CN101589163B - Method and apparatus for collection of indium from etching waste solution containing indium and ferric chloride - Google Patents
Method and apparatus for collection of indium from etching waste solution containing indium and ferric chloride Download PDFInfo
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- CN101589163B CN101589163B CN2007800503564A CN200780050356A CN101589163B CN 101589163 B CN101589163 B CN 101589163B CN 2007800503564 A CN2007800503564 A CN 2007800503564A CN 200780050356 A CN200780050356 A CN 200780050356A CN 101589163 B CN101589163 B CN 101589163B
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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
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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
- 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
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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
- 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
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Abstract
The invention provides a method and an apparatus for the recovery of indium, which do not need for collecting indium in the form of indium hydroxide, can collect indium at a high concentration, have a good handling property during the collection, can collect indium readily by using a filter or the like, and have a remarkably improved recovery rate. The method comprises the steps of: adding a precipitation-inducing metal to an etching waste solution containing at least indium and ferric chloride to thereby cause the precipitation of indium contained in the etching waste solution onto the surface of the precipitation-inducing metal, wherein the precipitation-inducing metal comprises a metal having higher ionization tendency than indium, and the etching waste solution is so prepared as to contain ferric chloride at a concentration of 20 wt% or less; detaching indium precipitated on the precipitation-inducing metal from the precipitation-inducing metal by a detachment means; and separating the detached solid indium or indium alloy from the liquid fraction and collecting the separated indium or indium alloy.
Description
Technical field
The present invention relates to reclaim the recovery method and the device thereof of the indium of indium from the etching waste liquor that contains indium and iron(ic)chloride; More particularly; Relate to from the etching waste liquor that the manufacturing processed of the flat-panel monitor of for example liquid-crystal display, plasma display etc., takes place, reclaim the method and apparatus of valuable substance indium (In) with forms such as alloy or metal simple-substances.
Background technology
The flat-panel monitor of liquid-crystal display, plasma display etc. (FPD) is used for the various electronicss of indicating meter, the TV imagescope of computingmachine, display part of portable phone etc. in recent years morely.In the manufacturing processed of such FPD, can produce waste liquid certainly, must handle aspect such waste liquid, the liquid crystal plant that not only manages such FPD, and with the situation of semiconductor manufacturing factory, plating factory too.And one of waste liquid that in the manufacturing processed of such FPD, takes place has the etching waste liquor that contains indium and iron(ic)chloride.
Usually; Often contain all metals in the industry waste liquid; Carry out containing In etc. in the liquid crystal plant waste liquid of manufacturing etc. of above-mentioned FPD; Contain copper (Cu), gallium (Ga) etc. in the semiconductor manufacturing factory waste liquid, contain nickel (Ni), copper (Cu), zinc (Zn) etc. in the plating workshop-sink, just attempting they are reclaimed with the form as the metal simple-substance of valuable substance.If can they forms with metal simple-substance or alloy be reclaimed, then can these metals be utilized etc. again.
As the liquid waste disposal technique that reclaims the heavy metal class, the past generally adopts the coagulative precipitation that makes with medicament to handle, be total to heavy processing etc., when concentration is low, also uses sorbent material to remove metal species.For example make the coagulative precipitation Treatment Technology of with medicament, the invention that has following patent documentation 1 to relate to as utilization.
Yet; The above-mentioned etching waste liquor that contains indium and iron(ic)chloride is used the occasion of above-mentioned coagulative precipitation processing; Though can reclaim with the indium hydroxide form, iron(ic)chloride is also with hydroxide form deposition, the problem that exists the generating capacity of oxyhydroxide dregs to increase as a whole.And, therefore also there is the problem that does not become valuable substance because major part becomes the state of ferruginous dregs.
On the other hand, as about removing the method for indium and the prior art of recovery method from the etching waste liquor that contains indium and iron(ic)chloride, uniquely there are following patent documentation 2 described patent Shen feelings in the result that present inventors retrieve.That is, the invention that this patent documentation 2 relates to as its claim 1 is described, is the removing of a kind of indium, recovery method, the method is characterized in that, adds iron, nickel compound to the etching waste liquor that contains indium and iron(ic)chloride.
In addition,, in the paragraph [0022] of the specification sheets of this patent documentation 2, put down in writing: " in this waste liquid, add nickel compound, add iron and carry out stirring heating, nickel is separated out and indium is separated out about concrete recovering means.Thus, can remove indium from this waste liquid.Promptly; Can be from the recycling precipitate indium ... ", and; In paragraph [0023], put down in writing: " thereby to the etching waste liquor that contains indium and iron(ic)chloride add mixture that indium that iron separates out and nickel etc. are formed attached to iron on, so can from solution, separate simply as throw out.As this sedimentary separation method, can enumerate the gravity type boat davit sedimentation, filter, utilize the method for the cf-of cyclone etc.”。
Put down in writing by these and to judge; In the method for patent documentation 2,, follow this evolution reaction and the evolution reaction of indium takes place through adding the evolution reaction that nickel ion causes nickel; Therefore in the indium alloy that is reclaimed; Indium concentration is very low, reclaims as the alloy that with nickel is main body, so be difficult to effectively utilize the indium that reclaims.At that point, in this patent documentation 2, not refer to the concentration that makes the indium in the alloy be desirable concentration with on reclaim.Therefore, the method for this patent documentation 2 is even can also may not confirm effectively to be used as the technology that only indium is reclaimed as valuable substance as the techniques make use of removing indium from waste liquid.In addition, indium attached on the iron, need adopt various separation methods to separate as throw out, and common separation method is very difficult to indium is reclaimed as valuable substance with the form of the mixture of itself and nickel etc.
Patent documentation 1: the spy of Japan opens the 2005-342694 communique
Patent documentation 2: the spy of Japan opens the 2004-75463 communique
Summary of the invention
The present invention is the research of accomplishing in order to solve the above problems; Its problem provides the state that does not need as before with indium hydroxide and reclaims; Or the occasion that reclaims at the alloy of conduct and other metal; The concentration of the indium in the alloy can step-down, can reclaim as the high density indium, therefore when reclaiming, does not have the malfunction as the situation of indium hydroxide; Can use strainer etc. easily to reclaim, and the recovery method and the device of the good significantly indium of the recovery of indium.
The present invention is in order to solve above-mentioned problem; The method and the device thereof that reclaim indium from the etching waste liquor that contains indium and iron(ic)chloride are provided; Characteristic as the recovery method of indium is; This method be from the etching waste liquor that contains indium and iron(ic)chloride at least reclaim indium, from the recovery method of the indium of etching waste liquor; The concentration of the iron(ic)chloride in being adjusted to waste liquid is that the etching waste liquor below the 20 weight % adds by separating out of constituting of the ionization tendency metal bigger than indium and uses metal, the indium that contains in the above-mentioned etching waste liquor is separated out, then above-mentioned separating out with metallic surface; Adopt the stripping off device to separate out with metal-stripping at the above-mentioned indium of separating out of separating out, the indium of the solid shape of having peeled off is separated from liquid and reclaims with metal from above-mentioned.
In addition, be as the characteristic of the retrieving arrangement of indium, this device be from the etching waste liquor that contains indium and iron(ic)chloride at least reclaim indium, from the retrieving arrangement of the indium of etching waste liquor, have:
Reclaim with reactor drum 1; It is used to carry out the metal evolution reaction; Promptly flowing into the ferric chloride concn that is adjusted in the waste liquid is the etching waste liquor below the 20 weight %; Or the ferric chloride concn that when flowing into etching waste liquor, it is adjusted in this waste liquid is below the 20 weight %, adds by separating out of constituting of the ionization tendency metal bigger than indium and uses metal, the indium that contains in the above-mentioned etching waste liquor separated out in above-mentioned separating out use metallic surface; With
Stripping off device, it is separated out with metal-stripping at the above-mentioned indium of separating out with metal of separating out from above-mentioned.
Moreover, as the indium of recycle object thing of the present invention, except reclaiming as metal simple-substance; Sometimes also reclaim or wait and reclaim as compound as alloy; In addition, the indium that contains in the etching waste liquor is the state of ion, compound etc. normally, therefore is difficult to all strict and difference clearly with them; In addition, may not need all differences clearly.Therefore, when only being called " indium " in the present invention, except the situation that means metal simple-substance, also be included as the situation of alloy, compound etc.
More preferably regulate so that the concentration of the iron(ic)chloride in the waste liquid is below the 9 weight %, further preferably be adjusted to below the 6 weight %.Use metal as separating out of constituting by the ionization tendency metal bigger, for example can use zinc or aluminium than indium.
In addition, for example utilize UW to make the means of metallics vibration or utilize electro-magnet to stir the means that metallics makes its means of colliding each other and so on as separating out the means of the indium of separating out from separating out at this, can adopting with metal with metal-stripping.The adjusting of the concentration of the iron(ic)chloride in the waste liquid, thus can regulating tank 2 is set in this regulating tank 2, carry out reclaiming leading portion side with reactor drum 1, can also carry out concentration adjustment in reactor drum 1 in recovery.
The present invention as stated, the ferric chloride concn in being adjusted to waste liquid is that the etching waste liquor that contains indium and iron(ic)chloride below the 20 weight % adds by separating out of constituting of the ionization tendency metal bigger than indium and uses metal, and the indium that contains in the above-mentioned etching waste liquor is separated out above-mentioned separating out with metallic surface; Then, adopt the means of peeling off to separate out with metal-stripping at the above-mentioned indium of separating out of separating out, the indium of the solid shape of having peeled off is separated from liquid and reclaims with metal from above-mentioned; Therefore; During from etching waste liquor recovery indium, through cementation (cementation) reaction and the lift-off technology combination that will utilize ionization tendency, promptly through using ionization tendency to use metal than big the separating out of indium; The total surface area that is used for the metal of metal evolution reaction increases; Evolution reaction speed improves, and in addition, logical employing is peeled off means and peeled off the precipitating metal of growth to a certain degree; New metallic surface is exposed; Can keep speed of response, therefore compare, all have and to improve the effect that from waste liquid, reclaims the recovery of indium significantly with any method in the past.
Especially under the situation of the etching waste liquor that contains indium and iron(ic)chloride that becomes object of the present invention; Usually the concentration of iron(ic)chloride is very high; Be more than the 30 weight %; If will adopt the cementation reaction that utilizes above-mentioned ionization tendency, it is fierce then to separate out with the solubilizing reaction of metal, is difficult to control reduction evolution reaction.In addition, separate out with the dissolution rate of metal sooner than the speed of separating out of indium, so iron and indium separate out at zinc surface, and before the solubilizing reaction of zinc stopped, zinc particles is dissolving all, its result, and the indium of separating out dissolves once more, can not reclaim.Relative therewith, in the present invention, as stated owing to regulate so that the ferric chloride concn in the etching waste liquor is below the 20 weight %; Be preferably below the 9 weight %; More preferably below the 6 weight %, it is so not fierce therefore to separate out with the solubilizing reaction of metal, so; Be not difficult to control reduction evolution reaction yet, and separate out with metal and can not be dissolved into more than necessity yet.
In addition; Need not resemble that the sedimentary state with indium hydroxide etc. reclaims the method in the past, and, even the occasion that reclaims as alloy; The concentration of the indium in the alloy can step-down yet; Therefore can reclaim as the high density indium, when reclaiming, also not have operation bad as the situation of indium hydroxide, have the effect that to use strainer etc. easily to reclaim.
As previously discussed; According to the present invention; The recovery method of the high indium of the recovery can be provided; Therefore even for example give under the situation of recovery circulation obligation of FPD etc. according to household electrical appliances circulation method or the law suitable with it in the future, the recovery method that also has as the indium in the process recycling in the recycling factory of LCD TV can adopt actual benefit of the present invention.
Description of drawings
Fig. 1 is the general positive map that reclaims the retrieving arrangement of indium as a kind of etching waste liquor from containing indium and iron(ic)chloride of embodiment.
Fig. 2 is that recovery in this indium retrieving arrangement is with the general positive map of reactor drum.
Fig. 3 is the general positive map of the recovery of another embodiment with reactor drum.
The drawing reference numeral explanation
1-reclaims with reactor drum, 2-regulating tank
Embodiment
Followingly embodiment of the present invention is described according to accompanying drawing.
(embodiment 1)
The etching waste liquor from containing indium and iron(ic)chloride of this embodiment reclaims the retrieving arrangement of indium (In), and is as shown in Figure 1, is to have the retrieving arrangement that reclaims with reactor drum 1, regulating tank 2 and strainer 3.
Reclaiming with reactor drum 1 is the reactor drum that as the back is said, is used for separating out from waste liquid through cementation reaction (metal evolution reaction) In; Regulating tank 2 is the regulating tanks that before reactor drum 1, are used for regulating the ferric chloride concn of waste liquid, and strainer 3 is the strainers that are used for separating, be recovered in the In that above-mentioned recovery separates out with reactor drum 1.Moreover also can constitute separated treatment solution can constitute and can need make to be processed liquid round-robin pump etc. to the occasion of the separated treatment solution of regulating tank 2 foldbacks to above-mentioned regulating tank foldback.
Above-mentioned recovery is with the reactor body 5 of reactor drum 1, and as shown in Figure 2 is vertically long main body, comprises reactor drum top 6, reactor drum pars intermedia 7 and reactor lower part 8, connects through connection section 9,10 respectively.Reactor drum top 6, reactor drum pars intermedia 7 and reactor lower part 8 each several parts form with same widths; But the sectional area the earth of the sectional area ratio reactor drum pars intermedia 7 on reactor drum top 6 forms, and the sectional area the earth of the sectional area ratio reactor lower part 8 of reactor drum pars intermedia 7 forms.Its result, the sectional area that constitutes reactor body 5 as a whole increases towards the top discontinuously.Moreover connection section 9,10 forms the wide taper of width towards the top.
At the downside of reactor lower part 8, be provided for flowing into inflow as the conical shaped of the etching waste liquor that contains In and iron(ic)chloride of process object with chamber 11, and be provided with inflow pipe 12 in its underpart.On inflow pipe 12,, be provided with vacuum breaker though do not illustrate.In addition, the upside on reactor drum top 6 is provided with upper chambers 13, is provided with the vent pipe 14 of the recycle object metal In that is used to discharge be recovered laminar, finely particulate at its sidepiece.
In this embodiment, can use the particle of zinc (Zn), aluminium (Al) as the metallics that drops into.It is the metallics of 0.1～8mm that the metallics that drops into preferably uses median size, in this embodiment, uses the metallics of median size as 2mm.Moreover median size can adopt image analysis method or JIS Z8801 size analysis method etc. to measure.
The method that comprises the In retrieving arrangement recovery In of such formation for use describes; The waste liquid of at first supplying with as process object to regulating tank 2; In this regulating tank 2, regulate the concentration of the iron(ic)chloride in the etching waste liquor; Specifically, water is added to dilute in the regulating tank 2 so that the concentration of iron(ic)chloride is below the 6 weight %.
Then, with the etching waste liquor of having regulated ferric chloride concn in this wise, flow in the reactor body 5 with chamber 11 via flowing into from inflow pipe 12.On the other hand, drop into the metallics (Zn or Al particle) that is used to produce the cementation reaction from upper chambers 13.In reactor body 5, the etching waste liquor that flows on the one hand vertically rises, and the metallics that drops into from upper chambers 13 on the other hand becomes flow state with the mode that forms fluidized-bed.
Then, based on the In that contains in the waste liquid different with as the ionization tendency of the Zn of the metallics that drops into or Al, produce so-called cementation reaction.This is illustrated in greater detail, and each reduction of metal ion reaction is expressed the standard potential (E of each metals ion respectively as shown in the formula shown in (1)～(3)
o).Moreover, containing iron(ic)chloride in the waste liquid, Fe also participates in the cementation reaction, therefore Fe ionic reduction reaction is shown in the following formula (1), also expresses its standard potential (E
o).
In
3++3e→In ......(1)-0.34V
Zn
2++2e→Zn ......(2)-0.76V
Al
3++3e→Al ......(3)-1.66V
Fe
2++2e→Fe ......(4)-0.44V
Be clear that by above-mentioned (1)～(4), with In
3+, Fe
2+Compare Zn
2+, Al
3+Standard electrode potential little.In other words, compare with In, Fe, the ionization tendency of Zn, Al is big.Therefore, under the state that becomes above-mentioned flow state, Zn, Al that ionization tendency is big become Zn
3+Or Al
3+Thereby stripping in waste liquid, meanwhile, the In that contains in the waste liquid
3+Become In, Fe
2+Become Fe, separate out on the surface of the particle of Zn, Al.
Therefore in this case, owing to contain iron(ic)chloride in the etching waste liquor, when the concentration of iron(ic)chloride was high, under the situation that produces above-mentioned cementation reaction, the solubilizing reaction of Zn particle or Al particle was fierce, might be difficult to control and reduce evolution reaction.And,, therefore also produce loss economically because Zn particle or Al particle are dissolved into more than necessity.
Yet; In this embodiment; As above-mentioned, regulate so that the ferric chloride concn in the etching waste liquor is below the 6 weight %, so the solubilizing reaction of Zn particle or Al particle is so not fierce, so not so difficult with control reduction evolution reaction; And Zn particle or Al particle can not be dissolved into more than necessity.In addition; Cementation reaction by above-mentioned can obtain precipitate with the alloy state of In and Fe; But because the etching waste liquor that flow in the above-mentioned reactor body 5 is diluted in advance so that ferric chloride concn is below the 6 weight %; Therefore for the alloy of In that obtains and Fe, In contains proportional to be more than the 90 weight %, can to obtain the In alloy of very high concentration.
In addition, make In after separating out on the surface of Zn, Al particle, make ultrasonic vibration body 15a, 15b, 15c work through such cementation reaction.Through making this ultrasonic vibration body 15a, 15b, 15c work; UW by this UW 15a, 15b, 15c starting of oscillation is given vibration force and whipping force to above-mentioned Zn particle or Al particle of having separated out In, forcibly peels off the In that separates out from Zn particle or Al particle thus.
Utilize the occasion of ultrasonic vibration in order to peel off the In that separates out in this wise, can partly have the ultrasonic vibration body at reactor drum through the outward appearance Visual Confirmation of treatment unit.In addition; Even occasion that can not Visual Confirmation; Owing to produce the high pitch about tens kilohertzs when the ultrasonic vibration body makes the metallics contact vibration of Zn in the reactor drum, Al in processing, therefore can easily confirm to have carried out utilizing hyperacoustic processing.
The treatment solution that contains the In that peels off in this wise is discharged to the outside of reactor body 5 from upper chambers 13 via vent pipe 14, is separated by strainer 3, and isolating In is recovered.In this case; In this embodiment; As using metal for making In as the recycle object metal separate out separating out of dropping into, used emboliform separating out to use metal, therefore compare with the situation of the fragment that for example drops into Zn, Al; The surface-area that is used to produce the metal (Zn, Al) of cementation reaction increases, and the evolution reaction speed of In improves.And, after the separating out of the metal that can see to a certain degree growth, peel off through the pressure that utilizes above-mentioned hyperacoustic vibration, new metallic surface (surface of Zn particle) is exposed, can keep speed of response.In addition, compare with method in the past, in the recovery metal of having peeled off, as stated, the impurity beyond the In is considerably less.
In addition, the metallics that is made up of Zn or Al flows in reactor body 5, through above-mentioned cementation reaction, Zn
2+Or Al
3+Therefore the particle diameter of input during the initial stage of the metallics in the upper chambers 13 put in stripping, along with the migration of time must reduce.Its result, because original waste liquid rises in reactor body 5 with roughly the same upwards mobile speed, therefore particle diameter reduces more towards top more, the metallics that diminishes might be in spite of oneself from reactor body 5 overflows.
Yet; In this embodiment, the sectional area that forms reactor body 5 increases towards the top more more discontinuously, and therefore the upwards mobile speed of the waste liquid in reactor body 5 reduces gradually; Therefore the metallics that as above-mentioned, causes particle diameter to reduce owing to cementation reaction etc.; The top of the reactor body 5 that increases at sectional area can be by overflow independently, and the possibilities that remain in the reactor body 5 increase.
In addition; Etching waste liquor flows into from the lower side of reactor body 5; Through reactor body 5 time,, on the metallics that constitutes by Zn or Al, separate out the In that becomes recycle object through the cementation reaction; Therefore get over the top of orientating reaction device main body 5, the recycle object concentration of metal reduces more in the waste liquid.
Yet; In this embodiment; The top of reactor body 5 exists fine Zn or the particle of Al more, and because the upwards mobile speed of etching waste liquor little by little reduces, can see that therefore the quantity of Zn or Al particle increases; Therefore the top of reactor body 1, the total surface area of Zn or Al particle increases more.Its result, the speed of response (effect that In separates out) of cementation reaction improves, and therefore, even be the top of the reactor body 5 of lower concentration in the concentration of In, also can recycle the In as the recycle object metal expeditiously.
(embodiment 2)
In this embodiment, the structure of reactor body 5 is different with above-mentioned embodiment 1, promptly; In this embodiment; As shown in Figure 3, the mode that upwards is taper with the side face integral body of reactor body 5 forms, and the sectional area that constitutes reactor body 5 increases towards the top continuously.At that point, the embodiment 1 that increases towards the top discontinuously with the sectional area of reactor body 5 is different.Owing to be not discontinuous, but the mode that increases towards the top continuously with sectional area constitutes, and therefore in this embodiment, is not as enforcement mode 1, to be distinguished into reactor drum top 6, reactor drum pars intermedia 7, reactor lower part 8 to constitute.
Yet ultrasonic vibration body 15a, 15b, 15c are arranged on from the top of reactor body 5 to 3 positions of bottom, and this point is identical with embodiment 1.Therefore; In this embodiment; Also same with embodiment 1, can obtain can through by the forced ultrasonic property of ultrasonic vibration body 15a, 15b, 15c starting of oscillation peel off the effect of the recycle object metal In of on the metallics (Zn, Al etc.) of separating out, separating out with metal.
In addition; Though have discontinuous or successive different; But with sectional area towards above the mode that increases constitute on this point, identical with embodiment 1, even therefore in this embodiment; Also be the fine metallics that keeps particle diameter to reduce on the top of reactor body 5, produce and prevent the effect of overflow in spite of oneself and be the effect that the top of the reactor body 5 of lower concentration also can recycle the recycle object metal expeditiously in the recycle object concentration of metal.
(other embodiment)
Moreover in the above-described embodiment, making the ferric chloride concn in the etching waste liquor is below the 6 weight %, therefore can obtain the good ideal effect of the recovery of In, but the ferric chloride concn in the etching degree waste liquid is not limited to this embodiment.As long as be below the 20 weight %, still, the ferric chloride concn in making etching waste liquor is under the situation below the 6 weight %, and can make the In that reclaimed and the ratio of Fe is about 9: 1.Relative therewith, when being 10～20 weight % left and right sides,, under this situation, also can reach the object of the invention that can the alloy of In or In and Fe be reclaimed as valuable substance though the ratio of In and Fe is about 1: 1.
In addition; In the above-described embodiment, regulating tank 2 is set, in this regulating tank 2, has carried out the concentration adjustment of the iron(ic)chloride in the waste liquid in the leading portion side that reclaims with reactor drum 1; But be not limited thereto, also can wait and carry out concentration adjustment through direct interpolation diluent in reclaiming with reactor drum 1.
In addition; In the above-described embodiment; The situation that reclaims In for the particle that adds Zn or Al is illustrated, and is not limited to the Zn of this embodiment or the particle of Al but add to reclaim with the metallics in the reactor drum, so long as use the ionization tendency metal bigger than In to get final product.
In addition, in this embodiment, the particle diameter of metallics is made as about 2mm, but the particle diameter of metallics is not limited to this embodiment, is preferably 0.1～8mm.When less than 0.1mm, cementation reaction may not be carried out well, the recovery of the precipitating metal that can not easily carry out peeling off from metallics.Especially when the concentration of iron(ic)chloride is high, can not carry out the cementation reaction well.In addition, when surpassing 8mm, the quantity of the metallics that can in reactor body 1, keep reduces, and the total surface area of metallics reduces as a result, and the efficient of possible evolution reaction reduces.In addition, the precious metals metal in addition that reclaims target might be separated out on metallics.
Moreover the median size of metallics according to above-mentioned that kind, can adopt image analysis method, JIS Z 8801 size analysis methods etc. to measure.When adopting the image analysis method to measure median size, can use the for example ミ リ ト ラ Star Network JPA (particle size distribution device) of Nikkiso Company Limited's system.As an example, be made as in the median size of metallics under the situation of scope of 1～2mm, use in the method for sieving of JIS under the specified size 2000 μ m sieve, the metallics on the 1000 μ m sieves gets final product.
In addition, in above-mentioned embodiment 1,2, the sectional area that forms reactor body 1 increases towards top more more, therefore can obtain above-mentioned ideal effect, is not condition essential to the invention but form reactor body 1 in this wise.
In addition; The means of peeling off the recycle object metal from metallics also are not limited to the means of employing electro-magnet of the hyperacoustic means of employing and the embodiment 3 of above-mentioned embodiment 1,2, also can be the means beyond it, in addition; In the above-described embodiment; Used metallics as separating out, but be not limited thereto, also can use metal wire, metal wire is processed webbed metal, tabular metal etc. with metal.
Embodiment
For testing as the correlationship of the In concentration in the ferric chloride concn of the etching waste liquor of treatment solution and the metal of separating out.Specifically; As shown in table 1; Prepare to adopt water to be diluted to 2 times, 4 times, 6 times, 10 times liquid respectively,, use the device of above-mentioned embodiment to make an experiment for difference concentration different liquid as the etching waste liquor (concentration of iron(ic)chloride is about 36 weight %) of stoste.Test-results is shown in table 1.
Table 1
| Dilution ratio | In concentration (weight %) in the precipitate |
| 2 | 50 |
| 4 | 50 |
| 6 | 90 |
| 10 | 90 |
Be clear that by table 1; Dilution ratio is that 2 times (concentration of iron(ic)chloride is about 18 weight %) and dilution ratio are the liquid of 4 times (concentration of iron(ic)chloride is about 9 weight %); In concentration in the precipitate is about 50 weight %; Dilution ratio is that 6 times (concentration of iron(ic)chloride is about 6 weight %) and dilution ratio are the liquid of 10 times (concentration of iron(ic)chloride is about 3.6 weight %), and the In concentration in the precipitate is about 90 weight %.Hence one can see that, and the concentration of the iron(ic)chloride in the liquid is low more, and then the concentration of In is high more.The recovery that is In is high more.
Moreover; Metal major part beyond the In in the precipitate is Fe, so the concentration of In is under the situation of about 50 weight %, precipitate roughly consist of In: Fe=1: 1; The concentration of In is under the situation of about 90 weight %, precipitate roughly consist of In: Fe=9: 1.
Among the present invention the expression numerical range " more than " and " following " include given figure.
Claims (12)
1. method that reclaims indium from the etching waste liquor that contains indium and iron(ic)chloride; Be the method that reclaims indium from the etching waste liquor that contains indium and iron(ic)chloride at least, it is characterized in that the ferric chloride concn in being adjusted to waste liquid is that the etching waste liquor below the 20 weight % adds by separating out of constituting of the ionization tendency metal bigger than indium and uses metal; The indium that contains in the said etching waste liquor is separated out in said separating out use metallic surface; Adopt stripping off device then, separate out with metal-stripping at the said indium of separating out of separating out with metal from said, with the indium of the solid shape of peeling off from liquid separation and reclaim; It is wherein, said that to separate out with metal be zinc or aluminium.
2. want 1 describedly to reclaim the method for indium according to right, wherein, regulate so that the ferric chloride concn in the waste liquid is below the 9 weight % from the etching waste liquor that contains indium and iron(ic)chloride.
3. want 1 describedly to reclaim the method for indium according to right, wherein, regulate so that the ferric chloride concn in the waste liquid is below the 6 weight % from the etching waste liquor that contains indium and iron(ic)chloride.
4. according to the described method that reclaims indium from the etching waste liquor that contains indium and iron(ic)chloride of each of claim 1～3; Wherein, After in reclaiming, regulating the ferric chloride concn in the waste liquid, separate out to the etching waste liquor interpolation in this recovery and to use metal with reactor drum with reactor drum.
5. reclaiming the method for indium according to each of claim 1～3 is said from the etching waste liquor that contains indium and iron(ic)chloride, wherein, is the device that utilizes UW that metallics is vibrated from the device of separating out with the metal-stripping indium.
6. reclaiming the method for indium according to claim 4 is said from the etching waste liquor that contains indium and iron(ic)chloride, wherein, is the device that utilizes UW that metallics is vibrated from the device of separating out with the metal-stripping indium.
7. reclaim the method for indium according to each of claim 1～3 is described from the etching waste liquor that contains indium and iron(ic)chloride, wherein, separating out and using metal is that particle diameter is the metallics of 0.1～8mm.
8. want 4 describedly to reclaim the method for indium from the etching waste liquor that contains indium and iron(ic)chloride according to right, wherein, separating out and using metal is that particle diameter is the metallics of 0.1～8mm.
9. one kind is reclaimed the device of indium from the etching waste liquor that contains indium and iron(ic)chloride, is from the device of the etching waste liquor recovery indium that contains indium and iron(ic)chloride at least, it is characterized in that having:
Reclaim with reactor drum (1); It is used to carry out the metal evolution reaction; Promptly when inflow is adjusted to ferric chloride concn in the waste liquid and is the etching waste liquor below the 20 weight %; Interpolation is used metal by separating out of constituting of the ionization tendency metal bigger than indium, the indium that contains in the said etching waste liquor is separated out in said separating out use metallic surface; With
Stripping off device, it is separated out with metal-stripping at the said indium of separating out with metal of separating out from said,
It is wherein, said that to separate out with metal be zinc or aluminium.
10. according to claim 9ly reclaim the device of indium, wherein,, be provided with the regulating tank (2) of the ferric chloride concn that is used for regulating waste liquid in the leading portion side that reclaims with reactor drum (1) from the etching waste liquor that contains indium and iron(ic)chloride.
11. one kind is reclaimed the device of indium from the etching waste liquor that contains indium and iron(ic)chloride, is from the device of the etching waste liquor recovery indium that contains indium and iron(ic)chloride at least, it is characterized in that having:
Reclaim with reactor drum (1); It is used to carry out the metal evolution reaction; Promptly when flowing into etching waste liquor; Regulate so that the ferric chloride concn in this waste liquid is below the 20 weight %, and add by separating out of constituting of the ionization tendency metal bigger and use metal, the indium that contains in the said etching waste liquor is separated out in said separating out use metallic surface than indium; With
Stripping off device, it is separated out with metal-stripping at the said indium of separating out with metal of separating out from said
It is wherein, said that to separate out with metal be zinc or aluminium.
12. reclaim the device of indium from the etching waste liquor that contains indium and iron(ic)chloride, wherein, be the device that utilizes UW that metallics is vibrated from the device of separating out with the metal-stripping indium according to each of claim 9～11 is described.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007012811 | 2007-01-23 | ||
| JP012811/2007 | 2007-01-23 | ||
| PCT/JP2007/072408 WO2008090671A1 (en) | 2007-01-23 | 2007-11-19 | Method and apparatus for collection of indium from etching waste solution containing indium and ferric chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101589163A CN101589163A (en) | 2009-11-25 |
| CN101589163B true CN101589163B (en) | 2012-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800503564A Expired - Fee Related CN101589163B (en) | 2007-01-23 | 2007-11-19 | Method and apparatus for collection of indium from etching waste solution containing indium and ferric chloride |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20110132146A1 (en) |
| JP (1) | JP5068772B2 (en) |
| KR (1) | KR101133484B1 (en) |
| CN (1) | CN101589163B (en) |
| WO (1) | WO2008090671A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5810639B2 (en) * | 2011-06-03 | 2015-11-11 | 栗田工業株式会社 | Method and apparatus for treating selenium-containing water |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7509341A (en) * | 1975-08-06 | 1977-02-08 | Philips Nv | PROCESS FOR THE MANUFACTURE OF ELECTRICALLY CONDUCTIVE INDIUM OXIDE CARTRIDGES ON AN INSULATING SUPPORT. |
| US4152143A (en) * | 1977-09-08 | 1979-05-01 | Klockner-Humboldt-Deutz Aktiengesellschaft | Method and apparatus for precipitating metal cement |
| IT1185549B (en) * | 1985-04-12 | 1987-11-12 | Samim Soc Azionaria Minero Met | PROCEDURE FOR THE SEPARATION OF INDIO FROM ACID SOLUTIONS THAT CONTAIN IT |
| US5976383A (en) * | 1991-04-08 | 1999-11-02 | Romar Technologies, Inc. | Recycle process for removing dissolved heavy metals from water with aluminum particles |
| US5208004A (en) * | 1992-01-15 | 1993-05-04 | Metals Recycling Technologies Corp. | Method for the recovery of zinc oxide |
| JP3024396B2 (en) * | 1992-10-13 | 2000-03-21 | 住友金属鉱山株式会社 | In recovery method |
| CN1054888C (en) * | 1994-09-08 | 2000-07-26 | 金属回收技术有限公司 | Method for recovering metal and chemical values |
| MY115542A (en) * | 1996-06-28 | 2003-07-31 | Astec Irie Co Ltd | Method for recovering etchand from etching waste liquid containing iron chloride |
| JP2001192709A (en) * | 2000-01-05 | 2001-07-17 | Sony Corp | Recycle alloy powder and its manufacturing method |
| KR100335601B1 (en) * | 2000-02-15 | 2002-05-08 | 박호군 | Apparatus for continuously reducing iron chloride aqueous solution |
| JP4161636B2 (en) * | 2002-08-19 | 2008-10-08 | 東亞合成株式会社 | Method for removing indium from indium-containing ferrous chloride aqueous solution |
| JP2007009274A (en) * | 2005-06-30 | 2007-01-18 | Mitsubishi Materials Corp | Method for recovering indium |
| KR20080027911A (en) * | 2005-07-06 | 2008-03-28 | 가부시키가이샤 신꼬오 간쿄우 솔루션 | Process for recovery of metals and equipment therefor |
| KR20080031661A (en) * | 2005-08-04 | 2008-04-10 | 가부시키가이샤 신꼬오 간쿄우 솔루션 | Method and apparatus for recovering indium from waste liquid crystal display |
| 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 |
-
2007
- 2007-11-19 KR KR1020097016517A patent/KR101133484B1/en not_active IP Right Cessation
- 2007-11-19 CN CN2007800503564A patent/CN101589163B/en not_active Expired - Fee Related
- 2007-11-19 WO PCT/JP2007/072408 patent/WO2008090671A1/en active Application Filing
- 2007-11-19 US US12/524,081 patent/US20110132146A1/en not_active Abandoned
- 2007-11-19 JP JP2008554975A patent/JP5068772B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US20110132146A1 (en) | 2011-06-09 |
| JPWO2008090671A1 (en) | 2010-05-13 |
| CN101589163A (en) | 2009-11-25 |
| JP5068772B2 (en) | 2012-11-07 |
| WO2008090671A1 (en) | 2008-07-31 |
| KR101133484B1 (en) | 2012-04-10 |
| KR20090100440A (en) | 2009-09-23 |
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