WO2023099076A1 - Procédé de séparation de rhodium - Google Patents

Procédé de séparation de rhodium Download PDF

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Publication number
WO2023099076A1
WO2023099076A1 PCT/EP2022/079164 EP2022079164W WO2023099076A1 WO 2023099076 A1 WO2023099076 A1 WO 2023099076A1 EP 2022079164 W EP2022079164 W EP 2022079164W WO 2023099076 A1 WO2023099076 A1 WO 2023099076A1
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WO
WIPO (PCT)
Prior art keywords
rhodium
chloro
iridium
aqueous solution
ruthenium
Prior art date
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PCT/EP2022/079164
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German (de)
English (en)
Inventor
Marco STEMMLER
Andre SAUER
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Heraeus Deutschland GmbH & Co. KG
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Filing date
Publication date
Application filed by Heraeus Deutschland GmbH & Co. KG filed Critical Heraeus Deutschland GmbH & Co. KG
Publication of WO2023099076A1 publication Critical patent/WO2023099076A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/28—Amines
    • C22B3/282—Aliphatic amines
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/06—Chloridising

Definitions

  • the invention relates to an efficient process for separating rhodium as a sparingly soluble rhodium chloro complex salt from an aqueous solution containing hydrochloric acid (hydrochloric acid) noble metal chloro complexes.
  • ble metal chloro complexes refers to chloro complexes of the noble metals rhodium, iridium, ruthenium, gold, platinum and palladium respectively.
  • a precipitation of sparingly soluble precious metal chlorocomplex salts from hydrochloric acidic aqueous solutions containing precious metal chlorocomplexes is state of the art in wet-chemical precious metal recycling or in wet-chemical precious metal refining.
  • hydrochloric acid such aqueous solutions containing hydrochloric acid can also contain other acids, in particular inorganic acids such as, for example, nitric acid.
  • the pH of such hydrochloric acid aqueous solutions is usually in the range of ⁇ 2.
  • pooled noble metal chloro complex salt used herein refers to its poor solubility in hydrochloric acid or in a hydrochloric acidic aqueous medium in the pH range of ⁇ 2. Quantified, this means a solubility of the precious metal in question, expressed as the solubility of the precious metal present in a sparingly soluble precious metal chlorocomplex salt, of ⁇ 100 mg per liter.
  • Concentrations of dissolved noble metals in hydrochloric acid aqueous solutions can be determined using ICP-OES (inductively coupled plasma optical emission spectrometry; optical emission spectrometry using inductively coupled plasma).
  • ICP-OES inductively coupled plasma optical emission spectrometry; optical emission spectrometry using inductively coupled plasma.
  • noble metal chlorocomplexes contained in said hydrochloric acid aqueous solutions include in particular chloronoble metal acids, in the case of rhodium hexachlororhodium(III) acid HsRhCh, in the case of iridium depending on the redox potential of the solution hexachloroiridium(III) acid HsIrCh and/or Hexachloroiridium(IV) acid ⁇ IrCle, in the case of ruthenium hexachlororuthenium(IV) acid H2RUCI6, in the case of gold tetrachloroauric(III) acid HAuCL, in the case of platinum hexachloroplatinic(IV) acid H2PtCle, and in the case of palladium depending on the redox potential of the Solution Tetrachloropalladium(II) acid H2PdCk and/or Hexachloropalla
  • Said sparingly soluble chloro complex salts are in particular corresponding polyamine hexachlororhodate(III), hexachloroiridate(III), hexachlororuthenate(III) or hexachlororuthenate(IV); needless to say for the person skilled in the art that the nitrogen atoms of the respective aliphatic polyamine component are present in protonated form in such chloro complex salts.
  • Any gold present can, for example, be separated beforehand, i.e.
  • any platinum and palladium present can be separated, for example before or after the joint rhodium/iridium/ruthenium precipitation, by precipitation in Form of sparingly soluble chloro complex salts using ammonium or potassium chloride.
  • the sparingly soluble chlorocomplex salts of rhodium, iridium and ruthenium which are precipitated together using aliphatic polyamine can then first be boiled in aqua regia for the purpose of further processing.
  • a hydrochloric acidic aqueous solution comprising dissolved chloro complexes of rhodium, iridium and ruthenium, in particular in the form of their aforementioned chloronoble metal acids.
  • a common way of further refining is the separation of the rhodium at a comparatively high redox potential by precipitation as a sparingly soluble chloro complex salt using aliphatic polyamine and subsequent further rhodium refining to obtain metallic rhodium or a purified rhodium compound such as hexachlororhodium(III) acid HsRhCh.
  • the iridium and ruthenium can then be separated from the aqueous phase containing dissolved iridium and ruthenium chlorocomplexes at a comparatively low redox potential by precipitation as sparingly soluble chlorocomplex salts using aliphatic polyamine and then fed to a further iridium or ruthenium refining process.
  • US 5,478,376 discloses a process for the separation of rhodium and/or iridium from a starting solution containing at least one ruthenium chloro complex, hydrochloric acid and rhodium and/or iridium chloro complexes, the process comprising the conversion of ruthenium chloro complex to a nitrosyl complex in the divalent state and the precipitation of rhodium and/or iridium by manipulation of their oxidation states.
  • the invention has set itself the task of a particularly efficient separation of rhodium from hydrochloric acidic aqueous solutions containing chlorocomplexes of rhodium and iridium and/or ruthenium (chlorocomplexes of rhodium and iridium or of rhodium and ruthenium or of rhodium and iridium and ruthenium). , to allow.
  • the invention solves this problem in a surprisingly simple manner by a process for separating rhodium from a hydrochloric acid aqueous solution which contains at least one chloro-complex of rhodium and at least one chloro-complex of iridium and/or at least one chloro-complex of ruthenium (i.e.
  • the rhodium explicitly dispensing with a previously taking place joint separation with the iridium and / or the ruthenium at a redox potential of> 950 to 1050 mV (at a redox potential in the range of> 950 to 1050 mV) using aliphatic polyamine as a sparingly soluble rhodium chlorocomplex salt from the hydrochloric acidic aqueous solution is precipitated.
  • the process according to the invention does not recognize any nitrosyl complexes, let alone nitrosyl complexes of the noble metals rhodium, iridium and ruthenium.
  • the process according to the invention dispenses with nitrosyl complexes of any kind. Nitrosyl complexes are at no time during the process according to the invention in said hydrochloric acid aqueous solution which contains at least one chloro-complex of rhodium and at least one chloro-complex of iridium and/or at least one chloro-complex of ruthenium.
  • All other substances used during the process according to the invention are also free from nitrosyl complexes or from substances capable of forming nitrosyl complexes with said hydrochloric acid aqueous solution.
  • nitrosyl complexes not formed or used anywhere in the process of the present invention, but there is no need for them.
  • the method according to the invention comprises in particular the following steps (1) to (4): (1) Providing a hydrochloric acid aqueous solution which contains at least one rhodium chlorocomplex and at least one iridium chlorocomplex or at least one rhodium chlorocomplex and at least one ruthenium chlorocomplex or at least one rhodium chlorocomplex, at least one iridium chlorocomplex and at least one chlorocomplex of contains ruthenium,
  • the method according to the invention preferably comprises further steps (5) to (7) following step (4):
  • a hydrochloric acid aqueous solution containing at least one rhodium chlorocomplex and at least one iridium chlorocomplex or at least one rhodium chlorocomplex and at least one ruthenium chlorocomplex or at least one rhodium chlorocomplex is at least one iridium chlorocomplex and containing at least one chloro-complex of ruthenium.
  • the proportion of said at least one dissolved chloro complex of rhodium in the hydrochloric acid aqueous solution can for example in the range corresponding to 0.5 to 15 g rhodium per liter; it is preferably hexachlororhodium acid.
  • the proportion of said at least one dissolved chloro complex of iridium in the hydrochloric acid aqueous solution can be, for example, in the range corresponding to 0.5 to 15 g of iridium per liter; it is preferably hexachloroiridic acid.
  • the proportion of said at least one dissolved chloro complex of ruthenium in the hydrochloric acid aqueous solution can be, for example, in the range corresponding to 0.5 to 15 g of ruthenium per liter; it is preferably hexachlororuthenic acid.
  • the method according to the invention explicitly dispenses with a joint separation of the rhodium together with the iridium, together with the ruthenium or together with the iridium and the ruthenium.
  • a redox potential of the hydrochloric acid aqueous solution in the range from >950 to 1050 mV, for example in the range from >950 to 1000 mV prevails. If this is not the case, such a redox potential is adjusted by adding an oxidizing agent. Said adjustment of the redox potential can be effected by mixing the hydrochloric acid aqueous solution with one or more oxidizing agents under the potentiometric control customary in the art.
  • the oxidizing agent or agents can be added to the hydrochloric acid aqueous solution as such or dissolved in water. Examples of particularly suitable oxidizing agents include chlorine, bromates, chlorates and perchlorates. If aqueously dissolved oxidizing agents are used, the person skilled in the art will appropriately endeavor not to use such in unnecessarily low concentrations.
  • Step (2) it may be appropriate to ensure good mixing, for example by stirring.
  • Step (2) can expediently be carried out in the temperature range from, for example, 55 to 90.degree.
  • the hydrochloric acid aqueous solution in step (3) is aliphatic polyamine in order to completely precipitate the at least one chloro complex of rhodium as a sparingly soluble rhodium chloro complex salt at least added sufficient or even excess amount.
  • the person skilled in the art understands the concept of complete precipitation as precipitation of the material in excess of the solubility product.
  • the aliphatic polyamine can be added as such or as an aqueous solution, preferably as an aqueous solution neutralized with acid, in particular as an aqueous solution neutralized with hydrochloric acid.
  • the aliphatic polyamine can be one or a combination of two or more aliphatic polyamines; the use of a single aliphatic polyamine is preferred.
  • the proportion of aliphatic polyamine in such an acid-neutralized aqueous solution can be, for example, in the range from 15 to 25% by weight.
  • aliphatic polyamines suitable as such a precipitating agent include diethylene triamine (DETA), triethylene triamine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine, tris(2-aminoethyl) amine (TAEA), dipropylene triamine, 1-(2-aminoethyl)piperazine.
  • DETA is particularly suitable and is therefore used with preference.
  • the rhodium is immediately and at least largely selectively precipitated at a high redox potential of >950 to 1050 mV, for example in the range from >950 to 1000 mV, using an aliphatic polyamine as a poorly soluble rhodium chlorocomplex salt and is thus initially separated from iridium and/or or ruthenium separated.
  • the material precipitated in step (3) is a poorly soluble salt of aliphatic polyamine such as DETA and rhodium chloro complex such as trihydrogen hexachlorohodic acid, for example diethylenetriammonium hexachlororhodate of the formula H3(DETA)RhCle or (H3NC2H4NH2C2H4NH3XRI-1CI6).
  • Step (3) it may be appropriate to ensure thorough mixing, for example by stirring.
  • Step (3) can expediently be carried out in the temperature range from, for example, 55 to 90.degree.
  • step (3) it may be expedient to allow the mixture formed to come to rest, for example by allowing it to stand still for one to three hours. In this way, settling of the precipitated material and formation of a supernatant in the form of a hydrochloric acid aqueous solution can be effectively supported.
  • the sparingly soluble rhodium chlorocomplex salt can be separated from the supernatant hydrochloric acid aqueous solution in step (4) of the process according to the invention by means of a conventional solid-liquid separation.
  • suitable solid-liquid separation processes include methods known to the person skilled in the art, such as decanting, squeezing, filtering, suction filtration, centrifuging or combinations thereof.
  • rhodium can be removed in the order of 80 to 99%, based on the rhodium content of the hydrochloric acid aqueous solution provided in step (1). This succeeds at least largely selectively to the extent that iridium or ruthenium does not co-precipitate or only to an extent of, for example, >0 to 15%, based on the iridium or ruthenium content of the hydrochloric acid aqueous solution originally provided in step (1). .
  • the sparingly soluble rhodium chloro complex salt which has been separated off can be fed to a conventional rhodium refinery.
  • the hydrochloric acid aqueous solution which has been separated off also includes iridium and/or ruthenium in the form of their dissolved chloro complexes which have not coprecipitated.
  • Steps (1) to (4) of the method according to the invention are sequential steps.
  • the method according to the invention preferably comprises further steps (5) to (7), of which steps (5) and (6) can take place in the sequence of steps (5)-(6) or (6)-(5), however, the sequence of steps (5)-(6) is preferred.
  • a comparatively low redox potential of the hydrochloric acid aqueous solution in the range from 400 to 550 mV, preferably from 440 to 470 mV, is set by adding reducing agent.
  • the adjustment of the redox potential can expediently be effected by mixing the hydrochloric acid aqueous solution with the reducing agent under potentiometric control.
  • the reducing agent can be added to the hydrochloric acid aqueous solution as such or as an aqueous solution.
  • the reducing agent can be one or a combination of two or more reducing agents.
  • Suitable reducing agents include stannous salts such as stannous chloride and stannous sulfate, but especially ferrous salts such as ferrous chloride, ferrous sulfate and ferrous nitrate.
  • stannous salts such as stannous chloride and stannous sulfate
  • ferrous salts such as ferrous chloride, ferrous sulfate and ferrous nitrate.
  • aqueous dissolved reducing agents the person skilled in the art will expediently endeavor not to use such in unnecessarily low concentrations.
  • Step (5) it may be appropriate to ensure thorough mixing, for example by stirring.
  • Step (5) can expediently be carried out in the temperature range from, for example, 50 to 70.degree.
  • step (6) which may be optional in this respect, further aliphatic polyamine, i.e. aliphatic polyamine in the complete precipitation of the at least one chloro complex of iridium as a sparingly soluble Iridium chloro complex salt and/or the at least one chloro complex of ruthenium can be added as a sparingly soluble ruthenium chloro complex salt in at least a sufficient or even excess amount.
  • further aliphatic polyamine i.e. aliphatic polyamine in the complete precipitation of the at least one chloro complex of iridium as a sparingly soluble Iridium chloro complex salt and/or the at least one chloro complex of ruthenium can be added as a sparingly soluble ruthenium chloro complex salt in at least a sufficient or even excess amount.
  • the amount of aliphatic polyamine that is at least sufficient for the complete precipitation of the at least one chloro complex of iridium or of ruthenium as a sparingly soluble chloro complex salt is the amount which, even with further addition, causes no more precipitation; in this respect, the person skilled in the art understands the concept of complete precipitation as precipitation of the material in excess of the solubility product.
  • the need to add aliphatic polyamine and thus to implement step (6) depends on whether there is a lack of aliphatic polyamine necessary for complete precipitation, more precisely whether and to what extent the aliphatic polyamine originating from the addition in step (2) is present in contained in the hydrochloric acid aqueous solution.
  • step (6) takes place.
  • the aliphatic polyamine can be added as such or in aqueous solution, but preferably in the form of an aqueous solution neutralized with acid, in particular in the form of hydrochloric acid.
  • the proportion of the aliphatic polyamine in such an acid-neutralized aqueous solution can range, for example, from 15 to 25% by weight.
  • Examples of aliphatic polyamines useful as such a precipitating agent include the aliphatic polyamines previously mentioned.
  • step (6) can be omitted because it is not necessary, i.e. if after the conclusion of step (5) a sufficient amount of aliphatic polyamine added in the course of step (2) is present in the hydrochloric acid aqueous solution, the iridium and/or ruthenium is precipitated "automatically" so to speak.
  • step (6) The material precipitated in this respect in the course of or after the conclusion of step (5) or step (6) is a poorly soluble salt of aliphatic polyamine and chloro-complex of iridium and/or chloro-complex of ruthenium.
  • step (6) it may be appropriate to ensure thorough mixing, for example by stirring.
  • Step (6) can conveniently be carried out in the temperature range of, for example, 55 to 90°C.
  • the precipitated, sparingly soluble iridium chloro-complex salt and/or the precipitated, sparingly-soluble ruthenium chloro-complex salt can be separated from the hydrochloric acid aqueous solution in step (7) by means of a conventional solid-liquid separation.
  • suitable solid-liquid separation processes include methods known to those skilled in the art, such as decanting, squeezing, filtering, suction filtration, centrifuging or combinations thereof.
  • the separated sparingly soluble iridium chloro complex salt and/or the sparingly soluble ruthenium chloro complex salt can be fed to a conventional iridium or ruthenium refinery.
  • the precipitate consisting essentially of DETA hexachlororhodate was suction filtered and washed with a little distilled water.
  • the filtrate volume on the one hand and the content of the respective noble metals in the filtrate on the other hand were determined by means of ICP-OES and related to the 200 ml volume and noble metal content of the original precious metal solution.
  • the table below shows the precious metal content of the original

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
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  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Manufacture And Refinement Of Metals (AREA)
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Abstract

L'invention concerne un procédé de séparation de rhodium d'une solution aqueuse d'acide chlorhydrique contenant au moins un complexe chloro de rhodium et au moins un complexe chloro d'iridium et/ou au moins un complexe chloro de ruthénium. L'invention est caractérisée en ce que le rhodium est précipité à partir de la solution aqueuse d'acide chlorhydrique avec un potentiel redox supérieur ou égal à 950 et allant jusqu'à 1 050 mV à l'aide d'une polyamine aliphatique en tant que sel complexe chloro de rhodium peu soluble tout en arrêtant explicitement d'utiliser une séparation groupée effectuée préalablement avec l'iridium et/ou le ruthénium.
PCT/EP2022/079164 2021-12-02 2022-10-20 Procédé de séparation de rhodium WO2023099076A1 (fr)

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EP21211870.7 2021-12-02
EP21211870 2021-12-02

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WO2023099076A1 true WO2023099076A1 (fr) 2023-06-08

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105442A (en) * 1976-06-21 1978-08-08 The National Institute For Metallurgy Separation and purification of ruthenium
US5478376A (en) 1994-09-21 1995-12-26 Matthey Rustenburg Refiners (Pty) Limited Method for the separation of rhodium and/or iridium from solution
CN106282562A (zh) * 2016-08-29 2017-01-04 金川集团股份有限公司 一种分离铑铱的新工艺
RU2693285C1 (ru) * 2018-11-06 2019-07-02 Игорь Владимирович Федосеев Способ разделения металлов из сплава платина, палладий, родий Pt-Pd-Rh
RU2742994C1 (ru) * 2020-06-09 2021-02-12 Игорь Владимирович Федосеев Способ селективного выделения родия Rh, рутения Ru и иридия Ir из солянокислых растворов хлорокомплексов платины Pt(IV), палладия Pd(II), золота Au(III), серебра Ag(I), родия Rh(III), рутения Ru(IV) и иридия Ir(IV)
CN113430376A (zh) * 2021-07-06 2021-09-24 湖南省南铂新材料有限公司 溶液中贵金属高效分离及高纯贵金属的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105442A (en) * 1976-06-21 1978-08-08 The National Institute For Metallurgy Separation and purification of ruthenium
US5478376A (en) 1994-09-21 1995-12-26 Matthey Rustenburg Refiners (Pty) Limited Method for the separation of rhodium and/or iridium from solution
CN106282562A (zh) * 2016-08-29 2017-01-04 金川集团股份有限公司 一种分离铑铱的新工艺
RU2693285C1 (ru) * 2018-11-06 2019-07-02 Игорь Владимирович Федосеев Способ разделения металлов из сплава платина, палладий, родий Pt-Pd-Rh
RU2742994C1 (ru) * 2020-06-09 2021-02-12 Игорь Владимирович Федосеев Способ селективного выделения родия Rh, рутения Ru и иридия Ir из солянокислых растворов хлорокомплексов платины Pt(IV), палладия Pd(II), золота Au(III), серебра Ag(I), родия Rh(III), рутения Ru(IV) и иридия Ir(IV)
CN113430376A (zh) * 2021-07-06 2021-09-24 湖南省南铂新材料有限公司 溶液中贵金属高效分离及高纯贵金属的制备方法

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