CN102892931A - 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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- CN102892931A CN102892931A CN2011800232304A CN201180023230A CN102892931A CN 102892931 A CN102892931 A CN 102892931A CN 2011800232304 A CN2011800232304 A CN 2011800232304A CN 201180023230 A CN201180023230 A CN 201180023230A CN 102892931 A CN102892931 A CN 102892931A
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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- C—CHEMISTRY; METALLURGY
- 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 from plating waste water, reclaim the method for precious metal ion, relate to especially the bad method that from plating waste water, reclaims precious metal ion of performance that can from the plating waste water of plating accumulator tank and plating rinse bath, reclaim efficiently precious metal ion and can suppress the plating object being treated.
Background technology
Precious metal is because its physical property characteristic, reliability and aesthetic property are excellent, industrial be very useful material, as coating material, be used in in the wide spectrum headed by the e-machine fields such as electronic component or printed wiring board.On the other hand, precious metal exists rare, is expensive material.Therefore, require to reclaim as much as possible precious metal and the re-using that contains in the plating waste water.
Usually, 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 behind the plating is carried out in plating accumulator tank performance in the plating groove, therefore be compared to waste water from the plating groove from the waste water of plating accumulator tank, contains the precious metal ion of lower concentration.In addition, because the plating rinse bath is the effect of performance secondary or three rinse baths, therefore be compared to waste water from the plating accumulator tank from the waste water of plating rinse bath, contain the precious metal ion of lower concentration.The precious metal ion concentration of the plating waste water of therefore, discharging from each groove is different.
In addition, also require to manage in the groove to the plating accumulator tank, in order to be eluted in and be attached to precious metal ion or salt component on the plating object being treated in plating accumulator tank and the 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 from plating waste water, reclaims precious metal ion, common known have electrolytic recovery method, resin absorption method and charcoal absorption absorption method.The electrolytic recovery method is excellent when reclaiming precious metal ion from the high plating waste water of precious metal ion concentration, if but be the plating waste water of lower concentration, even then make it at the electrolyzer internal recycle, current density can not raise yet, the organic efficiency variation of precious metal ion.On the other hand, resin absorption method and charcoal absorption absorption method are excellent when reclaiming precious metal ion from the low plating waste water of precious metal ion concentration, if but pass into the plating waste water of high density, then can't fully reclaim precious metal ion.Thus, the concentration that is necessary the precious metal ion to by the draining of plating rinse bath the time manages.
Method as high efficiente callback precious metal from the polytype waste liquid that contains precious metal with various concentration, for example known have a following methods: will cross chelating with the lower concentration waste liquid that lower concentration contains precious metal is ion exchange resin, making precious metal be adsorbed in chelating is ion exchange resin, with the precious metal taking-up of absorption; To in electrolyzer, carry out electrolysis treatment with the high-concentration waste liquid that high density contains precious metal, precious metal is separated out at electrode, the method (patent documentation 1) that the precious metal of separating out is reclaimed.
The 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, the method as partial drainage from the plating accumulator tank was to adopt the method for regular overflow; Perhaps by the timer automatic setting, with the time management method of regular draining; The perhaps manual regularly method of draining of operator.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 the plating accumulator tank is regularly reduced.
Yet the precious metal ion concentration of the liquid of accommodating in the plating accumulator tank does not always raise in certain proportion, according to circumstances can sharply raise yet.In addition, according to the turnout of plating object being treated, the precious metal ion concentration of the liquid of accommodating in the plating accumulator tank has various changes.Therefore, the plating waste water for the precious metal ion that contains lower concentration then 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 automatic setting, can't 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 the plating accumulator tank excessively raises, then 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 the problem that can't utilize resin absorption method, charcoal absorption absorption method that precious metal ion is fully reclaimed can occur.
The object of the present invention is to provide and a kind ofly can and can suppress the bad method of performance of plating object being treated from high efficiente callback precious metal ion from plating accumulator tank and plating rinse bath plating waste water that discharge, that contain precious metal ion.
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 the plating rinse bath is kept within the limits prescribed, has finally finished the present invention based on this opinion.Namely, the present invention is the method that reclaims precious metal ion from plating waste water, it is characterized in that, making water displacement each time from the plating accumulator tank is in 10～50% the scope of full water amount of plating accumulator tank, and the liquid measure in the plating accumulator tank is for can guarantee the amount that the plating object being treated is impregnated, concentration with the precious metal ion of the liquid of accommodating in the plating accumulator tank maintains certain scope with high density thus, and the concentration of the precious metal ion of the liquid of accommodating in the plating rinse bath is maintained 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, with 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, need not to stop the plating to the plating object being treated, can be from high efficiente callback precious metal ion from plating accumulator tank and plating rinse bath plating waste water that discharge, that contain 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, namely contains following steps: the dipping object being treated is to carry out the step of plating in containing the plating groove of plating liquid; Flood object being treated in the liquid of in the plating accumulator tank, accommodating, clean at first the step of object being treated; And flood object being treated in the liquid of in the plating rinse bath, accommodating, finally clean the step of object being treated; For the plating waste water from the plating accumulator tank, with 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 the plating rinse bath, utilize resin absorption method or charcoal absorption absorption method to reclaim precious metal ion.
Such as electronic component or printed wiring board etc., above-mentioned object being treated is for carrying out continuously the goods of plating with pair of rolls, and in plating groove etc., repeatedly flood, mention step, in batches by the goods of plating.In addition, the liquid of accommodating in plating accumulator tank and the plating rinse bath is generally the ion exchanged water of crossing through ion exchange resin treatment, also the suitable pure water that has carried out activated carbon treatment or reverse osmosis membrane processing from the liquid that the plating rinse bath is accommodated behind the recovery precious metal ion that adopts.
In the present invention, making water displacement each time from the plating accumulator tank is in 10～50% the scope of full water amount of plating accumulator tank, and the liquid measure in the plating accumulator tank is for can guarantee the amount that the plating object being treated is impregnated, precious metal ion concentration with the liquid of accommodating in the plating accumulator tank maintains certain scope with high density thus, and the precious metal ion concentration of the liquid of accommodating in the plating rinse bath is maintained 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, with 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 the liquid measure in the plating accumulator tank is for can guarantee the amount that the plating object being treated is impregnated.If water displacement each time surpass the plating accumulator tank the full water amount 50%, then because water filling so that the water temperature in the plating accumulator tank significantly change, reclaim the precious metal ion of the surplus of adhering on the plating object being treated or the Efficiency Decreasing of salt component, and mould or bacterium etc. are breeding easily, owing to cause the bad or yield rate reduction of performance adhering on the plating object being treated.
On the other hand, if water displacement each time at below 10% of full water amount, then the draining of the management of precious metal ion concentration and plating accumulator tank, water filling operation become miscellaneous.In addition, that management occurs is bad owing to operation miscellaneous, reclaims the precious metal ion of the surplus of adhering on the plating object being treated or the Efficiency Decreasing of salt component, and not only the plating object being treated is contaminated, and the organic efficiency of precious metal ion also can reduce.In addition, make each time water displacement for can guarantee that the reason of the amount that the plating object being treated is impregnated is for plating is stopped.
In addition, the water temperature of the liquid of accommodating in the plating accumulator tank is preferably more than 35 ℃, more preferably more than 40 ℃.Needn't initiatively carry out temperature regulation to the plating accumulator tank, but particularly preferably not make the water temperature excessive descent.Especially, if water temperature is below 35 ℃, to the excessive precious metal ion that adheres on the plating object being treated or the elution efficiency variation of salt component, can promote the breeding of mould or bacterium etc., the adhering to of residual or mould or bacterium of precious metal ion or salt component arranged on the plating object being treated, cause that thus performance is bad or yield rate is low.
In conventional plating groove, under the warm-up mode about 60～90 ℃, implement plating.The plating liquid that adheres on the plating object being treated of heating and the plating object being treated moves in the plating accumulator tank, the reason that this water temperature that becomes the plating accumulator tank raises.Another becomes raise on the water temperature of plating accumulator tank former because because plating groove and plating accumulator tank are to arrange continuously, be to be caused by the radiant heat from the plating groove.
Yet water temperature rises, and must not cause the performance of the plating object being treated in the plating accumulator tank bad or yield rate is low.Opposite to above-mentioned record, the water temperature of the liquid of accommodating in the plating accumulator tank is preferred more than 35 ℃, more preferably more than 40 ℃, especially, the excessive precious metal ion that adheres to from the plating object being treated or the elution efficiency breeding good, mould or bacterium of salt component are suppressed consideration, and preferred water temperature is high.
Usually, when the treatment capacity of plating object being treated was few, in time management method or press over system and full dose Shift Method in the past, excessively carrying out draining and water filling was the reason that causes that water temperature reduces.
Therefore, in the present invention, as described below, importantly in the 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 is the amount of 10～50% scope of the full water amount of plating accumulator tank and make each time water displacement from the plating accumulator tank.For example following management: pass through heat Calculation, when the water temperature of plating accumulator tank is 50 ℃, with 20 ℃ water fillings displacement full water amounts 50% the time, water temperature is for reducing by 10 ℃ scope, when even the treatment capacity of plating object being treated is less, water temperature is down to below 35 ℃.
The precious metal ion concentration of the liquid of accommodating in the 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 fit to electrolytic recovery method and resin absorption method or charcoal absorption absorption method and usefulness.
Herein maintain certain limit with high density, refer to the plating rinse bath in the precious metal ion concentration of the liquid of accommodating maintain certain limit with lower concentration and compare, keep with high density.
In addition, in the equipment design that precious metal ion reclaims, 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 a plurality of plating accumulator tanks that are set up in parallel, if contain same precious metal ion, just can under same stream, collect each plating waste water, carry out electrolytic recovery.
As embodiments of the present invention, when precious metal ion is high density, be fit to select with electrolytic recovery method and resin absorption method or charcoal absorption absorption method and usefulness; On the other hand, during for lower concentration, be fit to select resin absorption method or charcoal absorption absorption method.
For the precious metal ion of the liquid of accommodating in the electrolytic recovery groove expeditiously, in recovery system, adding fashionablely, preferably precious metal ion concentration is maintained certain scope.In the conventional electrolysis recovery method, it is the recovery system that number etc. is set that precious metal ion concentration during according to the plater draining or the wastewater treatment capacity of unit time design electrolytic recovery device.First will be from the fluid storage of accommodating of plating accumulator tank discharge, certain treatment capacity is being transferred to electrolytic recovery with in the groove from the groove of described storage, the liquid of accommodating is circulated in groove and electrolytic recovery device, simultaneously the electrolytic recovery precious metal ion in electrolytic recovery.Electrolytic recovery is according to setting cycling time, for the change of precious metal ion concentration, suits to adjust cycling time.Thus, certain scope refers to keep the concentration that precious metal ion is maintained the handling property that is fit to designed recovery system, if surpass certain scope, then surpassing resin after the electrolytic recovery or charcoal absorption can recoverable capacity in reclaiming, and the organic efficiency that becomes reduces.On the other hand, if below certain scope, then in electrolytic recovery, the organic efficiency under the 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, the result can realize high yield.
In addition, even the liquid of accommodating from the plating accumulator tank according to the kind of plating liquid, has the situation that current density can't fully raise, for the rising of current density, can append arbitrarily ionogen such as adding caustic soda.
For example, when the precious metal ion with the liquid of accommodating in the plating accumulator tank of the present invention regulation maintains certain scope 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 the plating accumulator tank surpasses 200mg/L, even with electrolytic recovery method and resin absorption method or charcoal absorption absorption method and usefulness, the recovery of precious metal ion is also insufficient; In addition, because superfluous precious metal ion flows out in the plating rinse bath, the possibility that the precious metal ion concentration of plating rinse bath surpasses 10mg/L uprises, and become the organic efficiency of the precious metal ion that contains in the plating waste water from the 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 the plating accumulator tank with electrolytic recovery method and resin absorption method or charcoal absorption absorption method and with becoming surplus design, becomes that efficient is low economically.In addition, below 10mg/L, this does not almost have as embodiment, and is unrealistic with the precious metal ion concentration management that contains in the liquid of accommodating in the plating accumulator tank.
In the present invention, the precious metal ion concentration of the liquid of accommodating in the plating rinse bath, for the precious metal ion concentration in the plating accumulator tank is maintained certain concentration range, the precious metal ion of being transferred to the plating rinse bath by the plating accumulator tank is maintained within a certain range with lower concentration.In addition, the liquid of accommodating in the plating accumulator tank after the electrolytic recovery method is processed, this liquid of accommodating too maintain certain limit with lower concentration.Owing to can maintain certain scope with lower concentration whichsoever, therefore can select aptly according to the treatment capacity of precious metal ion concentration and unit time the loading level etc. of resin and gac.
For example, when the precious metal concentration with the liquid of accommodating in the plating rinse bath of stipulating among the present invention maintains certain scope with lower concentration, preferably maintain below the 10mg/L.If surpass 10mg/L, the precious metal ion that then reclaims 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 the plating accumulator tank is 200mg/L to the maximum, and therefore, the peak concentration of the precious metal ion of the surplus that the plating object being treated of sending from the plating accumulator tank adheres to is 200mg/L; If for example in the plating rinse bath the above-mentioned liquid that adheres to is diluted to 25～50 times with pure water, the precious metal ion concentration during 25 times of dilutions is 8mg/L, becomes 4mg/L during 50 times of dilutions, maintains below the 10mg/L.
In the present invention, by from the plating waste water reclamation precious metal ion of plating accumulator tank the time, with 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 making up with resin absorption method or charcoal absorption absorption method, can improve significantly the organic efficiency of precious metal ion.
The electrolytic recovery method is to import plating waste water in electrolyzer, the method that makes precious metal ion separate out and reclaim at electrode by electrolysis.Employed anode can exemplify by the Ti material of the Ti material of plating Pt, sintering Ir or the electrode that Ferrite Material consists of; Negative electrode can exemplify the electrode that is made of Ti material, SUS material or Ferrite Material.In the present invention, reclaim the condition of precious metal as the ground of high electrolytic efficiency 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 produces through the hydrolysis of water can be shelled isolated platinum family, so 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, utilizes the removing of precious metal that chloroazotic acid etc. peels off to separate out, when reclaiming, and the suitable Ti material that uses is as negative electrode.
The resin absorption method is that plating waste water is passed into resin, captures precious metal ion, and this resin is burned and the method for recovery precious metal.As the resin that uses in the resin absorption method, for example can enumerate: Zeo-karb, anionite-exchange resin, resin, synthetic sorbing material, but the material of preferred 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, have the weak-base ion-exchange resin of primary amino, secondary amino group or uncle's 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 the 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 to capture precious metal ion with the charcoal absorption absorption method of electrolytic recovery method and usefulness, with described gac burning ashing, from the calcination that obtains, reclaim the method for precious metal ion.When using gac to capture precious metal ion, for example, gac be impregnated in the plating waste water, plating waste water is passed in the gac that is filled in the post carries out.
When from the plating waste water of plating rinse bath, reclaiming precious metal ion, carry out with resin absorption method or charcoal absorption absorption method.Resin absorption method or charcoal absorption absorption method are as previously mentioned.
When making water displacement each time from the plating accumulator tank be 10～50% the scope of full water amount of plating accumulator tank, the draining of plating accumulator tank and water filling are preferably undertaken by partial drainage, fractional flooding.Usually, industrial in order to carry out a large amount of platings, to require in the plating accumulator tank, to process continuously, not hinder the manufacturing of plating object being treated, if once implement the full dose draining, the plating of plating object being treated is stopped, and the production cycle is elongated, the problem of production development reduction.And, if carry out full dose draining, the new water filling of full dose, because so that the water temperature of 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 full water amount of plating accumulator tank as making each time water displacement from the plating accumulator tank, for example, two electrodes are set in the 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., the plating accumulator tank is switched on, and the current value that passes through to measure or potential value are controlled the action of motorized valve of draining and water filling etc.
Particularly, for example switch between the electrode that is arranged at the plating accumulator tank with constant voltage or constant current, the liquid of accommodating for the plating accumulator tank, make in advance the working curve of the relation of the precious metal ion concentration that contains in expression current value or potential value and this liquid of accommodating, switch between the electrode that is arranged at the plating accumulator tank with constant voltage or constant current, measure this interelectrode current value or potential value, based on the measured value that obtains and above-mentioned working curve, precious metal ion to the liquid of accommodating in the plating accumulator tank carries out quantitatively, when the quantitative values that obtains reaches the set(ting)value of regulation, by draining and/or the water filling of carrying out the plating accumulator tank, the precious metal ion concentration of the liquid of accommodating in the plating accumulator tank is maintained in certain scope with high density.
As above-mentioned electrode, anode preferably can stripping when improving current density, the Ti material by plating Pt, the Ti material of sintering Ir or the electrode that Ferrite Material consists of, the electrode that negative electrode preferably is made 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 when considering to install, more preferably use the shape of pole or cylinder.
When making above-mentioned working curve, and when current value and potential value are switched on, measured to reality to the plating accumulator tank, about electrode shape, electrode length, interelectrode distance and the impressed voltage that is arranged at the electrode in the plating accumulator tank, the selection that can cooperate the specific conductivity of the plating waste water of plating accumulator tank to suit.The specific conductivity of this plating waste water is the specific conductivity that contains the plating waste water integral body of precious metal ion and other ionogen etc., if precious metal ion concentration is high, then specific conductivity uprises.The precious metal ion concentration of plating waste water-when the current value slope of a curve is large, can relatively take to add low voltage, electrode diameter reduces, shortens electrode, widens 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 12～24V so that corresponding to the current value of the above-mentioned higher limit of precious metal ion concentration at 200～800mA, so that be 100～500mA corresponding to the current value of the above-mentioned lower value of precious metal ion concentration.Preferred selection can be with the difference management of the above-mentioned higher limit of precious metal ion concentration and the above-mentioned lower value electrode condition in the scope of 100～300mA.
The draining of plating accumulator tank and/or water filling for example can be adopted the mode that draining is used and water filling is worked simultaneously with motorized valve; Draining motorized valve work, water filling was with the mode of motorized valve work after draining was finished; In the drainage procedure, water filling can utilize controlling board automatically to control and carry out with mode of motorized valve work etc.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 simultaneously with motorized valve is: if the current value of the liquid of accommodating in the plating accumulator tank reaches the higher limit of setting, then draining is with working simultaneously with motorized valve with water filling, if reach the lower value of setting, then draining is with stopping with motorized valve with water filling.Control time of draining and water filling by the current value of the liquid of accommodating in the plating accumulator tank, thus higher limit and the lower value of management precious metal ion concentration.
Draining motorized valve work, after draining was finished, water filling with the mode of motorized valve work was: if the current value of the liquid of accommodating in the plating accumulator tank reaches the higher limit of setting, then only draining motorized valve work, draining is till the lower limit water level.At this moment, the current value of described liquid of accommodating can not change.If draining is finished, then, water filling motorized valve work then stops if water filling arrives full-water level.Control time of draining by the current value of the liquid of accommodating in the 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.
Water filling with the mode of motorized valve work is in the drainage procedure: if the current value of the liquid of accommodating in the plating accumulator tank reaches the higher limit of setting, then draining is worked with motorized valve, water filling is worked with motorized valve in this drainage procedure, if above-mentioned current value reaches the lower value of setting, then draining usefulness and water filling stop with the work of motorized valve, and water filling finishes.Control time of draining and water filling by the current value of the liquid of accommodating in the 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, be the plating liquid that contains more than at least a among Au, Pd, Ag, Pt and the Rh in the kind of the plating liquid that the plating object being treated is processed, also can be and contain above-mentioned precious metal and Ni, Co, the non-noble metal alloy plating liquid such as 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 the plating groove in addition, uses precious metal ion concentration usually.
Below, implementing in the situation of the present invention, enumerate the relevant embodiment that keeps the precious metal ion concentration of the liquid of accommodating in plating accumulator tank and the plating rinse bath.
Embodiment 1
(Japanese electroplating engineering (EEJA) company makes, trade(brand)name: Temperex MLA 100 to use the Au plating liquid; When Au 6～10g/L) carries out plating, the water temperature of the liquid of in setting the plating accumulator tank, accommodating be 50 ℃, the higher limit of the Au ionic concn of this liquid of accommodating be 50～59mg/L, when lower value is 34～43mg/L, an example as the only condition of the electrode that in the plating accumulator tank, arranges, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 24V, the above-mentioned higher limit current value that then shows the Au ionic concn is 350mA, and the current value that shows above-mentioned lower value is 250mA; The above-mentioned higher limit of Au ionic concn and the difference of above-mentioned lower limit management value are represented with current value, management is when the scope of 100mA, the negative electrode that only electrode can exemplify anode that the Ti material by plating Pt consists of, be made of the Ti material, be the pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 35mm.
With draining with and the water filling mode of working simultaneously with motorized valve when implementing the draining of plating accumulator tank and water filling, when reaching above-mentioned higher limit 350mA, draining is with working simultaneously with motorized valve with water filling, and when reaching above-mentioned lower value 250mA, draining usefulness and water filling stop with the work of motorized valve.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 the plating accumulator tank 20% exchanged.The Au ionic concn of adhering to liquid that the plating object being treated of cleaning in the plating accumulator tank adheres to is 59mg/L to the maximum, and in the plating rinse bath, this adheres to liquid and dilutes through water, and the Au ionic concn is maintained lower concentration below the 10mg/L.The water temperature of water filling is about 20 ℃, and the water temperature of the plating accumulator tank of continuous operation is 44～46 ℃.
The electrolytic recovery of the Au ion of the high density that contains in the plating waste water from the plating accumulator tank be the cathode electrode that uses the anode contain the Ti material by sintering Ir and to consist of, consisted of by the Ti material, the about 200L of circular treatment capacity electrolytic recovery device (manufacturing of Tanaka's precious metal industrial: MINI Recover Cell), with electrolysis density 130～200mA/dm
2The Au ion is reclaimed.
The resin of the Au ion of the lower concentration that contains in the waste liquid after the above-mentioned electrolytic recovery and the plating waste water from the plating rinse bath reclaims can use respectively same resin, and (Tanaka's precious metal industrial makes: EagleRE) the Au ion is reclaimed to use the Di 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 makes, trade(brand)name: Temperex 8400 to use the Au plating liquid; Au3～when 5g/L) carrying out plating, the water temperature of the liquid of in setting the plating accumulator tank, accommodating be 50 ℃, the higher limit of the Au ionic concn of this liquid of accommodating be 50～63mg/L, when lower value is 33～42mg/L, an example as the only condition of the electrode that in the plating accumulator tank, arranges, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 24V, the current value that then 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 higher limit of Au ionic concn and the difference of lower value are represented with current value, management is when the scope of 100mA, the negative electrode that only electrode can exemplify anode that the Ti material by plating Pt consists of, be made of the Ti material, be the 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 working simultaneously with motorized valve when implementing the draining of plating accumulator tank and water filling, when reaching above-mentioned higher limit 370mA, draining is with working simultaneously with motorized valve with water filling, when reaching above-mentioned lower value 270mA, draining usefulness and water filling are stopped with the work of motorized valve.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 the plating accumulator tank 20% exchanged.The Au ionic concn of adhering to liquid of adhering on the plating object being treated of cleaning in the plating accumulator tank is 63mg/L to the maximum, and in the plating rinse bath, this adheres to liquid and dilutes through water, and the Au ionic concn is maintained lower concentration below the 10mg/L.The water temperature of water filling is about 20 ℃, and the water temperature of the plating accumulator tank of continuous operation is 44～46 ℃.
The electrolytic recovery of the Au ion of the high density that contains in the plating waste water from the plating accumulator tank be the cathode electrode that uses the anode contain the Ti material by sintering Ir and to consist of, consisted of by the Ti material, the about 200L of circular treatment capacity electrolytic recovery device (manufacturing of Tanaka's precious metal industrial: MINI Recover Cell), take electrolysis density as 130～200mA/dm
2The Au ion is reclaimed.
The resin of the Au ion of the lower concentration that contains in the waste liquid after the above-mentioned electrolytic recovery and the plating waste water from the plating rinse bath reclaims can use respectively same resin, and (Tanaka's precious metal industrial makes: EagleRE) the Au ion is reclaimed to use the Di 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 makes, trade(brand)name: Aurobond TN to use the Au plating liquid; When Au 1～3g/L) carries out plating, the water temperature of the liquid of in setting the plating accumulator tank, accommodating be 50 ℃, the higher limit of the Au ionic concn of this liquid of accommodating be 28～95mg/L, when lower value is 17～74mg/L, an example as the only condition of the electrode that in the plating accumulator tank, arranges, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 12V, the current value that then shows the above-mentioned higher limit of Au ionic concn is 450mA, shows 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 when the scope of 100mA, the negative electrode that only electrode can exemplify anode that the Ti material by plating Pt consists of, be made of the Ti material, be the 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 working simultaneously with motorized valve when implementing the draining of plating accumulator tank and water filling, when reaching above-mentioned higher limit 450mA, draining is with working simultaneously with motorized valve with water filling, when reaching above-mentioned lower value 350mA, draining usefulness and water filling stop with the work of motorized valve.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 the plating accumulator tank 20% exchanged.The Au ionic concn of adhering to liquid of adhering on the plating object being treated of cleaning in the plating accumulator tank is 95mg/L to the maximum, and in the plating rinse bath, this adheres to liquid and dilutes through water, and the Au ionic concn is maintained lower concentration below the 10mg/L.The water temperature of water filling is about 20 ℃, and the water temperature of the plating accumulator tank of continuous operation is 44～46 ℃.
The electrolytic recovery of the Au ion of the high density that contains in the plating waste water from the plating accumulator tank be the cathode electrode that uses the anode contain the Ti material by sintering Ir and to consist of, consisted of by the Ti material, the about 200L of circular treatment capacity electrolytic recovery device (manufacturing of Tanaka's precious metal industrial: MINI Recover Cell), take electrolysis density as 130～200mA/dm
2The Au ion is reclaimed.
The resin of the Au ion of the lower concentration that contains in the waste liquid after the above-mentioned electrolytic recovery and the plating waste water from the plating rinse bath reclaims can use respectively same resin, and (Tanaka's precious metal industrial makes: EagleRE) the Au ion is reclaimed to use the Di 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 makes, trade(brand)name: Palladex 100 to use the Pd plating liquid; When Pd 25～30g/L) carries out plating, the water temperature of the liquid of in setting the plating accumulator tank, accommodating be 50 ℃, this higher limit of accommodating the Pd ion of liquid be 129～157mg/L, when lower value is 38～77mg/L, an example as the only condition of the electrode that in the plating accumulator tank, arranges, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 12V, the current value that then 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 when the scope of 100mA, the cathode electrode that only electrode can exemplify anode that the Ti material by plating Pt consists of, be made of the Ti material, be the pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 45mm.
When making again water filling implement the draining of plating accumulator tank and water filling with the mode of motorized valve work after finishing with motorized valve work, draining with draining, when reaching above-mentioned higher limit 550mA, draining motorized valve work is when 40% of full water amount is discharged from, water filling motorized valve work stops when full water.Therefore, the Pd ionic concn that is 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 the plating object being treated of cleaning in the plating accumulator tank is 157mg/L to the maximum, and in the plating rinse bath, this adheres to liquid and dilutes through water, and the Pd ionic concn is maintained lower concentration below the 10mg/L.The water temperature of water filling is about 20 ℃, and the water temperature of the plating accumulator tank of continuous operation is 40～42 ℃.
The electrolytic recovery of the Pd ion of the high density that contains in the plating waste water from the plating accumulator tank be the cathode electrode that uses the anode contain the Ti material by plating Pt and to consist of, consisted of by the Ti material, the about 200L of circular treatment capacity electrolytic recovery device (manufacturing of Tanaka's precious metal industrial: MINI Recover Cell), take electrolysis density as 100～270mA/dm
2The Pd ion is reclaimed.
The resin of the Pd ion of the lower concentration that contains in the waste liquid after the above-mentioned electrolytic recovery and the plating waste water from the plating rinse bath reclaims can use respectively same resin, and (Tanaka's precious metal industrial makes: Eagle RE) the Pd ion is reclaimed to use the Di 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 makes, trade(brand)name: AG-10 to use the Ag plating liquid; When Ag 50～70g/L) carries out plating, the water temperature of the liquid of in setting the plating accumulator tank, accommodating be 50 ℃, the higher limit of the Ag ionic concn of this liquid of accommodating be 148～195mg/L, when lower value is 49～83mg/L, an example as the only condition of the electrode that in the plating accumulator tank, arranges, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 12V, the current value that then 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 when the scope of 100mA, the negative electrode that only electrode can exemplify anode that the Ti material by plating Pt consists of, be made of the Ti material, be the pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 55mm.
Similarly to Example 4, when making again water filling implement the draining of plating accumulator tank and water filling with the mode of motorized valve work after finishing with motorized valve work, draining with draining, when reaching above-mentioned higher limit 650mA, draining is worked with motorized valve, when 50% of full water amount is discharged from, water filling motorized valve work stops when 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 the plating object being treated of cleaning in the plating rinse bath is 195mg/L to the maximum, and in the plating rinse bath, this adheres to liquid and dilutes through water, and the Ag ionic concn is maintained lower concentration below the 10mg/L.The water temperature of water filling is about 20 ℃, and the water temperature of the plating accumulator tank of continuous operation is 39～41 ℃.
The electrolytic recovery of the Ag ion of the high density that contains in the plating waste water from the plating accumulator tank be the cathode electrode that uses the anode contain the Ti material by sintering Ir and to consist of, consisted of by the Ti material, the about 200L of circular treatment capacity electrolytic recovery device (manufacturing of Tanaka's precious metal industrial: MINI Recover Cell), take electrolysis density as 130～200mA/dm
2The Ag ion is reclaimed.
The resin of the Ag ion of the lower concentration that contains in the waste liquid after the above-mentioned electrolytic recovery and the plating waste water from the plating rinse bath reclaims can use respectively same resin, and (Tanaka's precious metal industrial makes: EagleRE) the Ag ion is reclaimed to use the Di 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 makes, trade(brand)name: Precious fab Pt100 to use the Pt plating liquid; Pt10～when 14g/L) carrying out plating, the water temperature of the liquid of in setting the plating accumulator tank, accommodating be 50 ℃, the higher limit of the Pt ionic concn of this liquid of accommodating be 96～120mg/L, when lower value is 45～63mg/L, an example as the only condition of the electrode that in the plating accumulator tank, arranges, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 15V, the current value that then 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 when the scope of 100mA, the negative electrode that only electrode can exemplify anode that the Ti material by plating Pt consists of, be made of the Ti material, be the pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 40mm.
When implementing the draining of plating accumulator tank and water filling in the mode of carrying out water filling work in the drainage procedure, when reaching higher limit 500mA, draining motorized valve work, water filling is worked with motorized valve in the drainage procedure, when reaching lower value 400mA, draining usefulness and water filling stop with the work of motorized valve.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 the plating accumulator tank 40% exchanged.The Pt ionic concn of adhering to liquid of adhering on the plating object being treated of cleaning in the plating rinse bath is 120mg/L to the maximum, and in the plating rinse bath, this adheres to liquid and dilutes through water, maintains the following lower concentration of 10mg/L.The water temperature of water filling is about 20 ℃, and the water temperature of the plating accumulator tank of continuous operation is 40～42 ℃.
The electrolytic recovery of the Pt ion of the high density that contains in the plating waste water from the plating accumulator tank be the cathode electrode that uses the anode contain the Ti material by plating Pt and to consist of, consisted of by the Ti material, the about 200L of circular treatment capacity electrolytic recovery device (manufacturing of Tanaka's precious metal industrial: MINI Recover Cell), take electrolysis density as 30～140mA/dm
2The Ag ion is reclaimed.
The resin of the Pt ion of the lower concentration that contains in the waste liquid after the above-mentioned electrolytic recovery and the plating waste water from the plating rinse bath reclaims can use respectively same resin, and (Tanaka's precious metal industrial makes: EagleRE) the Pt ion is reclaimed to use the Di 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 makes, trade(brand)name: RH221 to use the Rh plating liquid; When Rh 3～5g/L) carries out plating, the water temperature of the liquid of in setting the plating accumulator tank, accommodating be 50 ℃, the higher limit of the Rh ionic concn of this liquid of accommodating be 42～60mg/L, when lower value is 16～32mg/L, an example as the only condition of the electrode that in the plating accumulator tank, arranges, electrode shape, electrode length, interelectrode distance and impressed voltage, if impressed voltage is 24V, the current value that then 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 when the scope of 100mA, the negative electrode that only electrode can exemplify anode that the Ti material by plating Pt consists of, be made of the Ti material, be the pole shape, electrode diameter is Φ 15mm, the long 23mm of electrode, pole distance 35mm.
Similarly to Example 6, when implementing the draining of plating accumulator tank and water filling in the mode of carrying out water filling work in the drainage procedure, when reaching higher limit 450mA, draining is worked with motorized valve, water filling is worked with motorized valve in the drainage procedure, when reaching lower value 350mA, draining usefulness and water filling stop with the work of motorized valve.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 the plating accumulator tank 30% exchanged.The Rh ionic concn of adhering to liquid of adhering on the plating object being treated of cleaning in the plating rinse bath is 60mg/L to the maximum, and in the plating rinse bath, this adheres to liquid and dilutes through water, maintains the following lower concentration of 10mg/L.The water temperature of water filling is about 20 ℃, and the water temperature of the plating accumulator tank of continuous operation is 42～44 ℃.
The electrolytic recovery of the Rh ion of the high density that contains in the plating waste water from the plating accumulator tank be the cathode electrode that uses the anode contain the Ti material by plating Pt and to consist of, consisted of by the Ti material, the about 200L of circular treatment capacity electrolytic recovery device (manufacturing of Tanaka's precious metal industrial: MINI Recover Cell), take electrolysis density as 30～140mA/dm
2The Rh ion is reclaimed.
The resin of the Rh ion of the lower concentration that contains in the waste liquid after the above-mentioned electrolytic recovery and the plating waste water from the plating rinse bath reclaims can use respectively same resin, and (Tanaka's precious metal industrial makes: EagleRE) the Rh ion is reclaimed to use the Di that is filled with Zeo-karb.
The not enough 0.5mg/L of residual Rh ionic concn after the present embodiment recycling.
Comparative Examples 1
Make the each time water displacement from the plating accumulator tank of embodiment 3 come draining according to 60% of plating accumulator tank full water amount, thus higher limit and the lower value of the Au ionic concn of the liquid of accommodating are set.Yet, 60% draining so that the water temperature of plating accumulator tank below 35 ℃, the excessive precious metal ion that adheres on the plating object being treated or the elution efficiency of salt component reduce, and the breeding of mould or bacterium occurs, and generation is owing to the yield rate of the plating object being treated that quality lowly causes reduces.
Comparative example 2
The each time water displacement from the plating accumulator tank of embodiment 5 is come draining according to 5% of plating accumulator tank full water amount, thus higher limit and the lower value of the Ag ionic concn of the liquid of accommodating are set.Yet, 5% water displacement so that can't in the scope of higher limit and lower value, set poor fully, become and to manage by the current value of Ag ionic concn, the concentration of Ag ion surpasses 800mg/L as a result, Efficiency Decreasing to the excessive precious metal ion that adheres on the plating object being treated or salt component reclaim occurs because the yield rate reduction of the object being treated that quality lowly causes.And in the plating rinse bath, the Ag ionic concn has surpassed the recovery ability of Di, and the rate of recovery of precious metal reduces.
Claims (3)
1. method that from plating waste water, reclaims precious metal ion, it is characterized in that, making each time water displacement from the plating accumulator tank is in 10～50% the scope of full water amount of plating accumulator tank, and, liquid measure in the plating accumulator tank is for can guarantee the amount that the plating object being treated is impregnated, precious metal ion concentration with the liquid of accommodating in the plating accumulator tank maintains certain scope with high density thus, and, the precious metal ion concentration of the liquid of accommodating in the plating rinse bath is maintained certain scope with lower concentration; Simultaneously, for the concentration of precious metal ion with high density maintain certain scope, from the plating waste water of plating accumulator tank, with 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 with lower concentration maintain certain scope, from the plating waste water of plating rinse bath, utilize resin absorption method or charcoal absorption absorption method to reclaim precious metal ion.
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 that is selected from the group that is comprised of Au, Pd, Ag, Pt and Rh.
3. the method for recovery precious metal ion according to claim 1 and 2, it is characterized in that, between the electrode that in the plating accumulator tank, arranges, switch on constant voltage or constant current, about the liquid of accommodating in the plating accumulator tank, make in advance expression current value or potential value and the working curve of the relation of the precious metal ion concentration that the liquid of accommodating contains; Between the electrode that in the plating accumulator tank, arranges, switch on constant voltage or constant current, measure this interelectrode current value or potential value, based on the measured value that obtains and above-mentioned working curve, precious metal ion concentration to the liquid of accommodating in the plating accumulator tank carries out quantitatively precious metal ion concentration being maintained certain scope.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010243830A JP4756103B1 (en) | 2010-10-29 | 2010-10-29 | Method for recovering precious metal ions from plating wastewater |
| JP2010-243830 | 2010-10-29 | ||
| PCT/JP2011/074747 WO2012057242A1 (en) | 2010-10-29 | 2011-10-27 | Method for recovering precious-metal ions from plating wastewater |
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| CN102892931A true CN102892931A (en) | 2013-01-23 |
| CN102892931B CN102892931B (en) | 2014-08-06 |
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| CN201180023230.4A Expired - Fee Related CN102892931B (en) | 2010-10-29 | 2011-10-27 | Method for recovering precious-metal ions from plating wastewater |
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| JP (1) | JP4756103B1 (en) |
| KR (1) | KR101267201B1 (en) |
| CN (1) | CN102892931B (en) |
| HK (1) | HK1180736A1 (en) |
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| WO (1) | WO2012057242A1 (en) |
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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 |
| TWI561686B (en) * | 2015-03-09 | 2016-12-11 | Unimicron Technology Corp | Metal ion solution recovery apparatus and method thereof |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53140235A (en) * | 1977-03-02 | 1978-12-07 | Okubo Katsuhiro | Continuous circulation system electrolytic treatment method of silver plating wash water and its device |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| SG149818A1 (en) * | 2003-10-09 | 2009-02-27 | Ebara Corp | Clarification method and apparatus for material contaminated with heavy metals |
-
2010
- 2010-10-29 JP JP2010243830A patent/JP4756103B1/en active Active
-
2011
- 2011-10-27 KR KR1020127028736A patent/KR101267201B1/en active IP Right Grant
- 2011-10-27 WO PCT/JP2011/074747 patent/WO2012057242A1/en active Application Filing
- 2011-10-27 CN CN201180023230.4A patent/CN102892931B/en not_active Expired - Fee Related
- 2011-10-28 TW TW100139360A patent/TWI409365B/en active
-
2013
- 2013-07-11 HK HK13108119.4A patent/HK1180736A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53140235A (en) * | 1977-03-02 | 1978-12-07 | Okubo Katsuhiro | Continuous circulation system electrolytic treatment method of silver plating wash water and its device |
| 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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| Publication number | Publication date |
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| TWI409365B (en) | 2013-09-21 |
| KR101267201B1 (en) | 2013-05-27 |
| KR20120131239A (en) | 2012-12-04 |
| WO2012057242A1 (en) | 2012-05-03 |
| JP4756103B1 (en) | 2011-08-24 |
| HK1180736A1 (en) | 2013-10-25 |
| CN102892931B (en) | 2014-08-06 |
| TW201226632A (en) | 2012-07-01 |
| JP2012097292A (en) | 2012-05-24 |
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