EP0609507A1 - Electrolytic process for obtaining high purity platinum from impure platinum - Google Patents
Electrolytic process for obtaining high purity platinum from impure platinum Download PDFInfo
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- EP0609507A1 EP0609507A1 EP93118981A EP93118981A EP0609507A1 EP 0609507 A1 EP0609507 A1 EP 0609507A1 EP 93118981 A EP93118981 A EP 93118981A EP 93118981 A EP93118981 A EP 93118981A EP 0609507 A1 EP0609507 A1 EP 0609507A1
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- EP
- European Patent Office
- Prior art keywords
- platinum
- hydrochloric acid
- cathode
- solutions
- contaminated
- Prior art date
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 52
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 150000003057 platinum Chemical class 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005341 cation exchange Methods 0.000 claims description 9
- 239000010953 base metal Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 platinum metals Chemical class 0.000 claims description 3
- SSVFCHUBLIJAMI-UHFFFAOYSA-N platinum;hydrochloride Chemical compound Cl.[Pt] SSVFCHUBLIJAMI-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- 239000010931 gold Substances 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 6
- JLIGOPWLDBRXCZ-UHFFFAOYSA-L azane;dichloroplatinum Chemical compound N.Cl[Pt]Cl JLIGOPWLDBRXCZ-UHFFFAOYSA-L 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
Definitions
- the present invention relates to an electrolytic process for obtaining high purity platinum from concentrated hydrochloric acid solutions from the contaminated platinum.
- these platinum scrap must now be refined, for example to provide purities of 99.95% platinum for device platinum or 99.99% platinum for thermocouples, as required.
- certain orders of magnitude of certain contaminants must be observed.
- Refined platinum can be refined by multiple precipitation of the platinum as ammonium platinum chloride.
- this method has the disadvantage that it is very labor-intensive and time-consuming and has a large number of sources of loss.
- the processing personnel are at risk of allergies due to the ammonium platinum chloride.
- the electrolysis cell is equipped with a cation exchange membrane, the advantages of which cannot be seen, however, since platinum and palladium can also be separated without the cation exchange membrane in the concentration ratio and voltage range described.
- this method has the same disadvantage as all other methods that only a maximum concentration of ⁇ 100 g / l can be used.
- the invention was therefore based on the object of providing a process for the production of platinum of high purity, in which the precious and base metals are separated from contaminated platinum in a short time with minimal losses and with little labor using small apparatus.
- the invention therefore relates to an electrolytic process for obtaining high purity platinum from concentrated hydrochloric acid solutions of contaminated platinum.
- the process according to the invention is characterized in that the cleaning process takes place in an electrolysis cell which is divided by a cation exchange membrane under potentiostatic or voltage-controlled conditions of 2.5 V to 8 V and a current density of 0.3 to 12.5 A / dm2 and the deposited platinum alloy metals are worked up.
- the platinum metal solutions have a content of 50 to 700 g / l and total impurities of ⁇ 5000 ppm.
- Platinum metal solutions containing 500 to 700 g / l of contaminated platinum are preferably used in the process according to the invention.
- the concentrated platinum metal solutions used for the process according to the invention have impurities in the elements Rh and / or Pd, Ir, Au, Ag, Cu, Fe, Co, Ni, Sb, As, Pb, Cd, Al, Mn, Mo, Si, Zn, Sn, Zr, W, Ti, Cr on.
- Hydrochloric acid platinum metal solutions preferably hexachloroplatinic acid
- 6 to 8 N hydrochloric acid preferably 6 N hydrochloric acid
- the anode is made of platinum metal, while the cathode is made of platinum metal, titanium or graphite.
- a Teflon membrane (Nafion® membrane) is used as the preferred cation exchange membrane loaded with sulfonic acid groups.
- the method according to the invention preferably works under potentiostatic or voltage-controlled conditions of 4.5 V to 5 V and a current density of 9 to 10 A / dm2.
- Platinum purity levels of 99.95% can be achieved in one step from platinum metal solutions with a content of ⁇ 300 g / l of contaminated platinum and total impurities of ⁇ 5000 ppm.
- When changing the anode and the Anode liquid can be refined up to a platinum purity of 99.99%.
- the method according to the invention can thus be carried out in several stages depending on the purity of the platinum required.
- the acid concentration drops due to the development of chlorine and the transport of water into the cathode compartment, while maintaining the volume of the anode and cathode liquid by withdrawing dilute hydrochloric acid from the cathode compartment and adding water to the anode compartment.
- the complex bound ions dissociate, migrate through the cation exchange membrane and are deposited on the cathode.
- the deposited precipitate also contains small amounts of Pt. This precipitate is mechanically removed from the cathode and processed separately.
- the chlorine gas developing in the process according to the invention is removed by known methods.
- the inventive method can be refined 1 kg of platinum within 48 h.
- the metallic platinum can be recovered electrolytically or chemically from the solutions of the platinum metals cleaned by the method according to the invention.
- a hydrochloric acid platinum solution with the following impurities (concentration information based on platinum) Ir 1020 ppm Rh 630 ppm Pd 440 ppm Au 120 ppm Cu 250 ppm Fe 280 ppm Ni 230 ppm Sb 100 ppm Pb 80 ppm Al 80 ppm and a platinum content of 250 g / l (pH ⁇ 1) is electrolyzed in an electrolysis cell, the cathode and anode space are divided by a cation exchange membrane, at a voltage of 4.5 V and a current density of 9 A / dm2.
- the base metals are depleted to ⁇ 20 ppm, the iridium, rhodium and gold content is reduced by 50%, the palladium content by 20%.
- the noble metal impurities are reduced to the following values Ir ⁇ 200 ppm Rh ⁇ 50 ppm Pd ⁇ 200 ppm Au ⁇ 20 ppm
- the pre-refined solution from Example 1 is diluted to a platinum content of 120 g / l (pH value 0.1) and transferred to another electrolysis cell, which is also provided with a cation exchange membrane, and at a voltage of 5 V and 10 A / dm2 electrolyzed.
- the analysis after an electrolysis time of 10 hours, showed that the base metal impurities and gold to values ⁇ 10 ppm, the platinum metals Ir ⁇ 20 ppm Rh ⁇ 5 ppm Pd ⁇ 10 ppm were depleted.
- the platinum solution which was refined according to Example 1, is left in the electrolysis cell, the cathode liquid is replaced by freshly prepared 6 N hydrochloric acid.
- the anode liquid is diluted to a platinum content of 120 g / l
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein elektrolytisches Verfahren zur Gewinnung von Platin hoher Reinheit aus konzentrierten salzsauren Lösungen vom verunreinigten Platin.The present invention relates to an electrolytic process for obtaining high purity platinum from concentrated hydrochloric acid solutions from the contaminated platinum.
In der Praxis wird z. B. in Geräten, Thermoelementen und Katalysatoren eingesetztes Platin bedingt durch den jeweiligen Produktionsprozeß nach einem gewissen Zeitablauf mit Unedel- und Edelmetallen verunreinigt. Dadurch fallen ständig Platinschrotte mit Gesamtverunreinigungen von bis zu 5000 ppm an.In practice, e.g. B. Platinum used in devices, thermocouples and catalysts due to the respective production process after a certain period of time contaminated with base and precious metals. As a result, platinum scraps with total contamination of up to 5000 ppm accumulate.
Für den weiteren Einsatz müssen diese anfallenden Platinschrotte nun raffiniert werden, um zum Beispiel Reinheiten von 99,95 % Platin für Geräteplatin oder 99,99 % Platin für Thermoelemente, wie gefordert, bereitzustellen. Darüber hinaus müssen in Abhängigkeit vom Einsatzzweck bestimmte Größenordnungen von bestimmten Verunreinigungen eingehalten werden.For further use, these platinum scrap must now be refined, for example to provide purities of 99.95% platinum for device platinum or 99.99% platinum for thermocouples, as required. In addition, depending on the intended use, certain orders of magnitude of certain contaminants must be observed.
Die Raffination von verunreinigtem Platin kann über eine Mehrfachfällung des Platins als Ammoniumplatinchlorid erfolgen.
Pt→H₂[PtCl₆]→(NH₄)₂[PtCl₆]→Pt
Dieses Verfahren hat aber den Nachteil, daß es sehr arbeitsintensiv und zeitaufwendig ist und eine Vielzahl von Verlustquellen aufweist. Darüber hinaus kommt es beim Bearbeitungspersonal zur Allergiegefährdung durch das Ammoniumplatinchlorid.Refined platinum can be refined by multiple precipitation of the platinum as ammonium platinum chloride.
Pt → H₂ [PtCl₆] → (NH₄) ₂ [PtCl₆] → Pt
However, this method has the disadvantage that it is very labor-intensive and time-consuming and has a large number of sources of loss. In addition, the processing personnel are at risk of allergies due to the ammonium platinum chloride.
Durch die Anwendung des Ionenaustauscherverfahrens nach WP 147 688 konnte eine Reduzierung der angeführten Nachteile erreicht werden. Maximalverunreinigungen an Unedel- und Edelmetallen bis zu 1000 ppm im Platin können nach diesem Verfahren abgereichert werden, wobei als weiterer Raffinationsschritt eine Einfach- bzw. Mehrfachfällung von Ammoniumplatinchlorid erforderlich ist. Durch eine Kombination von Solventextraktion und Fällung als Ammoniumplatinchlorid kann das Verfahren verkürzt werden. Beide Verfahren besitzen jedoch den Nachteil eines hohen apparativen und steuerungstechnischen Aufwandes.By using the ion exchange process according to WP 147 688, a reduction of the disadvantages mentioned could be achieved. Maximum impurities in base and noble metals up to 1000 ppm in the platinum can be depleted by this process, with a further refining step requiring single or multiple precipitation of ammonium platinum chloride. The process can be shortened by combining solvent extraction and precipitation as ammonium platinum chloride. However, both methods have the disadvantage of a high expenditure on equipment and control technology.
Elektrolytische Verfahren zum Raffinieren von Gold sind seit langem bekannt (Gmelin Au, Syst. Nr. 62, 1949) und ständig weiterentwickelt worden (EP 0253783).Electrolytic processes for refining gold have long been known (Gmelin Au, Syst. No. 62, 1949) and have been continuously developed (EP 0253783).
Aus der GB-PS 157785 und der deutschen Patentschrift 594408 sind elektrolytische Platinraffinationsverfahren bekannt, die teilweise mit Kombinationen von chemischen und elektrolytischen Verfahren arbeiten (US-PS 3 891,741).From GB-PS 157785 and German patent 594408 electrolytic platinum refining processes are known, some of which work with combinations of chemical and electrolytic processes (US Pat. No. 3,891,741).
Diese Verfahren sind alle äußerst zeitaufwendig und lassen sich nicht in allen Punkten technisch einwandfrei nachvollziehen.These procedures are all extremely time-consuming and cannot be technically followed in every respect.
Die US-PS 4,382,845 beschreibt eine teilweise elektrolytische Abtrennung von Palladium aus Lösungen, die im Überschuß Palladium enthalten. Eine Trennung ist nach diesem Verfahren aber nur bis zu der Grenze möglich, bei der Platin und Palladium im gleichen Verhältnis vorliegen. Die Abtrennung von weiteren Unedel- und Edelmetallen wird dabei nicht erwähnt.US Pat. No. 4,382,845 describes a partial electrolytic separation of palladium from solutions which contain palladium in excess. However, separation using this method is only possible up to the limit at which platinum and palladium are present in the same ratio. The separation of other base and precious metals is not mentioned.
Zur Trennung von Platin und Palladium ist die Elektrolysezelle mit einer Kationenaustauschermembran ausgestattet, deren Vorteile allerdings nicht ersichtlich sind, da sich Platin und Palladium in dem angegebenen Konzentrationsverhältnis und dem beschriebenen Spannungsbereich auch ohne Kationenaustauschermembran trennen lassen. Darüber hinaus weist dieses Verfahren den gleichen Nachteil wie auch alle anderen Verfahren auf, daß nur mit einer Maximalkonzentration von ≦ 100 g/l gearbeitet werden kann.For the separation of platinum and palladium, the electrolysis cell is equipped with a cation exchange membrane, the advantages of which cannot be seen, however, since platinum and palladium can also be separated without the cation exchange membrane in the concentration ratio and voltage range described. In addition, this method has the same disadvantage as all other methods that only a maximum concentration of ≦ 100 g / l can be used.
Der Erfindung lag daher die Aufgabe zugrunde, ein Verfahren zur Gewinnung von Platin hoher Reinheit zur Verfügung zu stellen, bei dem mit geringen apparativen Mitteln innerhalb kurzer Zeit mit minimalen Verlusten und geringem Arbeitsaufwand aus verunreinigtem Platin die Edel- und Unedelmetalle abgetrennt werden.The invention was therefore based on the object of providing a process for the production of platinum of high purity, in which the precious and base metals are separated from contaminated platinum in a short time with minimal losses and with little labor using small apparatus.
Überraschenderweise wurde gefunden, daß man auf elektrolytischem Wege aus mit Unedel- und Edelmetallen verunreinigten Platinmetallösungen Platin hoher Reinheit gewinnen kann.Surprisingly, it was found that platinum metal solutions of high purity can be obtained electrolytically from platinum metal solutions contaminated with base and noble metals.
Gegenstand der Erfindung ist daher ein elektrolytisches Verfahren zur Gewinnung von Platin hoher Reinheit aus konzentrierten salzsauren Lösungen von verunreinigtem Platin. Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, daß der Reinigungsprozeß in einer Elektrolysezelle, die durch eine Kationenaustauschermembran unterteilt ist, unter potentiostatischen oder spannungskontrollierten Bedingungen von 2,5 V bis 8 V und einer Stromdichte von 0,3 bis 12,5 A/dm² erfolgt und die abgeschiedenen Platinlegierungsmetalle aufgearbeitet werden.The invention therefore relates to an electrolytic process for obtaining high purity platinum from concentrated hydrochloric acid solutions of contaminated platinum. The process according to the invention is characterized in that the cleaning process takes place in an electrolysis cell which is divided by a cation exchange membrane under potentiostatic or voltage-controlled conditions of 2.5 V to 8 V and a current density of 0.3 to 12.5 A / dm² and the deposited platinum alloy metals are worked up.
Erfindungsgemäß weisen die Platinmetallösungen einen Gehalt von 50 bis 700 g/l und Gesamtverunreinigungen von ≦ 5000 ppm auf.According to the invention, the platinum metal solutions have a content of 50 to 700 g / l and total impurities of ≦ 5000 ppm.
Bevorzugt werden bei dem erfindungsgemäßen Verfahren Platinmetallösungen mit einem Gehalt von 500 bis 700 g/l verunreinigtem Platin eingesetzt.Platinum metal solutions containing 500 to 700 g / l of contaminated platinum are preferably used in the process according to the invention.
Die für das erfindungsgemäße Verfahren eingesetzten konzentrierten Platinmetallösungen weisen Verunreinigungen der Elemente Rh und/oder Pd, Ir, Au, Ag, Cu, Fe, Co, Ni, Sb, As, Pb, Cd, Al, Mn, Mo, Si, Zn, Sn, Zr, W, Ti, Cr auf.The concentrated platinum metal solutions used for the process according to the invention have impurities in the elements Rh and / or Pd, Ir, Au, Ag, Cu, Fe, Co, Ni, Sb, As, Pb, Cd, Al, Mn, Mo, Si, Zn, Sn, Zr, W, Ti, Cr on.
Als Anodenflüssigkeit werden salzsaure Platinmetallösungen, bevorzugt Hexachlorplatinsäure, und als Katodenflüssigkeit 6 bis 8 N Salzsäure, bevorzugt 6 N Salzsäure, eingesetzt.Hydrochloric acid platinum metal solutions, preferably hexachloroplatinic acid, are used as the anode liquid and 6 to 8 N hydrochloric acid, preferably 6 N hydrochloric acid, are used as the cathode liquid.
Die Anode besteht aus Platinmetall, während die Katode aus Platinmetall, Titan oder Graphit beschaffen ist.The anode is made of platinum metal, while the cathode is made of platinum metal, titanium or graphite.
Als bevorzugte mit Sulfonsäuregruppen beladene Kationenaustauschermembran wird eine Teflonmembran (Nafion®-Membran) eingesetzt.A Teflon membrane (Nafion® membrane) is used as the preferred cation exchange membrane loaded with sulfonic acid groups.
Das erfindungsgemäße Verfahren arbeitet bevorzugt unter potentiostatischen oder spannungskontrollierten Bedingungen von 4,5 V bis 5 V und einer Stromdichte von 9 bis 10 A/dm².The method according to the invention preferably works under potentiostatic or voltage-controlled conditions of 4.5 V to 5 V and a current density of 9 to 10 A / dm².
Aus Platinmetallösungen mit einem Gehalt ≧ 300 g/l verunreinigtem Platin und Gesamtverunreinigungen von ≦ 5000 ppm können in einer Stufe Platinreinheiten von 99,95 % erreicht werden. Beim Wechsel der Anode und der Anodenflüssigkeit ist eine Raffination bis zu einer Platinreinheit von 99,99 % möglich.Platinum purity levels of 99.95% can be achieved in one step from platinum metal solutions with a content of ≧ 300 g / l of contaminated platinum and total impurities of ≦ 5000 ppm. When changing the anode and the Anode liquid can be refined up to a platinum purity of 99.99%.
Das erfindungsgemäße Verfahren kann somit je nach geforderter Reinheit des Platins mehrstufig durchgeführt werden.The method according to the invention can thus be carried out in several stages depending on the purity of the platinum required.
Beim Einsatz einer Hexachlorplatinsäure mit einem Gehalt von 300 g/l Platinmetall im Anodenraum und dem Einsatz einer 6 N Salzsäure im Katodenraum werden beim erfindungsgemäßen Verfahren zunächst Ir, Rh sowie Anteile der Unedelmetalle und des Goldes abgetrennt.When using a hexachloroplatinic acid with a content of 300 g / l platinum metal in the anode compartment and using 6 N hydrochloric acid in the cathode compartment, Ir, Rh and portions of the base metals and gold are first separated off in the process according to the invention.
Im Verlauf der erfindungsgemäßen Elektrolyse sinkt, bedingt durch die Chlorentwicklung und den Wassertransport in den Katodenraum, bei Aufrechterhaltung des Volumens der Anoden- und Katodenflüssigkeit durch den Entzug von verdünnter Salzsäure aus dem Katodenraum und Zusatz von Wasser in den Anodenraum, die Säurekonzentration.In the course of the electrolysis according to the invention, the acid concentration drops due to the development of chlorine and the transport of water into the cathode compartment, while maintaining the volume of the anode and cathode liquid by withdrawing dilute hydrochloric acid from the cathode compartment and adding water to the anode compartment.
Die komplex gebundenen Ionen dissoziieren, wandern durch die Kationenaustauschermembran und werden an der Katode abgeschieden. Der abgeschiedene Niederschlag enthält neben den abgetrennten Edel- und Unedelmetallverunreinigungen noch geringe Anteile an Pt. Dieser Niederschlag wird mechanisch von der Katode entfernt und gesondert aufgearbeitet.The complex bound ions dissociate, migrate through the cation exchange membrane and are deposited on the cathode. In addition to the separated noble and base metal impurities, the deposited precipitate also contains small amounts of Pt. This precipitate is mechanically removed from the cathode and processed separately.
Das sich beim erfindungsgemäßen Verfahren entwickelnde Chlorgas wird nach bekannten Methoden abgeführt.The chlorine gas developing in the process according to the invention is removed by known methods.
In einer Apparatur, die ein Fassungsvermögen von je 3 l Lösung im Anoden- und Katodenraum besitzt, kann nach dem erfindungsgemäßen Verfahren innerhalb von 48 h 1 kg Platin raffiniert werden.In an apparatus that has a capacity of 3 l solution in the anode and cathode compartment, according to the The inventive method can be refined 1 kg of platinum within 48 h.
Dabei findet innerhalb von 20 h z. B. folgende Abreicherung von Verunreinigungen statt:
Aus den durch das erfindungsgemäße Verfahren gereinigten Lösungen der Platinmetalle kann nach bekannten Methoden das metallische Platin elektrolytisch oder chemisch zurückgewonnen werden.It takes place within 20 h. B. The following depletion of contaminants instead:
The metallic platinum can be recovered electrolytically or chemically from the solutions of the platinum metals cleaned by the method according to the invention.
Mit dem erfindungsgemäßen Verfahren sind folgende Vorteile verbunden:
- es erfodert einen minimalen apparativen und sicherheitstechnischen Aufwand
- es arbeitet mit minimaler ökologischer Belastung
- es ist gegenüber den herkömmlichen Verfahren wesentlich zeit- und kostensparender.
- it requires minimal outlay in terms of equipment and safety
- it works with minimal ecological impact
- it is much more time and cost saving compared to conventional processes.
Die Erfindung wird nachstehend an einigen Beispielen näher erläutert.The invention is explained in more detail below using a few examples.
Eine salzsaure Platinlösung mit folgenden Verunreinigungen (Konzentrationsangaben bezogen auf Platin)
und einem Platingehalt von 250 g/l (pH-Wert ≦ 1) wird in einer Elektrolysezelle, deren Katoden- und Anodenraum durch eine Kationenaustauschermembran unterteilt sind, bei einer Spannung von 4,5 V und einer Stromdichte von 9 A/dm² elektrolysiert.A hydrochloric acid platinum solution with the following impurities (concentration information based on platinum)
and a platinum content of 250 g / l (pH ≦ 1) is electrolyzed in an electrolysis cell, the cathode and anode space are divided by a cation exchange membrane, at a voltage of 4.5 V and a current density of 9 A / dm².
Nach 15 Stunden wird eine Abreicherung der Unedelmetalle auf Werte ≦ 20 ppm erreicht, der Iridium-, Rhodium- und Goldgehalt verringert sich um 50 %, der Palladiumgehalt um 20 %.After 15 hours, the base metals are depleted to ≦ 20 ppm, the iridium, rhodium and gold content is reduced by 50%, the palladium content by 20%.
Nach einer Elektrolysezeit von weiteren 15 Stunden wird eine Abreicherung der Edelmetallverunreinigungen auf folgende Werte erreicht
Die vorraffinierte Lösung vom Beispiel 1 wird auf einen Platingehalt von 120 g/l (PH-Wert 0,1) verdünnt in eine andere Elektrolysezelle, die ebenfalls mit einer Kationenaustauschermembran versehen ist, überführt und bei einer Spannung von 5 V und 10 A/dm² elektrolysiert. Die Analyse, nach einer Elektrolysezeit von 10 Stunden, ergab, daß die Unedelmetallverunreinigungen und Gold auf Werte ≦ 10 ppm, die Platinmetalle
abgereichert wurden.The pre-refined solution from Example 1 is diluted to a platinum content of 120 g / l (pH value 0.1) and transferred to another electrolysis cell, which is also provided with a cation exchange membrane, and at a voltage of 5 V and 10 A / dm² electrolyzed. The analysis, after an electrolysis time of 10 hours, showed that the base metal impurities and gold to values ≦ 10 ppm, the platinum metals
were depleted.
Die Platinlösung, die nach dem Beispiel 1 raffiniert wurde, wird in der Elektrolysezelle belassen, die Katodenflüssigkeit durch frischangesetzte 6 N Salzsäure ersetzt. Die Anodenflüssigkeit wird auf einen Platingehalt von 120 g/l verdünntThe platinum solution, which was refined according to Example 1, is left in the electrolysis cell, the cathode liquid is replaced by freshly prepared 6 N hydrochloric acid. The anode liquid is diluted to a platinum content of 120 g / l
Nach einer Elektrolysezeit von 12 Stunden wird der im Beispiel 2 beschriebene Reinheitsgrad erreicht.After an electrolysis time of 12 hours, the degree of purity described in Example 2 is reached.
Claims (15)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4243699 | 1992-12-18 | ||
| DE4243699A DE4243699C1 (en) | 1992-12-18 | 1992-12-18 | Refining impure platinum@ in electrolytic cell - using PTFE membrane as a cation exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0609507A1 true EP0609507A1 (en) | 1994-08-10 |
| EP0609507B1 EP0609507B1 (en) | 1996-03-27 |
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ID=6476277
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93118981A Expired - Lifetime EP0609507B1 (en) | 1992-12-18 | 1993-11-25 | Electrolytic process for obtaining high purity platinum from impure platinum |
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| Country | Link |
|---|---|
| US (1) | US5393389A (en) |
| EP (1) | EP0609507B1 (en) |
| JP (1) | JP3286823B2 (en) |
| AT (1) | ATE136066T1 (en) |
| CA (1) | CA2111793C (en) |
| DE (2) | DE4243699C1 (en) |
| FI (1) | FI100607B (en) |
| RU (1) | RU2093607C1 (en) |
| ZA (1) | ZA938994B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19829274C2 (en) * | 1998-07-01 | 2002-06-20 | Otb Oberflaechentechnik Berlin | Process for the recovery of precious metals |
| JP4607303B2 (en) * | 2000-09-13 | 2011-01-05 | 株式会社フルヤ金属 | Method for recovering platinum group metals from metal electrodes |
| US7255798B2 (en) * | 2004-03-26 | 2007-08-14 | Ion Power, Inc. | Recycling of used perfluorosulfonic acid membranes |
| DE102006056017B4 (en) * | 2006-11-23 | 2016-02-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the recovery of precious metals |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0238536A (en) * | 1988-07-29 | 1990-02-07 | Tanaka Kikinzoku Kogyo Kk | Separation of noble metal in acidic iridium solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB157785A (en) * | 1919-12-19 | 1922-04-10 | Eulampiu Slatineanu | Electrolytic process and apparatus for the separation of platinum from other metals contained in platiniferous materials |
| DE594408C (en) * | 1928-10-13 | 1934-03-16 | Degussa | Process for refining platinum |
| US3891741A (en) * | 1972-11-24 | 1975-06-24 | Ppg Industries Inc | Recovery of fission products from acidic waste solutions thereof |
| US4382845A (en) * | 1981-08-10 | 1983-05-10 | Chevron Research Company | Selective electrowinning of palladium |
| EG19633A (en) * | 1983-12-22 | 1995-08-30 | Dynamit Nobel Ag | Process for chronologically staggered release of electronic explosive detonating device |
| DE3672956D1 (en) * | 1985-04-25 | 1990-08-30 | Chlorine Eng Corp Ltd | METHOD FOR DISSOLVING AND RECOVERING PRECIOUS METALS. |
| CA1322855C (en) * | 1986-07-16 | 1993-10-12 | Mamoru Hirako | Process for refining gold and apparatus employed therefor |
-
1992
- 1992-12-18 DE DE4243699A patent/DE4243699C1/en not_active Expired - Fee Related
-
1993
- 1993-11-25 EP EP93118981A patent/EP0609507B1/en not_active Expired - Lifetime
- 1993-11-25 AT AT93118981T patent/ATE136066T1/en not_active IP Right Cessation
- 1993-11-25 DE DE59302052T patent/DE59302052D1/en not_active Expired - Fee Related
- 1993-12-01 ZA ZA938994A patent/ZA938994B/en unknown
- 1993-12-16 FI FI935661A patent/FI100607B/en not_active IP Right Cessation
- 1993-12-17 JP JP34329093A patent/JP3286823B2/en not_active Expired - Fee Related
- 1993-12-17 CA CA002111793A patent/CA2111793C/en not_active Expired - Fee Related
- 1993-12-17 RU RU9393056629A patent/RU2093607C1/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0238536A (en) * | 1988-07-29 | 1990-02-07 | Tanaka Kikinzoku Kogyo Kk | Separation of noble metal in acidic iridium solution |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 14, no. 197 (C - 0712) 23 April 1990 (1990-04-23) * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3286823B2 (en) | 2002-05-27 |
| FI100607B (en) | 1998-01-15 |
| US5393389A (en) | 1995-02-28 |
| CA2111793A1 (en) | 1994-06-19 |
| RU2093607C1 (en) | 1997-10-20 |
| ZA938994B (en) | 1994-08-03 |
| JPH06280074A (en) | 1994-10-04 |
| DE4243699C1 (en) | 1994-02-10 |
| ATE136066T1 (en) | 1996-04-15 |
| DE59302052D1 (en) | 1996-05-02 |
| FI935661A (en) | 1994-06-19 |
| FI935661A0 (en) | 1993-12-16 |
| EP0609507B1 (en) | 1996-03-27 |
| CA2111793C (en) | 2003-05-13 |
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