CN101218359B - Process for recovery of metals and equipment therefor - Google Patents

Process for recovery of metals and equipment therefor Download PDF

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Publication number
CN101218359B
CN101218359B CN2006800245426A CN200680024542A CN101218359B CN 101218359 B CN101218359 B CN 101218359B CN 2006800245426 A CN2006800245426 A CN 2006800245426A CN 200680024542 A CN200680024542 A CN 200680024542A CN 101218359 B CN101218359 B CN 101218359B
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Prior art keywords
metal
reactor body
separating out
recycle object
metallics
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CN101218359A (en
Inventor
前背户智晴
岛田光重
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Shinko Pantec Co Ltd
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Kobelco Eco Solutions Co Ltd
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Priority claimed from JP2006055074A external-priority patent/JP2007039788A/en
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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
    • 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
    • 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
    • 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
    • C22B3/02—Apparatus therefor
    • 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
    • C22B5/00—General methods of reducing to metals
    • 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
    • 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 invention relates to a process for recovering heavy metals such as nickel (Ni), copper (Cu), tin (Sn), indium (In), and gallium (Ga) as valuable simple substances or alloys from a raw effluent (such as wastewater) containing them and equipment for the recovery and aims at providing a process for recovery by which only objective metals can be recovered as valuable simple substances or alloys little containing impurity metals from a raw effluent such as wastewater with high recovery and at high purity; and equipment for the recovery. The process is characterized by incorporating a raw effluent containing objective metals in the form of ions with a precipitating metal having an ionization tendency higher than those of the objective metals, making the objective metals contained in the raw effluent deposit on the surface of the precipitating metal by utilizing the difference between both in ionization tendency, and then scaling the objective metals from the precipitating metal by a scaling means to recover them.

Description

The recovery method of metal and device thereof
Technical field
The present invention relates to the recovery method and the device thereof of metal, more specifically, relate to from the processed liquid such as waste liquid that contain Ni (nickel), Cu (copper), Sn (tin), In (indium), Ga heavy metals such as (galliums) method and apparatus that they are reclaimed with the form as the metal simple-substance of valuable substance or alloy.
Background technology
In general, in industrial effluent, often contain various metals, attempting they are reclaimed with the form as the metal simple-substance of valuable substance always.For example, in the plating workshop-sink, contain Ni, Cu, Zn etc., in the semiconductor fabrication factory waste liquid, contain Cu, Ga etc., in liquid crystal manufacturing works waste liquid, contain In etc., if they can be reclaimed as metal simple-substance or alloy, just can utilize these metals etc. again.
As the treatment technology of the waste liquid that reclaims the heavy metal class, all the time, generally adopt the coagulation sedimentation processing that makes with medicament, co-precipitation processing etc., under the low situation of concentration, also use sorbent material that metal species is removed.In addition, when from waste plating solution, reclaiming metal, have iron filings are dropped in the waste plating solution, thereby reclaim the method for recycle object metals such as Cu with cementation (Cementation) method.For example, as the technology of utilizing co-precipitation to handle, the related invention of following patent documentation 1 is arranged.
Patent documentation 1: the spy of Japan opens the 2002-126758 communique
But, in the coagulation sedimentation that makes with medicament is handled, have problems of sediment formation with the form generation oxyhydroxide of sludge.In addition, iron filings are dropped in the waste plating solution, utilizing method of cementation to make in the method that Cu etc. separates out, the moment evolution reaction that covers the iron filings surface at the Cu that separates out finishes, what reclaim is to apply the material that iron forms by Cu, can not only metal target be reclaimed as the recycle object metal.In addition, also there is the problem that the rate of recovery is low, can only obtain the low material of purity.
Summary of the invention
The present invention finishes in order to solve such problem, and its problem provides a kind of recovery method that possibility is little, the rate of recovery is high, the purity of recycle object metal is high and device that can be from processed liquid such as waste liquid only metal target be reclaimed and contain the impurity beyond the recycle object metal with the form as the metal simple-substance of valuable substance or alloy.
The present invention finishes in order to solve such problem, a kind of metal recovery processes is provided, it is characterized in that, in the processed liquid that contains the recycle object metal with ionic condition, add ionization tendency than big the separating out of above-mentioned recycle object metal metal, utilize the difference of ionization tendency that the recycle object metal that is contained in the above-mentioned processed liquid is separated out above-mentioned separating out with metallic surface, then, utilize the means of peeling off to peel off above-mentioned recycle object metal and reclaim from above-mentioned separating out with metal.In such metal recovery processes, can make the processed intravital while of liquid inflow reactor master of containing the recycle object metal with ionic condition, in this reactor body, add to separate out and use metal.
As from separating out the means of peeling off the recycle object metal with metal, can adopt following means, that is: utilize ultrasonic wave to make and separate out the means of vibrating with metal; Utilize electro-magnet to stir to separate out and use metal, make a plurality of means of colliding mutually of separating out with metal; Stir the means of separating out with metal by air spray or jet of water; Cylindrical portion is set in reactor body, in this cylindrical portion, is blown into gas and stirs the means of separating out with metal; Outer setting at reactor body makes the processed liquid in the above-mentioned reactor body and separates out stream and the pump that circulates and carry with metal, by making above-mentioned processed liquid and separating out with metal circulation and carry, stir the above-mentioned means of separating out with metal; Or the like.
As precipitating metal, can use for example metallics.The median size of this metallics is preferably 0.1～8mm, more preferably 0.5～6mm, more preferably 1.0～2.0mm.
At metallics is that median size is preferably 1.5～5.5mm under the situation of aluminium.In addition, be that median size is preferably 1.5～4.0mm under the situation of zinc at metallics.
Make under the intravital situation of processed liquid inflow reactor master that contains the recycle object metal with ionic condition, preferably be constituted as of the bottom inflow of processed liquid, flowing out from the top of reactor body from reactor body.
And then, making under the intravital situation of processed liquid inflow reactor master, the mode that can increase towards the top by the basal area of reactor body constitutes above-mentioned reactor body.In addition, can utilize the reactor body of multistage, adopt different two or more separating out to reclaim two or more recycle object metals with metal selective ground.In addition, also can reclaim the recycle object metal of being stripped from strainer.
And then, except the recycle object metal of ionic condition, also contain in the processed liquid under the situation of nitrate ion, can add chloride-ion source in this processed liquid in the same way with separating out with metal one.In addition, under this occasion, can when making processed liquid flow into the adjustment groove, in this adjustment groove, add chloride-ion source, then the processed intravital while of liquid inflow reactor master in making this adjustment groove, in this reactor body, add to separate out and use metal.And then, under the situation of such interpolation chloride-ion source, can will add in the processed liquid as stoste and handle once again by having separated out with metal recovery treatment solution after the recycle object metal.
In addition, the invention provides a kind of retrieving arrangement of metal, it is characterized in that, possesses the reactor body that is used to carry out the metal evolution reaction, with for reclaim above-mentioned recycle object metal of separating out be used to make it from the above-mentioned stripping off device of peeling off with metal of separating out, above-mentioned metal evolution reaction is when the processed liquid that contains the recycle object metal with ionic condition is flowed into, add ionization tendency and use metal than big the separating out of above-mentioned recycle object metal, the recycle object metal that utilizes the difference of ionization tendency to make to be contained in the above-mentioned processed liquid is separated out the reaction of separating out with metallic surface above-mentioned.
In such apparatus for recovering metal, as from separating out the device of peeling off the recycle object metal with metal, can adopt following apparatus, that is: utilize ultrasonic wave to make and separate out the device that vibrates with metal; Utilize electro-magnet to stir to separate out and use metal, make a plurality of devices that collide mutually with metal of separating out; Stir the device of separating out with metal by air spray or jet of water; Cylindrical portion is set in reactor body, in this cylindrical portion, is blown into gas and stirs the device of separating out with metal; The stream and the pump that make processed liquid in the above-mentioned reactor body and metallics circulation and carry in the outer setting of reactor body by making above-mentioned processed liquid and separating out with the metal circulation and carry, stir above-mentioned device of separating out with metal; Or the like.
Reactor body for example is constituted as, and has the inflow portion of processed liquid in its underpart, has liquid outflow portion on top, and processed liquid flows out from above-mentioned liquid outflow portion in above-mentioned inflow portion inflow reactor main body.
And then reactor body can constitute, and its basal area increases towards the top.In addition, can set the reactor body of multistage.And then, can set the strainer that is used to reclaim the recycle object metal of being stripped from the back segment of reactor body.
And then, can be provided with the adjustment groove in the leading portion side of reactor body, above-mentioned adjustment groove is to hold with ionic condition to contain the recycle object metal and contain the processed liquid of nitrate ion, adds the adjustment groove that chloride-ion source is adjusted.And then, can be provided with and will add the loopback stream of handling once again in the processed liquid as stoste to by having separated out with metal recovery treatment solution after the recycle object metal.
The invention effect
The present invention as mentioned above, it is a kind of like this method, that is: in the processed liquid that contains the recycle object metal with ionic condition, add ionization tendency than big the separating out of above-mentioned recycle object metal metal, utilize the difference of ionization tendency that the recycle object metal that is contained in the above-mentioned processed liquid is separated out above-mentioned separating out with metallic surface, then, utilization is peeled off means from the above-mentioned method of peeling off above-mentioned recycle object metal and reclaiming with metal of separating out, therefore, peeling off means by utilization peels off separating out with the metallic surface and has carried out the recycle object metal of growth to a certain degree, make to separate out and always expose new metallic surface with metal, can keep speed of response, therefore have the effect of the organic efficiency that can improve the recycle object metal.
Especially, in that use median size with metal be under the situation of metallics of 0.1～8mm as separating out, compare with the method for for example using iron filings, the total surface area of separating out with metal that is used for the metal evolution reaction increases, evolution reaction speed improves, and the organic efficiency of recycle object metal further improves.
In addition, in making processed liquid inflow reactor main body, in this reactor body, add under the situation as the metallics of separating out the median size 0.1～8mm that uses metal, metallics is flowed in this reactor body well, thereby can further improve the effect of peeling off the recycle object metal with metal from separating out.
In addition, flow into from the reactor body bottom reactor body being constituted processed liquid, flow out from reactor body top, and the basal area of reactor body is under the situation of top increase, the upwards mobile speed of the processed liquid in reactor body reduces lentamente, by metal evolution reaction as described above etc. and particle diameter reduces that to separate out with metal be metallics, top at the ever-increasing reactor body of basal area, not overflow at random can remain in the reactor body.
In addition, flow in the lower side of processed liquid from reactor body, when in reactor body, passing through, above-mentioned recycle object metal is separated out on separating out with metal above-mentioned, therefore get over the top of orientating reaction device main body, recycle object concentration of metal in the processed liquid reduces more, reduce as the particle diameter of separating out as mentioned above in addition with the metallics of metal, therefore there is fine metallics more in the top of reactor body, and the upwards mobile speed of processed liquid slowly reduces, the quantity that can find metallics increases, therefore the total surface area of the upper metal particle of reactor body is big more, its result, has such effect, that is: the speed of response of metal evolution reaction improves, even become the top of the reactor body of lower concentration in the recycle object concentration of metal, also can efficient recycle the recycle object metal well.
And then, the reactor body of multistage is being set, be provided with at its back segment under the situation of strainer, in becoming the processed liquid of object, contain under the situation of two or more metals, certain metal is separated out and reclaim this metal with first section strainer, other metals are separated out and reclaim this other metals, possess and to use the different two or more effects that from processed liquid, optionally reclaim two or more recycle object metals with metal of separating out with second section strainer.
And then, except the recycle object metal of ionic condition, the processed liquid that also contains nitrate ion, especially the recycle object metal is under the situation of indium (In), sometimes the metal evolution reaction of the difference of ionization tendency that utilizes as described above does not take place well, but by except separating out with the metal, in processed liquid, also add chloride-ion source, although in processed liquid, have nitrate ion, because the existence of above-mentioned chloride-ion source, the recycle object metal of In and so on can be separated out on separating out with metal well, peels off means by utilization and peels off In from separating out with metal, compare with existing method, can reclaim In more simply.
Like this, exist in processed liquid under the situation of nitrate ion, although In is separated out on separating out with metal, by add chloride-ion source in processed liquid, the reason that In is separated out is tentatively considered as follows.Promptly, In is owing to exist the nitrate ion of concentration to a certain degree, and the metamorphosis in solution, can find that thus the standard electrode potential of In compares reduction with the common value of considering, can think on the other hand, constitute separate out Al with metal, the standard electrode potential of Zn also raises, as the In that reclaims metal, with diminish as the potential difference of separating out Al, Zn etc. with metal, the reduction of In is separated out and is become difficult.Therefore can think that when as muriate, hydrochloric acid such as chloride-ion source interpolation sodium-chlor, Repone K, In forms chloro-complex, the standard electrode potential that reduces because of nitrate ion raises once more, and thus, In can reduce on separating out with metal and separate out.
In addition, as other reason, can think, owing in processed liquid, have nitrate ion, make the potential variation of In, become as the In ion and the zone in the stable pH-Electric Potential Graph, be difficult to generation by the reduction reaction of bringing as the Al that separates out with metal thus, but, become as the In metal and the zone in the stable pH-Electric Potential Graph is easy to generation by separating out the reduction reaction of bringing with metal A l by adding the Cl ion.
And, the nitrate ion in the solution with constitute Al, the Zn reaction separate out with metal, form nitrogen peroxide, nitrogen protoxide, become gas and emit.
In addition, add under the situation about handling once again in the processed liquid as stoste utilization being separated out the treatment solution of separating out from processed liquid with metal after reclaiming indium, reclaiming residually in the treatment solution behind the indium has a chlorion, therefore reach the result that this residual chlorion is reused, consequently, have the amount that can reduce the chloride-ion source of appending, and even can seek the effect that processing cost is cut down.
Description of drawings
Fig. 1 is the general principal view as the apparatus for recovering metal of an embodiment.
Fig. 2 is the general principal view of the apparatus for recovering metal of other embodiments.
Fig. 3 is the approximate three-dimensional map of the apparatus for recovering metal of other embodiments.
Fig. 4 is the general profile chart of the apparatus for recovering metal of other embodiments.
Fig. 5 is that inflow in the apparatus for recovering metal of other embodiments is with the general view of chamber.
Fig. 6 is the A-A line sectional view of Fig. 5.
Fig. 7 is the general principal view of the apparatus for recovering metal of other embodiments.
Fig. 8 is the employed general view that possesses the slide plate of electro-magnet of the embodiment of Fig. 7.
Fig. 9 is the schematic block diagram of the apparatus for recovering metal of other embodiments.
Figure 10 is the schematic block diagram of the apparatus for recovering metal of other embodiments.
Figure 11 is the general principal view of the apparatus for recovering metal of other embodiments.
Figure 12 is the general principal view of the apparatus for recovering metal of other embodiments.
Figure 13 is the general principal view of the apparatus for recovering metal of other embodiments.
Figure 14 is the schematic block diagram as the retrieving arrangement of the indium of an embodiment.
Figure 15 is the schematic block diagram of the testing apparatus of expression embodiment.
Figure 16 is the graphic representation of expression test-results.
Nomenclature
1,1a, 1b, 1c reactor body
11a, 11b, 11c, 11d ultra-sonic oscillation body
12 electro-magnet, 17,18,19 strainers
25 cylindrical portion, 32 streams
33 pumps
Embodiment
Below, with reference to the accompanying drawings embodiments of the present invention are described.
(embodiment 1)
The apparatus for recovering metal of present embodiment as shown in Figure 1, is the reactor body 1 with lengthwise.In the present embodiment, to being that the situation of object describes as processed liquid with the waste liquid.Above-mentioned reactor body 1, as shown in the drawing, comprise reactor top 2, reactor pars intermedia 3 and reactor lower part 4, be connected with by the portion of being connected with 5,6 respectively.Reactor top 2, reactor pars intermedia 3 and reactor lower part 4 form with same widths separately, but the basal area on reactor top 2 forms greater than the basal area of reactor pars intermedia 3, and the basal area of reactor pars intermedia 3 forms greater than the basal area of reactor lower part 4.Its result is constituted as a whole, and the basal area of reactor body 1 increases discontinuously towards the top.In addition, be connected with the taper that portion 5,6 is formed towards top width broadening.
At the downside of reactor lower part 4, be provided with the inflow that is used to make the conical shaped that the waste liquid as process object flows into chamber 7, and then be provided with inflow pipe 8 in its underpart.On inflow pipe 8, though not shown, be provided with check valve.In addition, the upside on reactor top 2 is provided with upper chambers 9, is provided with the vent pipe 10 that the metal that is used for laminar, the finely particulate that will be reclaimed is discharged at its sidepiece.Upper chambers 9 is to be used for the part of the metal that reclaimed being discharged by such vent pipe 10, and also be drop into be used for based on the difference of ionization tendency and with the recycle object metal take place so-called cementation reaction (metal evolution reaction), ionization tendency than recycle object metal big separate out part with metal (metallics).In fact, separate out cementation reaction, in the integral body of above-mentioned reactor body 1, take place with metal and recycle object metal.
In addition, be constituted as, the waste liquid that flows into from inflow pipe 8 till arriving vent pipe 10 during, Yi Bian form fluidized-bed by metallics Yi Bian this waste liquid rises in vertical direction.And, on reactor top 2, reactor pars intermedia 3 and reactor lower part 4 be respectively equipped with, as the metal that will be contained in the waste liquid, i.e. ultra-sonic oscillation body 11a, 11b, the 11c of the stripping off device of the recycle object metal-stripping of on the metallics of above-mentioned input, separating out by above-mentioned cementation reaction.
In the present embodiment, can use the particle of zinc (Zn) as the metallics that drops into.In addition, as the waste liquid that becomes object, can use metal finishing workshop-sink that contains the metal ion of copper (Cu), tin (Sn) etc. for example etc.In this case, Cu, Sn are recovered as metal.It is the metallics of 0.1～8mm that the metallics that drops into can use median size, but uses the particle of median size 2mm in the present embodiment.In addition, median size is measured by image analysis method or JISZ8801 size analysis method etc.
Secondly, utilization is comprised the method for the apparatus for recovering metal recovery metal of such formation describes, at first, make as the waste liquid of process object and use in the 7 inflow reactor main bodys 1 of chamber through flowing into from inflow pipe 8.On the other hand, drop into the metallics (Zn particle) that is used to make cementation reaction generation from upper chambers 9.Reach flow state in reactor body 1, make the waste liquid that is flowed into rise in vertical direction, on the other hand, this waste liquid forms fluidized-bed with the metallics that drops into from upper chambers 9.
Then, take place based on the difference of metals such as the Cu that is contained in the waste liquid, Sn and the ionization tendency of input metallics Zn, so-called cementation reacts.Be explained in more detail, each reduction of metal ion reaction illustrates the standard potential (E °) of each metal ion respectively as shown in the formula shown in (1)～(3).
Zn 2++2e→Zn...(1) -0.76V
Cu 2++2e→Cu...(2) +0.34V
Sn 2++2e→Sn...(3) -0.14V
Show by above-mentioned (1)～(3), with Cu 2+, Sn 2+Compare Zn 2+The standard electrode potential minimum.In other words, compare the ionization tendency maximum of Zn with Cu, Sn.Therefore, reaching under the state of flow state as described above, the Zn that ionization tendency is big becomes Zn 2+(with the opposite reaction of above-mentioned (1) formula), stripping in waste liquid, the Cu that is contained in the waste liquid meanwhile 2+, Sn 2+Become Cu, Sn, on the Zn particle surface, separate out.
Then, utilizing such cementation reaction to make after each metal of Cu, Sn separates out, make ultra-sonic oscillation body 11a, 11b, 11c work on the surface of Zn particle.By making this ultra-sonic oscillation body 11a, 11b, 11c work, the ultrasonic wave of being vibrated from this ultra-sonic oscillation body 11a, 11b, 11c, give vibration force and whipping force to above-mentioned Zn particle of having separated out Cu, Sn, thus each metal of Cu, Sn of separating out is forced to peel off from the Zn particle.In this case, though can make ultra-sonic oscillation body 11a, 11b, 11c non-stop run,, exist to be difficult to possibility that the ultra-sonic oscillation body is worked long hours if non-stop run then ultra-sonic oscillation are known from experience heating.In addition, if make the non-stop run of ultra-sonic oscillation body, then the size of growing, reaching to a certain degree at the metal of separating out (Cu, Sn) is peeled off before in turn, and its result might be able to not get the precipitating metal of size to a certain degree.Because this point, if the ultra-sonic oscillation body is worked off and on, the possibility that the metal of then separating out was at random peeled off before the size that reaches to a certain degree is less, therefore, and the metal separate easily of peeling off.Therefore, the work of preferred ultra-sonic oscillation body 11a, 11b, 11c is carried out off and on.The work at the intermittence of this occasion, for example the ON by 2 seconds, 8 seconds OFF wait and carry out.
The Cu of being stripped from like this, Sn are expelled to the outside of reactor body 1 from upper chambers 9 through vent pipe 10, are reclaimed as recycle object metal (in the present embodiment for Cu and Sn alloy).In this case, in the present embodiment, as the metal that drops into for the recycle object metal is separated out, use emboliform, therefore such with for example dropping into zinc bits situation is compared, the surface area that is used to make cementation react the metal (Zn) that takes place increases, thereby the speed of the evolution reaction of Cu, Sn improves.
Secondly, after the separating out of the metal of confirming to grow to a certain degree, peel off by the pressure that utilizes hyperacoustic vibration to carry out as described above, thereby always expose new metallic surface (surface of Zn particle), can keep speed of response.In addition, compare with the method for the input zinc bits that carried out in the past, the impurity in the recycle object metal of peeling off beyond Cu, the Sn is considerably less.
In addition, the metallics that is formed by Zn flows the stripping Zn by above-mentioned cementation reaction in reactor body 1 2+, therefore drop into the particle diameter of input during the initial stage of the metallics of upper chambers 9, all reduce in any case be accompanied by the passage of time.Its result, if the reactor section from reactor lower part to reactor top is identical, waste liquid rises in reactor body 1 with identical substantially upwards mobile speed so, therefore, past more top particle diameter reduces more, and the metallics that diminishes might be from reactor body 1 overflow at random.
But in the present embodiment, the basal area of reactor body 1 forms, and increases more discontinuously towards the top more, and therefore, the upwards mobile speed of the waste liquid in reactor body 1 reduces lentamente.Therefore, the metallics that reduces by particle diameters such as cementation reactions as described above, on the top of the ever-increasing reactor body 1 of basal area, can overflow outside reactor body at random, the possibility that is maintained in the reactor body 1 uprises.
In addition, flow in the lower side of waste liquid from reactor body 1, when in reactor body 1, passing through, react by cementation, on the metallics that forms by Zn, separate out the metals such as Cu, Sn that become recycle object, therefore get over the top of orientating reaction device main body 1, the recycle object concentration of metal in the waste liquid reduces more.
But in the present embodiment, there is fine metallics more in the top by past more reactor body 1, the upwards mobile speed of waste liquid slowly reduces in addition, the quantity that can find metallics increases, and therefore, the total surface area of the upper metal particle of past more reactor body 1 increases more.Its result, the speed of response (efficient that the recycle object metal is separated out) of cementation reaction improves, and therefore, even become the top of the reactor body 1 of lower concentration in the recycle object concentration of metal, also can efficient recycle the recycle object metal well.
(embodiment 2)
In the present embodiment, the structure of reactor body 1 is different with above-mentioned embodiment 1.That is to say that in the present embodiment, as shown in Figure 2, the whole peripheral surface of reactor body 1 forms towards the top and becomes taper, the basal area that is constituted as reactor body 1 increases continuously towards the top.This point, the situation of the embodiment 1 that increases discontinuously towards the top with the basal area of reactor body 1 is different.
Because be constituted as, basal area is not to increase towards the top discontinuously but continuously, so in the present embodiment, does not resemble and distinguishes, constitutes reactor top 2, reactor pars intermedia 3, reactor lower part 4 embodiment 1.
But it is common being provided with to three positions of bottom from the top of reactor body 1 on ultra-sonic oscillation body 11a, 11b, the 11c this point with embodiment 1.Therefore, even in the present embodiment, also with embodiment 1 similarly, can access the ultrasonic wave that utilization is vibrated from ultra-sonic oscillation body 11a, 11b, 11c, the effect that the recycle object metal of separating out on metallics is peeled off forcibly.
In addition, though have discontinuous, successive is different, but be constituted as basal area towards above to increase on this point with embodiment 1 be common, therefore, even in the present embodiment, also produce following effect, that is: the fine metallics that particle diameter is reduced remains on the top of reactor body 1, prevent from random to overflow to the outer effect of reactor body, and, in the recycle object concentration of metal is the top of the reactor body 1 of lower concentration, can efficient recycles the effect of recycle object metal well.
(embodiment 3)
The reactor body 1 of present embodiment is a lengthwise, this point and above-mentioned embodiment the 1, the 2nd, common, but as Fig. 3 and shown in Figure 4, it is identical that it forms on above-below direction basal area, and this point is with to be constituted as the above-mentioned embodiment 1,2 that basal area increases towards the top different.
In the present embodiment, same with above-mentioned embodiment 1, be provided with in the lower side of reactor body 1 and flow into, and be provided with upper chambers 9, but its shape is different with the embodiment 1 that is formed conical shaped in the upper side of reactor body 1 with chamber 7.That is to say, upper chambers 9 is as Fig. 3 and be formed shallow cylindric as shown in Figure 4, flow into chamber 7,, be formed the shape that the side tube part 21,21 that is provided with about being communicated with also by tube portion 20 of central authorities with this tube portion of central authorities 20 constitutes as Fig. 5 and shown in Figure 6.
In the present embodiment, inflow pipe 8,8 is located at the front of above-mentioned inflow with the side tube part 21,21 of chamber 7 respectively.And, be constituted as, respectively be provided with two traverse baffles 22,23 in the vertical at the side tube part 21,21 that flows into chamber 7, from the processed liquid that inflow pipe 8,8 flows into, disarrayed the flow direction by these traverse baffles 22,23.
In addition, upper chambers 9 as shown in Figure 4, is made of inner core 9a and logical outward 9b, and as shown in the drawing, inner core 9a is entrenched in the top of reactor body 1 outward, thereby upper chambers 9 is installed on the reactor body 1.In addition, vent pipe 10 is installed in the bottom of upper chambers 9, on the position between promptly above-mentioned inner core 9a and the urceolus 9b.The result of Gou Chenging is like this, and the processed liquid of circulation upwards in the inside of reactor body 1 overflows between urceolus 9b and the inner core 9a from the upper opening portion of inner core 9a, is expelled to the outside from above-mentioned vent pipe 10.
In addition, be used to make the upper opening portion input of the metallics of cementation reaction generation from inner core 9a.And be constituted as, the waste liquid that flows into from the inflow pipe 8 that flows into chamber 7 is during till the vent pipe 10 that arrives upper chambers 9, processed liquid rises on one side in vertical direction on one side and forms fluidized-bed by metallics, the cementation of input metal and recycle object metal is reflected in the whole reactor main body 1 and takes place, and this point and above-mentioned embodiment 1,2 are common.
And, in the present embodiment, the metal that contains as making in the waste liquid, promptly be reflected at the stripping off device of the recycle object metal-stripping of separating out on the metallics by cementation, adopt the ultra-sonic oscillation body.That is to say, in the present embodiment, 4 ultra-sonic oscillation body 11a, 11b, 11c, 11d are installed on the periphery of reactor body 1.These 4 ultra-sonic oscillation body 11a, 11b, 11c, 11d, the angles that all relative horizontal plane constitutes about 45 degree are installed on the reactor body 1, install towards ground but wherein two ultra-sonic oscillation body 11a, 11c are identical, in addition two ultra-sonic oscillation body 11b, 11d install towards reverse direction.
In the present embodiment, use waste liquid,, for example use with the same metal finishing workshop-sink that contains metal ions such as Cu, Sn of above-mentioned embodiment 1 etc. as this waste liquid as processed liquid.In this case, same with embodiment 1, can use the Zn particle as the metallics that drops into, Cu, Sn are reclaimed as metal.
And, reclaim at the apparatus for recovering metal that utilizes present embodiment under the situation of metal, at first, waste liquid is used in the 7 inflow reactor main bodys 1 of chamber through flowing into from inflow pipe 8.In this case, flow into chamber 7, constitute by tube portion 20 of central authorities and side tube part 21,21 as mentioned above, vertically respectively be provided with two traverse baffles 22,23 at side tube part 21,21, therefore, from the waste liquid that flows into respect to the side tube part 21 horizontal inflow pipes of installing 8,8, do not flow at a heat in the horizontal, but flow along traverse baffle 22, the 23 upper-lower interactive ground in side tube part 21 that is provided with in the vertical on one side, flow on one side in the tube portion 20 of central authorities, from these tube portion of central authorities 20 upwards circulations of orientating reaction device main body 1.Therefore,, disarrayed the flow direction, do not produce bias current and become and in reactor body 1, be easy to the upwards state of circulation by traverse baffle 22,23 from the waste liquid that inflow pipe 8,8 flows into.In addition, if necessary, can in flowing into chamber 7, the object of the ball of for example pack into glass or pottery system be set in chest cylindraceous, can prevent bias current more reliably thus.
Based on effect difference, so-called cementation reaction of the ionization tendency of metal such as the Cu that is contained in the waste liquid, Sn and input metallics Zn, utilize the stirring that the ultra-sonic oscillation body carries out and the effect of peeling off of metal etc., identical with above-mentioned embodiment, omit its detailed description.
(embodiment 4)
In the present embodiment,, replace the device that utilizes ultrasonic wave that the ultra-sonic oscillation body is vibrated to vibrate of above-mentioned embodiment 1～3, adopted the device that uses electro-magnet to stir as the device of peeling off the recycle object metal of separating out from metallics.That is to say, in the present embodiment, the slide plate with electro-magnet 12 13 as shown in Figure 8, lifting is installed on the guide rail 14 of the side that is arranged at reactor body 1 freely like that shown in 7.Slide plate 13 as shown in Figure 8, has spatial portion 15 in central authorities, reactor body 1 is inserted in this spatial portion 15 set in the mode of surrounding this reactor body 1.In addition, in Fig. 8, do not illustrate reactor body 1.In addition, in the present embodiment, it is oblong-shaped that reactor body 1 forms horizontal section, and this point and section are circular, and just reactor body 1 forms above-mentioned embodiment 1～3 difference cylindraceous.
And, shown in the arrow 16 of Fig. 7,, when the metallics in the reactor body 1 is stirred, a plurality of metallicss are collided mutually by moving with making its alternatively up and down, from metallics, peel off precipitating metal forcibly thus.Electro-magnet 12 applies in turn with for example 2 seconds etc. certain intervals, in addition the mobile compartment of terrain up and down of slide plate 13 or carry out continuously.Though peel off the device difference of the recycle object metal of separating out from metallics, in the present embodiment, also can well the recycle object metal be peeled off and reclaim from metallics.In addition, employed metallics under the situation of present embodiment can use the iron particle as magnetic substance.
In addition, iron (Fe) ionic reduction reaction and standard potential are as follows.
Fe 2++2e→Fe...(4) -0.44V
Relative therewith, the reduction reaction of Cu, Sn, standard potential, shown in above-mentioned (2), (3) formula, the numerical value of standard potential, ratio Cu, the Sn's of Fe is little, therefore, the ionization tendency of Fe is bigger than the ionization tendency of Cu, Sn, so present embodiment also goes for containing the waste liquid of Cu, Sn.
(embodiment 5)
In the present embodiment, as shown in Figure 9, be equipped with two reactors, this point is different with the situation of the embodiment 1～4 that only comprises a reactor.That is to say, in the present embodiment, the back segment of first section reactor body 1a promptly the leading portion side of second section reactor body 1b be provided with strainer 17, and be provided with strainer 18 at the rear section side of second section reactor body 1b.As strainer, can use for example built in type strainer, cylinder filter etc.In addition, also can replace strainer and use equipment for separating liquid from solid such as belt press, pressure filter.
In the present embodiment, for example become in the waste liquid of object and contain under the situation of Cu and Sn, can in first section reactor body 1a, drop into the Fe particle, Cu is separated out on this Fe particle and reclaim Cu by first section strainer 17, in second section reactor body 1b, drop into the Zn particle, Sn is separated out on this Zn particle and reclaim Sn by second section strainer 18.
This occasion, from numerical value by the standard potential shown in above-mentioned (2), (3), (4) formula, the ionization tendency of Cu, Sn is all littler than Fe, but its ionization tendency is poor, the difference of Fe and Cu is poor much larger than Fe and Sn's, therefore, in first section reactor body 1a, Cu preferentially separates out on the Fe particle.On the other hand, from numerical value by the standard potential shown in above-mentioned (1) formula, the ionization tendency of Zn is bigger than the ionization tendency of Cu, Sn, therefore, in second section reactor body 1b, Cu, Sn all should separate out on the Zn particle, but because Cu separates out on the Fe particle of first section reactor body 1a, therefore, in second section reactor body 1b, Sn mainly separates out on the Zn particle.But the lingering section of the Cu that does not separate out on the Fe particle in first section reactor body 1a is separated out on the Zn particle in second section reactor body 1b.
Like this, in the present embodiment, has the advantage that to use two kinds of different metallicss from waste liquid, optionally to reclaim two kinds of metals.In addition,, be not particularly limited, can utilize the above-mentioned method of utilizing the ultra-sonic oscillation body, use electro-magnet stirring method, additive method described later though the means of peeling off the recycle object metal of being separated out from metallics are not are not recorded and narrated.
(embodiment 6)
In the present embodiment, as shown in figure 10, be equipped with three reactors, this point and the embodiment 1～4 that only comprises a reactor, the situation of embodiment 5 that is equipped with two reactors are different.In the present embodiment, the rear section side at this three reactor body 1a, reactor body 1b, reactor body 1c is provided with strainer 17, strainer 18, strainer 19.In the present embodiment, same with above-mentioned embodiment 5, in first section reactor body 1a, drop into the Fe particle, in second section reactor body 1b, drop into the Zn particle, in the 3rd section reactor body 1c, drop into aluminium (Al) particle.
When present embodiment being applicable to when similarly containing the waste liquid of Cu and Sn with above-mentioned embodiment 5, same with embodiment 5 in first section reactor body 1a, Cu separates out on the Fe particle, and reclaim Cu by first section strainer 17, in second section reactor body 1b, also same with embodiment 5, Sn separates out on the Zn particle and reclaims Sn by second section strainer 18.
But, in the 3rd section reactor body 1c, produce 5 not effects of expectability of embodiment.That is to say, as mentioned above in first section reactor body 1a by the cementation reaction Fe of stripping, with in second section reactor body 1b by the cementation reaction Zn of stripping, separate out on the Al particle in putting into the 3rd section reactor body 1c.
Illustrate in greater detail this point, Al ionic reduction reaction and standard potential are illustrated by following formula (5).
Al +3+3e→Al...(5) -1.66V
Input Fe particle in first section reactor body 1a, with input Zn particle in second section reactor body 1b, constitute by the ionization tendency metal bigger as mentioned above than recycle object metal, but from relatively by the numerical value of the standard potential shown in (1), (4), (5) formula, the ionization tendency that shows Al is bigger than the ionization tendency of Fe, Zn.Therefore, the Zn of the Fe of stripping and stripping in second section reactor body 1b all separates out on the Al particle in the 3rd section reactor body 1c in first section reactor body 1a.And, utilize the Al particle to be reclaimed as the Fe-Zn alloy.
Therefore, need not make in back segment in the reactor body 1b of first section reactor body 1a and second section separately that the Fe and the Zn of stripping carry out the operation of coagulation sedimentation etc., can suppress the sludge generating capacity.In addition, Al stripping in the 3rd section reactor body 1c, but the stripping quantity stripping that tervalent Al lacks with Zn and Fe than divalence, the proportion of Al is also light, thereby sludge weight is reduced, and therefore, the sludge generating capacity can not increase.In the present embodiment, the means to the recycle object metal of separating out is peeled off from metallics are not particularly limited.
(embodiment 7)
In the present embodiment, as the device that the recycle object metal of separating out is peeled off from metallics, the device that replaces the use electro-magnet of device that the ultrasonic wave of utilizing the ultra-sonic oscillation body to vibrate of above-mentioned embodiment 1～3 vibrates and embodiment 4 to stir has adopted device that the gas that is blown into air and so on stirs, that what is called is utilized the air lift effect.That is to say in the present embodiment, as shown in figure 11, possess cylindrical portion 25, be connected with gas inflow pipe 26 in the bottom of this cylindrical portion 25 in the substantial middle of reactor body 1.One distolateral peristome of this gas inflow pipe 26 is the outside that gas inflow entrance 27 extend out to above-mentioned reactor body 1, and the other end side opening portion 28 of gas inflow pipe 26 is in and above-mentioned cylindrical portion 25 connected states.In addition, below the lower openings portion 29 of cylindrical portion 25, be provided with traverse baffle 30.
In the present embodiment, same with above-mentioned embodiment 3, reactor body 1 forms roughly cylindric, and is same with above-mentioned embodiment 1～3 in addition, is provided with in the bottom of reactor body 1 to flow into chamber 7, is provided with upper chambers on top.But in Figure 11,, do not illustrate upper chambers though illustrate vent pipe 10.In the present embodiment, can use the particle of Al or Zn as the metallics that drops into.In addition, as the waste liquid that becomes object, can use and contain indium (In) ionic flat-panel screens (FPD) manufacturing works waste liquid etc.In this case, In is recovered as metal.
It is the metallics of 0.1～8mm as mentioned above that the metallics that drops into can use median size, but is under the situation of Al at metallics, and preferred 1.5～5.5mm's is under the situation of Zn at metallics, preferred 1.5～4.0mm's.Its reason is under the situation that is the Zn particle, if median size surpasses 4.0mm, under the situation that is the Al particle, if median size surpasses 5.5mm, the necessary flow velocity of these particle flow is increased, and the gas amount of being blown into to increase in addition.On the other hand, because cementation reaction, the particle diameter of metallics reduces lentamente, therefore, if the particle diameter of initial metallics is little, then as mentioned above, exist metallics and treatment solution together from reactor body 1 effusive possibility, from this viewpoint, under the situation of Zn particle, Al particle, preferred median size is more than the 1.5mm.
Then, the method that the apparatus for recovering metal that utilizes present embodiment is reclaimed metal describes, and is same with the respective embodiments described above, at first makes waste liquid in flowing into chamber 7 inflow reactor main bodys 1, and drops into metallics from upper chambers.In addition, make gas flow into cylindrical portion 25 through gas inflow pipe 26.Thus, the proportion of the gas in the cylindrical portion 25 and the mixing portion of water reduces, and liquid and gas together are pushed to top.
Like this, flow into cylindrical portion 25 and upwards circulation by making gas, thus also upwards circulation of the processed liquid in the cylindrical portion 25.Like this, processed liquid is at the internal circulation of cylindrical portion 25, but inside and the outside pressure difference that produces in cylindrical portion 25, therefore in the circulation speed difference of the inside and outside processed liquid of cylindrical portion 25, its result, metallics is stirred in reactor body 1, thereby the In that separates out on the surface of metallics is stripped from.
In this case, recycle object metal In in the present embodiment, separate out with spongy, therefore compare with Cu, the Sn of above-mentioned embodiment 1 grade, poor adhesion to metallicss such as Zn, therefore do not force the device of peeling off even do not adopt the use electro-magnet that utilizes device that ultrasonic vibration forces to peel off, resembles embodiment 4 that resembles above-mentioned embodiment 1～3, resemble and only use the whipping appts that utilizes the air lift effect the present embodiment, also can with comparalive ease In be peeled off from metallics.That is to say, can adopt the device of device to reclaim In with simple and easy and low power consuming.
Secondly, take place based on the difference of the ionization tendency of the metallics Zn of the In that is contained in the waste liquid and input or Al, so-called cementation reacts.Be explained in more detail, In ionic reduction reaction is shown below, and also shows standard potential (E °).
In 3++3e→In...(6) -0.34V
Show by above-mentioned (1), (5), (6) formula, with In 3+Compare Zn 2+, Al 3+Standard electrode potential little.In other words, compare with In, the ionization tendency of Zn, Al is big.Therefore, the Zn that ionization tendency is big, Al become Zn 2+Or Al 3+And stripping is in waste liquid, meanwhile the In that is contained in the waste liquid 3+Become In, on the surface of the particle of Zn, Al, separate out.Make after In separates out on the surface of Zn particle or Al particle by such cementation reaction, by the stirring that utilizes the air lift effect as described above, the In that separates out peels off from Zn particle or Al particle, the In of being stripped from is expelled to the outside of reactor body 1 and is recovered through vent pipe 10.
In addition, in the present embodiment, below the lower openings portion 29 of cylindrical portion 25, be provided with traverse baffle 30, therefore, do not flow directly into cylindrical portion 25 from the current that flow into the waste liquid that flows into chamber 7, but meet, thereby stop the circulation speed of the processed liquid in the cylindrical portion 25 extremely to be accelerated well with traverse baffle 30.
(embodiment 8)
In the present embodiment,, adopt air spray stirring or jet of water to stir as the means that the recycle object metal is peeled off from metallics, different with above-mentioned embodiment 1～7 in this.That is to say, in the present embodiment, as shown in figure 12, be constituted as, stir the week face that is installed in reactor body 1 with ejection apparatus 31, spray from this and stir apparatus 31 ejection air or water, in reactor body 1, produce fine bubble spraying.That is to say that so-called air spray is stirred, mean gas, the fine bubbles of generation such as ejection air, so-called jet of water stirs, and means liquid such as spraying water, produces fine bubble.
The shape of reactor body 1 flows into the formation of chamber 7, vent pipe 10 identically with above-mentioned embodiment 7 with being provided with, so omits its explanation.In addition, the metallics of input, become the waste liquid of object kind, also have the cementation reaction effect etc. also all identical with above-mentioned embodiment 7, therefore omit its detailed description.In the present embodiment, stir gas or the water (for example treatment solution) that sprays air and so on ejection apparatus 31 from above-mentioned injection, in reactor body 1, produce turbulent flow, utilize the metallics in this turbulent flow stirred reactor main body 1, thus, the In that separates out on the surface of metallics is stripped from.
In the present embodiment, as the In of recycle object metal poor adhesion to metallicss such as Zn, therefore, do not force the device of peeling off even do not adopt the use electro-magnet that utilizes device that ultrasonic vibration forces to peel off, resembles embodiment 4 that resembles above-mentioned embodiment 1～3, utilize and only carry out the device that air spray or jet of water stir, also can with comparalive ease In be peeled off from metallics.That is to say, can adopt the device of device to reclaim In with simple and easy and low power consuming.
(embodiment 9)
In the present embodiment,, adopt the device utilize the solid-liquid transferpump to stir as the device that the recycle object metal is peeled off from metallics, different with above-mentioned embodiment 1～8 in this.That is to say, in the present embodiment, as shown in figure 13, adopted following device, that is: stream 32 and the pump 33 that makes processed liquid in the reactor body 1 and metallics circulation and carry in the outer setting of reactor body 1, by utilizing said pump 33 that processed liquid and metallics are circulated in above-mentioned stream 32 and reactor body 1 and carrying, come above-mentioned metallics is stirred.
The shape of reactor body 1 flows into the formation of chamber 7, vent pipe 10 identically with above-mentioned embodiment 7,8 with being provided with, so omits its explanation.In addition, the kind of the metallics of input and the waste liquid that becomes object, the effect etc. that also has the cementation reaction are also all identical with above-mentioned embodiment 7,8, therefore omit its detailed description.
In the present embodiment, by pump 33 processed liquid and metallics are together flowed out to stream 32 from reactor body 1, circulation in this stream 32, and be sent back to reactor body 1 once again, its result, metallics in the reactor body 1 is stirred, and thus, the In that separates out on the surface of metallics is stripped from.
In the present embodiment, because as the In of precipitating metal poor adhesion to metallicss such as Zn, therefore, do not force the device of peeling off even do not adopt the use electro-magnet that utilizes device that ultrasonic vibration forces to peel off, resembles embodiment 4 that resembles above-mentioned embodiment 1～3, utilize and use pump 33 and stream 32 only to carry out the device that the solid-liquid transferpump stirs, also can with comparalive ease In be peeled off from metallics.That is to say, can adopt the device of device to reclaim In with simple and easy and low power consuming.
(embodiment 10)
The retrieving arrangement of the indium of present embodiment as shown in figure 14, has reactor body 1, adjusts groove 42 and strainer 43.Reactor body 1 is used for by cementation reaction (metal evolution reaction) In being separated out from waste liquid (processed liquid) as hereinafter described, and adjusting groove 42 is to be used for adding chloride-ion source (Cl to waste liquid before this -Thereby) chlorine ion concentration in the processed liquid is adjusted, strainer 43 is to be used for separating, be recovered in In's that above-mentioned reactor body 1 separates out.Moreover, be constituted as, separated treatment solution can be transmitted back in the above-mentioned adjustment groove 42, the stream that is used for loopback is set between strainer 43 and the adjustment groove 42.In addition, also be provided with from adjust groove 42 to the stream of reactor body 1 and from reactor body 1 to strainer 43 stream.In Figure 14, do not illustrate the processed liquid round-robin pump etc. of sening as an envoy to.
In the present embodiment, to being that the situation of object describes as processed liquid with the waste liquid.The formation of reactor body 1 is identical with above-mentioned embodiment 1, therefore omits its detailed description.
In the present embodiment, can use the particle of zinc (Zn), aluminium (Al) as the metallics that drops into.In addition, as the waste liquid that becomes object, for example can use and also contain nitrate ion (NO simultaneously at the ionic that contains In 3 -) the scrub raffinate of aluminium target, perhaps utilized the etching waste liquor etc. of the FPD of nitric acid.
Next, utilization is comprised that the method that the retrieving arrangement of the In of such formation reclaims In describes, at first,, adjust in groove 42 at this and add as chlorion (Cl to adjusting the waste liquid that groove 42 is supplied with as process object -) muriate of sodium-chlor, Repone K and so in source.In addition, because if the pH value increases, then indium can form the throw out of oxyhydroxide, so in advance the pH value is adjusted into below 1.5 in order not form throw out.In addition,, then can promote and employed reaction of separating out, H takes place with metal if the pH value is low excessively 2, NO, NO 2Gas consumes to separate out meaninglessly and uses metal, and therefore, the pH value is preferably more than 0.5.
In addition preferably, under the situation of pH value, utilize hydrochloric acid to carry out the pH value and adjust, be lower than in pH value under the situation of above-mentioned scope and carry out the adjustment of pH value by adding alkali such as NaOH greater than above-mentioned scope.
Then, make and add the processed liquid that muriate has carried out adjustment in this wise, use in the 7 inflow reactor main bodys 1 of chamber through flowing into from inflow pipe 8.On the other hand, drop into the metallics (Zn or Al particle) that is used to make cementation reaction generation from upper chambers 9.In reactor body 1, become flow state, and make the waste liquid that is flowed into rise in vertical direction, form fluidized-bed from upper chambers 9 input metallicss on the other hand.
Then, take place to react with different, so-called cementation as the ionization tendency of the Zn of the metallics that is dropped into or Al based on the In that is contained in the waste liquid.
Be explained in more detail, each reduction of metal ion reaction is as indicated in above-mentioned (1), (5), (6) formula, with In 3+Compare Zn 2+, Al 3+Standard electrode potential little.
In other words, compare with In, the ionization tendency of Zn, Al is big.Therefore, becoming under the state of flow state as described above, Zn, Al that ionization tendency is big become Zn 2+Or Al 3+, stripping in waste liquid, the In that is contained in the waste liquid meanwhile 3+Become In, on the surface of the particle of Zn, Al, separate out.
In this case, because contain nitrate ion (NO in the waste liquid 3 -), so standard electrode potential that might In reduces, and standard electrode potential that might Al, Zn raises, and the potential difference of In and Al or Zn diminishes, and reduction that might In is separated out and is become difficult.But, in the present embodiment, processed liquid is supplied to adjusts groove 42 in advance, and be added with chlorion (Cl -) source, therefore, in the time of in this processed liquid inflow reactor main body 1, chlorion (Cl -) form the chloro-complex of In, thus, the standard electrode potential of In raises once more, and its result can not hinder In and separate out on the surface of the particle of Zn, Al.
Other effect that makes cementation reaction generation and stripping process etc., identical with the respective embodiments described above, therefore omit its explanation.
(other embodiment)
In addition, in the above-described embodiment, situation to etching waste liquor of being applicable to the situation of the waste liquid of the ionic metal finishing factory of containing Cu, Sn, the scrub raffinate that is applicable to the aluminium target, FPD as waste liquid (processed liquid) etc. is illustrated, but the kind that becomes the waste liquid of object is not limited to this, can also be applicable to plating workshop-sink, semiconductor fabrication factory waste liquid, liquid crystal manufacturing works waste liquid etc.In addition, as processed liquid, though be the main starting point to use waste liquid in the present invention, but also go for the processed liquid beyond the waste liquid, for example, make medicine contact such as acid contain the solid waste of metal, the metal that dissolving should be reclaimed carries out ionization and the aqueous solution that obtains.
Therefore, the metal that becomes the object of recovery also is not limited to Cu, Sn, the In of this embodiment, and for example Ni, Ga, Zn etc. also can be used as the recycle object metal, and the kind of recycle object metal is not limit.
In addition, in this embodiment, the median size of metallics is defined as about 2mm, but the median size of metallics is not limited by this embodiment.But be preferably 0.1～8mm.If not enough 0.1mm, then exist the cementation reaction to carry out well, can't easily carry out the recuperability of the recycle object metal peeled off from metallics in addition, if surpass 8mm, then the quantity of the metallics that can keep in reactor body reduces, the total surface area of metallics reduces as a result, the efficient of possible evolution reaction reduces, in addition, need to improve flow velocity for metallics is flowed, need make reactor maximization (increasing the height of reactor) in order to keep the necessary reaction times.From this viewpoint, 0.5～6mm more preferably.And, become well in order to make flowability, reactivity in the reactor body, in order easily to carry out the maintenance in reactor body, the more preferably scope of 1.0～2.0mm.
In addition, the median size of metallics, as previously described, by mensuration such as image analysis method, JIS Z8801 size analysis methods.Utilize the mensuration of the median size of image analysis method, use for example ミ リ ト ラ Star Network JPA of Nikkiso Company Limited's system.In addition, in the method for sieving of JIS, be under the situation of scope of 1～2mm in median size, for example use under the sieve of nominal size 2000 μ m and the metallics on the sieve of 1000 μ m.
In addition, from the viewpoint of processing efficiency, operation control etc., the uniformity coefficient of preferable alloy particle is less than 5.Here, the uniformity coefficient of so-called metallics, be meant by formed transmittance curves such as particle size distribution or screenings (less than the quality of the particle of certain particle diameter percentage with respect to whole sample masses, promptly draw the curve of transmitance with respect to certain particle diameter, be also referred to as sieve summation curve down) in, 60% particle diameter is divided by sieving the resulting value of 10% particle diameter down under the sieve.It is the width of expression size-grade distribution.
And in the respective embodiments described above, metallics has utilized metal simple-substance, but also can be alloy.As alloy, can use iron-aluminium alloy, calcium-silicon alloy etc.
And in above-mentioned embodiment 1,2, the basal area that forms reactor body 1 is big more towards the top more, has therefore obtained ideal effect as described above, but has formed the optional in the present invention condition of reactor body 1 like this.Also can be as embodiment 3,7,8,9, the basal area that forms reactor body 1 is identical, and integral body becomes roughly cylindric.
And, peel off the device of precipitating metal from metallics, also be not limited to each device of above-mentioned embodiment 1～9, can be the devices beyond these devices.
And, in above-mentioned embodiment 10, used muriates such as sodium chloride, Repone K as the chloride-ion source of adding, but be not limited to such muriate, can also use hydrochloric acid.But if use hydrochloric acid, then the acid concentration of processed liquid increases, and the solubilizing reaction of separating out with metal of use is promoted, produces hydrogen.This causes unwanted consumption increase and hydrogen generating capacity of separating out with metal to increase, and then causes running cost to increase, and therefore, as chloride-ion source, preferably uses the muriate of above-mentioned embodiment 10.
On the other hand, if add the reduction evolution reaction that chloride-ion source is carried out In, the metal ion that then uses dissolving, and also hydrogen must take place, and therefore, the H in the solution +Be consumed, the pH value of processed liquid raises.If the pH value is greater than about 1.5, the In in the then processed liquid becomes oxyhydroxide and separates out precipitation, and is therefore sour for pH value being reduced need to add.Under these circumstances, preferably add hydrochloric acid.
In addition, in above-mentioned embodiment 10, as shown in figure 14, treatment solution after using is transmitted back to adjustment groove 42, therefore the result is, remains in chloride-ion source in this treatment solution and is added to as in the processed liquid (waste liquid) of stoste and be reused, therefore, the ideal effect that has obtained making the necessary muriatic amount of appending of ensuing In recycling to reduce, to utilize chloride-ion source again be not condition essential among the present invention but resemble the above-mentioned embodiment loopback treatment solution.And, in the above-described embodiment, be provided with the adjustment groove 42 that is used to add chloride-ion source mutually distinctively with reactor body 1, be not limited to this, also can in reactor body 1, directly add chloride-ion source and adjust.
In addition, use metal, used metallics, but be not limited to this, also can utilize metal wire, metal wire is processed into the material that mesh-like forms, tabular metal etc. as separating out of the respective embodiments described above.
Embodiment
(embodiment 1)
Use Zn as metallics, as the processed liquid use of the simulation of test usefulness copper-bath.Use device as test, as shown in figure 14, use except the reactor body 1 that possesses ultra-sonic oscillation body 11 in central authorities the device that also is provided with two jars 34,35, two pumps 36,37, deep bed filter 39 and connects their stream 39,40,41.
The pH value of copper-bath is 5, starting point concentration is 65.5mg/L, treatment solution is 70L, is the metallics of 0.05mm, 1mm, 2mm, 5mm, 10mm for median size, tests thereby supply with processed liquid and make to circulate in testing apparatus shown in Figure 15.Test-results is shown in table 1～5 and Figure 16.
As indicated in table 1～5 and Figure 16, be under the situation of metallics of 1mm, 2mm, 5mm adopting median size, compare with the situation of the metallics that adopts 0.05mm, 10mm, good as the rate of removing of the copper (Cu) of precipitating metal.
Table 1 (median size is 0.05mm)
Treatment time (minute) Cu concentration (mg/L) Cu removes rate (%)
0.0 65.5 0
1.0 53.5 18
2.0 48.5 26
3.0 42.5 35
5.0 36.2 45
10.0 25.0 62
20.0 15.4 76
Table 2 (median size is 1mm)
Treatment time (minute) Cu concentration (mg/L) Cu removes rate (%)
0.0 65.5 0
1.0 45.1 31
2.0 43.1 37
3.0 35.0 47
5.0 23.6 64
10.0 10.4 84
20.0 1.5 98
Table 3 (median size is 2mm)
Treatment time (minute) Cu concentration (mg/L) Cu removes rate (%)
0.0 65.5 0
1.0 50.2 23
2.0 43.9 33
3.0 37.6 43
5.0 27.7 58
10.0 15.5 76
20.0 1.9 97
Table 4 (median size is 5mm)
Treatment time (minute) Cu concentration (mg/L) Cu removes rate (%)
0.0 65.5 0
1.0 58.2 11
2.0 47.7 27
3.0 41.4 37
5.0 33.6 49
10.0 22.8 65
20.0 10.1 85
Table 5 (median size is 10mm)
Treatment time (minute) Cu concentration (mg/L) Cu removes rate (%)
0.0 65.5 0
1.0 62.2 5
2.0 60.8 7
3.0 59.0 10
5.0 57.5 12
10.0 55.0 16
20.0 51.5 21
(embodiment 2)
As the simulated solution of waste liquid, prepared the salpeter solution that is dissolved with indium.Simulated solution uses the liquid that is dissolved with In in 2.8% salpeter solution with the concentration of 400mg/L.In the beaker with its 1L that packs into, at first add the sodium-chlor of 50g, use the median size that records by the image analysis method Al metallics, the recycling of beginning In alloy as 2mm.When handling, H takes place 2Gas and the main NO that produces 2Gas.Along with processing, H +Become H 2Gas is consumed, so the pH value raises, and therefore decides pH value in the solution with pH value instrumentation, is no more than 1.5 and interpolation hydrochloric acid carries out 120 minutes stir process with the immobilising degree of particle in order to make the pH value.The In alloy of separating out on the Al metallics is spongy, carry out stir process during aggegation, become bigger piece, therefore, utilize ultrasonication can easily peel off recovery.Ultrasonication was carried out once every two minutes, carried out for two seconds respectively.Illustrate in passing that resulting In alloy is the size of hundreds of μ m～number mm.If become big like this piece, then promptly use the strainer of the cheapness of deep bed filter and so on also can reclaim.
Add the new stoste (salpeter solution that contains indium) of 1L in the liquid after above-mentioned processing, add 25g sodium-chlor, begin to handle, thereby can handle with technology same as described above.Therefore, the muriatic amount of being added can be cut down, the attenuating of processing cost can be sought.
With the result that condition as described above is tested, the rate of recovery that reclaims In from solution is 95%, has obtained very good result.
(embodiment 3)
The Al metallics that replaces the foregoing description 2 uses the Zn metallics, tests under other all identical conditions.In the present embodiment, the rate of recovery that has also obtained In is 90% good result.
(comparative example 1)
In the foregoing description 2, do not add sodium-chlor in the prepared simulated solution, only add the Al metallics, carried out same processing.In addition, the part of nitrate ion and Al metallics reacts, and the pH value becomes more than 1.5, therefore uses sulfuric acid to carry out the adjustment of pH value.Carry out 120 minutes solution stirring, but on Al metallics surface, do not find separating out of In alloy.
(comparative example 2)
Replace the Al metallics in the above-mentioned comparative example 1 and use the zinc metallics, under other all identical conditions, test.In this comparative example, do not find separating out of In yet.
Among the present invention the expression numerical range " more than " and " following " comprise given figure.

Claims (26)

1. the recovery method of a metal, it is characterized in that, make with ionic condition and contain in the processed liquid inflow reactor main body of recycle object metal, described reactor body is constituted as the described processed liquid that contains the recycle object metal with ionic condition and flows into from the bottom and flow out from top, and constitute basal area and increase towards the top, in described reactor body, add ionization tendency than big the separating out of described recycle object metal metal, utilize the difference of ionization tendency that the recycle object metal that is contained in the described processed liquid is separated out described separating out with metallic surface, then, utilize the means of peeling off to peel off described recycle object metal and reclaim from described separating out with metal.
2. the recovery method of metal according to claim 1 wherein, is means of utilizing ultrasonic wave to make to separate out with the metal vibration from separating out the means of peeling off the recycle object metal with metal.
3. the recovery method of metal according to claim 1 wherein, is to utilize electro-magnet to stir to separate out to use metal from separating out the means of peeling off the recycle object metal with metal, makes a plurality of means of colliding mutually with metal of separating out.
4. the recovery method of metal according to claim 1 wherein, is to stir the means of separating out with metal by air spray or jet of water from separating out the means of peeling off the recycle object metal with metal.
5. the recovery method of metal according to claim 1 wherein, is that cylindrical portion is set in reactor body from separating out the means of peeling off the recycle object metal with metal, is blown into gas and separates out means with metal with stirring in this cylindrical portion.
6. the recovery method of metal according to claim 1, wherein, from separating out the means of peeling off the recycle object metal with metal is that outer setting at reactor body makes the processed liquid in the described reactor body and separates out with metal circulation and stream and the pump carried, by making described processed liquid and separating out with metal circulation and carry, stir the described means of separating out with metal.
7. the recovery method of metal according to claim 1 wherein, utilizes the reactor body of multistage, adopts different two or more separating out with metal selective ground to reclaim two or more recycle object metals.
8. the recovery method of metal according to claim 1 wherein, adopts strainer to reclaim the recycle object metal of being stripped from.
9. the recovery method of metal according to claim 1 wherein, except the recycle object metal of ionic condition, also contains nitrate ion in the processed liquid, adds chloride-ion source in this processed liquid in the same way with separating out with metal one.
10. according to the recovery method of each the described metal in the claim 1～9, wherein, separating out with metal is that median size is the metallics of 0.1～8mm.
11. according to the recovery method of each the described metal in the claim 1～9, wherein, separating out with metal is that median size is the metallics of 0.5～6mm.
12. according to the recovery method of each the described metal in the claim 1～9, wherein, separating out with metal is that median size is the metallics of 1.0～2.0mm.
13. according to the recovery method of each the described metal in the claim 1～9, wherein, separating out with metal is aluminium, this is separated out with metal is that median size is the metallics of 1.5～5.5mm.
14. according to the recovery method of each the described metal in the claim 1～9, wherein, separating out with metal is zinc, this is separated out with metal is that median size is the metallics of 1.5～4.0mm.
15. the recovery method of metal according to claim 9, wherein, when making processed liquid flow into the adjustment groove, in this adjustment groove, add chloride-ion source, then the processed intravital while of liquid inflow reactor master in making this adjustment groove, in this reactor body, add to separate out and use metal.
16., wherein, will add in the processed liquid as stoste and handle once again by having separated out with metal recovery treatment solution after the recycle object metal according to the recovery method of claim 9 or 15 described metals.
17. the retrieving arrangement of a metal, it is characterized in that, possesses reactor body, with the stripping off device that makes it in order to reclaim the recycle object metal of separating out to peel off with metal from separating out, described reactor body is used to make the processed liquid inflow that contains the recycle object metal with ionic condition, and add ionization tendency than big the separating out of described recycle object metal metal, utilize the difference of ionization tendency to make the recycle object metal that is contained in the described processed liquid at the described metal evolution reaction of separating out of separating out with metallic surface, and, described reactor body constitutes the inflow portion that has processed liquid in the bottom of this reactor body, has liquid outflow portion on the top of reactor body, processed liquid is in described inflow portion inflow reactor main body, flow out from described liquid outflow portion, and the basal area that described reactor body constitutes this reactor body increases towards the top.
18. the retrieving arrangement of metal according to claim 17 wherein, is the device that utilizes ultrasonic wave to make to separate out with the metal vibration from separating out the stripping off device of peeling off the recycle object metal with metal.
19. the retrieving arrangement of metal according to claim 17 wherein, is to utilize electro-magnet to stir to separate out to use metal from separating out the device of peeling off the recycle object metal with metal, makes a plurality of devices that collide mutually with metal of separating out.
20. the retrieving arrangement of metal according to claim 17 wherein, is to stir the device of separating out with metal by air spray or jet of water from separating out the device of peeling off the recycle object metal with metal.
21. the retrieving arrangement of metal according to claim 17 wherein, is that cylindrical portion is set in reactor body from separating out the device of peeling off the recycle object metal with metal, is blown into gas and separates out device with metal with stirring in this cylindrical portion.
22. the retrieving arrangement of metal according to claim 17, wherein, from separating out the device of peeling off the recycle object metal with metal is stream and the pump that outer setting at reactor body makes processed liquid in the described reactor body and metallics circulation and carries, by making described processed liquid and separating out with metal circulation and carry, stir described device of separating out with metal.
23., wherein, be equipped with the reactor body of multistage according to the retrieving arrangement of each the described metal in the claim 17～22.
24., wherein, be equipped with the strainer that is used to reclaim the recycle object metal of being stripped from the back segment of reactor body according to the retrieving arrangement of each the described metal in the claim 17～22.
25. retrieving arrangement according to each the described metal in the claim 17～22, wherein, leading portion side at reactor body is provided with the adjustment groove, described adjustment groove is to hold with ionic condition to contain the recycle object metal and contain the processed liquid of nitrate ion, adds the adjustment groove that chloride-ion source is adjusted.
26. the retrieving arrangement of metal according to claim 25 wherein, is provided with and will adds the loopback stream of handling once again in the processed liquid as stoste to by having separated out with metal recovery treatment solution after the recycle object metal.
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