産株式会社 | Indium recovery method |
| JP4549501B2 (en) * | 2000-08-28 | 2010-09-22 | 日鉱金属株式会社 | Indium recovery method |
-
2006
- 2006-07-25 KR KR20077018087A patent/KR20080031661A/en not_active Application Discontinuation
- 2006-07-25 JP JP2007529217A patent/JPWO2007015392A1/en active Pending
- 2006-07-25 US US11/997,884 patent/US20100101367A1/en not_active Abandoned
- 2006-07-25 WO PCT/JP2006/314626 patent/WO2007015392A1/en active Application Filing
- 2006-07-25 CN CNB2006800070686A patent/CN100554454C/en not_active Expired - Fee Related
- 2006-08-03 TW TW95128432A patent/TWI385255B/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011481A (en) * | 2016-06-30 | 2016-10-12 | 华南理工大学 | Method for recovering indium (In) from waste liquid crystal displays |
| DE102020100243A1 (en) | 2020-01-08 | 2021-07-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Process for reconditioning glass-plastic-metal composite materials |
| DE102020100243B4 (en) | 2020-01-08 | 2023-06-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Process for processing glass-plastic-metal composite materials |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200712219A (en) | 2007-04-01 |
| WO2007015392A1 (en) | 2007-02-08 |
| CN101133172A (en) | 2008-02-27 |
| JPWO2007015392A1 (en) | 2009-02-19 |
| KR20080031661A (en) | 2008-04-10 |
| US20100101367A1 (en) | 2010-04-29 |
| TWI385255B (en) | 2013-02-11 |
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