CN101073835A - Method of recycling metallic grains - Google Patents
Method of recycling metallic grains Download PDFInfo
- Publication number
- CN101073835A CN101073835A CNA2007101046089A CN200710104608A CN101073835A CN 101073835 A CN101073835 A CN 101073835A CN A2007101046089 A CNA2007101046089 A CN A2007101046089A CN 200710104608 A CN200710104608 A CN 200710104608A CN 101073835 A CN101073835 A CN 101073835A
- Authority
- CN
- China
- Prior art keywords
- slurry
- aqueous solution
- silver
- discarded object
- chemical treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Powder Metallurgy (AREA)
- Processing Of Solid Wastes (AREA)
- Conductive Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to a method for recycling metal particles from metal slurry wastes. The mentioned method includes: chemistry treatment step that mixing the mentioned metal slurry wastes and acidity or alkalescence water solution to form slurry, and cleaning the polymer resin composition or glass powder and polymer resin composition from the mentioned metal slurry wastes; ultrasonic treatment step that beating up the slurry, at the same time, irradiating ultrasonic using ultrasonic oscillator to make the atomic binding of the mentioned polymer resin disconnect so as to promote chemistry reaction, and the shock wave generated by the air bladder breach of the slurry peels off the glass power or polymer resin from the metal particle peripheral. According to this invention, the mentioned method is environmental protection, the metal particle can be reclaimed simply and the industry outlay can be reduced greatly through recycling metal particle, also the mentioned method restrains environmental pollution caused by metal slurry wastes.
Description
Technical field
The present invention relates to a kind of recovery method of metallic particles, relate in particular to the method that reclaims the high purity metal particle in conjunction with utilizing the chemical method of the hyperacoustic physical method and the feature of environmental protection.
Background technology
PDP (Plasma Display Panel) electrode is the kernel component of PDP, by addressing (Address) the electrode formation of the transparency electrode (ITO) of upper glass plates and conflux (bus) electrode and lower glass plate.Described bus electrode and described addressing electrode utilize conductive metal slurry (paste) to form by photolithography (Photolithography).
The conductive metal slurry that is used for the electrode typography uses the slurry that contains silver (Ag), gold (Au), platinum (Pt), nickel (Ni), copper (Cu), palladium conductive gold metal particles such as (Pd).Especially, the main silver slurry that contains silver-colored particle that uses of conductive metal slurry.This silver slurry by the silver-colored particle of 1～3 μ m size (about 60～80wt%), be used to strengthen with the glass dust (Frit Glass) of the close property of glass substrate (2～5wt%), the binder of acrylate (acrylate) class (7～10wt%), solvent and additive (dispersant, antifoaming agent (antifoam), levelling agent formations such as (leveler).
Fig. 1 a to Fig. 1 e is the profile that to utilize photolithography to form the method for PDP electrode and illustrate in order to illustrate.
Shown in Fig. 1 a to Fig. 1 e, if starch the drying process through being scheduled to after 20 in the one side coating and the printed silver of glass substrate 10, then the slurry of the silver on the glass substrate 10 20 is dried.Utilize photomask 30 optionally to cover exposure afterwards, use developer solution to develop then and can form the electrode pattern of optionally removing silver slurry 20.Finish after the developing process, form electrode 40 through oversintering (firing) technology.
So, the PDP electrode forms by a succession of processes such as printing, drying, exposure, development, sintering.In the technology of this formation electrode, can generate silver slurry discarded object at developing process.Because silver-colored particle is the high price material in the silver slurry, therefore it is abandoned or reprocess as discarded object and use not as good as it is reclaimed.
Contain in this silver slurry discarded object silver of removing solvent starch dry ingredient, as the sodium carbonate (Na of remover
2CO
3) or caustic soda (NaOH) etc.
Silver-colored particle accounts for 80wt% greatly in the silver slurry discarded object, and residual components mainly is made of the binder of glass dust and macromolecule resin.The main component of described glass dust is PbO, B
2O
3And SiO
2, its size is about 0.5～1 μ m.And the binder major part of described macromolecule resin composition is an esters of acrylic acid, and exists with the state that combines with silver-colored particle surface or glass dust surface chemistry through drying process.
When silver slurry discarded object is reprocessed silver-colored particle, can remove the macromolecule resin composition through the whole described silver slurry discarded objects of dissolving under hot conditions, and remove the glass dust composition by refining (refining) technology and prepare silver bullion, synthesis of high purity silver particle then.But, because this reprocessing process carries out under hot conditions, therefore may be because of organic carbonization cause environmental pollution, and because energy consumption is big, so the expense costliness.And, need use harmful high price chemical industry medicine and complete equipment from the silver-colored particle of the synthetic micron size of silver bullion, therefore need a lot of expenses.
In addition, the 10-2003-0080529 korean patent application discloses a kind of PDP barrier and has ground the recovery method of using particle.The 10-2003-0080529 korean patent application discloses and has been applicable to Al
2O
3Particle, SiC particle, glass particle or stainless steel particle etc. grind the recovery method with particle.
But industrial circle has the demand that reclaims metallic particles with high-purity always.Especially, for the silver-colored particle that will reclaim recycling in PDP electrode etc., the electric conductivity and the shape of silver particle can not be impaired, and will have the high-purity that contains glass dust and macromolecule resin composition hardly, therefore reclaim metallic particles with present technology and have very big difficulty.
If the recovery technology of silver-colored particle is success not, make and then use the conductance of the PDP electrode that reclaims silver-colored particle to reduce by residual a lot of glass dust in the silver-colored particle that reclaims.
And, when the macromolecule resin composition organic components of residual deformation in the silver-colored particle, be used for the PDP electrode if use the silver-colored preparation of granules silver slurry of this recovery, then in typography, cause problems such as viscosity increase, printing functionality deterioration, thereby bring serious adverse consequences for the PDP electrode.
Summary of the invention
The object of the present invention is to provide a kind of method of recycling metallic grains, come environmental protection and remove macromolecule resin or glass dust and the macromolecule resin that exists in the metal slurry discarded object simply by the method that the chemical method that will utilize hyperacoustic physical method and use acidity or alkaline aqueous solution combines.
Method of recycling metallic grains provided by the present invention, be used for reclaiming metallic particles from the metal slurry discarded object that produces because of the metal slurry, this method comprises: (a) described metal slurry discarded object is mixed with acidity or alkaline aqueous solution to stir and form and starch, utilize described acidity or alkaline aqueous solution to remove described metal and starch the macromolecule resin composition in the discarded object or the chemical treatment step of glass dust and macromolecule resin composition; (b) utilize stirring arm the time ultrasonic oscillator interatomic bond make and break of described macromolecule resin is opened and to be promoted chemical reaction to slurry irradiation ultrasonic wave, and making the bubble in the described slurry acutely expand and break at its limit point because of high pressure, the shock wave that produces when bubble breaks acts on described metal slurry discarded object and peels off the glass dust of described metallic particles periphery or the ultrasonic wave treatment step of macromolecule resin; (c) carry out removing the filtering technique of mother liquor and forming the step of filter cake from described slurry; (d) filter cake that obtains by described filtering technique is carried out the step that drying process obtains metallic particles.
Carry out described filtering technique and form after the filter cake, can also comprise: filter cake that will obtain by described filtering technique and alkalescence or acidic aqueous solution mix to stir and form slurry, utilize described alkalescence or acidic aqueous solution to remove described metal and starch the macromolecule resin composition in the discarded object or the chemical treatment step second time of glass dust and macromolecule resin composition; Utilize ultrasonic oscillator to slurry irradiation hyperacoustic second time of ultrasonic wave treatment step in the time of stirring arm; Carry out removing the filtering technique of mother liquor and forming the step of filter cake from described slurry; If the chemical treatment step at described (a) has used acidic aqueous solution, then described second time chemical treatment step use alkaline aqueous solution and carry out chemical treatment, if the chemical treatment step at described (a) has used alkaline aqueous solution, then described second time chemical treatment step use acidic aqueous solution and carry out chemical treatment, perhaps use the aqueous solution of employed aqueous solution same physical properties in the chemical treatment step with described (a) to carry out the described chemical treatment second time.
Before the chemical treatment step of described (a), can also comprise the step that the difference in specific gravity of utilizing between described metallic particles and the described glass dust uses wet classifier or dry classification machine that described metal slurry discarded object is carried out classification.
Before the chemical treatment step of described (a), can also be included in less than the temperature conditions of the softening point temperature of the described glass dust described metal slurry discarded object of burning and remove the step of described macromolecule resin down.
And, before the chemical treatment step of described (a), can also comprise described metal slurry discarded object put into and stir in the solvent and dissolve and remove the step of described macromolecule resin.
And, can also be included in the step of mixed solvent in described acidic aqueous solution or the described alkaline aqueous solution, can utilize the mixed liquor of described acidic aqueous solution and described solvent or described alkaline aqueous solution and described solvent to carry out chemical treatment.
And described solvent can use the material that comprises at least a material of selecting from the aromatic hydrocarbons that comprises toluene, dimethylbenzene or benzene and the ester class that comprises butyl acetate, propylene glycol methyl ether acetate or ethylene acetate.
And; described metal slurry can be silver (Ag) slurry, gold (Au) slurry, platinum (Pt) slurry, nickel (Ni) slurry, copper (Cu) slurry or palladium (Pd) slurry, and described metallic particles can be silver (Ag) particle, gold (Au) particle, platinum (Pt) particle, nickel (Ni) particle, copper (Cu) particle or palladium (Pd) particle of electric conductivity.
And described metal slurry is the slurry that is used to form the PDP electrode, and described metal slurry discarded object is the discarded object that discharges in the developing process in the technology that forms the PDP electrode, and described metallic particles can be the silver-colored particle of electric conductivity.
And described acidic aqueous solution can use the material that comprises at least a acid of selecting from the organic acid that comprises acetate, lactic acid and citric acid.
And, described alkaline aqueous solution can use the material that comprises at least a alkaline inorganic compound of selecting from the alkaline inorganic compound that comprises NaOH, potassium hydroxide and ammonia, perhaps can use to comprise from comprising the material that amount of carbon atom is at least a alkaline organic compound selected the alkaline organic compound of 1～10 primary amine, secondary amine and tertiary amine.
And, can also comprise the step of adding surfactant in oxytropism or the alkaline aqueous solution.
And the ultrasonic frequency with 28～40kHz in the described ultrasonic wave treatment step was shone 30 minutes to 2 hours.
Description of drawings
Fig. 1 a to Fig. 1 e is used to illustrate the profile that utilizes photolithography to form the method for PDP electrode;
Fig. 2 is SEM (SEM:ScanningElectron Microscope) photo at silver slurry discarded object before reclaiming;
Though Fig. 3 reclaims silver-colored particle, the SEM photo when not shining ultrasonic wave in whipping process according to experimental example 1;
Fig. 4 is the SEM photo according to the silver-colored particle of experimental example 1 recovery;
Fig. 5 is the SEM photo according to the silver-colored particle of experimental example 2 recovery;
Fig. 6 is the SEM photo according to the silver-colored particle of experimental example 3 recovery;
Fig. 7 is the SEM photo according to the silver-colored particle of experimental example 4 recovery;
Fig. 8 is the SEM photo according to the silver-colored particle of experimental example 5 recovery;
Fig. 9 is for forming the SEM photo of PDP electrode silver-colored particle normal goods before.
Main symbol description: 10 is glass substrate, and 20 is the silver slurry, and 30 is photomask, and 40 is the PDP electrode.
The specific embodiment
Below, the preferred embodiment that present invention will be described in detail with reference to the accompanying is provided.But the following examples just are used for making the personnel with common knowledge of this area to fully understand the present invention, and can be deformed into various other forms, so protection scope of the present invention is not limited to the following embodiment that will describe.The identical identical inscape of symbolic representation in the accompanying drawing.
The open method that from conductive metal slurry discarded object, reclaims metallic particles of the present invention.Described metallic particles can comprise silver (Ag) particle, gold (Au) particle, platinum (Pt) particle, nickel (Ni) particle, copper (Cu) particle, palladium (Pd) particle etc.Preferred embodiment of the present invention illustrated is starched the method that discarded object reclaims silver-colored particle from silver, and disclosed recovery method can also be applicable to from metal slurry discarded object and reclaim gold (Au), platinum (Pt), nickel (Ni), copper (Cu), palladium metallic particles such as (Pd) among the following embodiment.
And described metal slurry discarded object is except comprising the metal slurry discarded object that contains oxide fine particles such as glass dust, can also comprise the metal slurry discarded object that does not contain glass dust.Owing on glass substrate, form the PDP electrode, therefore in the typography of PDP electrode, use the metal slurry that contains glass dust in order to improve with the close property of glass substrate, the metal slurry that does not contain glass dust is mainly used in general typography.
The silver slurry that is mainly used in PDP electrode typography is by silver-colored particle, the glass dust that is used for the close property of enhancing and PDP (or down) glass substrate, the formations such as esters of acrylic acid binder, solvent and additive of macromolecule resin composition.
The proportion that is mingled in the glass powder particles in the silver slurry discarded object is about 1.4, and average grain diameter is below the 1 μ m.Silver particle proportion is about about 10, and to be average grain diameter be sphere about 1～3 μ m.Though the proportion deviation between glass dust and the silver-colored particle is bigger, the deviation of average grain diameter is little.And, because the maximum particle size of silver-colored particle and glass dust is below 5 μ m, therefore be difficult to optionally remove glass powder particles by general classification (classification) technology, need remove by disclosed method in the special technology such as the preferred embodiment of the present invention.
The recovery method of the metallic particles that provides according to the preferred embodiment of the present invention is provided.
＜embodiment 1 〉
Can starch from silver by the physico-chemical process that utilizes ultrasonic wave and acidic aqueous solution and optionally to isolate silver-colored particle the discarded object.
In order optionally only to isolate silver-colored particle, the acid slurry of preparation (slurry).
Specifically, use agitator to stir after the oxytropism aqueous solution input silver slurry discarded object and form acidity slurry about 0.01～50wt%, and the macromolecule resin composition that utilizes described acidic aqueous solution to remove to contain in the described silver slurry discarded object or the chemical treatment technology of glass dust and macromolecule resin composition.At this moment, when utilizing the agitator stirring arm, utilize ultrasonic wave (ultrasonic wave) oscillator to carry out the ultrasonic wave treatment process to slurry irradiation ultrasonic wave.Can also add surfactant (surfactant) in the described acidic aqueous solution.And, can also add solvent in the described acidic aqueous solution.Can use toluene (toluene), dimethylbenzene (xylene), benzene aromatic hydrocarbonses such as (benzene) or butyl acetate (butyl acetate), propylene glycol methyl ether acetate (Propylene glycol monomethylether acetate), ethylene acetate ester classes such as (ethylene glycol diacetate) as described solvent.The normally photosensitive acrylate of macromolecule resin (acrylate) class of silver slurry discarded object, solvent can be used for dissolving this acrylic ester high molecular type resin and be removed.
The concentration of described acidic aqueous solution is preferably about 0.001～30wt%, and the concentration of input silver slurry discarded object is preferably 0.01～50wt%.Described acid slurry is preferably in preparation under 10～100 ℃ of environment.
Mixing speed when preparing described acid slurry is preferably 300～2000rpm, is fully disperseed and reacts so that be mingled in glass powder particles in the silver slurry discarded object.
Described acidic aqueous solution can use the material that comprises at least a acid of selecting from organic acid, and described organic acid comprises acetate (acetic acid), lactic acid (lactic acid) and citric acid (citric acid).Because inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid may make silver dissolve, therefore preferably use organic acid.
Utilize ultrasonic oscillator to slurry irradiation ultrasonic wave when utilizing the agitator stirring arm, the ultrasonic frequency of being shone can be 28～40kHz.Ultrasonic wave preferably shone 30 minutes to 2 hours.The ultrasonic wave of general indication is to have the sound wave of 20kHz with upper frequency.When to slurry irradiation ultrasonic wave, the gas molecule (bubble) in the described slurry is violent to expand, and has very high pressure and breaks at its limit point thereupon described gas molecule.The shock wave that produces when bubble breaks acts on silver slurry discarded object, peels off the glass dust or the macromolecule resin of periphery thus from silver particles.
And when to slurry irradiation ultrasonic wave, its interatomic bonding of the binder of acrylic ester high molecular type resinous principle is disconnected, and promotes the binder of macromolecule resin composition and the chemical reaction between the acidic aqueous solution thus.Therefore, can promote to peel off the binder that surrounds silver from silver particles.And, promote the reaction between acidic aqueous solution and the glass dust, the segment glass pruinescence is dissolved in acidic aqueous solution, the segment glass powder that is not dissolved then is dispersed in the acidic aqueous solution.
So,, peel off the binder that surrounds silver, and that glass dust is dispersed in the acidic aqueous solution is dissolved from silver particles by chemical method with as the ultrasonic wave of physical method.Its interatomic bonding of the binder of macromolecule resin composition is disconnected and is dissolved.
Then, be used to remove the filtering technique of the mother liquor of slurry.Described filtering technique can utilize cyclone, pressure filter (Filter Press), filtration under diminished pressure device (Nutsche Filter) or decant (Decantation) method etc., removes the mother liquor of described slurry and obtains filter cake (Cake) by described filtering technique.
Then, the filter cake of making by described filtering technique is carried out drying process.Described drying process can be undertaken by general drying processes such as heated-air drying, vacuum drying, spray-drying or freeze dryings, carries out can obtaining silver-colored particle after the described drying process.
In addition, the chemical treatment technology that utilizes described acidic aqueous solution that can also be more than repeating at least once before carrying out described drying process, utilize described hyperacoustic ultrasonic wave treatment process and described filtering technique.
＜embodiment 2 〉
Can from silver slurry discarded object, optionally isolate silver-colored particle by the physico-chemical process that utilizes ultrasonic wave and alkaline aqueous solution.
In order optionally only to isolate silver-colored preparation of granules alkalescence slurry.
Specifically, use agitator to stir after the alcaliotropism aqueous solution input silver slurry discarded object and form alkalescence slurry about 0.01～50wt%, and the macromolecule resin composition that utilizes described alkaline aqueous solution to remove to contain in the described silver slurry discarded object or the chemical treatment technology of glass dust and macromolecule resin composition.At this moment, when utilizing the agitator stirring arm, utilize ultrasonic wave (ultrasonic wave) oscillator to carry out the ultrasonic wave treatment process to slurry irradiation ultrasonic wave.Can also add surfactant in the described alkaline aqueous solution.And, can also add solvent in the described alkaline aqueous solution.Can use ester classes such as aromatic hydrocarbonses such as toluene, dimethylbenzene, benzene or butyl acetate, propylene glycol methyl ether acetate, ethylene acetate as described solvent.The normally photosensitive esters of acrylic acid of macromolecule resin of silver slurry discarded object, solvent can be used for dissolving this acrylic ester high molecular type resin and be removed.
The concentration of described alkaline aqueous solution is preferably about 0.001～10wt%, and the concentration of input silver slurry discarded object is preferably 0.01～50wt%.Described alkalescence slurry is preferably in preparation under 10～100 ℃ of environment.
The mixing speed for preparing described when slurry alkalescence is preferably 300～2000rpm, is fully disperseed and reacts so that be mingled in glass powder particles in the silver slurry discarded object.
Described alkaline aqueous solution can use the material that comprises from least a alkaline inorganic compound of alkaline inorganic compound selection, and described alkaline inorganic compound comprises NaOH, potassium hydroxide and ammonia.And described alkaline aqueous solution can also use the material that comprises at least a alkaline organic compound of selecting from alkaline organic compound, and it is 1～10 primary amine, secondary amine and tertiary amine that described alkaline organic compound comprises the carbon number amount.
Utilize ultrasonic oscillator to slurry irradiation ultrasonic wave when utilizing the agitator stirring arm, the ultrasonic frequency of being shone can be 28～40kHz.Ultrasonic wave preferably shone 30 minutes to 2 hours.When to slurry irradiation ultrasonic wave, gas molecule (bubble) is violent to expand, and has very high pressure and breaks at its limit point thereupon gas molecule.The shock wave that produces when bubble breaks acts on silver slurry discarded object, peels off the glass dust or the macromolecule resin of periphery thus from silver particles.
And when to slurry irradiation ultrasonic wave, its interatomic bonding of the binder of acrylic ester high molecular type resinous principle is disconnected, and promotes the binder of macromolecule resin composition and the chemical reaction between the alkaline aqueous solution thus.Its part of the binder of macromolecule resin composition is with alkaline aqueous solution reaction and by saponification.
So,, peel off the binder that surrounds silver, and that glass dust is dispersed in the alkaline aqueous solution is dissolved from silver particles by chemical method with as the ultrasonic wave of physical method.Its interatomic bonding of the binder of macromolecule resin composition is disconnected and by alkaline aqueous solution saponification or dissolving.
Then, be used to remove the filtering technique of the mother liquor of slurry.Described filtering technique can utilize cyclone, pressure filter (Filter Press), filtration under diminished pressure device (Nutsche Filter) or decant (Decantation) method etc., removes the mother liquor of described slurry and obtains filter cake (Cake) by described filtering technique.
Then, the filter cake of making by described filtering technique is carried out drying process.Described drying process can be undertaken by general drying processes such as heated-air drying, vacuum drying, spray-drying or freeze dryings, carries out can obtaining silver-colored particle after the described drying process.
In addition, the chemical treatment technology that utilizes described alkaline aqueous solution more than before carrying out described drying process, can also repeating at least once again, utilize described hyperacoustic ultrasonic wave treatment process and described filtering technique.
＜embodiment 3 〉
Can also reclaim metallic particles by the physico-chemical process that utilizes ultrasonic wave and alkaline aqueous solution again and obtain highly purified metallic particles at first by after the physico-chemical process recovery metallic particles that utilizes ultrasonic wave and acidic aqueous solution.So, when reclaiming metallic particles through two stages, the metallic particles purity that is obtained is very high.
Specifically, at first preparation is acid starches.For this reason, use agitator to stir after the oxytropism aqueous solution input silver slurry discarded object and form acidity slurry about 0.01～50wt%.At this moment, when utilizing the agitator stirring arm, utilize ultrasonic oscillator to slurry irradiation ultrasonic wave.Can also add surfactant in the described acidic aqueous solution.And, can also add solvent in the described acidic aqueous solution.
Then, be used to remove the filtering technique of the mother liquor of slurry, remove mother liquor and obtain filter cake (Cake) from described slurry according to described filtering technique.
Described filter cake is put in the alkaline aqueous solution, used agitator to stir then and form alkalescence slurry about 0.01～50wt%.At this moment, when utilizing the agitator stirring arm, utilize ultrasonic oscillator to slurry irradiation ultrasonic wave.Can also add surfactant in the described alkaline aqueous solution.And, can also add solvent in the described alkaline aqueous solution.
Then, be used to remove the filtering technique of slurries.Remove described slurries and obtain filter cake according to described filtering technique.
Then, the filter cake that obtains by described filtering technique is carried out drying process and obtain silver-colored particle.
＜embodiment 4 〉
Can also reclaim metallic particles by the physico-chemical process that utilizes ultrasonic wave and acidic aqueous solution again and obtain highly purified metallic particles at first by after the physico-chemical process recovery metallic particles that utilizes ultrasonic wave and alkaline aqueous solution.So, when reclaiming metallic particles through two stages, the metallic particles purity that is obtained is very high.
Specifically, at first preparation alkalescence slurry.For this reason, use agitator to stir after the alcaliotropism aqueous solution input silver slurry discarded object and form alkalescence slurry about 0.01～50wt%.At this moment, when utilizing the agitator stirring arm, utilize ultrasonic wave (ultrasonic wave) oscillator to slurry irradiation ultrasonic wave.Can also add surfactant in the described alkaline aqueous solution.And, can also add solvent in the described alkaline aqueous solution.
Then, be used to remove the mother's of slurry filtering technique.Remove mother liquor and obtain filter cake from described slurry according to described filtering technique.
Described filter cake is put in the acidic aqueous solution, used agitator to stir then and form acidity slurry about 0.01～50wt%.At this moment, when utilizing the agitator stirring arm, utilize ultrasonic oscillator to slurry irradiation ultrasonic wave.Can also add surfactant in the described acidic aqueous solution.And, can also add solvent in the described acidic aqueous solution.
Then, be used to remove the filtering technique of the mother liquor of slurry.Remove mother liquor and obtain filter cake from described slurry according to described filtering technique.
Then, the filter cake that obtains by described filtering technique is carried out drying process and obtain silver-colored particle.
＜embodiment 5 〉
Silver slurry discarded object contains silver-colored particulate component, glass dust composition and binder composition, and the binder composition is to exist with silver-colored particle and the chemically combined state of glass dust.Because the proportion of silver-colored particle is relatively greater than glass dust proportion, thus the binder discarded object specific adhesion agent that is incorporated into the form of silver to be combined in the discarded object of glass dust form heavy.
Can utilize silver-colored particle proportion to starch discarded object greater than the character of glass dust proportion with physical method classification silver relatively.Described physical method is a method of utilizing wet classifier or dry classification machine that the relative little discarded object with proportion of heavy discarded object is classified.
Further specify the method for utilizing described physical method to classify below.
Utilize centrifugal wet classifier or forced vortex streaming dry classification machine that silver slurry discarded object is carried out classification.
When utilizing centrifugal wet classifier, silver is starched that discarded object is diluted in the water and preparation silver slurry waste concentration is the slurry about 5～80wt%, described slurry is put into carried out classification in the centrifugal wet classifier then.The rotary speed of wet classifier is preferably 500～3000rpm, and the input speed of slurry is preferably 5～50kg/ hour.
When utilizing forced vortex streaming dry classification machine, preferably making silver slurry discarded object input speed is 10～500kg/ hour, and the rotary speed that makes the dry classification machine is 500～5000rpm.Compressed air is preferably 0.05～0.5MPa and carries out classification.
As mentioned above, can utilize wet classifier or dry classification machine from silver slurry discarded object, optionally to isolate the discarded object that contains the relatively large silver of proportion with physical method.The discarded object that contains silver is light because the discarded object that contains glass dust compares, and therefore can optionally carry out classification by described classification process.Can isolate once by binder according to above-mentioned grading technology and to mix the form discarded object in conjunction with silver and glass dust in conjunction with the discarded object of silver and by binder.
The silver slurry discarded object that does not contain oxide particle such as glass dust can not carry out above-mentioned grading technology.
Then, reclaim the technology of silver-colored particle by the physico-chemical process that utilizes ultrasonic wave and acidic aqueous solution as above-mentioned embodiment 1.
Specifically, will put in the acidic aqueous solution by the silver slurry discarded object that centrifugal wet classifier or forced vortex streaming dry classification machine carry out classification earlier, and utilize agitator to stir then and prepare acidity slurry about 0.01～50wt%.At this moment, when utilizing the agitator stirring arm, utilize ultrasonic oscillator to slurry irradiation ultrasonic wave.Can also add surfactant in the described acidic aqueous solution.And, can also add solvent in the described acidic aqueous solution.
Then, be used to remove the filtering technique of the mother liquor of slurry.Remove mother liquor and obtain filter cake (Cake) from described slurry according to described filtering technique.
Then, the filter cake that obtains by described filtering technique is carried out drying process and obtain silver-colored particle.
＜embodiment 6 〉
As embodiment 5, utilize centrifugal wet classifier or forced vortex streaming dry classification machine that silver slurry discarded object is carried out classification.
Then, embodiment 2 is described as described, reclaims the technology of silver-colored particle by the physico-chemical process that utilizes ultrasonic wave and alkaline aqueous solution.
Specifically, will put in the alkaline aqueous solution by the silver slurry discarded object that centrifugal wet classifier or forced vortex streaming dry classification machine carry out classification earlier, and utilize agitator to stir then and prepare alkalescence slurry about 0.01～50wt%.At this moment, when utilizing the agitator stirring arm, utilize ultrasonic oscillator to slurry irradiation ultrasonic wave.Can also add surfactant in the described alkaline aqueous solution.And, can also add solvent in the described alkaline aqueous solution.
Then, be used to remove the filtering technique of the mother liquor of slurry.Remove mother liquor and obtain filter cake (Cake) from described slurry according to described filtering technique.
Then, the filter cake that obtains by described filtering technique is carried out drying process and obtain silver-colored particle.
＜embodiment 7 〉
As embodiment 5, utilize centrifugal wet classifier or forced vortex streaming dry classification machine that silver slurry discarded object is carried out classification.
Then, carry out the process identical with embodiment 3.That is, elder generation reclaims after the silver-colored particle by the physico-chemical process that utilizes ultrasonic wave and acidic aqueous solution, reclaims silver-colored particle by the physico-chemical process that utilizes ultrasonic wave and alkaline aqueous solution again.Owing to describe in detail among the embodiment 3, therefore omit its explanation at this.
＜embodiment 8 〉
As embodiment 5, utilize centrifugal wet classifier or forced vortex streaming dry classification machine that silver slurry discarded object is carried out classification.
Then, carry out the process identical with embodiment 4.That is, elder generation reclaims after the silver-colored particle by the physico-chemical process that utilizes ultrasonic wave and alkaline aqueous solution, reclaims silver-colored particle by the physico-chemical process that utilizes ultrasonic wave and acidic aqueous solution again.Owing to describe in detail among the embodiment 4, therefore omit its explanation at this.
In addition, can starch softening point (the Softening Point of the glass dust softening transform in the discarded object at silver, Ts) burn below the temperature silver slurry discarded object technology (Binder-Burn Out Step claims " BBO " below) and remove the part macromolecule resin in the silver slurry discarded object or make its distortion.Specifically, not impaired and carry out 30 minutes to 2 hours BBO technology under temperature only decomposing macromolecular resin (temperature the softening point temperature below) condition (300～400 ℃) and remove the silver-colored part macromolecule resin of starching in the discarded object at silver and glass dust.This BBO technology was carried out before the chemical treatment step that utilizes acidic aqueous solution or alkaline aqueous solution in the various embodiments described above, thereby can remove part macromolecule resin composition.
And the macromolecule resin that is used for the silver slurry of PDP electrode is generally photosensitive esters of acrylic acid material, therefore can also use the solvent of this acrylic ester high molecular type resin of dissolving to remove.Described solvent can use ester classes such as aromatic hydrocarbonses such as toluene, dimethylbenzene, benzene and butyl acetate, propylene glycol methyl ether acetate, ethylene acetate.In this solvent, drop into described metal slurry and stir, can dissolve and remove described macromolecule resin.Utilizing solvent to remove macromolecule resin can carry out before the chemical treatment step that utilizes acidic aqueous solution or alkaline aqueous solution.
In addition, as the description among the above-mentioned embodiment, can also the oxytropism aqueous solution or alkaline aqueous solution in mixed solvent and form slurry, and use the mixed liquor of described acidic aqueous solution and described solvent or described alkaline aqueous solution and described solvent to carry out chemical treatment.So, when with solvent and acidic aqueous solution or alkaline aqueous solution and time spent, preferably mix the solvent of about 20～50wt% with respect to acidic aqueous solution or alkaline aqueous solution.
And, in the various embodiments described above, can also carry out the ultrasonic wave treatment process specially in the front and back of chemical treatment step.Specifically, drop into water (H
2O) and silver slurry discarded object stir and the preparation slurry with agitator after mixing, when utilizing the agitator stirring arm, utilize ultrasonic oscillator to slurry irradiation ultrasonic wave and carry out the ultrasonic wave treatment process specially.
Below, with reference to following experimental example the present invention is described in more details, but these embodiment are used for limiting protection domain of the present invention.
＜experimental example 1 〉
Preparation alkalescence slurry.Specifically, the silver slurry discarded object of NaOH (NaOH) aqueous solution 4kg of 8wt% and 1kg put in the 5L beaker mix, utilize agitator to stir preparation alkalescence slurry then and carry out chemical treatment technology.
Utilize ultrasonic oscillator to carry out the ultrasonic wave treatment process when utilizing the agitator stirring arm to the ultrasonic wave that the slurry irradiation continues 1 hour 28kHz.At this, the mixing speed of setting described agitator is 800rpm, and whipping temp is 70 ℃, and mixing time is 2 hours.
Carry out from described alkalescence slurry, removing the filtering technique of mother liquor.Described filtering technique uses cyclone to carry out.The rotary speed of described cyclone is set at 2000rpm.
The filter cake that obtains by described filtering technique is carried out drying process.Described drying process utilizes hot-air drier, and under 110 ℃ of conditions dry 24 hours, thereby obtained highly purified silver-colored particle.
＜experimental example 2 〉
The acid slurry of preparation.Specifically, put in the 5L beaker with the acetic acid aqueous solution 4kg of 10wt% with by the 1kg filter cake that described filtering technique obtains and to mix, utilize agitator to stir the acid slurry of preparation then and carry out chemical treatment technology.
Utilize ultrasonic oscillator to carry out the ultrasonic wave treatment process when utilizing the agitator stirring arm to the ultrasonic wave that the slurry irradiation continues 1 hour 30kHz.At this, the mixing speed of setting described agitator is 1200rpm, and whipping temp is 50 ℃, and mixing time is 2 hours.
Carry out from described acid slurry, removing the filtering technique of slurries.Described filtering technique uses the filtration under diminished pressure device to carry out.
The filter cake that obtains by described filtering technique is carried out drying process.Described drying process utilizes hot-air drier, and under 110 ℃ of conditions dry 24 hours, thereby obtained highly purified silver-colored particle.
＜experimental example 3 〉
Utilize centrifugal wet classifier that silver slurry discarded object is carried out classification.At this, the concentration of setting slurry is 30wt%, and the input speed of silver slurry discarded object is 50kg/ hour, and the rotary speed of wet classifier is 1500rpm.
Preparation alkalescence slurry.Specifically, put in the 5L beaker with NaOH (NaOH) aqueous solution 4kg of 8wt% with through the 1kg silver slurry discarded object of grading technology and to mix, utilize agitator to stir preparation alkalescence slurry then and carry out chemical treatment technology.Utilize ultrasonic oscillator to carry out the ultrasonic wave treatment process when utilizing the agitator stirring arm to the ultrasonic wave that the slurry irradiation continues 1 hour 28kHz.At this, the mixing speed of setting described agitator is 800rpm, and whipping temp is 70 ℃, and mixing time is 2 hours.
Carry out from described alkalescence slurry, removing the filtering technique of mother liquor.Described filtering technique uses cyclone to carry out.The rotary speed of described cyclone is set at 2000rpm.
Then, the acid slurry of preparation.Specifically, put in the 5L beaker with the acetic acid aqueous solution 4kg of 10wt% with by the 1kg filter cake that described filtering technique obtains and to mix, utilize agitator to stir the acid slurry of preparation then and carry out chemical treatment technology.Utilize ultrasonic oscillator to carry out the ultrasonic wave treatment process when utilizing the agitator stirring arm to the ultrasonic wave that the slurry irradiation continues 1 hour 30kHz.At this, the mixing speed of setting described agitator is 1200rpm, and whipping temp is 50 ℃, and mixing time is 2 hours.
Carry out from described acid slurry, removing the filtering technique of mother liquor.Described filtering technique uses the filtration under diminished pressure device to carry out.
The filter cake that obtains by described filtering technique is carried out drying process.Described drying process utilizes hot-air drier, and under 110 ℃ of conditions dry 24 hours, thereby obtained highly purified silver-colored particle.
＜experimental example 4 〉
The acid slurry of preparation.Specifically, the dry thing of the 2kg that obtains with the acetic acid aqueous solution 8kg of 5wt% with according to wet classification is put in the 10L beaker and is mixed, and utilizes agitator to stir the acid slurry of preparation then and carries out chemical treatment technology.Utilize ultrasonic oscillator to carry out the ultrasonic wave treatment process when utilizing the agitator stirring arm to the ultrasonic wave that the slurry irradiation continues 30 minutes 28kHz.At this, the mixing speed of setting described agitator is 1000rpm, and whipping temp is 50 ℃, and mixing time is 2 hours.
Carry out from described acid slurry, removing the filtering technique of mother liquor.Described filtering technique uses the filtration under diminished pressure device to carry out.
Then, preparation alkalescence slurry.Specifically, the filter cake of the 2kg that obtains with potassium hydroxide (KOH) aqueous solution 8kg of 10wt% with by described filtering technique is put in the 10L beaker and is mixed, and utilizes agitator to stir preparation alkalescence slurry then and carries out chemical treatment technology.Utilize ultrasonic oscillator to carry out the ultrasonic wave treatment process when utilizing the agitator stirring arm to the ultrasonic wave that the slurry irradiation continues 30 minutes 28kHz.At this, the mixing speed of setting described agitator is 500rpm, and whipping temp is 30 ℃, and mixing time is 2 hours.
Carry out from described alkalescence slurry, removing the filtering technique of mother liquor.Described filtering technique uses cyclone to carry out
The filter cake that obtains by described filtering technique is carried out drying process.Described drying process utilizes vacuum desiccator, and under 700mm Hg and 90 ℃ of conditions dry 12 hours, thereby obtained highly purified silver-colored particle.
＜experimental example 5 〉
Do not carry out grading technology and prepare slurry and carry out the ultrasonic wave treatment process.Specifically, with water (H
2O) and the silver of 2kg slurry discarded object put into and stir and the preparation slurry with agitator after mixing in the 10L beaker, utilize ultrasonic oscillator to continue the ultrasonic wave of 2 hours 28kHz to the slurry irradiation when utilizing the agitator stirring arm.At this, the mixing speed of setting described agitator is 500rpm, and whipping temp is 30 ℃, and mixing time is 2 hours.
The acid slurry of preparation.Specifically, the described ultrasonic wave of the aqueous citric acid solution 8kg of 5wt% and 2kg is handled dry thing put in the 10L beaker and mix, utilize agitator to stir the acid slurry of preparation then and carry out chemical treatment technology.Utilize ultrasonic oscillator to carry out the ultrasonic wave treatment process when utilizing the agitator stirring arm to the ultrasonic wave that the slurry irradiation continues 30 minutes 28kHz.At this, the mixing speed of setting described agitator is 800rpm, and whipping temp is 50 ℃, and mixing time is 2 hours.
Carry out from described acid slurry, removing the filtering technique of mother liquor.Described filtering technique uses the filtration under diminished pressure device and obtains filter cake.
Carry out after the described filtering technique, preparation utilizes the acidity slurry of aqueous citric acid solution to carry out chemical treatment technology and ultrasonic wave treatment process once more.
Carry out from described acid slurry, removing after the filtering technique of mother liquor, carry out the ultrasonic wave treatment process once more.Specifically, with water (H
2O) put into from the 2kg filter cake that described filtering technique obtains and to stir and the preparation slurry with agitator after mixing the 10L beaker, utilize ultrasonic oscillator to continue the ultrasonic wave of 2 hours 28kHz to the slurry irradiation when utilizing the agitator stirring arm.At this, the mixing speed of setting described agitator is 500rpm, and whipping temp is 30 ℃, and mixing time is 2 hours.
Carry out from described slurry, removing the filtering technique of mother liquor.Described filtering technique uses the filtration under diminished pressure device to carry out.
The filter cake that obtains by described filtering technique is carried out drying process.Described drying process utilizes vacuum desiccator, and under 700mm Hg and 110 ℃ of conditions dry 24 hours, thereby obtained highly purified silver-colored particle.
Fig. 2 is SEM (SEM:ScanningElectron Microscope) photo at silver slurry discarded object before reclaiming.Though Fig. 3 reclaims silver-colored particle according to described experimental example 1, the SEM photo when not shining ultrasonic wave in whipping process, Fig. 4 are the SEM photo according to the silver-colored particle of described experimental example 1 recovery.Fig. 5 is the SEM photo according to the silver-colored particle of described experimental example 2 recovery.Fig. 6 is the SEM photo according to the silver-colored particle of described experimental example 3 recovery.Fig. 7 is the SEM photo according to the silver-colored particle of described experimental example 4 recovery.Fig. 8 is the SEM photo according to the silver-colored particle of described experimental example 5 recovery.Fig. 9 is for forming the SEM photo of PDP electrode silver-colored particle normal goods before.
Table 1 is at the silver slurry discarded object before reclaiming with according to the silver-colored particle of described experimental example 3 recovery and XRF (the X-Ray Fluorescence of the normal goods before the formation PDP electrode; XRF) analysis result." ND " means " No Detect " in the table 1, and the expression composition does not have detected.
[table 1]
| Silver slurry discarded object (%) | Recovery article (%) | Normal goods (%) | |
| Ag | 84.0176 | 99.9036 | 99.8540 |
| Pb | 12.0850 | ND | ND |
| Si | 1.4791 | 0.0140 | 0.0137 |
| Bi | 1.4447 | ND | ND |
| Na | 0.5017 | ND | ND |
| Al | 0.1723 | 0.0195 | 0.0114 |
| Zn | 0.1625 | ND | ND |
| Pt | 0.0635 | ND | ND |
| Cr | 0.0321 | ND | ND |
| Ni | 0.0237 | ND | ND |
| Fe | 0.0180 | ND | 0.0310 |
| Ca | ND | 0.0425 | 0.0642 |
| S | ND | 0.0204 | 0.0257 |
With reference to Fig. 2 to Fig. 9 and table 1, as shown in Figure 3, when in removal process, not shining ultrasonic wave, still there are glass dust composition and macromolecule resin composition as can be seen in the recovery article.But, different fully according to the silver-colored grain shape of the recovery article that the preferred embodiment of the present invention provided and the Impurity Distribution that contained with silver slurry discarded object, but with normal goods much at one.Especially, as shown in table 1, according to the Pb, the Bi that do not contain in the recovery article that the preferred embodiment of the present invention provided as the glass dust principal component, this is just meaning that glass dust removed fully by the method for recycling metallic grains that the foundation preferred embodiment of the present invention is provided.
According to method of recycling metallic grains provided by the present invention; by the washing process that will utilize hyperacoustic physical method and the chemical method of using acidity or alkaline aqueous solution to combine; macromolecule resin or glass dust and the macromolecule resin in the metal slurry discarded object also removed in environmental protection simply, thereby can reclaim metallic particles.
And, the present invention especially can be from the PDP electrode with almost reclaiming silver-colored particle in good condition the silver slurry discarded object, and by reclaiming silver-colored particle at high price and it being re-used on the industry, can reduce industry funds and production cost greatly, and compare with the situation of reprocessing silver slurry discarded object and can suppress environmental pollution.
And,, therefore can improve the problem of environmental pollution of reprocessing metal slurry discarded object in the past and causing because the present invention can also be applicable to the metal slurry discarded object that does not comprise glass dust.
Though above enumerate the preferred embodiment of the present invention and be illustrated, the present invention is not limited to described embodiment, the personnel with common knowledge of this area can carry out various distortion in the scope that does not break away from the technology of the present invention thought.
Claims (13)
1, a kind of method of recycling metallic grains is used for reclaiming metallic particles from the metal slurry discarded object that produces because of the metal slurry, and this method comprises:
(a) described metal slurry discarded object is mixed with acidity or alkaline aqueous solution to stir and form starch, utilize described acidity or alkaline aqueous solution to remove described metal and starch the macromolecule resin composition in the discarded object or the chemical treatment step of glass dust and macromolecule resin composition;
(b) utilize stirring arm the time ultrasonic oscillator interatomic bond make and break of described macromolecule resin is opened and to be promoted chemical reaction to slurry irradiation ultrasonic wave, and making the bubble in the described slurry acutely expand and break at its limit point because of high pressure, the shock wave that produces when bubble breaks acts on described metal slurry discarded object and peels off the glass dust of described metallic particles periphery or the ultrasonic wave treatment step of macromolecule resin;
(c) carry out removing the filtering technique of mother liquor and forming the step of filter cake from described slurry;
(d) filter cake that obtains by described filtering technique is carried out the step that drying process obtains metallic particles.
2, method of recycling metallic grains according to claim 1 is characterized in that carrying out described filtering technique and forms after the filter cake, also comprises:
Filter cake that will obtain by described filtering technique and alkalescence or acidic aqueous solution mix to stir and form slurry, utilize described alkalescence or acidic aqueous solution to remove described metal and starch the macromolecule resin composition in the discarded object or the chemical treatment step second time of glass dust and macromolecule resin composition;
Utilize ultrasonic oscillator to slurry irradiation hyperacoustic second time of ultrasonic wave treatment step in the time of stirring arm;
Carry out removing the filtering technique of mother liquor and forming the step of filter cake from described slurry;
At this, if the chemical treatment step at described (a) has used acidic aqueous solution, then described second time chemical treatment step use alkaline aqueous solution and carry out chemical treatment, if the chemical treatment step at described (a) has used alkaline aqueous solution, then described second time chemical treatment step use acidic aqueous solution and carry out chemical treatment, perhaps use the aqueous solution of employed aqueous solution same physical properties in the chemical treatment step with described (a) to carry out the described chemical treatment second time.
3, method of recycling metallic grains according to claim 1 and 2; it is characterized in that before the chemical treatment step of described (a), also comprise the step that the difference in specific gravity of utilizing between described metallic particles and the described glass dust uses wet classifier or dry classification machine that described metal slurry discarded object is carried out classification.
4, method of recycling metallic grains according to claim 1; it is characterized in that before the chemical treatment step of described (a), also be included in less than the temperature conditions of the softening point temperature of the described glass dust described metal slurry discarded object of burning and remove the step of described macromolecule resin down.
5, method of recycling metallic grains according to claim 1 is characterized in that before the chemical treatment step of described (a), also comprises described metal slurry discarded object put into to stir in the solvent and dissolve and remove the step of described macromolecule resin.
6, method of recycling metallic grains according to claim 1; it is characterized in that also being included in the step of mixed solvent in described acidic aqueous solution or the described alkaline aqueous solution, utilize the mixed liquor of described acidic aqueous solution and described solvent or described alkaline aqueous solution and described solvent to carry out chemical treatment.
7,, it is characterized in that described solvent uses the material that comprises at least a material of selecting from the aromatic hydrocarbons that comprises toluene, dimethylbenzene or benzene and the ester class that comprises butyl acetate, propylene glycol methyl ether acetate or ethylene acetate according to claim 5 or 6 described method of recycling metallic grains.
8, method of recycling metallic grains according to claim 1; it is characterized in that described metal slurry is silver-colored slurry, gold paste, platinum slurry, nickel slurry, copper slurry or palladium slurry, described metallic particles is silver-colored particle, gold grain, platinum particle, nickel particle, copper particle or the palladium particle of electric conductivity.
9, method of recycling metallic grains according to claim 1; it is characterized in that described metal slurry is the slurry that is used to form the PDP electrode; described metal slurry discarded object is the discarded object that discharges in the developing process in the technology that forms the PDP electrode, and described metallic particles is the silver-colored particle of electric conductivity.
10, method of recycling metallic grains according to claim 1 is characterized in that described acidic aqueous solution uses the material that comprises at least a acid of selecting from the organic acid that comprises acetate, lactic acid and citric acid.
11, method of recycling metallic grains according to claim 1; it is characterized in that described alkaline aqueous solution uses the material that comprises at least a alkaline inorganic compound of selecting from the alkaline inorganic compound that comprises NaOH, potassium hydroxide and ammonia, perhaps use to comprise from comprising the material that amount of carbon atom is at least a alkaline organic compound selected the alkaline organic compound of 1～10 primary amine, secondary amine and tertiary amine.
12, method of recycling metallic grains according to claim 1 is characterized in that also comprising the step of adding surfactant in described acidity or alkaline aqueous solution.
13, method of recycling metallic grains according to claim 1 is characterized in that the ultrasonic frequency with 28～40kHz was shone 30 minutes to 2 hours in the described ultrasonic wave treatment step.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060044839 | 2006-05-18 | ||
| KR20060044839A KR100769352B1 (en) | 2006-05-18 | 2006-05-18 | Method of recycling metallic grains |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101073835A true CN101073835A (en) | 2007-11-21 |
| CN100542721C CN100542721C (en) | 2009-09-23 |
Family
ID=38815546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101046089A Expired - Fee Related CN100542721C (en) | 2006-05-18 | 2007-05-18 | Method of recycling metallic grains |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4523617B2 (en) |
| KR (1) | KR100769352B1 (en) |
| CN (1) | CN100542721C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102066024A (en) * | 2008-06-26 | 2011-05-18 | Dic株式会社 | Silver-containing powder, method for producing the same, conductive paste using the same, and plastic substrate |
| CN105296758A (en) * | 2015-11-03 | 2016-02-03 | 苏州优康通信设备有限公司 | Extracting method for noble metal on optical device |
| CN105983479A (en) * | 2015-03-19 | 2016-10-05 | 株式会社吴羽 | Method of recovering metallic foreign matter and method of inspecting metallic foreign matter of polymer |
| CN106103752A (en) * | 2014-03-20 | 2016-11-09 | 田中贵金属工业株式会社 | Reclaim the method for metal dust and the renovation process of platinum slurry from platinum slurry |
| CN108480647A (en) * | 2018-01-23 | 2018-09-04 | 珠海纳金科技有限公司 | A kind of recoverying and utilizing method of nano-Ag particles waste liquid |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4573138B2 (en) * | 2008-06-26 | 2010-11-04 | Ｄｉｃ株式会社 | Method for producing silver-containing powder, silver-containing powder and dispersion thereof |
| KR101075934B1 (en) * | 2009-10-07 | 2011-10-21 | 주식회사 랜코 | Method of recycling metallic grains using eco-friendly process |
| KR101730143B1 (en) * | 2016-04-18 | 2017-04-25 | (주)한청알에프 | Method for preparing ITO powder capable of controlling particle shapes from ITO scrap |
| JPWO2019039209A1 (en) * | 2017-08-24 | 2020-08-06 | 東洋紡株式会社 | Conductive paste, three-dimensional printed circuit, touch sensor and their manufacturing method |
| KR20210151403A (en) | 2020-06-05 | 2021-12-14 | 박정욱 | Regeneration method of Pd catalyst using ultrasonic excitation |
| KR102602595B1 (en) | 2021-11-22 | 2023-11-16 | (주)선영시스텍 | Metal powder washing machine |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01287229A (en) * | 1988-05-12 | 1989-11-17 | Tanaka Kikinzoku Kogyo Kk | Method for recovering noble metal |
| JP3149783B2 (en) * | 1996-05-10 | 2001-03-26 | 住友金属工業株式会社 | Processing method of hydrogen storage alloy powder |
| JP3134189B2 (en) | 1997-09-18 | 2001-02-13 | 福島県 | How to collect abrasives |
| JP2001009283A (en) * | 1999-07-02 | 2001-01-16 | Matsushita Electric Ind Co Ltd | Method for utilizing waste copper material |
| JP3893101B2 (en) * | 2002-11-21 | 2007-03-14 | 東邦チタニウム株式会社 | Manufacturing method of high purity titanium |
| KR100548163B1 (en) | 2003-11-14 | 2006-02-02 | 주식회사 대하맨텍 | Method of recycling abrasive grains for forming barrier ribs of plasma display panel |
| KR100586642B1 (en) * | 2004-05-10 | 2006-06-08 | 학교법인 영남학원 | The Recovery of SiC from Wire Saw Slurry |
-
2006
- 2006-05-18 KR KR20060044839A patent/KR100769352B1/en active IP Right Grant
-
2007
- 2007-05-10 JP JP2007125134A patent/JP4523617B2/en not_active Expired - Fee Related
- 2007-05-18 CN CNB2007101046089A patent/CN100542721C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102066024A (en) * | 2008-06-26 | 2011-05-18 | Dic株式会社 | Silver-containing powder, method for producing the same, conductive paste using the same, and plastic substrate |
| CN102066024B (en) * | 2008-06-26 | 2014-06-11 | Dic株式会社 | Silver-containing powder, method for producing the same, conductive paste using the same, and plastic substrate |
| CN106103752A (en) * | 2014-03-20 | 2016-11-09 | 田中贵金属工业株式会社 | Reclaim the method for metal dust and the renovation process of platinum slurry from platinum slurry |
| CN105983479A (en) * | 2015-03-19 | 2016-10-05 | 株式会社吴羽 | Method of recovering metallic foreign matter and method of inspecting metallic foreign matter of polymer |
| CN105983479B (en) * | 2015-03-19 | 2018-06-22 | 株式会社吴羽 | The recovery method of metallic foreign body and the metallic foreign body inspection method of polymer |
| CN105296758A (en) * | 2015-11-03 | 2016-02-03 | 苏州优康通信设备有限公司 | Extracting method for noble metal on optical device |
| CN108480647A (en) * | 2018-01-23 | 2018-09-04 | 珠海纳金科技有限公司 | A kind of recoverying and utilizing method of nano-Ag particles waste liquid |
| CN108480647B (en) * | 2018-01-23 | 2022-01-18 | 珠海纳金科技有限公司 | Recycling method of nano-silver particle waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100542721C (en) | 2009-09-23 |
| JP4523617B2 (en) | 2010-08-11 |
| KR100769352B1 (en) | 2007-10-24 |
| JP2007308797A (en) | 2007-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101073835A (en) | Method of recycling metallic grains | |
| CN1640822A (en) | Method for clarifying waste water containing organic material | |
| CN1705525A (en) | Method for clarifying soil | |
| US20100143219A1 (en) | Process for the production of nano lead oxides | |
| CN103159250A (en) | Method for recovery of cerium oxide | |
| Yousef et al. | Sustainable technology for mass production of Ag nanoparticles and Al microparticles from damaged solar cell wafers | |
| CN1534111A (en) | Method of recovering copper metal from waste printed circuit board and copper containing waste liquid and its device | |
| CN1732589A (en) | Method of recovering cobalt from lithium ion battery and cobalt recovering system | |
| JP2009185389A (en) | Recycling method for valuable metal | |
| KR20150088843A (en) | Silver powder and silver paste | |
| JP2010168560A (en) | Method for decomposing composite material | |
| CN103773357B (en) | A kind of method removing glass dregs and sieve and silica-sesquioxide in waste and old fluorescent RE powder | |
| CN1868949A (en) | Preparation method of nanometer grade indium tin oxide composite powder | |
| JP5484722B2 (en) | Method for separating and regenerating components of waste solder paste | |
| CN1920666A (en) | Photosensitive slurry | |
| CN1552925A (en) | Processing method for industrial waste material | |
| JP2010179205A (en) | Adsorbent for metal ion, and adsorption method using the same | |
| CN101037219A (en) | Production process of magnesia used for rear earth solution precipitator | |
| KR102528871B1 (en) | Method of Removing Impurities for Recycling Waste Touch Panel Glass | |
| KR101075934B1 (en) | Method of recycling metallic grains using eco-friendly process | |
| JP5768553B2 (en) | Silver powder manufacturing method | |
| CN110639940A (en) | Method for debrominating waste circuit board | |
| CN104986897A (en) | Method for recovering valuable metals in wastewater | |
| CN1308088C (en) | Improved flotation | |
| CN216550633U (en) | Device for extracting and recycling indium from liquid crystal display panel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090923 Termination date: 20180518 |