CN102892931B - Method for recovering precious-metal ions from plating wastewater - Google Patents
Method for recovering precious-metal ions from plating wastewater Download PDFInfo
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- CN102892931B CN102892931B CN201180023230.4A CN201180023230A CN102892931B CN 102892931 B CN102892931 B CN 102892931B CN 201180023230 A CN201180023230 A CN 201180023230A CN 102892931 B CN102892931 B CN 102892931B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/20—Regeneration of process solutions of rinse-solutions
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/22—Regeneration of process solutions by ion-exchange
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Abstract
To provide a method that can: efficiently recover precious-metal ions from precious-metal-ion-containing plating wastewater discharged from a plating recovery tank and a plating cleaning tank; and minimize performance problems in objects being plated. The present invention is a method for recovering precious-metal ions from plating wastewater. Said method keeps the concentration of precious-metal ions in a solution in a plating recovery tank high, within a certain range, by setting the wastewater discharge volume per discharge from the plating recovery tank to an amount, from 10% to 50% of the capacity of said plating recovery tank, such that the object being plated stays immersed in said plating recovery tank. Said method also keeps the concentration of precious-metal ions in a solution in a plating cleaning tank low, within a certain range.
Description
Technical field
The present invention relates to reclaim the method for precious metal ion from plating waste water, relate to especially the bad method that reclaims precious metal ion from plating waste water of performance that can reclaim efficiently precious metal ion from the plating waste water of plating accumulator tank and plating rinse bath and can suppress plating object being treated.
Background technology
Precious metal is due to its physical property characteristic, reliability and aesthetic property excellence, industrial be very useful material, as coating material, be used in in the wide spectrum headed by the e-machine such as electronic component or printed wiring board field.On the other hand, precious metal exists rare, is expensive material.Therefore, require to reclaim as much as possible the precious metal containing in plating waste water and re-use.
Conventionally, plating waste water is divided into the waste water from plating groove, plating accumulator tank and plating rinse bath.The effect of a rinse bath after plating is carried out in the performance of plating accumulator tank in plating groove, is therefore compared to the waste water from plating groove from the waste water of plating accumulator tank, the precious metal ion that contains lower concentration.In addition, because plating rinse bath is the effect of performance secondary or three rinse baths, be therefore compared to the waste water from plating accumulator tank from the waste water of plating rinse bath, the precious metal ion that contains lower concentration.The precious metal ion concentration of the plating waste water of therefore, discharging from each groove is different.
In addition, also require managing in the groove of plating accumulator tank, to be eluted in and be attached to precious metal ion or the salt component on plating object being treated in plating accumulator tank and plating rinse bath superfluously, further restrain the generation as the mould or bacterium due to the organism of plating liquid composition.
As the method that reclaims precious metal ion from plating waste water, common known have electrolytic recovery method, resin absorption method and charcoal absorption absorption method.Electrolytic recovery method excellence for reclaim precious metal ion from the high plating waste water of precious metal ion concentration time, but the plating waste water of lower concentration if, even if make it at electrolyzer internal recycle, current density also can not raise, the organic efficiency variation of precious metal ion.On the other hand, resin absorption method and charcoal absorption absorption method excellence for reclaim precious metal ion from the low plating waste water of precious metal ion concentration time, if but pass into the plating waste water of high density, cannot fully reclaim precious metal ion.Thus, the concentration that is necessary the precious metal ion when by the draining of plating rinse bath manages.
As the method for high efficiente callback precious metal from the polytype waste liquid that contains precious metal with various concentration, for example known have a following methods: it is ion exchange resin that the lower concentration waste liquid that contains precious metal with lower concentration is crossed to chelating, making precious metal be adsorbed in chelating is ion exchange resin, and the precious metal of absorption is taken out; The high-concentration waste liquid that contains precious metal with high density is carried out in electrolyzer to electrolysis treatment, precious metal is separated out on electrode, the method (patent documentation 1) that the precious metal of separating out is reclaimed.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-279343 communique
Summary of the invention
The technical problem that invention will solve
In the past, be the method that adopts regular overflow as the method for partial drainage from plating accumulator tank; Or by timer automatically set, with the time management method of regular draining; Or operator are the method for regularly draining manually.Like this, by the liquid of accommodating in a certain amount of plating accumulator tank is regularly discharged, water filling, the precious metal ion concentration of the liquid of accommodating in plating accumulator tank is regularly reduced.
But the precious metal ion concentration of the liquid of accommodating in plating accumulator tank does not always raise in certain proportion, according to circumstances also can sharply raise.In addition, according to the turnout of plating object being treated, the precious metal ion concentration of the liquid of accommodating in plating accumulator tank has various variations.Therefore, for the plating waste water of the precious metal ion that contains lower concentration, can not get sufficient current density, the precious metal ion organic efficiency variation of electrolytic recovery method.In addition, for the plating waste water of the precious metal ion that contains higher concentration, may within the cycling time of automatically setting, cannot finish dealing with, the reason that this organic efficiency that becomes precious metal ion reduces.
And, if the precious metal ion concentration of the liquid of accommodating in plating accumulator tank excessively raises, from the treatment trough of later process---the concentration of the precious metal ion that contains in the plating waste water of plating rinse bath raises, and there will be and cannot utilize resin absorption method, charcoal absorption absorption method precious metal ion to be carried out to the problem fully reclaiming.
The object of the present invention is to provide a kind of can be from the plating waste water that discharge, that contain precious metal ion from plating accumulator tank and plating rinse bath high efficiente callback precious metal ion and can suppress the bad method of performance of plating object being treated.
The means of dealing with problems
The inventor conducts in-depth research for addressing the above problem, and found that, the precious metal ion concentration of the liquid of accommodating in plating accumulator tank and plating rinse bath is maintained within the limits prescribed, has finally completed the present invention based on this opinion.; the present invention is the method that reclaims precious metal ion from plating waste water; it is characterized in that; making from the water displacement each time of plating accumulator tank is in 10～50% the scope of full water amount of plating accumulator tank; and the liquid measure in plating accumulator tank is the amount that can guarantee that plating object being treated is impregnated; thus the concentration of the precious metal ion of the liquid of accommodating in plating accumulator tank is maintained to certain scope with high density, and the concentration of the precious metal ion of the liquid of accommodating in plating rinse bath is maintained to certain scope with lower concentration.
In the present invention, be maintained within a certain range with high density for the concentration of precious metal ion, from the plating waste water of plating accumulator tank, by electrolytic recovery method and resin absorption method or charcoal absorption absorption method and be used for reclaiming precious metal ion; Be maintained within a certain range with lower concentration for the concentration of precious metal ion, from the plating waste water of plating rinse bath, can utilize resin absorption method or charcoal absorption absorption method to reclaim precious metal ion.
The effect of invention
According to the present invention, without the plating stopping plating object being treated, can be from the plating waste water that discharge, that contain precious metal ion from plating accumulator tank and plating rinse bath high efficiente callback precious metal ion, and it is bad to suppress the performance of plating object being treated.
Embodiment
The present invention is applicable to conventional plating, contains following steps: in the plating groove that contains plating liquid, flood object being treated to carry out the step of plating; In the liquid of accommodating, flood object being treated in plating accumulator tank, clean at first the step of object being treated; And flood object being treated in the liquid of accommodating in plating rinse bath, finally clean the step of object being treated; For the plating waste water from plating accumulator tank, by electrolytic recovery method and resin absorption method or charcoal absorption absorption method and be used for reclaiming precious metal ion; On the other hand, for the plating waste water from plating rinse bath, utilize resin absorption method or charcoal absorption absorption method to reclaim precious metal ion.
As electronic component or printed wiring board etc., above-mentioned object being treated is the goods that carry out continuously plating by pair of rolls, and in plating groove etc., repeatedly floods, mentions step, is plated in batches the goods of processing.In addition, the liquid of accommodating in plating accumulator tank and plating rinse bath is generally the ion exchanged water of crossing through ion exchange resin treatment, reclaims the pure water that has carried out activated carbon treatment or reverse osmosis membrane processing after precious metal ion the liquid that also suitable employing is accommodated from plating rinse bath.
In the present invention, making from the water displacement each time of plating accumulator tank is in 10～50% the scope of full water amount of plating accumulator tank, and the liquid measure in plating accumulator tank is the amount that can guarantee that plating object being treated is impregnated, thus the precious metal ion concentration of the liquid of accommodating in plating accumulator tank is maintained to certain scope with high density, and the precious metal ion concentration of the liquid of accommodating in plating rinse bath is maintained to certain limit with lower concentration.Then, for the concentration of precious metal ion with high density maintain certain scope, from the plating waste water of plating accumulator tank, by electrolytic recovery method and resin absorption method or charcoal absorption absorption method and be used for reclaiming precious metal ion, for maintain with lower concentration certain limit, from the plating waste water of plating rinse bath, can utilize resin absorption method or charcoal absorption absorption method to reclaim precious metal ion.
Preferably from the water displacement each time of plating accumulator tank in 10～50% scope of the full water amount of plating accumulator tank, and liquid measure in plating accumulator tank is the amount that can guarantee that plating object being treated is impregnated.If water displacement each time exceed plating accumulator tank full water amount 50%, because making the water temperature in plating accumulator tank, water filling significantly changes, the superfluous precious metal ion adhering on recovery plating object being treated or the Efficiency Decreasing of salt component, and mould or bacterium etc. are breeding easily, owing to causing the bad or yield rate of performance to reduce adhering on plating object being treated.
On the other hand, if water displacement each time at below 10% of full water amount, the draining of the management of precious metal ion concentration and plating accumulator tank, water filling operation become miscellaneous.In addition, due to operation miscellaneous, that management occurs is bad, reclaims the superfluous precious metal ion that adheres on plating object being treated or the Efficiency Decreasing of salt component, and not only plating object being treated is contaminated, and the organic efficiency of precious metal ion also can reduce.In addition, making water displacement is each time to guarantee that the reason of the impregnated amount of plating object being treated is in order not make plating stop.
In addition, the water temperature of the liquid of accommodating in plating accumulator tank is preferably more than 35 DEG C, more preferably more than 40 DEG C.Needn't initiatively carry out temperature adjusting to plating accumulator tank, but particularly preferably not make water temperature excessive descent.Especially, if water temperature is below 35 DEG C, to the elution efficiency variation of the excessive precious metal ion adhering on plating object being treated or salt component, can promote the breeding of mould or bacterium etc., the adhering to of residual or mould or bacterium that has precious metal ion or salt component on plating object being treated, cause that thus performance is bad or yield rate is low.
In conventional plating groove, under the warm-up mode of 60～90 DEG C of left and right, implement plating.The plating liquid adhering on the plating object being treated of heating and plating object being treated moves in plating accumulator tank, the reason that this water temperature that becomes plating accumulator tank raises.Another becomes raise in the water temperature of plating accumulator tank former because because plating groove and plating accumulator tank are to arrange continuously, be by causing from the radiant heat of plating groove.
But water temperature rises and must not cause that the performance of the plating object being treated in plating accumulator tank is bad or yield rate is low.Contrary to above-mentioned record, the water temperature of the liquid of accommodating in plating accumulator tank is preferably more than 35 DEG C, more preferably more than 40 DEG C, especially, the breeding good, mould or bacterium of the excessive precious metal ion adhering to from plating object being treated or the elution efficiency of salt component is suppressed consideration, and preferably water temperature is high.
Usually, when the treatment capacity of plating object being treated is few, in time management method or press over system and full dose Shift Method in the past, excessively carrying out draining and water filling is the reason that causes that water temperature reduces.
Therefore, in the present invention, as described below, importantly in plating accumulator tank, electrode is set, estimate precious metal ion concentration by working curve by current value, the treatment capacity of estimation plating object being treated, and to make from the water displacement each time of plating accumulator tank be the amount of 10～50% scope of the full water amount of plating accumulator tank.For example management as follows: pass through heat Calculation, in the time that the water temperature of plating accumulator tank is 50 DEG C, with the water fillings displacements full water amounts of 20 DEG C 50% time, water temperature is to reduce the scope of 10 DEG C, even when the treatment capacity of plating object being treated is less, can not make water temperature be down to below 35 DEG C yet.
The precious metal ion concentration of the liquid of accommodating in plating accumulator tank in the present invention, maintains certain scope with high density.For the waste water that maintains certain limit with high density, be applicable to electrolytic recovery method and resin absorption method or charcoal absorption absorption method and use.
Herein maintain certain limit with high density, refer to that maintaining certain limit with the precious metal ion concentration of the liquid of accommodating in plating rinse bath with lower concentration compares, and maintains with high density.
In addition, in the equipment design of reclaiming at precious metal ion, suitably select the loading level that number or resin and gac are set of electrolytic recovery device etc. according to the treatment capacity of precious metal ion concentration or unit time.And, if use precious metal ion recovery method of the present invention, even from the plating waste water of the multiple plating accumulator tanks that are set up in parallel, if contain same precious metal ion, just can collect each plating waste water under same stream, carry out electrolytic recovery.
As embodiments of the present invention, in the time that precious metal ion is high density, is applicable to selecting by electrolytic recovery method and resin absorption method or charcoal absorption absorption method and uses; On the other hand, during for lower concentration, be applicable to selecting resin absorption method or charcoal absorption absorption method.
For the precious metal ion of the liquid of accommodating in electrolytic recovery groove expeditiously, adding fashionablely, preferably precious metal ion concentration is maintained to certain scope in recovery system.In conventional electrolysis recovery method, it is the recovery system that number etc. is set that precious metal ion concentration during according to plater draining or the wastewater treatment capacity of unit time design electrolytic recovery device.First by the fluid storage of accommodating of discharging from plating accumulator tank, certain treatment capacity being transferred to from the groove of described storage to electrolytic recovery with in groove, the liquid of accommodating is circulated in electrolytic recovery groove and electrolytic recovery device, simultaneously electrolytic recovery precious metal ion.Electrolytic recovery is according to setting cycling time, for the variation of precious metal ion concentration, and suitable adjustment cycling time.Thus, certain scope refers to and maintains the concentration that precious metal ion is maintained to the handling property that is applicable to designed recovery system, if exceed certain scope, exceeding resin after electrolytic recovery or charcoal absorption can recoverable capacity in reclaiming, and becomes organic efficiency and reduces.On the other hand, if below certain scope,, in electrolytic recovery, the organic efficiency under lower concentration is low, and the organic efficiency of unit time reduces.
Based on more than, when the precious metal ion concentration of the liquid of accommodating maintains certain limit with high density, can effectively utilize to greatest extent the organic efficiency of recovery system, result can realize high yield.
In addition, even the liquid of accommodating from plating accumulator tank, according to the kind of plating liquid, has the situation that current density cannot fully raise, for the rising of current density, can append arbitrarily ionogen such as adding caustic soda.
For example, when what the present invention specified maintains certain scope by the precious metal ion of the liquid of accommodating in plating accumulator tank with high density, preferably maintain the scope of 10～200mg/L.If the concentration of the precious metal ion of the liquid of accommodating in plating accumulator tank exceedes 200mg/L, even by electrolytic recovery method and resin absorption method or charcoal absorption absorption method use, the recovery of precious metal ion is also insufficient; In addition, because superfluous precious metal ion flows out in plating rinse bath, the possibility that the precious metal ion concentration of plating rinse bath exceedes 10mg/L uprises, and become, the organic efficiency of the precious metal ion containing in the plating waste water from plating rinse bath is reduced.
On the other hand, if the not enough 10mg/L of the precious metal ion concentration of the liquid of accommodating in plating accumulator tank, by electrolytic recovery method and resin absorption method or charcoal absorption absorption method and with becoming surplus design, becomes that efficiency is low economically.In addition, by the precious metal ion concentration management containing in the liquid of accommodating in plating accumulator tank, below 10mg/L, this does not almost have as embodiment, unrealistic.
In the present invention, the precious metal ion concentration of the liquid of accommodating in plating rinse bath, for the precious metal ion concentration in plating accumulator tank is maintained to certain concentration range, the precious metal ion of being transferred to plating rinse bath by plating accumulator tank is maintained within a certain range with lower concentration.In addition, the liquid of accommodating in plating accumulator tank through electrolytic recovery method process after, this liquid of accommodating too maintain certain limit with lower concentration.Owing to can maintaining certain scope with lower concentration whichsoever, therefore can select aptly according to the treatment capacity of precious metal ion concentration and unit time loading level of resin and gac etc.
For example, in the present invention, specify the precious metal concentration of the liquid of accommodating in plating rinse bath is maintained to certain scope with lower concentration time, preferably maintain below 10mg/L.If exceed 10mg/L, the precious metal ion reclaiming by resin absorption method or charcoal absorption absorption method becomes insufficient.
As mentioned above, the precious metal ion concentration of the liquid of accommodating in plating accumulator tank is 200mg/L to the maximum, and therefore, the peak concentration of the superfluous precious metal ion that the plating object being treated of sending from plating accumulator tank adheres to is 200mg/L; If for example the above-mentioned liquid pure water that adheres to is diluted to 25～50 times in plating rinse bath, precious metal ion concentration when 25 times of dilutions is 8mg/L, when 50 times of dilutions, becomes 4mg/L, maintains below 10mg/L.
In the present invention, during by plating waste water reclamation precious metal ion from plating accumulator tank, by electrolytic recovery method and resin absorption method or charcoal absorption absorption method and be used for carrying out.Not independent electrolytic recovery method, but by combining with resin absorption method or charcoal absorption absorption method, can improve significantly the organic efficiency of precious metal ion.
Electrolytic recovery method is in electrolyzer, to import plating waste water, the method that makes precious metal ion separate out on electrode and reclaim by electrolysis.The anode using can exemplify by the Ti material of the Ti material of plating Pt, sintering Ir or the electrode that Ferrite Material forms; Negative electrode can exemplify the electrode being made up of Ti material, SUS material or Ferrite Material.In the present invention, as the condition that reclaims to high electrolytic efficiency precious metal from the plating waste water of plating accumulator tank, can set aptly according to the kind of the kind of plating liquid and precious metal ion kind or the current density of electrode.For example, be the waste water of plating liquid for cyanogen, because cryanide ion can dissolve Pt, therefore use the Ti material electrode of sintering Ir.In addition, in the waste water of the plating liquid of the platinum family that contains Pt or Pd etc., because the hydrogen that the hydrolysis through water produces can be shelled isolated platinum family, therefore use with low current density.And the removing of the precious metal of separating out at negative electrode, there is no particular limitation for recovery method, while utilizing the removing, reclaim of precious metal that chloroazotic acid etc. peels off to separate out, suitable use Ti material is as negative electrode.
Resin absorption method is that plating waste water is passed into resin, and trapping precious metal ion, burns this resin and the method for recovery precious metal.As the resin using in resin absorption method, for example, can enumerate: Zeo-karb, anionite-exchange resin, resin, synthetic sorbing material, material that preferably can high efficiente callback precious metal ion.Preferred anionic exchange resin specifically, for example, have quaternary ammonium hydroxide (trimethyl ammonium alkali, dimethyl ethanol ammonium alkali etc.) strong basic ion exchange resin, there is weak-base ion-exchange resin of primary amino, secondary amino group or tertiary amino etc.; Zeo-karb, for example, has sulfonic strong-acid ion exchange resin, has the sulfonic superpower acidity ion exchange resin of fluorinated alkyl, has weak-acid ion exchange resin of carboxyl, phosphonate group, phospho acid base etc.; Resin, for example, suitable have imidino acetic acid type resin, a polyamine type resin.
Be to use gac trapping precious metal ion with the charcoal absorption absorption method of electrolytic recovery method use, by described gac burning ashing, from the calcination obtaining, reclaim the method for precious metal ion.While using gac trapping precious metal ion, for example, gac be impregnated in plating waste water, plating waste water is passed in the gac being filled in post and is carried out.
Reclaim precious metal ion from the plating waste water of plating rinse bath time, undertaken by resin absorption method or charcoal absorption absorption method.Resin absorption method or charcoal absorption absorption method are as previously mentioned.
In the time making to be 10～50% the scope of full water amount of plating accumulator tank from the water displacement each time of plating accumulator tank, the draining of plating accumulator tank and water filling are preferably undertaken by partial drainage, fractional flooding.Conventionally, industrial in order to carry out a large amount of platings, to require to process continuously in plating accumulator tank, not hinder the manufacture of plating object being treated, if once implement full dose draining, can make the plating of plating object being treated stop, the production cycle is elongated, the problem that production development reduces.And if carry out full dose draining, the new water filling of full dose, because the water temperature that makes plating accumulator tank changes significantly, the organic efficiency of precious metal reduces.
Be that there is no particular limitation for the method for 10～50% scope of the full water amount of plating accumulator tank as making from the water displacement each time of plating accumulator tank, for example, two electrodes are set in plating accumulator tank, pass into the power supply of constant voltage or constant current and carry out draining and the motorized valve of water filling action etc., plating accumulator tank is switched on, pass through measured current value or potential value and control the action of motorized valve of draining and water filling etc.
Particularly, for example switch between the electrode that is arranged at plating accumulator tank with constant voltage or constant current, the liquid of accommodating for plating accumulator tank, make in advance the working curve of the relation that represents the precious metal ion concentration containing in current value or potential value and this liquid of accommodating, switch between the electrode that is arranged at plating accumulator tank with constant voltage or constant current, measure this interelectrode current value or potential value, measured value based on obtaining and above-mentioned working curve, the precious metal ion of the liquid of accommodating in plating accumulator tank is carried out quantitatively, when the quantitative values obtaining reaches the set(ting)value of regulation, by carrying out draining and/or the water filling of plating accumulator tank, the precious metal ion concentration of the liquid of accommodating in plating accumulator tank is maintained in certain scope with high density.
As above-mentioned electrode, anode preferably improve when current density not can stripping, the Ti material by plating Pt, the Ti material of sintering Ir or the electrode that Ferrite Material forms, the electrode that negative electrode is preferably made up of Ti material, SUS material or Ferrite Material.In addition, the shape of this electrode can suitably be chosen as flat board, pole, cylinder, netted etc.If electrode is relative while considering to install, more preferably use the shape of pole or cylinder.
In the time making above-mentioned working curve, and in the time that current value and potential value are switched on, measured to reality to plating accumulator tank, about the electrode shape, electrode length, interelectrode distance and the impressed voltage that are arranged at the electrode in plating accumulator tank, can coordinate the useless electrical conductivity of water of plating of plating accumulator tank to carry out suitable selection.The useless electrical conductivity of water of this plating is the specific conductivity of the plating waste water entirety that contains precious metal ion and other ionogen etc., if precious metal ion concentration is high, specific conductivity uprises.When precious metal ion concentration-current value slope of a curve of plating waste water is large, can relatively take additional low voltage, electrode diameter to reduce, shorten electrode, widen interelectrode distance.On the other hand, when slope is little, can be relatively increases, add long electrode, widen interelectrode distance and regulate slope by applying high voltage, electrode diameter.For example, impressed voltage can be set in to 12～24V, make current value corresponding to the above-mentioned higher limit of precious metal ion concentration at 200～800mA, making corresponding to the current value of the above-mentioned lower value of precious metal ion concentration is 100～500mA.Preferably selection can be managed the electrode condition in the scope of 100～300mA by the difference of the above-mentioned higher limit of precious metal ion concentration and above-mentioned lower value.
The draining of plating accumulator tank and/or water filling for example can adopt the mode that draining is used and water filling is worked with motorized valve simultaneously; Draining motorized valve work, the mode of motorized valve work for water filling after draining completes; In drainage procedure, mode of motorized valve work etc. for water filling, can utilize controlling board automatically to control and carry out.The device that also can use magnetic valve etc. to have said function replaces motorized valve.
The mode that draining is used and water filling is worked with motorized valve is simultaneously: if the current value of the liquid of accommodating in plating accumulator tank reaches the higher limit of setting, draining is with work with water filling motorized valve simultaneously, if reach the lower value of setting, draining is with stopping with water filling motorized valve.Control the time of draining and water filling by the current value of the liquid of accommodating in plating accumulator tank, thus higher limit and the lower value of management precious metal ion concentration.
Draining motorized valve work, after draining completes, water filling by the mode of motorized valve work is: if the current value of the liquid of accommodating in plating accumulator tank reaches the higher limit of setting, only draining motorized valve work, draining is to till lower limit water level.The current value of the liquid of accommodating now, can not change.If draining completes, then, water filling motorized valve work, stops if water filling arrives full-water level.Control the time of draining by the current value of the liquid of accommodating in plating accumulator tank, thus the higher limit of management precious metal ion concentration, water displacement and water injection rate are managed by the mensuration of water level, thus the lower value of management precious metal ion concentration.
In drainage procedure, water filling by the mode of motorized valve work is: if the current value of the liquid of accommodating in plating accumulator tank reaches the higher limit of setting, draining is worked with motorized valve, in this drainage procedure, water filling is worked with motorized valve, if above-mentioned current value reaches the lower value of setting, the work of draining use and water filling motorized valve stops, and water filling finishes.Control the time of draining and water filling by the current value of the liquid of accommodating in plating accumulator tank, thus higher limit and the lower value of management precious metal ion concentration.
In the present invention, the precious metal that becomes the precious metal ion of recycle object is Au, Pd, Ag, Pt or Rh.Therefore, the kind of the plating liquid of processing on plating object being treated is plating liquid more than at least one containing in Au, Pd, Ag, Pt and Rh, also can be and contains the non-noble metal alloy plating liquid such as above-mentioned precious metal and Ni, Co, Fe, Zn.In addition, can enumerate as solution and coating method: cyanogen is that plating, non-cyanogen are that plating, electrolytic coating, electroless plating cover etc.It is the plating liquid of 1～70g/L that the plating liquid of accommodating in plating groove in addition, uses precious metal ion concentration conventionally.
Below, implementing, in situation of the present invention, to enumerate the embodiment of the precious metal ion concentration about maintaining the liquid of accommodating in plating accumulator tank and plating rinse bath.
Embodiment 1
(Japanese electroplating engineering (EEJA) company manufactures, trade(brand)name: Temperex MLA 100 to use Au plating liquid; Au 6～10g/L) while carrying out plating, be that 50 DEG C, the higher limit of the Au ionic concn of this liquid of accommodating are that 50～59mg/L, lower value are while being 34～43mg/L when setting the water temperature of the liquid of accommodating in plating accumulator tank, as an example of the most suitable condition of the electrode arranging in plating accumulator tank, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 24V, the above-mentioned higher limit current value that shows Au ionic concn is 350mA, and the current value that shows above-mentioned lower value is 250mA; The difference of the above-mentioned higher limit of Au ionic concn and above-mentioned lower limit management value is represented with current value, management is in the time of the scope of 100mA, most suitable electrode can exemplify the anode being made up of the Ti material of plating Pt, the negative electrode being made up of Ti material, for pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 35mm.
With draining with and the water filling mode of simultaneously working with motorized valve while implementing the draining of plating accumulator tank and water filling, in the time reaching above-mentioned higher limit 350mA, draining is with work with water filling motorized valve simultaneously, and in the time reaching above-mentioned lower value 250mA, draining is used and the work of water filling motorized valve stops.Therefore, the Au ionic concn of discharge is the scope of above-mentioned upper limit concentration 50～59mg/L and above-mentioned least concentration 34～43mg/L, the liquid of accommodating in plating accumulator tank 20% exchanged.The Au ionic concn of adhering to liquid of adhering on clean plating object being treated in plating accumulator tank is 59mg/L to the maximum, and in plating rinse bath, this adheres to liquid and dilutes through water, and Au ionic concn is maintained to the lower concentration below 10mg/L.The water temperature of water filling is about 20 DEG C, and the water temperature of the plating accumulator tank of continuous operation is 44～46 DEG C.
The electrolytic recovery of the Au ion of the high density containing in the plating waste water from plating accumulator tank be use contain the anode being formed by the Ti material of sintering Ir, the cathode electrode being formed by Ti material, the about 200L of circular treatment capacity electrolytic recovery device (Tanaka's precious metal industrial manufacture: MINI Recover Cell), with electrolysis density 130～200mA/dm
2au ion is reclaimed.
The resin of the Au ion of the lower concentration containing in the waste liquid after above-mentioned electrolytic recovery and the plating waste water from plating rinse bath reclaims can use respectively same resin, uses Di (the Tanaka's precious metal industrial manufacture: EagleRE) Au ion is reclaimed that is filled with anionite-exchange resin.
The not enough 0.2mg/L of residual Au ionic concn after the present embodiment recycling.
Embodiment 2
(EEJA company manufactures, trade(brand)name: Temperex 8400 to use Au plating liquid; Au3～5g/L) while carrying out plating, be that 50 DEG C, the higher limit of the Au ionic concn of this liquid of accommodating are that 50～63mg/L, lower value are while being 33～42mg/L when setting the water temperature of the liquid of accommodating in plating accumulator tank, as an example of the most suitable condition of the electrode arranging in plating accumulator tank, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 24V, the current value that shows the above-mentioned higher limit of Au ionic concn is 370mA, and the current value that shows above-mentioned lower value is 270mA; The difference of the higher limit of Au ionic concn and lower value is represented with current value, management is in the time of the scope of 100mA, most suitable electrode can exemplify the anode being made up of the Ti material of plating Pt, the negative electrode being made up of Ti material, for pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 35mm.
Similarly to Example 1, with draining with and the water filling mode of simultaneously working with motorized valve while implementing the draining of plating accumulator tank and water filling, in the time reaching above-mentioned higher limit 370mA, draining is with work with water filling motorized valve simultaneously, in the time reaching above-mentioned lower value 270mA, the work of draining use and water filling motorized valve is stopped.Therefore, the Au ionic concn of discharge is the scope of above-mentioned upper limit concentration 50～63mg/L and above-mentioned least concentration 33～42mg/L, the liquid of accommodating in plating accumulator tank 20% exchanged.The Au ionic concn of adhering to liquid of adhering on clean plating object being treated in plating accumulator tank is 63mg/L to the maximum, and in plating rinse bath, this adheres to liquid and dilutes through water, and Au ionic concn is maintained to the lower concentration below 10mg/L.The water temperature of water filling is about 20 DEG C, and the water temperature of the plating accumulator tank of continuous operation is 44～46 DEG C.
The electrolytic recovery of the Au ion of the high density containing in the plating waste water from plating accumulator tank be use contain the anode being formed by the Ti material of sintering Ir, the cathode electrode being formed by Ti material, the about 200L of circular treatment capacity electrolytic recovery device (Tanaka's precious metal industrial manufacture: MINI Recover Cell), taking electrolysis density as 130～200mA/dm
2au ion is reclaimed.
The resin of the Au ion of the lower concentration containing in the waste liquid after above-mentioned electrolytic recovery and the plating waste water from plating rinse bath reclaims can use respectively same resin, uses Di (the Tanaka's precious metal industrial manufacture: EagleRE) Au ion is reclaimed that is filled with anionite-exchange resin.
The not enough 0.2mg/L of residual Au ionic concn after the present embodiment recycling.
Embodiment 3
(EEJA company manufactures, trade(brand)name: Aurobond TN to use Au plating liquid; Au 1～3g/L) while carrying out plating, be that 50 DEG C, the higher limit of the Au ionic concn of this liquid of accommodating are that 28～95mg/L, lower value are while being 17～74mg/L when setting the water temperature of the liquid of accommodating in plating accumulator tank, as an example of the most suitable condition of the electrode arranging in plating accumulator tank, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 12V, shows that the current value of the above-mentioned higher limit of Au ionic concn is 450mA, show that the current value of above-mentioned lower value is 350mA; The above-mentioned higher limit of Au ionic concn and the difference of above-mentioned lower value are represented with current value, management is in the time of the scope of 100mA, most suitable electrode can exemplify the anode being made up of the Ti material of plating Pt, the negative electrode being made up of Ti material, for pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 35mm.
Similarly to Example 1, with draining with and the water filling mode of simultaneously working with motorized valve while implementing the draining of plating accumulator tank and water filling, in the time reaching above-mentioned higher limit 450mA, draining is with work with water filling motorized valve simultaneously, in the time reaching above-mentioned lower value 350mA, draining is used and the work of water filling motorized valve stops.Therefore, the Au ionic concn of discharge is the scope of 17～74mg/L of above-mentioned upper limit concentration 28～95mg/L and above-mentioned least concentration, the liquid of accommodating in plating accumulator tank 20% exchanged.The Au ionic concn of adhering to liquid of adhering on clean plating object being treated in plating accumulator tank is 95mg/L to the maximum, and in plating rinse bath, this adheres to liquid and dilutes through water, and Au ionic concn is maintained to the lower concentration below 10mg/L.The water temperature of water filling is about 20 DEG C, and the water temperature of the plating accumulator tank of continuous operation is 44～46 DEG C.
The electrolytic recovery of the Au ion of the high density containing in the plating waste water from plating accumulator tank be use contain the anode being formed by the Ti material of sintering Ir, the cathode electrode being formed by Ti material, the about 200L of circular treatment capacity electrolytic recovery device (Tanaka's precious metal industrial manufacture: MINI Recover Cell), taking electrolysis density as 130～200mA/dm
2au ion is reclaimed.
The resin of the Au ion of the lower concentration containing in the waste liquid after above-mentioned electrolytic recovery and the plating waste water from plating rinse bath reclaims can use respectively same resin, uses Di (the Tanaka's precious metal industrial manufacture: EagleRE) Au ion is reclaimed that is filled with anionite-exchange resin.
The not enough 0.2mg/L of residual Au ionic concn after the present embodiment recycling.
Embodiment 4
(EEJA company manufactures, trade(brand)name: Palladex 100 to use Pd plating liquid; Pd 25～30g/L) while carrying out plating, be that 50 DEG C, this higher limit of accommodating the Pd ion of liquid are that 129～157mg/L, lower value are while being 38～77mg/L when setting the water temperature of the liquid of accommodating in plating accumulator tank, as an example of the most suitable condition of the electrode arranging in plating accumulator tank, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 12V, the current value that shows the above-mentioned higher limit of Pd ionic concn is 550mA, and the current value that shows above-mentioned lower value is 450mA; The above-mentioned higher limit of Pd ionic concn and the difference of above-mentioned lower value are represented with current value, management is in the time of the scope of 100mA, most suitable electrode can exemplify the anode being made up of the Ti material of plating Pt, the cathode electrode being made up of Ti material, for pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 45mm.
While making again the mode of water filling motorized valve work implement the draining of plating accumulator tank and water filling after completing with motorized valve work for draining, draining, in the time reaching above-mentioned higher limit 550mA, draining motorized valve work, in the time that 40% of full water amount is discharged from, water filling motorized valve work stops in the time of full water.Therefore the Pd ionic concn, being discharged from is the scope of above-mentioned upper limit concentration 129～157mg/L.The Pd ionic concn of adhering to liquid of adhering on clean plating object being treated in plating accumulator tank is 157mg/L to the maximum, and in plating rinse bath, this adheres to liquid and dilutes through water, and Pd ionic concn is maintained to the lower concentration below 10mg/L.The water temperature of water filling is about 20 DEG C, and the water temperature of the plating accumulator tank of continuous operation is 40～42 DEG C.
The electrolytic recovery of the Pd ion of the high density containing in the plating waste water from plating accumulator tank be use contain the anode being formed by the Ti material of plating Pt, the cathode electrode being formed by Ti material, the about 200L of circular treatment capacity electrolytic recovery device (Tanaka's precious metal industrial manufacture: MINI Recover Cell), taking electrolysis density as 100～270mA/dm
2pd ion is reclaimed.
The resin of the Pd ion of the lower concentration containing in the waste liquid after above-mentioned electrolytic recovery and the plating waste water from plating rinse bath reclaims can use respectively same resin, uses Di (the Tanaka's precious metal industrial manufacture: Eagle RE) Pd ion is reclaimed that is filled with resin.
The not enough 0.5mg/L of residual Pd ionic concn after the present embodiment recycling.
Embodiment 5
(NE Chemcat company manufactures, trade(brand)name: AG-10 to use Ag plating liquid; Ag 50～70g/L) while carrying out plating, be that 50 DEG C, the higher limit of the Ag ionic concn of this liquid of accommodating are that 148～195mg/L, lower value are while being 49～83mg/L when setting the water temperature of the liquid of accommodating in plating accumulator tank, as an example of the most suitable condition of the electrode arranging in plating accumulator tank, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 12V, the current value that shows the above-mentioned higher limit of Ag ionic concn is 650mA, and the current value that shows above-mentioned lower value is 550mA; The above-mentioned higher limit of Ag ionic concn and the difference of above-mentioned lower value are represented with current value, management is in the time of the scope of 100mA, most suitable electrode can exemplify the anode being made up of the Ti material of plating Pt, the negative electrode being made up of Ti material, for pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 55mm.
Similarly to Example 4, while making again the mode of water filling motorized valve work implement the draining of plating accumulator tank and water filling after completing with motorized valve work for draining, draining, in the time reaching above-mentioned higher limit 650mA, draining is worked with motorized valve, in the time that 50% of full water amount is discharged from, water filling motorized valve work stops in the time of full water.Therefore, the Ag ionic concn of discharge is the scope of above-mentioned upper limit concentration 148～195mg/L.The Ag ionic concn of adhering to liquid of adhering on clean plating object being treated in plating rinse bath is 195mg/L to the maximum, and in plating rinse bath, this adheres to liquid and dilutes through water, and Ag ionic concn is maintained to the lower concentration below 10mg/L.The water temperature of water filling is about 20 DEG C, and the water temperature of the plating accumulator tank of continuous operation is 39～41 DEG C.
The electrolytic recovery of the Ag ion of the high density containing in the plating waste water from plating accumulator tank be use contain the anode being formed by the Ti material of sintering Ir, the cathode electrode being formed by Ti material, the about 200L of circular treatment capacity electrolytic recovery device (Tanaka's precious metal industrial manufacture: MINI Recover Cell), taking electrolysis density as 130～200mA/dm
2ag ion is reclaimed.
The resin of the Ag ion of the lower concentration containing in the waste liquid after above-mentioned electrolytic recovery and the plating waste water from plating rinse bath reclaims can use respectively same resin, uses Di (the Tanaka's precious metal industrial manufacture: EagleRE) Ag ion is reclaimed that is filled with anionite-exchange resin.
The not enough 0.2mg/L of residual Pd ionic concn after the present embodiment recycling.
Embodiment 6
(EEJA company manufactures, trade(brand)name: Precious fab Pt100 to use Pt plating liquid; Pt10～14g/L) while carrying out plating, be that 50 DEG C, the higher limit of the Pt ionic concn of this liquid of accommodating are that 96～120mg/L, lower value are while being 45～63mg/L when setting the water temperature of the liquid of accommodating in plating accumulator tank, as an example of the most suitable condition of the electrode arranging in plating accumulator tank, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 15V, the current value that shows the above-mentioned higher limit of Pt ionic concn is 500mA, and the current value that shows above-mentioned lower value is 400mA; The above-mentioned higher limit of Ag ionic concn and the difference of above-mentioned lower value are represented with current value, management is in the time of the scope of 100mA, most suitable electrode can exemplify the anode being made up of the Ti material of plating Pt, the negative electrode being made up of Ti material, for pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 40mm.
When carrying out draining that the mode of water filling work implements plating accumulator tank and water filling in drainage procedure, in the time reaching higher limit 500mA, draining motorized valve work, in drainage procedure, water filling is worked with motorized valve, in the time reaching lower value 400mA, draining is used and the work of water filling motorized valve stops.Therefore, the Pt ionic concn of discharge is the scope of above-mentioned upper limit concentration 96～120mg/L and above-mentioned least concentration 45～63mg/L, the liquid of accommodating in plating accumulator tank 40% exchanged.The Pt ionic concn of adhering to liquid of adhering on clean plating object being treated in plating rinse bath is 120mg/L to the maximum, and in plating rinse bath, this adheres to liquid and dilutes through water, maintains the lower concentration below 10mg/L.The water temperature of water filling is about 20 DEG C, and the water temperature of the plating accumulator tank of continuous operation is 40～42 DEG C.
The electrolytic recovery of the Pt ion of the high density containing in the plating waste water from plating accumulator tank be use contain the anode being formed by the Ti material of plating Pt, the cathode electrode being formed by Ti material, the about 200L of circular treatment capacity electrolytic recovery device (Tanaka's precious metal industrial manufacture: MINI Recover Cell), taking electrolysis density as 30～140mA/dm
2ag ion is reclaimed.
The resin of the Pt ion of the lower concentration containing in the waste liquid after above-mentioned electrolytic recovery and the plating waste water from plating rinse bath reclaims can use respectively same resin, uses Di (the Tanaka's precious metal industrial manufacture: EagleRE) Pt ion is reclaimed that is filled with Zeo-karb.
The not enough 0.5mg/L of residual Pd ionic concn after the present embodiment recycling.
Embodiment 7
(NE Chemcat company manufactures, trade(brand)name: RH221 to use Rh plating liquid; Rh 3～5g/L) while carrying out plating, be that 50 DEG C, the higher limit of the Rh ionic concn of this liquid of accommodating are that 42～60mg/L, lower value are while being 16～32mg/L when setting the water temperature of the liquid of accommodating in plating accumulator tank, as an example of the most suitable condition of the electrode arranging in plating accumulator tank, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 24V, the current value that shows the above-mentioned higher limit of Rh ionic concn is 450mA, shows that the current value of lower value is 350mA; The above-mentioned higher limit of Rh ionic concn and the difference of above-mentioned lower value are represented with current value, management is in the time of the scope of 100mA, most suitable electrode can exemplify the anode being made up of the Ti material of plating Pt, the negative electrode being made up of Ti material, for pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 35mm.
Similarly to Example 6, when carrying out draining that the mode of water filling work implements plating accumulator tank and water filling in drainage procedure, in the time reaching higher limit 450mA, draining is worked with motorized valve, in drainage procedure, water filling is worked with motorized valve, in the time reaching lower value 350mA, draining is used and the work of water filling motorized valve stops.Therefore, the Rh ionic concn of discharge is the scope of above-mentioned upper limit concentration 42～60mg/L and above-mentioned least concentration 16～32mg/L, the liquid of accommodating in plating accumulator tank 30% exchanged.The Rh ionic concn of adhering to liquid of adhering on clean plating object being treated in plating rinse bath is 60mg/L to the maximum, and in plating rinse bath, this adheres to liquid and dilutes through water, maintains the lower concentration below 10mg/L.The water temperature of water filling is about 20 DEG C, and the water temperature of the plating accumulator tank of continuous operation is 42～44 DEG C.
The electrolytic recovery of the Rh ion of the high density containing in the plating waste water from plating accumulator tank be use contain the anode being formed by the Ti material of plating Pt, the cathode electrode being formed by Ti material, the about 200L of circular treatment capacity electrolytic recovery device (Tanaka's precious metal industrial manufacture: MINI Recover Cell), taking electrolysis density as 30～140mA/dm
2rh ion is reclaimed.
The resin of the Rh ion of the lower concentration containing in the waste liquid after above-mentioned electrolytic recovery and the plating waste water from plating rinse bath reclaims can use respectively same resin, uses Di (the Tanaka's precious metal industrial manufacture: EagleRE) Rh ion is reclaimed that is filled with Zeo-karb.
The not enough 0.5mg/L of residual Rh ionic concn after the present embodiment recycling.
Comparative example 1
Make the water displacement each time from plating accumulator tank of embodiment 3 carry out draining according to 60% of plating accumulator tank full water amount, higher limit and the lower value of the Au ionic concn to the liquid of accommodating are set thus.But, 60% draining makes the water temperature of plating accumulator tank below 35 DEG C, the excessive precious metal ion adhering on plating object being treated or the elution efficiency of salt component reduce, and the breeding of mould or bacterium occurs, and the yield rate that the plating object being treated lowly causing due to quality occurs reduces.
Comparative example 2
The water displacement each time from plating accumulator tank of embodiment 5 is carried out to draining according to 5% of plating accumulator tank full water amount, and higher limit and the lower value of the Ag ionic concn to the liquid of accommodating are set thus.But, it is poor fully that 5% water displacement makes in the scope of higher limit and lower value, to set, become and can not manage by the current value of Ag ionic concn, the concentration of result Ag ion exceedes 800mg/L,, there is the yield rate reduction of the object being treated lowly causing due to quality in the Efficiency Decreasing that the excessive precious metal ion adhering on plating object being treated or salt component are reclaimed.And in plating rinse bath, Ag ionic concn has exceeded the recovery ability of Di, the rate of recovery of precious metal reduces.
Claims (2)
1. one kind is reclaimed the method for precious metal ion from plating waste water, it is characterized in that, making from the water displacement each time of plating accumulator tank is in 10～50% the scope of full water amount of plating accumulator tank, and, liquid measure in plating accumulator tank is the amount that can guarantee that plating object being treated is impregnated, thus the precious metal ion concentration of the liquid of accommodating in plating accumulator tank is maintained to the scope of 10～200mg/L, and, the precious metal ion concentration of the liquid of accommodating in plating rinse bath is maintained to the scope below 10mg/L; Meanwhile, maintain for the concentration of precious metal ion 10～200mg/L scope, from the plating waste water of plating accumulator tank, by electrolytic recovery method and resin absorption method or charcoal absorption absorption method and be used for reclaiming precious metal ion; For the concentration of precious metal ion maintain scope below 10mg/L, from the plating waste water of plating rinse bath, utilize resin absorption method or charcoal absorption absorption method to reclaim precious metal ion;
And between the electrode arranging in plating accumulator tank, switch on constant voltage or constant current, about the liquid of accommodating in plating accumulator tank, make in advance the working curve of the relation of the precious metal ion concentration that represents that current value or potential value and the liquid of accommodating contains; Between the electrode arranging in plating accumulator tank, switch on constant voltage or constant current, measure this interelectrode current value or potential value, measured value based on obtaining and above-mentioned working curve, the precious metal ion concentration of the liquid of accommodating in plating accumulator tank is carried out quantitatively, precious metal ion concentration being maintained to the scope of 10～200mg/L.
2. the method for recovery precious metal ion according to claim 1, is characterized in that, precious metal ion is more than one the ion of precious metal selecting in the group of free Au, Pd, Ag, Pt and Rh composition.
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| JP2010-243830 | 2010-10-29 | ||
| JP2010243830A JP4756103B1 (en) | 2010-10-29 | 2010-10-29 | Method for recovering precious metal ions from plating wastewater |
| PCT/JP2011/074747 WO2012057242A1 (en) | 2010-10-29 | 2011-10-27 | Method for recovering precious-metal ions from plating wastewater |
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| CN102892931B true CN102892931B (en) | 2014-08-06 |
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| JP (1) | JP4756103B1 (en) |
| KR (1) | KR101267201B1 (en) |
| CN (1) | CN102892931B (en) |
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| TWI561686B (en) * | 2015-03-09 | 2016-12-11 | Unimicron Technology Corp | Metal ion solution recovery apparatus and method thereof |
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| KR20160031617A (en) * | 2014-09-12 | 2016-03-23 | 삼성디스플레이 주식회사 | Collection method of silver ion and phosphoric acid in waste fluid |
| CN110629029B (en) * | 2019-10-31 | 2024-04-12 | 天津华勘集团有限公司 | Device and process for adsorbing noble metal in acid waste liquid of gold purification process |
| KR20210086497A (en) | 2019-12-30 | 2021-07-08 | 주식회사 동진쎄미켐 | Apparatus and method for recovering metal ion |
| KR20220015969A (en) | 2020-07-31 | 2022-02-08 | 주식회사 동진쎄미켐 | Apparatus for recovering metal ion, and electrode manufacturing method and electrode manufacturing device using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001279343A (en) * | 2000-03-29 | 2001-10-10 | Toppan Printing Co Ltd | Device and method for recovering noble metal |
| JP2004169072A (en) * | 2002-11-18 | 2004-06-17 | Ebara Udylite Kk | Closed acidic copper plating system and heat resistant acidic copper plating bath utilized for the same |
| JP2006322069A (en) * | 2005-04-19 | 2006-11-30 | Yuken Industry Co Ltd | Recovery type electrogalvanizing method and device |
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| JPS51148629A (en) * | 1975-06-16 | 1976-12-21 | Maruni Sangyo | Method of reclaiming silver salt in wash water of silver plating and complete circulation of said wash water |
| JPS53140235A (en) * | 1977-03-02 | 1978-12-07 | Okubo Katsuhiro | Continuous circulation system electrolytic treatment method of silver plating wash water and its device |
| JPH0726239B2 (en) * | 1989-07-04 | 1995-03-22 | 三菱電機株式会社 | How to collect the plating solution |
| JPH06184799A (en) * | 1990-03-29 | 1994-07-05 | Dezhong Hu | Process and equipment for discharging small amount of industrially produced rinsing solution |
| WO2005035149A1 (en) * | 2003-10-09 | 2005-04-21 | Ebara Corporation | Method of purifying matter contaminated by heavy metal and apparatus therefor |
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2010
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- 2011-10-27 CN CN201180023230.4A patent/CN102892931B/en not_active Expired - Fee Related
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- 2011-10-27 WO PCT/JP2011/074747 patent/WO2012057242A1/en active Application Filing
- 2011-10-28 TW TW100139360A patent/TWI409365B/en active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001279343A (en) * | 2000-03-29 | 2001-10-10 | Toppan Printing Co Ltd | Device and method for recovering noble metal |
| JP2004169072A (en) * | 2002-11-18 | 2004-06-17 | Ebara Udylite Kk | Closed acidic copper plating system and heat resistant acidic copper plating bath utilized for the same |
| JP2006322069A (en) * | 2005-04-19 | 2006-11-30 | Yuken Industry Co Ltd | Recovery type electrogalvanizing method and device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI561686B (en) * | 2015-03-09 | 2016-12-11 | Unimicron Technology Corp | Metal ion solution recovery apparatus and method thereof |
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| HK1180736A1 (en) | 2013-10-25 |
| WO2012057242A1 (en) | 2012-05-03 |
| JP2012097292A (en) | 2012-05-24 |
| TWI409365B (en) | 2013-09-21 |
| KR20120131239A (en) | 2012-12-04 |
| JP4756103B1 (en) | 2011-08-24 |
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