CN100408706C - Method for separating Te from Rh solution - Google Patents
Method for separating Te from Rh solution Download PDFInfo
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- CN100408706C CN100408706C CNB2006100086991A CN200610008699A CN100408706C CN 100408706 C CN100408706 C CN 100408706C CN B2006100086991 A CNB2006100086991 A CN B2006100086991A CN 200610008699 A CN200610008699 A CN 200610008699A CN 100408706 C CN100408706 C CN 100408706C
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- sub
- rhcl
- solution
- hydrochloric acid
- crystallization
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- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a method for efficiently separating Te from a hydrochloric acid solution containing Rh and a small amount of Te. In the method for removing Te from a hydrochloric acid solution containing Rh and a small amount of Te, in a step of crystallizing the Rh as (NH<SUB>4</SUB>)<SUB>3</SUB>RhCl<SUB>6</SUB> with ammonium chloride from the hydrochloric acid solution, alcohol is added to the solution before crystallization to precipitate the mixture of (NH<SUB>4</SUB>)<SUB>3</SUB>RhCl<SUB>6</SUB> and Te, this mixture is obtained by filtration and repulped with deionized water, whereby the (NH<SUB>4</SUB>)<SUB>3</SUB>RhCl<SUB>6</SUB>soluble in the deionized water is dissolved and recovered, and the Te insoluble in the deionized water is filtered off.
Description
Technical field
The present invention relates to a kind ofly for from cupric electrolysis recycling precipitate high purity Rh, and in the operation of purification Rh solution, remove method as a spot of Te of impurity.
Background technology
Open in 2004-332041 number (patent documentation 1) the spy, comprise the raw material of Te and platinum metals, in the chlorine atmosphere, carry out chloridizing volatilization and handle, remove Te, make platinum metals become the salt of solubility by volatile muriate, and the platinum group solution of the Te that has been removed.Then, from by distillation platinum group solution, solvent extraction, and operation removed the Rh solution of the composition beyond the Rh, utilize ammonium chloride to make Rh as sour the ammonium ((NH of chlorine rhodium (hexachloro-rhodium)
4)
3RhCl
6) crystallization, its calcining is obtained sponge grease (sponge metal).
(more than about 10mass%) contains the raw material of Te in a large number, by the chloridizing volatilization operation, Te is separated into the aqueous solution, but still has a spot of Te (about 100～5 with respect to Rh, 000mass ppm) to be blended in the aqueous solution.Because Te demonstrates the characteristic identical with Rh, so almost can't separate with Rh in the operation of distillation, solvent extraction, neutralization, crystallization, reduction etc.Therefore, have 100～5 approximately in the sponge grease of Rh, the Te of 000mass ppm sneaks into.
[patent documentation 1] spy opens 2004-332041 number
Summary of the invention
The present invention carries out in order to solve the above problems, and its purpose is, provides a kind of in order to reclaim high purity Rh, in the operation of purification Rh solution, removes the method as a spot of Te of impurity.
In the operation of utilizing ammonium chloride crystals Rh, filtration differentiation interpolation alcohols heats separates out (NH
4)
3RhCl
6And Te because if with them with the pure water repulp, (NH only then
4)
3RhCl
6So dissolving is with undissolved Te filtering separation.Consequently, can access the Rh solution that does not contain Te.
Be the present invention,
(1) is a kind of method of from the hydrochloric acid soln that contains Rh and a spot of Te, removing Te,, makes the Rh crystallization form (NH by ammonium chloride from the hydrochloric acid soln that contains Rh and a spot of at least Te
4)
3RhCl
6Operation in, add alcohols in the liquid before crystallization, make (NH
4)
3RhCl
6With the mixture precipitation of Te, will filter resultant these mixtures with the pure water repulp, (the NH that dissolves in pure water is reclaimed in dissolving
4)
3RhCl
6, will be not dissolved in the Te filtering separation of pure water and remove.
(2) be a kind of from the hydrochloric acid soln that contains Rh and a spot of Te with the isolating method of Te, the liquid before the crystallization of above-mentioned (1) record adds alcohols, generation (NH
4)
3RhCl
6Condition during with the precipitation of the mixture of Te is to keep more than 1 hour in temperature more than 50 ℃.
(3) be a kind of from the hydrochloric acid soln that contains Rh and a spot of Te with the isolating method of Te, it is characterized in that the alcohols in above-mentioned (1) is ethanol, methyl alcohol, Virahol or their mixture.
Adopt method of the present invention, add alcohols, be not dissolved in the Te of pure water from the crystallisate filtering separation, and the Te composition in the sponge grease of Rh can be reduced to below the 20mass ppm by Crystallization Procedure at Rh.
Make highly purified Rh and become possibility.
Description of drawings
Fig. 1 is the schema of embodiments of the invention.
Embodiment
Detailed content of the present invention is discussed.
Comprise as the Te of electrodeposit and the raw material of platinum metals, in the chlorine atmosphere, carry out chloridizing volatilization and handle, remove Te, make platinum metals become the salt of solubility by volatile muriate, and the platinum group solution of the Te that has been removed.Then, from by the purification process of the distillation of platinum group solution, solvent extraction, neutralization etc. having been removed the Rh solution of Rh composition in addition, utilize ammonium chloride to make Rh as chlorine rhodium acid ammonium ((NH
4)
3RhCl
6) crystallization, the operation of process reduction, calcining etc. obtains the sponge grease of Rh.
Here, the Te composition in raw material is low to moderate several mass% when following, handles by chloridizing volatilization and can remove Te fully.From very low solution of Te concentration so, utilize ammonium chloride to make the Rh crystallization, calcining and the sponge grease of the Rh that obtains contains Te hardly.
On the other hand, the Te composition height in raw material, is handled and can not be removed Te fully by chloridizing volatilization when above to 10mass%, contains a spot of Te in solution.Because Te demonstrates the characteristic identical with Rh, so almost can't separate with Rh in the purification process of distillation, solvent extraction, neutralization, crystallization, reduction etc.For this reason, residual approximately in the sponge grease of Rh have 100～5, and the Te of 000massppm is so can't obtain highly purified Rh.Therefore, proposed from the method for the Rh solution separating Te that contains a spot of Te.
Reclaiming the method for Rh the Rh solution of the composition from removed Rh by the purification process of distillation, solvent extraction, neutralization etc. beyond, is ammonium chloride to be added concentration of hydrochloric acid be adjusted in the solution of 3～6mol/L, is heated to about 70～95 ℃, as (NH
4)
3RhCl
6And crystallization.In this operation, because (NH
4)
3RhCl
6Generate, solubleness is big, so add alcohols in order to reduce solubleness to promote crystallization.This moment if with solution in heating more than 50 ℃ more than 1 hour, then Rh crystallization, and Te reduction separates out, and therefore obtains filtering (NH
4)
3RhCl
6Mixture with reduction Te.Because the reduction potential of Rh and Te is respectively near 0.43V, 0.52V, thus be difficult to by the reduction potential difference from.At this, because Rh utilizes the reduction reaction of alcohols slow, so as (NH
4)
3RhCl
6Crystallization.Therefore find that alcohols can only reduce Te in practicality.
If add ammonium chloride and alcohols simultaneously, then,, descend owing to add the alcohols boiling point, so can't generate (NH efficiently so unreacted ammonium chloride is separated out because alcohols reduces the solubleness of ammonium chloride
4)
3RhCl
6For this reason, preferably alcohols is made an addition to (NH
4)
3RhCl
6In the crystal solution that has generated.
The kind preferred alcohol of the alcohols that is added (ethyl alcohol), methyl alcohol (methyl alcohol), Virahol (isopropyl alcohol) or these mixture.The alcohols reducing power that the carbon number amount is many is big, but reduction generates undissolved Rh simultaneously in water, and it is separated with Te, thereby the rate of recovery reduces.
The amount of the alcohols that is added is if can reduce the Te crystallization for (NH
4)
3RhCl
6Then not having special stipulation, is 0.5～2 times amount of the aqueous solution as standard still.
Discuss heating condition in the reason of carrying out more than 50 ℃ more than 1 hour.This is because in Crystallization Procedure, Te and ammonium chloride reaction become water miscible ammonium tellurate ((NH
4)
2TeO
4), Te is for abundant reduction by the alcohols reduction.If reduction is insufficient, then water miscible ammonium tellurate ((NH
4)
2TeO
4) residual, but in the alcohols mixed solution because solubleness is little, thus with (NH
4)
3RhCl
6Crystallization together.Heating temperature is lower than 50 ℃ or discontented 1 hour of heat-up time, and the reduction of Te is insufficient, if with pure water repulp, then (NH
4)
3RhCl
6(NH
4)
2TeO
4Dissolving together, thereby can't filter differentiation.
In the present invention, so-called pure water is an ion exchanged water for example, distilled water etc.
As if (the NH that filtration is obtained by pure water
4)
3RhCl
6With the mixture repulp of reduction Te, the then (NH of solubility only
4)
3RhCl
6Be dissolved in pure water, insoluble Te is not dissolved in pure water and is residual.The Rh solution that its filtering separation is not contained Te.This filters used material, because undissolved reduction Te particle is very trickle, is membrane filter etc. below 1 micron so preferably adopt the aperture.
The Rh solution that has separated Te adds heating such as formic acid in reductive agent, reclaim the Rh that is black.Black Rh because particle is trickle the property handled bad, and contain aerobic, thus usually in hydrogen or inert gas atmosphere, the sponge grease recovery of formation Rh.The Rh sponge grease that so obtains can be reduced to the Te composition below the 20mass ppm.
The Rh solution that has perhaps separated Te also can add hydrochloric acid and ammonium chloride makes (NH
4)
3RhCl
6Recrystallize, filter to distinguish, decomposing and calcining crystallisate in hydrogen or inert gas atmosphere, and become the sponge grease of Rh.
Embodiment 1
Embodiments of the invention below are described.
Table 1 is illustrated in the composition of the raw material that comprises Te and platinum metals that uses among the embodiment 1.It is carried out chloridizing volatilization handle in the chlorine atmosphere, remove Te by volatile muriate after, add sodium-chlor and carry out chloridized, the salt that obtains solubility makes platinum metals become the aqueous solution.By it is distilled, solvent extraction, neutral purification process removed the composition beyond the Rh.
The liquid of the Rh solution before the Te that table 2 expression obtains with this method separates is formed.Because the Te composition height in the raw material, so residual in Rh solution have a spot of Te.
In this solution of 100mL, add the hydrochloric acid that concentration of hydrochloric acid becomes 6mol/L, add 2 equivalent (NH
4)
3RhCl
6Generate necessary ammonium chloride, 90 ℃ of heating 1 hour.Add 150ml ethanol to it, 70 ℃ of heating 1 hour, put cold after, filter with filter paper (JIS No.5C), obtain (NH
4)
3RhCl
6Mixture with reduction Te.With the pure water repulp of this mixture, at (NH with 200mL
4)
3RhCl
6After the dissolving, be that 0.1 micron membrane filter filters to separate reduction Te with the aperture.Liquid after table 2 expression Te separates is formed.The concentration of Te has been reduced to and has analyzed below the 1mg/L of gauge.
Rh liquid after Te separates adds the necessary formic acid of reduction of 5 equivalent Rh, 90 ℃ of heating 2 hours, reclaims black Rh.Black Rh 1000 ℃ of calcinings of carrying out 1 hour, becomes the sponge grease of Rh in 5% hydrogen-argon mixture gas.(GDMS) does the composition analysis to this Rh with the glow discharge mass spectrometry instrument.The analytical results of the sponge grease of table 3 expression Rh, the Te among the Rh is 1mass ppm.
Table 1
| Rh | Ru | Ir | Se | Te | |
| Raw material is formed (mass%) | 5.7 | 15.9 | 0.2 | 41.6 | 19.4 |
Table 2
Table 3
| Rh | Ru | Ir | Se | Te | |
| Rh forms (mass ppm) | 99.99mass％ | ＜1 | 3 | ＜1 | 1 |
Embodiment 2
Embodiment 2, except the alcohols that added in Crystallization Procedure uses Virahol, all with the condition enforcement identical with embodiment 1.Liquid before and after table 4 expression Te separates is formed, and the concentration of Te is low to moderate below the 1mg/L that analyzes gauge.
The analytical results of the sponge grease of table 5 expression Rh, the Te among the Rh is lower than 1mass ppm.
Table 4
Table 5
| Rh | Ru | Ir | Se | Te | |
| Rh forms (mass ppm) | 99.98mass％ | ＜1 | 110 | ＜1 | ＜1 |
Comparative example
Comparative example below is described.Comparative example is until add in crystallization till the ethanol, implements with the condition identical with embodiment 1.The composition of the liquid before the crystallization of table 6 expression comparative example.Comparative example adds ethanol does not make (NH by heating
4)
3RhCl
6Crystallization is filtered with filter paper (JIS No.5C).With its pure water repulp, at (NH with 200mL
4)
3RhCl
6After the dissolving, add the necessary formic acid of reduction of 5 equivalent Rh,, reclaim black Rh 90 ℃ of heating 2 hours.Black Rh 1000 ℃ of calcinings of carrying out 1 hour, becomes the sponge grease of Rh in 5% hydrogen-argon mixture gas.The analytical results of the sponge grease of table 7 expression Rh, the Te among the Rh reaches 4, and 100mass ppm fails to obtain highly purified Rh.
Table 6
Table 7
| Rh | Ru | Ir | Se | Te | |
| Rh forms (mass ppm) | 99.58mass％ | 1 | 20 | 3 | 4,100 |
Claims (2)
- One kind from the hydrochloric acid soln that contains Rh and a spot of Te with the isolating method of Te, it is characterized in that, from the hydrochloric acid soln that contains Rh and a spot of at least Te, make the Rh crystallization form (NH by ammonium chloride 4) 3RhCl 6Operation in, add alcohols in the liquid before crystallization, more than 50 ℃ to the heating of this solution more than 1 hour, and make (NH 4) 3RhCl 6With the mixture precipitation of Te, will filter resulting these mixtures with the pure water repulp, the soluble (NH in the pure water is reclaimed in dissolving 4) 3RhCl 6, will be not dissolved in the Te filtering separation of pure water and remove.
- 2. according to claim 1 from the hydrochloric acid soln that contains Rh and a spot of Te with the isolating method of Te, it is characterized in that described alcohols is ethanol, methyl alcohol, Virahol and therefrom optional mixture more than 2 kinds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005088185A JP4100696B2 (en) | 2005-03-25 | 2005-03-25 | Te separation method from Rh solution |
| JP2005088185 | 2005-03-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1837384A CN1837384A (en) | 2006-09-27 |
| CN100408706C true CN100408706C (en) | 2008-08-06 |
Family
ID=37014892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100086991A Expired - Fee Related CN100408706C (en) | 2005-03-25 | 2006-02-21 | Method for separating Te from Rh solution |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4100696B2 (en) |
| CN (1) | CN100408706C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4268646B2 (en) | 2007-03-30 | 2009-05-27 | 日鉱金属株式会社 | Recovery method of rhodium |
| JP4964814B2 (en) * | 2008-03-28 | 2012-07-04 | Ｊｘ日鉱日石金属株式会社 | Recovery method of rhodium |
| KR101451789B1 (en) | 2012-10-23 | 2014-10-16 | 한국과학기술연구원 | Separation of tellurium by solvent extraction method |
| CN102897853B (en) * | 2012-11-05 | 2014-08-13 | 中国海洋石油总公司 | Method for preparing water-soluble hexachlororhodate by medium-temperature chlorination of rhodium powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031567A (en) * | 1987-08-13 | 1989-03-08 | 中国有色金属工业总公司昆明贵金属研究所 | The dissolving and the purification of thick rhodium and high rhodium-containing alloyed scrap |
| JP2004332041A (en) * | 2003-05-07 | 2004-11-25 | Nippon Mining & Metals Co Ltd | Method for recovering high-purity platinum group metal |
-
2005
- 2005-03-25 JP JP2005088185A patent/JP4100696B2/en active Active
-
2006
- 2006-02-21 CN CNB2006100086991A patent/CN100408706C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031567A (en) * | 1987-08-13 | 1989-03-08 | 中国有色金属工业总公司昆明贵金属研究所 | The dissolving and the purification of thick rhodium and high rhodium-containing alloyed scrap |
| 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 |
|---|---|
| JP4100696B2 (en) | 2008-06-11 |
| JP2006265677A (en) | 2006-10-05 |
| CN1837384A (en) | 2006-09-27 |
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Owner name: JX NIPPON MINING + METALS CORPORATION Free format text: FORMER OWNER: NIPPON MINING + METALS CO., LTD. Effective date: 20110402 |
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Effective date of registration: 20110402 Address after: Tokyo, Japan, Japan Patentee after: JX Nippon Mining & Metals Corporation Address before: Tokyo, Japan Patentee before: Nippon Mining & Metals Co., Ltd. |
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Granted publication date: 20080806 Termination date: 20130221 |