CN1392107A - Process for recovering noble metal from noble metal microparticle dispersive liquid - Google Patents
Process for recovering noble metal from noble metal microparticle dispersive liquid Download PDFInfo
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Abstract
The noble metal recovering method can agglomerate noble metal particles from dispersing liquid to generate aggregate easy to deposit and filter and the noble metal is easy to separate from solution. Into dispersed noble metal particle liquid containing gold and/or silver particles, hydrosulphenyl compound as coagulator is added, so that the noble metal particle agglomerate and separate from solvent. The hydrosulphonyl compound with two or more hydrosulphonyl radicals is preferably used and some inorganic salt, acid or alkali as assistant coagulator may be also added.
Description
Invention field
The invention relates to from containing disperses gold or/and the fine particle of noble metal dispersion liquid of silver-colored fine particle of noble metal, reclaim the method for fine particle of noble metal rapidly and simply with coagulative precipitation.
Prior art
General as the recovery method that contains the heavy metallic salt of heavy metal class, be to use solution is neutralized, after the heavy metal class forms oxyhydroxide, add polymer agglomeration agent such as inorganic flocculant such as Tai-Ace S 150, poly aluminium chloride or polyacrylic acid amide again, make heavy metal particles form the method for aggregate.
For example, polymer coagulant is adsorbed on particle, and it is crosslinked that particle is formed to each other, finally forms huge aggregate.Inorganic flocculant destroys the double-deck electric of decentralized stabilization particle, makes particle agglomerated together each other.Any situation is because the cohesion of heavy metal particles has improved settleability and filterableness, so can utilize filtration to separate simply from solution.
Yet, be dispersed in the solvent when forming the fine particle of noble metal dispersion liquid at fine particle of noble metal, because the fine particle of noble metal surface is inertia, so, even it is crosslinked to use polymer coagulant can not fully form absorption, present flocculating result usually hardly.Again, use inorganic flocculant, only destroy double-deck electricity and can not fully make the fine particle of noble metal cohesion,, must leave standstill for a long time in order to generate the fine particle of noble metal aggregate.
And say that in recent years along with office automation (OA), a large amount of OA equipment have entered office, the indicating meter in the face of OA equipment carries out work all day, and has ignored so-called environment.Recently people begin to worry the detrimentally affect that has to the person of the low-frequency electromagnetic wave that produced by CRT.Do not leak into the outside of CRT so wish this hertzian wave.
Therefore, fine particle of noble metal below the median size 100nm is dispersed in forms dispersion liquid (hereinafter referred to as the fine particle of noble metal dispersion liquid) in the solvent, utilize method of spin coating etc., be coated on the front glass face of CRT, postheating is handled, to form the transparency conducting layer of electroconductibility.Generally use and contain golden monomer, silver-colored monomer, gold or/and the alloy particle of silver as fine particle of noble metal.
Theme of the present invention
Like this, on the CRT surface, form transparency conducting layer, owing to when the fine particle of noble metal dispersion liquid being coated on the CRT front glass face, can produce the waste liquid that contains fine particle of noble metal for preventing electromagnetic-wave leakage.Therefore, wish from the waste liquid that contains fine particle of noble metal, to reclaim this part precious metal.
Yet, as above-mentioned, carry out the dispersive metal particle when being precious metal, use polymer coagulant or inorganic flocculant, be difficult to form aggregate.In addition, in such use, used fine particle of noble metal dispersion liquid makes the fine particle of noble metal stabilization by macromolecule dispersing agent, because the steric hindrance of macromolecule dispersing agent, it is close that particle is difficult to each other, almost can not get the effect of flocculation agent.
And, form aggregate, as the recovery method beyond filtering, reclaiming, can consider that also the solvent that will be dispersed with fine particle of noble metal carries out the dry method of removing, but need large-scale device that also the consumes energy expense is unfavorable for industrial application.
Problem in view of above existence, the purpose of this invention is to provide a kind of very high precious metal recovery method of industrial applicibility that has, it is by the fine particle of noble metal dispersion liquid that is dispersed with fine particle of noble metal in the solvent, fine particle of noble metal is condensed at short notice, generate settleability and the good precious metal aggregate of filterableness, and precious metal is separated with solvent.Solve the method for theme
In order to achieve the above object, the present invention is conceived to make sulfydryl (SH) and precious metal, particularly to carry out deep research to forming very strong key with gold and silver, found that, disperse particles be contain gold or/and silver particulate the time, brought into play cohesion efficiently, and so far finished the present invention.
Promptly, the method that reclaims precious metal from the fine particle of noble metal dispersion liquid provided by the invention, feature is to be dispersed with to contain gold or/and in the fine particle of noble metal dispersion liquid of silver-colored particulate in solvent, as flocculation agent, add compound with sulfydryl, after making the cohesion of fine particle of noble metal, make fine particle of noble metal and the separated from solvent of cohesion again.
Yet, the method that reclaims precious metal from the fine particle of noble metal dispersion liquid provided by the invention, feature is to add tensio-active agent and dispersion resin etc. in solvent, make fine particle of noble metal form the stable dispersion state, in such fine particle of noble metal dispersion liquid,, add compound with sulfydryl as flocculation agent, after making the fine particle of noble metal cohesion, with fine particle of noble metal and the separated from solvent of cohesion.
In the precious metal recovery method of the invention described above, feature is that above-mentioned compound with sulfydryl is to have sulfydryl more than 2 at least at intramolecularly.In the compound that adds flocculation agent,, add inorganic salt, perhaps add acid or alkali as the cohesion auxiliary with above-mentioned sulfydryl.
As object fine particle of noble metal of the present invention, except golden monomer, silver-colored monomer, preferably contain gold or/and the particulate of silver.As containing gold or/and the specific examples of particulate of silver, gold except gold-silver alloy is arranged or/and the precious metal beyond silver and the gold and silver, for example the alloy of platinum, palladium, ruthenium, iridium, rhodium etc. or gold are or/and silver and the formed particulate of alloy of other metals etc.Comprise that also gold is used on surfaces such as metal and metal oxide or/and the particulate of silver coating.
As the solvent of fine particle of noble metal dispersion liquid, the general organic solvent of water or alcohol, ether, ester, ketone, aromatics etc. is arranged, and the mixture of water and organic solvent, this is not limited.The content of precious metal preferably more than 0.001 weight %, when fine particle of noble metal content is lower than 0.001 weight %, fully condenses in order to make fine particle of noble metal in the fine particle of noble metal dispersion liquid, need leave standstill for a long time.
As the compound with sulfydryl that is used as flocculation agent among the present invention, representational have dithioglycol, 1,3-dimercaptopropane, 1, a 10-mercaptan in the last of the ten Heavenly stems two etc.Also can use intramolecularly to have resin of several sulfydryls etc.Have the sulfydryl of these sulfhydryl compounds and gold and silver and form very strong key, contain gold, play the effect of cohesion or/and the fine particle of noble metal of silver carries out crosslinkedly each other.Therefore, have the compound of sulfydryl, preferably its intramolecularly has the compound of 2 above sulfydryls at least.
The skeleton part that keeps sulfydryl is the hydrocarbon etc. of straight chain preferably.This is the dimercapto compound because of straight chain, and the sulfydryl at 2 fine particle of noble metal and two ends has partly formed chemical bond, by this key, a plurality of fine particle of noble metal carry out combination mutually, as a result, the dispersive fine particle of noble metal is bonded to each other by this compound, thereby obtains to form the effect of aggregate.Therefore, above-mentioned skeleton partly is that long straight chain shape is better.
Particularly, adding tensio-active agent and dispersion resin etc., fine particle of noble metal is formed in the waste liquid of stable dispersion state, the compound that keeps sulfydryl in the two ends of the hydrocarbon of above-mentioned straight chain etc., by its three-dimensional arrangement and Chemical bond power, just make the fine particle of noble metal of stable dispersion agglomerated together, brought into play good effect.
As the addition with sulfhydryl compound of flocculation agent, according to the amount of dispersive fine particle of noble metal in the solution, generally be for fine particle of noble metal amount in the solution, be more than 1/100 preferably with weight ratio.
In the fine particle of noble metal dispersion liquid, the colloid of fine particle of noble metal generally has negative electricity, by adding inorganic salt, forms the Coulomb repulsion of the less bilayer that makes fine particle of noble metal liquid decentralized stabilization, makes micropartical be easy to cohesion each other.Therefore, interpolation simultaneously has the compound of sulfydryl and as the inorganic salt that condense auxiliary, can make the fine particle of noble metal cohesion in the shorter time.As this inorganic salt, use to have the cationic inorganic salt of 1 valency and have effect, but Al preferably
3+, Cu
2+, Mg
2+Have the above cationic inorganic salt of divalent.
Add compound simultaneously and also be effective as the acid or the alkali of cohesion auxiliary with sulfydryl.That is, before interpolation has sulfhydryl compound, in the fine particle of noble metal dispersion liquid, add acid or alkali,, can more effectively make the cohesion of fine particle of noble metal to adjust the pH value.As at this moment pH scope preferably more than 8 or below 6.
According to the present invention, in solvent, be dispersed with gold or/and in the sub-dispersion liquid of fine particle of noble metal of the fine particle of noble metal of silver, have the compound of sulfydryl by interpolation, fine particle of noble metal is condensed in the short period of time at the utmost point, can generate the good precious metal aggregate of settleability and filterableness.Therefore, can at an easy rate this precious metal aggregate be separated from solvent, can reclaim the high precious metal of availability in the industry simply.
Particularly, fine particle of noble metal in the fine particle of noble metal dispersion liquid is subjected to the steric hindrance of macromolecule dispersing agent and when forming stable dispersion, add ionogen and be difficult to make the fine particle of noble metal cohesion, but add compound according to the present invention with sulfydryl, the sub-Direct Bonding of sulfydryl and fine particle of noble metal, particle is cross-linked to each other, and can make the fine particle of noble metal cohesion of decentralized stabilization by macromolecule dispersing agent such as dispersion resin and tensio-active agent.
On the other hand, in the past as making precious metal ion form coordinate complex compound compound, known have a nitrogen-containing heterocycle compound with sulfydryl.Equally, these nitrogen-containing heterocycle compound and precious metal ions with sulfydryl carry out coordination, also can make their sedimentations.But not the ionic fine particle of noble metal formation aggregate that is bonded to each other, their sedimentations but are difficult to.
Embodiment 1
As the fine particle of noble metal dispersion liquid, preparation by the Au/Ag weight ratio of 0.1 weight % be 1: 1 fine particle of noble metal, 0.01 weight % macromolecule dispersing agent, and all the other parts be that water/ethanol weight ratio is 1: 9 a solvent, formed dispersion liquid.In this fine particle of noble metal dispersion liquid of 20g, the compound dithioglycol with sulfydryl as flocculation agent interpolation 25ppm stirred 1 minute with magnetic stirrer.Subsequently, at room temperature leave standstill, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 2
Except using 1 as flocculation agent, outside the 3-dimercaptopropane, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 3
Except using 1 as flocculation agent, outside the 10-mercaptan in the last of the ten Heavenly stems two, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 4
Except making the fine particle of noble metal Au/Ag weight ratio in the fine particle of noble metal dispersion liquid is 2: 1, and uses 1, and 10-mercaptan in the last of the ten Heavenly stems two is as outside the flocculation agent, and other are the same with embodiment 1, measures precipitation beginning formation time and supernatant liquor and reaches the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 5
Except making the fine particle of noble metal Au/Ag weight ratio in the fine particle of noble metal dispersion liquid be 4: 1 and use 1,10-mercaptan in the last of the ten Heavenly stems two is as flocculation agent, and other are the same with embodiment 1, measures precipitation beginning formation time and supernatant liquor and reaches the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 6
As the solvent of fine particle of noble metal dispersion liquid, except the operating weight ratio of mixture was water/methylcyclohexane solvent of 1: 9, other were the same with embodiment 1, measured precipitation beginning formation time and supernatant liquor and reached the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 7
As the solvent of fine particle of noble metal dispersion liquid, except the operating weight ratio of mixture was water/acetone solvent of 1: 9, other were the same with embodiment 1, measured precipitation beginning formation time and supernatant liquor and reached the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 8
As the solvent that contains in the fine particle of noble metal dispersion liquid, except the operating weight ratio of mixture was water/ethanol/methylcyclohexane solvent of 1: 5: 4, other were the same with embodiment 1, measured precipitation beginning formation time and supernatant liquor and reached the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 9
Solvent as the fine particle of noble metal dispersion liquid, the operating weight ratio of mixture is water/alcohol solvent of 1: 1 and as flocculation agent, adds the 50ppm dithioglycol, in addition other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 3 minutes.
Embodiment 10
Solvent as the fine particle of noble metal dispersion liquid, the operating weight ratio of mixture is water/methylcyclohexane solvent of 1: 1, with add the 50ppm dithioglycol as flocculation agent, in addition the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the complete transparent time.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 3 minutes.
Embodiment 11
As the fine particle of noble metal in the fine particle of noble metal dispersion liquid, except the operating weight ratio is 1: the 1Au/Pt fine particle of noble metal, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 12
As the fine particle of noble metal in the fine particle of noble metal dispersion liquid, except that the operating weight ratio was 1: 1 Au/Pd fine particle of noble metal, other were the same with embodiment 1, measured precipitation beginning formation time and supernatant liquor and reached the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 13
As fine particle of noble metal in the fine particle of noble metal dispersion liquid, except the operating weight ratio was 1: 1 Au/Ru fine particle of noble metal, other were identical with embodiment 1, measured precipitation beginning formation time and supernatant liquor and reached the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 14
As the fine particle of noble metal in the fine particle of noble metal dispersion liquid, except that using Au monomer particulate, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 15
Except the macromolecule dispersing agent that uses 0.05 weight %, other are the same with the foregoing description 5, promptly, at 20g is that 4: 1 the macromolecule dispersing agent of Au/Ag fine particle of noble metal, 0.05 weight % and rest part are that weight ratio is in 1: 9 the formed fine particle of noble metal dispersion liquid of water/alcohol solvent by the weight ratio of 0.1 weight %, add 1 of 25ppm as flocculation agent, 10-mercaptan in the last of the ten Heavenly stems two stirred after 1 minute, left standstill.Measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 16
Fine particle of noble metal in the fine particle of noble metal dispersion liquid is got 0.05 weight %, reach macromolecule dispersing agent and get 0.01 weight %, in addition other are the same with embodiment 15, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 3 minutes.
Embodiment 17
With the fine particle of noble metal in the fine particle of noble metal dispersion liquid get 0.01 weight %, macromolecule dispersing agent is got 0.01 weight %, and the flocculation agent 1 of interpolation 50ppm, 10-mercaptan in the last of the ten Heavenly stems two, in addition, other are the same with embodiment 15, as the cohesion auxiliary, also add 100ppm hydrochloric acid, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 3 minutes.
Embodiment 18
Fine particle of noble metal in the fine particle of noble metal dispersion liquid is got 0.05 weight %, get 0.01 weight % with macromolecule dispersing agent, in addition, other are the same with embodiment 15, as the cohesion auxiliary, also add the sal epsom of 25ppm, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 1 minute.
Embodiment 19
In order to make the electromagnetic wave shielding nesa coating, rotary coating forms the masking liquid that transparency conducting layer is used on glass substrate.At this moment reclaim the masking liquid that formation transparency conducting layer that vibration flows down is used around the substrate, with it as the precious metal waste liquid that contains fine particle of noble metal.This precious metal waste liquid except the masking liquid that contains above-mentioned formation transparency conducting layer, also contains all kinds of SOLVENTS composition, and an example of its composition is as follows.
Ag-Au particulate (weight ratio of Ag: Au is 1: 4): 0.15 weight %, Ag-Pd micropartical (weight ratio of Ag: Pd is 3: 7): 0.05 weight %, macromolecule dispersing agent: 0.01 weight %, SiO
2Micropartical: 0.1 weight %, water: 3 weight %, ethanol: 73 weight %, Virahol (IPA): 9 weight %, propylene glycol-methyl ether (PGM): 5 weight %, methylcyclohexane: 3 weight %, diacetone alcohol (DAA): 2 weight %, other solvents: 4.69 weight %.
In the above-mentioned waste liquid of 20g, as flocculation agent, add 1 of 30ppm, 10-mercaptan in the last of the ten Heavenly stems two, the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Leave standstill the back in 5 seconds, container bottom begins to form precipitation, and supernatant liquor reaches transparent fully after 3 minutes.
Comparative example 1
Except the ス ミ Off ロ Star Network FN13 (Sumitomo Chemical (strain) system polyacrylic acid amide is a polymer coagulant) that adds 100ppm as flocculation agent, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Container bottom began to form the sedimentary time after 3 hours, and through 24 hours, supernatant liquor was also opaque.
Comparative example 2
Except adding the ス ミ Off ロ Star Network FN13 of 1000ppm as flocculation agent, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Container bottom began to form the sedimentary time after 3 hours, and through 24 hours, supernatant liquor was also opaque.
Comparative example 3
Except adding the sal epsom of 100ppm as flocculation agent, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Do not form precipitation through container bottom after 24 hours yet.
Comparative example 4
Except adding the sal epsom of 1000ppm as flocculation agent, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Begin to form the sedimentary time after 12 hours at container bottom, also opaque through supernatant liquor after 24 hours.
Comparative example 5
Except adding the 100ppm sodium-chlor as flocculation agent, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Also form precipitation through container bottom after 24 hours.
Comparative example 6
Except adding the sodium hydroxide of 100ppm as flocculation agent, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully, and through 24 hours, container bottom did not form precipitation yet.
Comparative example 7
Except adding the hydrochloric acid of 100ppm as flocculation agent, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully.Do not form precipitation through container bottom after 24 hours.
Comparative example 8
Except adding as flocculation agent the hydrochloric acid of 1000ppm, other are the same with embodiment 1, measure precipitation beginning formation time and supernatant liquor and reach the transparent time fully, container bottom begins to form precipitation after 12 hours, and is still opaque through supernatant liquor after 24 hours.
About the various embodiments described above and comparative example, its condition and result separately compiles and is shown in table 1 and table 2.In table 1 and the table 2,, adopt test portion 1-19,, adopt relatively test portion 1-8 about comparative example 1-8 about embodiment 1-19.
From above embodiment and comparative example as can be known, be dispersed in and contain gold or/and the fine particle of noble metal of silver forms precipitation hardly with polymer coagulant and the inorganic flocculant that uses in the past metal particle cohesion in the dispersion liquid, even also extremely long time of cost of precipitation.In contrast, according to the present invention, the compound that will have sulfydryl can form precipitation at the utmost point simply as flocculation agent in the short period of time.For example, when comparing with embodiment 1 and comparative example 2, dithioglycol is with 1/400 addition of polymer coagulant as can be known, and fine particle of noble metal just can fully condense in the extremely short time.The effect of invention
According to the present invention, disperseing to contain gold or/and in the sub-dispersion liquid of fine particle of noble metal of the fine particle of noble metal of silver, only add compound and make flocculation agent with sulfydryl, just can make the cohesion of fine particle of noble metal at short notice, generate settleability and the good precious metal aggregate of filterableness, and can at an easy rate fine particle of noble metal be separated from solvent.
Therefore, the inventive method is applicable to that the waste liquid that is produced can reclaim at an easy rate and contain gold or/and the high price precious metal of silver in order to prevent electromagnetic-wave leakage from waste liquid when the CRT glass surface is coated with the fine particle of noble metal dispersion liquid with the formation transparency conducting layer.
The inventive method can not need large-scale device, does not remove operations such as solvent owing to do not contain drying, so energy cost is low, all has very high practicality for any environment.
When table 1 is the flocculation agent that adds in the embodiment of the invention in the fine particle of noble metal dispersion liquid, the table look-up of fine particle of noble metal precipitation result.
When table 2 is the flocculation agent that adds in the comparative example of the present invention in the fine particle of noble metal dispersion liquid, fine particle of noble metal sedimentation result's table look-up.
Table 1
* water: ethanol: IPA: PGM: methylcyclohexane: DAA: other solvent=3: 73: 9: 5: 3: 2: 4.69
| Fine particle of noble metal | Dispersion agent (wt%) | Solvent is formed (weight ratio) | Flocculation agent | The cohesion auxiliary | Precipitation beginning formation time | The transparent time of supernatant liquor | ||||
| Test portion | Weight ratio | (wt％) | Kind | ??(ppm) | Kind | ??(ppm) | ||||
| ????1 | ?Au∶Ag＝1∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | Dithioglycol | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????2 | ?Au∶Ag＝1∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | 1, the 3-dimercaptopropane | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????3 | ?Au∶Ag＝1∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | 1,10-mercaptan in the last of the ten Heavenly stems two | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????4 | ?Au∶Ag＝2∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | 1,10-mercaptan in the last of the ten Heavenly stems two | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????5 | ?Au∶Ag＝4∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | 1,10-mercaptan in the last of the ten Heavenly stems two | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????6 | ?Au∶Ag＝1∶1 | ?0.1 | ????0.01 | Water: methylcyclohexane=1: 9 | Dithioglycol | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????7 | ?Au∶Ag＝1∶1 | ?0.1 | ????0.01 | Water: acetone=1: 9 | Dithioglycol | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????8 | ?Au∶Ag＝1∶1 | ?0.1 | ????0.01 | Water: ethanol: methylcyclohexane=1: 5: 4 | Dithioglycol | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????9 | ?Au∶Ag＝1∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | Dithioglycol | ????50 | Do not have | ????0 | In 5 seconds | 3 minutes |
| ????10 | ?Au∶Ag＝1∶1 | ?0.1 | ????0.01 | Water: methylcyclohexane=1: 1 | Dithioglycol | ????50 | Do not have | ????0 | In 5 seconds | 3 minutes |
| ????11 | ?Au∶Pt＝1∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | Dithioglycol | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????12 | ?Au∶Pd＝1∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | Dithioglycol | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????13 | ?Au∶Ru＝1∶1 | ?0.1 | ????0.01 | Water: ethanol=1: 9 | Dithioglycol | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????14 | ?Au | ?0.1 | ????0.01 | Water: ethanol=1: 9 | Dithioglycol | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????15 | ?Au∶Ag＝4∶1 | ?0.1 | ????0.05 | Water: ethanol=1: 9 | 1,10-mercaptan in the last of the ten Heavenly stems two | ????25 | Do not have | ????0 | In 5 seconds | 1 minute |
| ????16 | ?Au∶Ag＝4∶1 | ?0.05 | ????0.01 | Water: ethanol=1: 9 | 1,10-mercaptan in the last of the ten Heavenly stems two | ????25 | Do not have | ????0 | In 5 seconds | 3 minutes |
| ????17 | ?Au∶Ag＝4∶1 | ?0.01 | ????0.01 | Water: ethanol=1: 9 | 1,10-mercaptan in the last of the ten Heavenly stems two | ????50 | Hydrochloric acid | ????100 | In 5 seconds | 3 minutes |
| ????18 | ?Au∶Ag＝4∶1 | ?0.05 | ????0.01 | Water: ethanol=1: 9 | 1,10-mercaptan in the last of the ten Heavenly stems two | ????25 | Sal epsom | ????25 | In 5 seconds | 1 minute |
| ????19 | ?Au∶Ag＝4∶1 ?Ag∶Pd＝3∶7 | ?0.15 ?0.05 | ????0.01 | ??* | 1,10-mercaptan in the last of the ten Heavenly stems two | ????30 | Do not have | ????0 | In 5 seconds | 3 minutes |
Table 2
| Fine particle of noble metal | Dispersion agent (wt%) | Solvent is formed (weight ratio) | Flocculation agent | Precipitation beginning formation time | The transparent time of supernatant liquor | |||
| Compare test portion | Weight ratio | (wt％) | Kind | ??(ppm) | ||||
| ????1 | ?Au∶Ag＝1∶1 | ????0.1 | ????0.01 | Water: ethanol=1: 9 | ??スミフロツクNF13 | ????100 | After 3 hours | Still coloured after 24 hours |
| ????2 | ?Au∶Ag＝1∶1 | ????0.1 | ????0.01 | Water: ethanol=1: 9 | ??スミフロツクNF13 | ????1000 | After 1 hour | Still coloured after 24 hours |
| ????3 | ?Au∶Ag＝1∶1 | ????0.1 | ????0.01 | Water: ethanol=1: 9 | Sal epsom | ????100 | Do not precipitate in 24 hours | - |
| ????4 | ?Au∶Ag＝1∶1 | ????0.1 | ????0.01 | Water: ethanol=1: 9 | Sal epsom | ????1000 | After 12 hours | Still coloured after 24 hours |
| ????5 | ?Au∶Ag＝1∶1 | ????0.1 | ????0.01 | Water: ethanol=1: 9 | Sodium-chlor | ????100 | Do not precipitate in 24 hours | - |
| ????6 | ?Au∶Ag＝1∶1 | ????0.1 | ????0.01 | Water: ethanol=1: 9 | Sodium hydroxide | ????100 | Do not precipitate in 24 hours | - |
| ????7 | ?Au∶Ag＝1∶1 | ????0.1 | ????0.01 | Water: ethanol=1: 9 | Hydrochloric acid | ????100 | Do not precipitate in 24 hours | - |
| ????8 | ?Au∶Ag＝1∶1 | ????0.1 | ????0.01 | Water: ethanol=1: 9 | Hydrochloric acid | ????1000 | After 12 hours | Still coloured after 24 hours |
Claims (5)
1. precious metal recovery method, feature is to be dispersed with to contain gold or/and in the fine particle of noble metal dispersion liquid of silver-colored particulate in solvent, interpolation is as the compound with sulfydryl of flocculation agent, make the fine particle of noble metal cohesion after, make the fine particle of noble metal and the separated from solvent of cohesion again.
2. according to the precious metal recovery method of claim 1 record, feature is, above-mentionedly contains gold or/and the particulate of silver utilizes dispersion agent or/and tensio-active agent is dispersed in the solvent.
3. according to the precious metal recovery method of claim 1 or 2 records, feature is that above-mentioned compound with sulfydryl is the compound that intramolecularly has 2 above sulfydryls at least.
4. according to the precious metal recovery method of each record of claim 1-3, feature is, the flocculation agent of above-mentioned compound with sulfydryl and add simultaneously as the inorganic salt of cohesion auxiliary.
5. according to the precious metal recovery method of each record among the claim 1-4, feature is, the flocculation agent of above-mentioned compound with sulfydryl adds simultaneously with acid or the alkali as the cohesion auxiliary.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01121037 CN1230386C (en) | 2001-06-15 | 2001-06-15 | Process for recovering noble metal from noble metal microparticle dispersive liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01121037 CN1230386C (en) | 2001-06-15 | 2001-06-15 | Process for recovering noble metal from noble metal microparticle dispersive liquid |
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| Publication Number | Publication Date |
|---|---|
| CN1392107A true CN1392107A (en) | 2003-01-22 |
| CN1230386C CN1230386C (en) | 2005-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 01121037 Expired - Fee Related CN1230386C (en) | 2001-06-15 | 2001-06-15 | Process for recovering noble metal from noble metal microparticle dispersive liquid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106574320A (en) * | 2014-08-04 | 2017-04-19 | 日本化药株式会社 | Metal recovery method and metal recovery agent |
| CN109266855A (en) * | 2018-06-18 | 2019-01-25 | 曹大平 | The non-cyanogen of non-ferrous metal rare precious metal extracts waste water complete alternation technique |
| CN110172585A (en) * | 2019-04-29 | 2019-08-27 | 北京理工大学 | A method of extracting golden simple substance from gold-containing scrap |
| CN111057861A (en) * | 2019-11-28 | 2020-04-24 | 中海油太原贵金属有限公司 | Method for recovering precious metal from wire drawing lubricating fluid |
| CN114752765A (en) * | 2021-01-08 | 2022-07-15 | 苏州诺菲纳米科技有限公司 | Method for recovering metal nano material dispersed by polyvinylpyrrolidone in assistance and application thereof |
-
2001
- 2001-06-15 CN CN 01121037 patent/CN1230386C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106574320A (en) * | 2014-08-04 | 2017-04-19 | 日本化药株式会社 | Metal recovery method and metal recovery agent |
| 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 |
| CN109266855A (en) * | 2018-06-18 | 2019-01-25 | 曹大平 | The non-cyanogen of non-ferrous metal rare precious metal extracts waste water complete alternation technique |
| CN110172585A (en) * | 2019-04-29 | 2019-08-27 | 北京理工大学 | A method of extracting golden simple substance from gold-containing scrap |
| CN111057861A (en) * | 2019-11-28 | 2020-04-24 | 中海油太原贵金属有限公司 | Method for recovering precious metal from wire drawing lubricating fluid |
| CN114752765A (en) * | 2021-01-08 | 2022-07-15 | 苏州诺菲纳米科技有限公司 | Method for recovering metal nano material dispersed by polyvinylpyrrolidone in assistance and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1230386C (en) | 2005-12-07 |
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