CN1322155C - Method for separating and recovering Ru from solution containing pt family - Google Patents
Method for separating and recovering Ru from solution containing pt family Download PDFInfo
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- CN1322155C CN1322155C CNB2005100910385A CN200510091038A CN1322155C CN 1322155 C CN1322155 C CN 1322155C CN B2005100910385 A CNB2005100910385 A CN B2005100910385A CN 200510091038 A CN200510091038 A CN 200510091038A CN 1322155 C CN1322155 C CN 1322155C
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Abstract
To provide a method for efficiently separating Ru from a solution containing a platinum group element by oxidation distillation. The method for separating and collecting Ru from the solution containing the platinum group element includes adjusting the pH of the solution containing one or more platinum group elements among Ru, Pt, Pd, Rh and Ir to 0.5 to 2.5, converting Ru to ruthenium tetroxide through oxidation with the use of sodium bromate as an oxidizing agent, and distilling the solution, wherein sodium bromate is excessively added in an amount of 1 equivalent weight required for oxidizing Ru into ruthenium tetroxide and further an amount required for adjusting the concentration of sodium bromate to 80 g/L or higher.
Description
Technical field
The present invention relates to from containing the solution of platinum family, for example separate the method for Ru after the leaching of cupric electrolysis mud in the solution.
Background technology
As the method for separating Ru, the known ruthenium tetroxide (RuO that utilizes
4) volatile oxidation distillation method.For example, from 493 pages to 500 pages (non-patent literature 1), put down in writing and in the residue of platinum group, add oxygenant and, feed chlorine, reclaimed the method for evaporable ruthenium tetroxide with in the solution behind the alkali dissolution at document Japan atom mechanics proceedings 28 volumes.But when feeding chlorine, the chlorine that is absorbed by the aqueous solution is decomposed into hypochlorous acid and hydrochloric acid and makes solution become acidity, makes oxidation distillation no longer carry out, and therefore, in order to improve the rate of recovery, needs to add the alkali distill repeatedly.
In the fair 1-30896 communique of spy (patent documentation 1), disclose containing the solution of gold and platinum family, with sodium bromate Ru and Os are oxidized to tetroxide, then the method that is removed by distillation.Disclose the oxidant content that whole Ru and Os are oxidized to tetroxide in this communique and be suitably stoichiometric 7～10 times, but the countermeasure when not have specifically to disclose Ru concentration change in the solution.That is, have 7～10 times of stoichiometric oxygenant deficiencies when Ru concentration is low, and when Ru concentration is high stoichiometric 7～10 times oxygenant surplus and undissolved problem.
Present inventors have been willing to disclose among the 2003-128828 (patent documentation 2) method of utilizing distillation separating and recovering Ru from the solution that contains platinum family the spy.That is,, utilize for example sodium bromate (NaBrO of oxygenant from containing the solution of platinum family
3), distill out Ru with the form of ruthenium tetroxide, separating and recovering Ru.In this method, before adding oxygenant pH is adjusted into 1, adds the about 3 times of normal sodium bromates of the Ru in the solution then, to form ruthenium tetroxide, then be heated to 80 ℃, distilled in matrass about 4 hours on bubbling air limit, limit.Therefore but can not isolate Ru fully with 1 time distillation procedure according to this method, 2 distillation procedures repeatedly.This is because along with distillatory carries out since with the reaction of acid, sodium bromate decomposes and consumption acids, pH rises to 4～5, causes oxidation distillation no longer to carry out.If reduction pH and add acid, then oxygenant decomposes and consumption acids, therefore, need pH be adjusted into 1, and then distill after the oxygenant that adds decompose fully.
In addition, in this method the ruthenium tetroxide steam to be imported to and be translated into ruthenium chloride in the hydrochloric acid soln and reclaim, and to distill on bubbling air limit, limit in order reclaiming effectively.But,, then exist deleterious ruthenium tetroxide steam to spill or, cause connection section to come off or the disruptive problem if stop up then the pressure increase from linking part if be blown into air to distillate.If gas is blown in the solution, exist especially on gas and leading section that liquid contacts crystallization to separate out and easy blocking problem.
In addition, when in the solution of reactive tank, being blown into air, the mist that contains ruthenium tetroxide steam and Ru platinum family element in addition can disperse, cause purity drop with the ruthenium chloride of hydrochloric acid soln recovery, therefore be provided with the mist trap, but the ruthenium tetroxide that rests in the mist trap can decompose gradually, is converted into the little ruthenium dioxide of volatility, therefore the problem that exists the rate of recovery to descend.
[non-patent literature 1] crosses work such as a sharp husband [Japanese atomic power association] periodical
Volume was from 484 pages to 492 pages in 1986 116
[patent documentation 1] special fair 1-30896 number
[patent documentation 2] is special is willing to 2003-128828 number
Summary of the invention
The present invention finishes in order to address the aforementioned drawbacks, and it is a kind of when utilizing oxidation distillation to separate Ru from the solution that contains platinum family that its purpose is to provide, and carries out isolating method effectively.
To the result that the method for utilizing oxidation distillation to separate Ru from the solution that contains platinum family is inquired into, obtained following conclusion, that is: Ru can be converted into the pH scope of ruthenium tetroxide be 0.5～2.5 to sodium bromate; If will before pH rises owing to the decomposition of oxygenant, effectively Ru be converted into ruthenium tetroxide, then need the oxygenant of enough concentration.And then the distillating method to the ruthenium tetroxide that is used for distilling out effectively hazardous property has carried out found that of research repeatedly, under reduced pressure, bubbling air limit, limit distill and prevent to manage in to take place to stop up be very important.
That is, the invention provides
(1) a kind of from the solution of platinum group the method for separating and recovering Ru, the pH of the solution of platinum family more than a kind that will contain among Ru and Pt, Pd, Rh, the Ir is adjusted into 0.5～2.5, use sodium bromate as oxygenant, Ru is converted into ruthenium tetroxide carries out oxidation distillation, wherein the addition of sodium bromate is, except adding Ru is oxidized to the 1 required equivalent of ruthenium tetroxide, excessive interpolation so that the concentration of sodium bromate reach more than the 80g/L.
(2) a kind of from the solution of platinum group the method for separating and recovering Ru, in above-mentioned (1), when oxidation distillation, use suction pump bubbling air under reduced pressure, ruthenium tetroxide is transferred to the hydrochloric acid soln from reactive tank, and fed water to prevent obstruction to the air leading-in conduit of reactive tank.
(3) a kind of from the solution of platinum group the method for separating and recovering Ru, in the oxidation distillation of above-mentioned (1) and (2), ruthenium tetroxide is transferred to from reactive tank the hydrochloric acid soln during, catch tank is set, in this groove, place sodium bromate solution as oxygenant, and in the aqueous solution of this groove, feed ruthenium tetroxide to prevent the generation of ruthenium dioxide, carry out demist simultaneously.
The method and apparatus of the application of the invention, from the solution that contains platinum family during separating and recovering Ru,
(1), separates Ru in the solution of the platinum family more than a kind that just can be from contain Ru and Pt, Pd, Rh, Ir with once distillation procedure.
(2) can prevent the decomposition of ruthenium tetroxide, reclaim ruthenium effectively.
(3) can easily obtain high-grade ruthenium.
(4) pipe arrangement in the water distilling apparatus does not stop up, and can realize stable operation.
Description of drawings
Fig. 1 is the explanatory view of the Ru water distilling apparatus that uses in embodiment and comparative example.
Embodiment
Below the present invention will be described in detail.The objective of the invention is to, from the solution that contains platinum family, isolate Ru effectively and reclaim isolated Ru.
The oxidation distillation method that people have known is to distill after Ru is converted into volatile ruthenium tetroxide, then ruthenium tetroxide is imported to the method that reclaims in hydrochloric acid soln or the sodium hydroxide solution.But,, then need to have the oxygenant of high oxidizing potential if Ru will be converted into ruthenium tetroxide.Owing to will from the solution that contains platinum family after separating Ru, reclaim platinum family, thereby to select not can be owing to heavy metal foul solution and can segregative oxygenant, as such oxygenant, can enumerate an alkali metal salt of perchloric acid, chloric acid, bromic acid, perhaps chlorine, ozone gas.
Use in the method for chlorine, as mentioned above, the chlorine that is absorbed in the aqueous solution is decomposed into chlorous acid and hydrochloric acid, causes the character of liquid to become acidity, and this moment, oxidation distillation no longer carried out, and therefore, need add alkali, distill repeatedly in order to improve the rate of recovery.In addition, be difficult in order to make gas absorption in solution and sharply increase oxidant concentration in the solution.
Use the method for ozone gas, can suppress the change of pH value of solution value, can make reaction continue to carry out, but because the meltage of ozone gas in the aqueous solution is few, thereby the ozone that is not absorbed fully is many, causes being difficult to Ru is converted into ruthenium tetroxide effectively.
In the method for an alkali metal salt of use perchloric acid, chloric acid, bromic acid, the pH scope that Ru can be converted into four oxidations nail is determined, and oxygenant decomposes and the pH value is changed in still-process, therefore with distill for 1 time do not have can abundant isolating situation under, after just needing the decomposing oxidation agent to readjust pH, distill again.
The present inventor finds: when using sodium bromate as oxygenant, the pH scope that Ru can be converted into ruthenium tetroxide is 0.5～2.5.Therefore it is desirable for before adding sodium bromate, the pH value that will contain the solution of platinum family is made as 0.5～2.5.But in this pH scope, sodium bromate is decomposed and consumption acids by acid, becomes stable after the pH value rises to about 4～5.
As if will just separating Ru fully, fully carry out oxidizing reaction rapidly under the condition of raising oxidant concentration with 1 distillation.And the clear and definite following fact:, wish the concentration of sodium bromate is set at more than the 80g/L if will reclaim highly purified platinum family element the solution after removing Ru.
Because sodium bromate is used for oxidizing reaction, so the amount of the sodium bromate that adds is Ru to be converted into 1 required in the reaction of ruthenium tetroxide equivalent add that the concentration that makes sodium bromate in the solution that contains platinum family reaches the amount more than the 80g/L.In the time of owing to the interpolation sodium bromate acid decomposition takes place and cause pH to rise, thereby hope is once added sodium bromate rapidly in the solution that contains platinum family.
In addition, the pH that adds sodium bromate is less than 0.5 o'clock, decomposed by acid and pH rises to for 0.5 the moment at sodium bromate, and the reaction that Ru is converted into ruthenium tetroxide begins, and still, must add this moment and adjust the excessive oxygenant that pH uses, not effective therefore.
Below, will narrate and use suction pump bubbling air under reduced pressure in the oxidation distillation, and feed the reason of water to prevent to stop up to the air leading-in conduit of reactive tank.Among the present invention the ruthenium tetroxide steam is imported to and be translated into ruthenium chloride in the hydrochloric acid soln of 6N and reclaim, wherein the boiling point of ruthenium tetroxide is about 130 ℃, than the boiling point height of water.
Therefore, in order to reclaim ruthenium tetroxide effectively, wish that bubbling air limit, limit distills, if but air is blown into distillate, then exist deleterious ruthenium tetroxide steam to spill from connection section, retaining pressure perhaps takes place to be increased, and connection section is come off or disruptive danger.
Also have,,, and preferably use glass or quartz etc. so the starting material of device preferably do not use resin or metal because ruthenium tetroxide has strong oxidizing property.Therefore, use thermal glass to make as shown in Figure 1 water distilling apparatus in the present invention, reclaimed Ru from the solution separating that contains platinum family.
Ru is that the hydrochloric acid soln with 6N joins in the absorption cell, and in solution, be blown into the ruthenium tetroxide steam, reclaim as ruthenium chloride solution, but, because a part does not react, so placed in-line 2 stage absorption cells are set, the absorption liquid of latter stage was used when distilling next time in the last stage, can reclaim roughly all Ru of amount like this.
Because the boiling point of ruthenium tetroxide is about 130 ℃, higher, so wish under 70～95 ℃, to distill, distillation time is increased if temperature is low, if temperature surpasses 95 ℃ then the evaporation of moisture becomes many, the liquid measure increase of absorption cell makes the concentration that reclaims liquid thinning.Under 70～95 ℃ of temperature, with more than 1 hour, just can roughly transferring in the absorption liquid fully with the Ru in the reactive tank.
Also have, use known method that the ruthenium chloride solution of absorption cell is reclaimed as the ruthenium powder.The method that can enumerate has, for example, add reductive agent such as formic acid be reduced to the ruthenium powder method, add ammonia chloride and be precipitated as chlorination ruthenic acid ammonia after, with this method that places reducing atmosphere to decompose.
Narration feeds water to the air lead of reactive tank and prevents the reason stopped up below.If Ru fully will be separated in 1 distillation, just need under the sufficiently high condition of the concentration of oxygenant, carry out oxidizing reaction rapidly, wish that the concentration of sodium bromate is at least more than the 80g/L, because can vapor away the Ru more than 99.9% like this.
During less than 80g/L, Ru can remain in the reactive tank in the concentration of sodium bromate, and so the obstacle when becoming the platinum family element that reclaims other is need be by distilling once more or methods such as solvent extration, ion exchange method are separated.
In reactive tank, therefore salt concn height such as sodium bromate and the Sodium Bromide that is generated by distillation reaction, sodium-chlor, especially salt out in the bottom of the air leading-in conduit that contact with air sometimes and cause obstruction.For this reason, dissolve the salt of separating out, can prevent to stop up by making the bottom that less water flows through air leading-in conduit.For the amount of the water that flows through air leading-in conduit, so long as can prevent to stop up, to the just not special regulation of its amount, benchmark substantially is, per hour, and about 1/100～1/10 of the liquid measure of reactive tank.
To narrate the reason that catch tank is set below.For the ruthenium tetroxide that will produce in reactive tank shifts effectively to absorption cell, make the ruthenium tetroxide volatilization when air being blown in the solution of reactive tank, be blown into the air that contains ruthenium tetroxide in the absorption liquid in absorption cell.In the time of in the solution that air is blown into the reactive tank that contains Ru platinum family element in addition, the part of reactive tank solution can become mist, together is sent to absorption cell with the air that contains ruthenium tetroxide, and Ru platinum family element in addition is blended in the absorption liquid.
Therefore, the catch tank of having put into the sodium bromate aqueous solution is set between reactive tank and absorption cell, and, captures the mist that contains Ru platinum family element in addition thus, so that it does not shift to absorption liquid to wherein feeding the air that contains ruthenium tetroxide.At catch tank, the part of ruthenium tetroxide is captured, and therefore, the heating catch tank makes the ruthenium tetroxide volatilization.
In addition, the reason of sodium bromate being put into catch tank is that ruthenium tetroxide is decomposed into ruthenium dioxide under reducing atmosphere, so by keeping oxidizing atmosphere to prevent the decomposition of ruthenium tetroxide.The concentration of the sodium bromate in catch tank, as long as keep oxidizing atmosphere, benchmark is 5～50g/L substantially.
Embodiment
(embodiment 1)
Below embodiments of the invention are described.Embodiment uses water distilling apparatus as shown in Figure 1.In the reactive tank that in mantle heater, is provided with (1), add pH is adjusted into 1 the hydrochloric acid acidic solution 7L that contains Ru and platinum family element.Because when described solution adds sodium bromate, can generate ruthenium tetroxide, thus the limit solution be heated to 80 ℃ of limits in solution with 10L/ minute bubbling air.
At this moment, in order to prevent to stop up, in air leading-in conduit, to feed pure water in 0.1L/ hour.The air that will contain the ruthenium tetroxide steam is passed in the 3% sodium bromate solution of the catch tank (2) that is heated to 80 ℃, imports to then in the absorption cell (3,4) of putting into the 6N hydrochloric acid soln, and the ruthenium tetroxide steam is reclaimed as ruthenium chloride solution.
Decompose the bromine gas that produces by containing in the air behind the absorption liquid, therefore absorb bromine, and come exhaust with off-gas pump with the 16mass% sodium hydroxide solution by sodium bromate.Distillation is under 80 ℃, is blown under 2 hours the condition of air to carry out.
The result of solution composition, solution amount and the Ru partition ratio of table 1 expression embodiment 1.In embodiment 1, the sodium bromate concentration of adding in the distillation forward reaction groove solution is set at 122g/L, make when 1 equivalent of the oxidizing reaction of Ru is 33g/L, the sodium bromate concentration of the reactive tank solution after the distillation is 89g/L.
Ru concentration is 0.005g/L in the reactive tank after the distillation, thereby has separated Ru from reactive tank.Almost staying in the reactive tank all of platinum family element beyond the Ru, and in absorption cell, do not contain platinum family beyond the Ru.In addition, be set to for 2 stages, can reclaim roughly whole Ru, Ru is isolated from other platinum family element by absorption cell.
Table 1
| Reactive tank before the distillation | Distillation afterreaction groove | Distillation post-absorption groove (1) | Distillation post-absorption groove (2) | |
| Ru | 26.6g/L | 0.005g/L | 22.5g/L | 0.73g/L |
| Rh | 18.5 | 17.1 | ＜0.001 | ＜0.001 |
| Ir | 2.6 | 2.6 | ＜0.001 | ＜0.001 |
| Pd | 13.2 | 11.4 | 0.001 | ＜0.001 |
| Pt | 6.9 | 6.5 | ＜0.001 | ＜0.001 |
| NaBrO3 | 122 | 89 | - | - |
| Solution amount | 7.0L | 8.1L | 8.0L | 7.0L |
| The Ru partition ratio | 100％ | 0.02％ | 96.7％ | 2.7％ |
(embodiment 2)
Result according to solution composition, solution amount and the Ru partition ratio of the embodiment in the table 22 describes embodiment 2 below.In embodiment 2, setting the sodium bromate concentration of adding in the distillation forward reaction groove solution is 221g/L, makes when 1 equivalent of the oxidizing reaction of Ru is 61g/L, and the sodium bromate concentration of the reactive tank solution after the distillation is 160g/L.
Ru concentration is below the 0.001g/L in the reactive tank after the distillation, thereby has separated Ru from reactive tank.Platinum family element beyond the Ru is almost stayed in the reactive tank all, and does not contain the platinum family beyond the Ru in absorption cell.In addition, be set to for 2 stages, can reclaim roughly whole Ru, Ru can be isolated from other platinum family element by absorption cell.
Table 2
| Reactive tank before the distillation | Distillation afterreaction groove | Distillation post-absorption groove (1) | Distillation post-absorption groove (2) | |
| Ru | 48.8g/L | ＜0.001g/L | 40.9g/L | 1.5g/L |
| Rh | 14.3 | 11.2 | ＜0.001 | ＜0.001 |
| Ir | 0.83 | 0.57 | ＜0.001 | ＜0.001 |
| Pd | 0.22 | 0.16 | 0.001 | ＜0.001 |
| Pt | 0.15 | 0.12 | ＜0.001 | ＜0.001 |
| NaBrO3 | 221 | 160 | - | - |
| Solution amount | 7.0L | 9.3L | 8.4L | 7.3L |
| The Ru partition ratio | 100％ | ＜0.01％ | 100.6％ | 3.2％ |
(comparative example 1)
Below comparative example 1 is described.Except the addition that reduces sodium bromate, the device identical, step have been used in the comparative example 1 with embodiment.The result of solution composition, solution amount and the Ru partition ratio of table 3 expression comparative example 1.In comparative example 1, setting the sodium bromate concentration of adding in the distillation forward reaction groove solution is 84g/L, makes when 1 equivalent of the oxidizing reaction of Ru is 28g/L, and the sodium bromate concentration of the reactive tank solution after the distillation is 56g/L.
Ru concentration is 0.026g/L in the reactive tank after the distillation, residual Ru in the reactive tank.This is because the sodium bromate concentration of adding in addition except 1 required equivalent of oxidation is few, is 56g/L, does not have the ability of remaining abundant oxidation Ru.When from the reactive tank after this distillation, reclaiming other platinum family, can not obtain enough qualities.
Table 3
| Reactive tank before the distillation | Distillation afterreaction groove | Distillation post-absorption groove (1) | Distillation post-absorption groove (2) | |
| Ru | 22.6g/L | 0.026g/L | 27.8g/L | 1.4g/L |
| Rh | 16.9 | 14.3 | 0.001 | ＜0.001 |
| Ir | 1.4 | 1.3 | ＜0.001 | ＜0.001 |
| Pd | 13.7 | 11.4 | 0.003 | ＜0.001 |
| Pt | 6.9 | 6.2 | ＜0.001 | ＜0.001 |
| NaBrO3 | 84 | 56 | - | - |
| Solution amount | 7.0L | 8.3L | 5.5L | 7.2L |
| The Ru partition ratio | 100％ | 0.14％ | 96.6％ | 6.4％ |
(comparative example 2)
Below comparative example 2 is described.Comparative example 2 is put into the catch tank except the sodium bromate aqueous solution is replaced with pure water, has used the device identical with embodiment, step.The result of the partition ratio of solution composition, solution amount and the Ru of table 4 expression comparative example 2.In comparative example 2, setting the sodium bromate concentration of adding in the distillation forward reaction groove solution is 210g/L, makes when 1 equivalent of the oxidizing reaction of Ru is 70g/L, and the sodium bromate concentration of the reactive tank solution after the distillation is 140g/L.
Ru concentration is 0.005g/L in the reactive tank after the distillation, can isolate Ru from reactive tank.Almost having stayed in the reactive tank all of platinum family element beyond the Ru.But the Ru amount in the absorption cell that is provided with by 2 stages is to be contained in 55% of Ru amount in the reactive tank before the distillation, and is less.This is because replace the sodium bromate aqueous solution pure water to be put into catch tank, becomes the black precipitate of ruthenium dioxide so the ruthenium tetroxide in catch tank takes place to decompose.Because the steam of ruthenium dioxide forces down, so can not distill.Therefore, the Ru that is recovered in absorption cell tails off, though with ruthenium dioxide with other approach reduce handle also effective inadequately.
Table 4
| Reactive tank before the distillation | Distillation afterreaction groove | Distillation post-absorption groove (1) | Distillation post-absorption groove (2) | |
| Ru | 56.3g/L | 0.005g/L | 25.9g/L | 0.62g/L |
| Rh | 28.6 | 20.7 | 0.005 | ＜0.001 |
| Ir | 2.6 | 2.4 | ＜0.001 | ＜0.001 |
| Pd | 26.3 | 18.5 | 0.008 | ＜0.001 |
| Pt | 7.2 | 5.8 | 0.001 | ＜0.001 |
| NaBrO3 | 210 | 140 | - | - |
| Solution amount | 7.0L | 9.7L | 8.2L | 7.8L |
| The Ru partition ratio | 100％ | 0.01％ | 53.9％ | 1.2％ |
(comparative example 3)
Below comparative example 3 is described.Comparative example 3 has used the device identical with embodiment, step except not to the air leading-in conduit feeding pure water of reactive tank.Table 5 is illustrated in when the air leading-in conduit of reactive tank feeds pure water and when not feeding pure water, the blocked state of ingress pipe.
When the air leading-in conduit to reactive tank feeds pure water, the situation that in still-process, does not exist air leading-in conduit to stop up.On the other hand, not when air leading-in conduit feeds pure water, air leading-in conduit is blocked and cause proceeding distillation as comparative example 3.This is because salts such as dissolved platinum family salt, sodium bromate and reaction generation thing Sodium Bromide have caused obstruction at the pipe arrangement internal crystallization in reactive tank.
Table 5
| Air leading-in conduit | Have or not obstruction |
| Feed pure water | Do not have |
| Do not feed pure water | Have |
Claims (2)
1. the method for a separating and recovering Ru from the solution that contains platinum family, it is characterized in that, for the solution of platinum family more than a kind that contains among Ru and Pt, Pd, Rh, the Ir, its pH is adjusted into 0.5～2.5, and use sodium bromate as oxygenant, and Ru is converted into ruthenium tetroxide carries out oxidation distillation, wherein the addition of sodium bromate is, except adding Ru is oxidized to the 1 required equivalent of ruthenium tetroxide, excessive interpolation so that the concentration of sodium bromate reach more than the 80g/L; In oxidation distillation, ruthenium tetroxide is transferred to from reactive tank the hydrochloric acid soln during, catch tank is set, in this groove, place sodium bromate solution as oxygenant, and in the aqueous solution of this groove, feed ruthenium tetroxide to prevent the generation of ruthenium dioxide, carry out demist simultaneously.
2. according to claim 1 from the solution that contains platinum family the method for separating and recovering Ru, it is characterized in that, when oxidation distillation, use suction pump bubbling air under reduced pressure, ruthenium tetroxide is transferred to the hydrochloric acid soln from reactive tank, and fed water to prevent obstruction to the air leading-in conduit of reactive tank.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004353480A JP4100695B2 (en) | 2004-12-07 | 2004-12-07 | Method for separating and recovering Ru from a solution containing a platinum group |
| JP2004353480 | 2004-12-07 |
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| CN1786224A CN1786224A (en) | 2006-06-14 |
| CN1322155C true CN1322155C (en) | 2007-06-20 |
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| JP5579357B2 (en) * | 2006-11-21 | 2014-08-27 | 株式会社フルヤ金属 | Ruthenium recovery method |
| JP5498686B2 (en) * | 2008-01-21 | 2014-05-21 | 株式会社東芝 | Precious metal recovery method and precious metal recovery system |
| DE102008006797B4 (en) * | 2008-01-30 | 2014-05-22 | Heraeus Precious Metals Gmbh & Co. Kg | Methods and apparatus for removing ruthenium by distillation as RuO4 from ruthenated solutions |
| JP2009203486A (en) * | 2008-02-26 | 2009-09-10 | Nippon Mining & Metals Co Ltd | Method for recovering ruthenium from scrap containing ruthenium |
| JP2010077510A (en) * | 2008-09-29 | 2010-04-08 | Nippon Mining & Metals Co Ltd | Method of separating rhodium from platinum and/or palladium |
| JP5339068B2 (en) * | 2009-03-20 | 2013-11-13 | 三菱マテリアル株式会社 | Ruthenium purification and recovery method |
| JP5339067B2 (en) * | 2009-03-20 | 2013-11-13 | 三菱マテリアル株式会社 | Method for separating ruthenium |
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| JP6222469B2 (en) * | 2014-03-28 | 2017-11-01 | 三菱マテリアル株式会社 | Platinum family recovery methods |
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| CN110423896B (en) * | 2019-08-13 | 2021-11-16 | 江苏理工学院 | Method for recovering ruthenium trichloride from ruthenium plating waste liquid |
| CN113430376A (en) * | 2021-07-06 | 2021-09-24 | 湖南省南铂新材料有限公司 | Method for efficiently separating noble metals in solution and preparing high-purity noble metals |
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| JPS5168498A (en) * | 1974-12-10 | 1976-06-14 | Japan Carlit Co Ltd | Kayoseiruteniumu mataha sonokagobutsunosankajoryuho |
| JPS542919B2 (en) * | 1974-12-10 | 1979-02-15 | ||
| JP2004332041A (en) * | 2003-05-07 | 2004-11-25 | Nippon Mining & Metals Co Ltd | Method for recovering high-purity platinum group metal |
-
2004
- 2004-12-07 JP JP2004353480A patent/JP4100695B2/en active Active
-
2005
- 2005-08-03 CN CNB2005100910385A patent/CN1322155C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5168498A (en) * | 1974-12-10 | 1976-06-14 | Japan Carlit Co Ltd | Kayoseiruteniumu mataha sonokagobutsunosankajoryuho |
| JPS542919B2 (en) * | 1974-12-10 | 1979-02-15 | ||
| JP2004332041A (en) * | 2003-05-07 | 2004-11-25 | Nippon Mining & Metals Co Ltd | Method for recovering high-purity platinum group metal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1786224A (en) | 2006-06-14 |
| JP2006161096A (en) | 2006-06-22 |
| JP4100695B2 (en) | 2008-06-11 |
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