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EP1051541B1 - Procede de regeneration electrolytique de solutions de rhodium contaminees - Google Patents

Procede de regeneration electrolytique de solutions de rhodium contaminees Download PDF

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Publication number
EP1051541B1
EP1051541B1 EP99910109A EP99910109A EP1051541B1 EP 1051541 B1 EP1051541 B1 EP 1051541B1 EP 99910109 A EP99910109 A EP 99910109A EP 99910109 A EP99910109 A EP 99910109A EP 1051541 B1 EP1051541 B1 EP 1051541B1
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EP
European Patent Office
Prior art keywords
rhodium
solution
electrolysis
acid
solutions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99910109A
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German (de)
English (en)
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EP1051541A2 (fr
Inventor
Sigrid Herrmann
Uwe Landau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
OTB Oberflaechentechnik in Berlin GmbH and Co
Original Assignee
OTB Oberflaechentechnik in Berlin GmbH and Co
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Filing date
Publication date
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Publication of EP1051541A2 publication Critical patent/EP1051541A2/fr
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Publication of EP1051541B1 publication Critical patent/EP1051541B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes

Definitions

  • the present invention relates to a method for electrolytic regeneration of contaminated rhodium solutions, especially for the regeneration of sulfur and / or phosphoric acid rhodium solutions or of rhodium chloride solutions suitable is.
  • Rhodium solutions or rhodium baths of the type mentioned are used, for example, in the jewelry and silverware industry for the electroplating of jewelry.
  • the solutions usually contain 1-3 g / l rhodium, 40-80 ml / l concentrated phosphoric acid and / or 25-80 ml / l sulfuric acid. Their temperature is between 40 ° C and 50 ° C.
  • the work is carried out with platinum anodes or platinized anodes, the current densities being 0.5-10 A / dm 2 .
  • rhodium sulfate solutions which contain 4 - 20 g / l rhodium and 25 - 50 ml / l concentrated sulfuric acid and have a temperature between 30 ° C and 50 ° C.
  • Platinum or platinized titanium is used as the anode material, the current densities being 0.5-3 A / dm 2 .
  • Organic contaminants are caused by dust, Buildup of masking tapes, masking lacquer, Circuit board material and organics from unsuitable Plastic tubs or plastic tanks entered.
  • organic Contamination cause voltages in the galvanic deposited precipitation. The layer becomes fragile and looks cloudy.
  • Organic compounds can be obtained through a Activated carbon treatment can be separated. The solutions are allowed don't be too acidic. For the separation of short-chain Another treatment with a hydrocarbon suitable activated carbon may be necessary.
  • the activated carbon In addition to the organic components, the activated carbon also takes Precious metal components that can only be obtained by ashing the Have activated carbon recovered as precious metal.
  • Rhodium baths that such complexes also tend to separate of layers with increasing proportion of anionic Rhodium complexes show an increased voltage rise.
  • Anionic rhodium complexes can be oxidized with chlorine in an alkaline medium and subsequent reduction with Hydroquinone can be converted into the trivalent cation.
  • To this treatment is the rhodium bath by the entry of Foreign ions can no longer be used.
  • Inorganic Contamination is usually caused by the base metal brought in.
  • the warm phosphoric acid or phosphoric acid and sulfuric acid or sulfuric acid solution is extremely aggressive. Parts that are hung into the bathroom without electricity are picked up by the Electrolyte immediately. This also applies to parts that accidentally fall into the bathroom.
  • the Major impurities found in rhodium baths were Cu, Fe, Sn, Pb, Ni, Au, Ag.
  • rhodium In order to obtain pure rhodium, one can do the sulfide precipitation coupled with nitrite precipitation (Brauer, Handbuch der preparative inorganic chemistry, 3rd volume, Gustav Enke Verlag, Stuttgart, 3rd ed., 1981, p. 1737; DE-OS-2835 159; GB-PS-1491521).
  • the impurities are precipitated as sulfide. This precipitation is only possible if Rhodium is bound in the anionic complex because Rhodium cations can also be precipitated as sulfide.
  • the Refining rhodium as rhodium nitrite sets a multiple Precipitation of the rhodium nitrite in advance. Then the Rhodium nitrite can be converted into the rhodium sulfate. This Process works with low yields, high ones Precious metal losses and an unacceptable Workload.
  • the object of the present invention is therefore in Creation of an economical process for regeneration contaminated rhodium solutions with which a costly metallurgical refurbishment, a new one Rhodium salt production and a new approach to the solutions can be avoided so that the cleaned solutions immediately returned to the industrial use mentioned above can be.
  • the rhodium solution to be regenerated is fed into the anode compartment of an electrolytic cell, which is separated from the associated cathode compartment filled with a dilute, highly conductive acid by a cation exchange membrane.
  • H 2 SO 4 , H 3 PO 4 , HCl or HNO 3 is preferably used as the acid, with 10-20% H 2 SO 4 being currently preferred.
  • the pH of the rhodium solution is increased to a value of more than 10 by adding a suitable alkali solution, a pH between 12 and 14 preferably being set. Concentrated potassium hydroxide solution can in particular be used as the alkali solution.
  • the electrolysis now takes place, the current density being chosen so high that trivalent rhodium is oxidized to hexavalent rhodium in the rhodium solution.
  • the current densities are preferably 1-20 A / dm 2 , which corresponds to a maximum current load of the membrane of 4 kA / m 2 (40 A / dm 2 ). A further increase in the current strength could lead to the destruction of the membrane.
  • the temperature of the anolyte here is preferably 20 - 50 ° C, so that industrially used rhodium solutions or Rhodium baths of the type mentioned above directly one Regeneration or cleaning supplied and then also are industrially usable again without this additional heat treatment of the solution would be required.
  • the preferred acidity is Rhodium solution with 40 - 80 ml / l concentrated phosphoric acid and / or 25 - 80 ml / l sulfuric acid to the above adapted industrial use of the rhodium solution.
  • Rhodium solutions with a higher acidity become Reduction in acidity and / or depletion any anionic components present are preferred first in an upstream electrolysis cell Subjected to electrolysis.
  • Appropriate solutions are here passed into the cathode compartment of the electrolytic cell, which is in front of the with an aqueous sodium sulfate solution or the like associated anode space filled by a Anion exchange membrane is separated so that the Acid residues and anionic impurities in the Anode compartment to be transferred.
  • the rhodium solution to be regenerated is used according to the invention in the anode compartment (12) of an electrolysis cell (10) passed through the associated cathode compartment (14) a cation exchange membrane (16) is separated.
  • anode compartment (12) of the electrolytic cell (10) is also concentrated from a storage container (18) Potassium hydroxide solution fed to adjust the pH of the Increase rhodium solution to 12-14.
  • This process will monitored by means of a measuring device (20) through which the Infeed is controlled accordingly. If necessary, you can however, other suitable alkali solutions can also be used.
  • the feed can also be located at a point outside of the Electrolysis cell (10) take place.
  • the cathode compartment (14) of the electrolytic cell (10) is filled with 20% H 2 SO 4 , which is circulated through a storage container (22).
  • a different concentration such as 10% H 2 SO 4 , or another suitable acid can also be used, H 3 PO 4 , HCl or HNO 3 being particularly worth mentioning.
  • the pH of the catholyte is adjusted to pH ⁇ 0.5 in order to enable the transferred noble metals to be separated.
  • the base metals are then removed with the catholyte when enriched to approx. 10 g / l.
  • the anolyte in the Cycle and continuously at the Pumped by cation exchange membrane its Flow rate is 1 - 4 l / min.
  • the temperature of the anolyte is 20 - 50 ° C, so that the in industrial sulfuric and / or phosphoric acids Rhodium solutions are directly regenerable.
  • the catholyte is transported through the resulting H 2 .
  • the current load on the membrane is 4 kA / m 2 (40 A / dm 2 ). A further increase in the current strength can destroy the membrane.
  • the acidity of the rhodium solution is 40-80 ml / l concentrated phosphoric acid and / or 25-80 ml / l sulfuric acid.
  • the rhodium solution to be cleaned is passed to reduce the acid content and / or to deplete any anionic components present in the cathode compartment of an additional electrolysis cell (not shown) in the anolyte circuit, which passes from the associated anode compartment filled with an aqueous potassium sulfate solution through an anion exchange membrane is separated.
  • the acid residue anions SO 4 - and / or PO 4 - are transferred into the anode compartment, the voltage being chosen to be lower than the voltage required for Rh deposition.
  • Example 1 50 ml of a rhodium sulfate solution according to Example 1 were without Add potassium hydroxide under the same conditions as electrolyzed in Example 1. After 6 hours the contained Anolyte solution only 1.5 g / l rhodium, so that about 50% of Rhodium had been transferred to the cathode compartment.
  • the current load on the membrane was 4 kA / m 2 (40 A / dm 2 ), with a further increase in the current strength leading to destruction.
  • a rhodium sulfate solution containing 3.4 g / l rhodium was adjusted to a pH of 12.5 with potassium hydroxide solution.
  • the rhodium solution was diluted to 3.0 g / l by the addition of the potassium hydroxide solution.
  • the solution was then subjected to membrane electrolysis, working with a current density of 1 A / dm 2 and a current load on the membrane of 4 kA / m 2 .
  • the rhodium concentration was limited after the electrolysis by the one done with the potassium ion transfer Water transfer 3.6 g / l. With a further decrease in pH Rhodium depletion occurs. After a Electrolysis time of 2 hours was the rhodium concentration in of the analytical solution dropped to 2.4 g / l.
  • a rhodium sulfate solution containing 5.3 g / l rhodium and 400 ppm impurities in iron and nickel was adjusted to a pH of 13 with potassium hydroxide.
  • a current density of 2 A / dm 2 With a current density of 2 A / dm 2 , a current load on the membrane of 4 kA / m 2 and a flow rate of the electrolyte of 3 l / min, the Fe / Ni impurities could be reduced to a value of 50 ppm within 5 hours.
  • the rhodium depletion was 0.3 g / l.
  • a rhodium solution containing 100 ml / l of sulfuric acid was placed in the cathode compartment of an electrolytic cell provided with an anion exchange membrane.
  • An aqueous sodium sulfate solution was used as the anolyte.
  • the acid content in the catholyte could be reduced to 80 ml / l.
  • This solution was then placed in the anode compartment of an electrolysis cell, the anode and cathode compartments of which were separated by a cation exchange membrane, and electrolyzed at 4 A / dm 2 .
  • the rhodium solution to be regenerated was directed past the cation exchange membrane at a rate of 3 l / min.
  • the movement of the catholyte which comprised 5% sulfuric acid, was caused by the evolution of hydrogen during the electrolysis.
  • potassium ions and most of the contaminants were transferred from the anode compartment to the cathode compartment during the electrolysis, so that the content of impurities in the rhodium solution was only 20 ppm after 6 hours.
  • the contaminants transferred into the cathode compartment separated out on the cathode.
  • the electrolysis process according to the invention is suitable not only for the regeneration of rhodium solutions containing sulfuric and / or phosphoric acid, but also for the regeneration of rhodium solutions containing chloride.
  • Potassium hydroxide solution was added to a rhodium chloride solution with a rhodium content of 10 g / l and with copper, nickel and iron impurities of 100 ppm in each case in order to raise the pH to 13.5.
  • This solution was placed in the anode compartment of an electrolytic cell, the anode compartment and cathode compartment of which were separated by a cathode exchange membrane and electrolyzed at a current density of 3.5 A / dm 2 .
  • the anolyte was moved past the membrane at a rate of 3 l / min, while the catholyte, which comprised 20% hydrochloric acid, was moved through the hydrogen produced during the electrolysis.
  • Cl - was converted into Cl 2 , with the chlorine released acting as an oxidizing agent.
  • potassium ions and most of the contaminants were transferred from the anode compartment to the cathode compartment, so that the contaminants were depleted to a value of 20 20 ppm after 5 hours.
  • Hydrochloric acid was carefully added to the anolyte during depletion.

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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 Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Removal Of Specific Substances (AREA)

Claims (13)

  1. Procédé pour la régénération électrolytique de solutions contaminées contenant du rhodium, caractérisé en ce que la solution contenant du rhodium à régénérer est envoyée dans le compartiment anodique (12) d'une cellule électrolytique (10), qui est séparé par une membrane échangeuse de cations (16) du compartiment cathodique (14) correspondant, rempli d'un acide dilué bon conducteur, le pH de la solution contenant du rhodium étant élevé à une valeur de plus de 10 par addition d'une solution alcaline et l'électrolyse étant effectuée à des densités de courant telles que le rhodium trivalent dans la solution contenant du rhodium est oxydé en rhodium hexavalent et les impuretés éventuellement présentes sont déconcentrées dans le catholyte par la membrane échangeuse de cations.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on ajuste un pH entre 12 et 14.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le pH de l'anolyte dans l'électrolyse est toujours = 1,5 et est éventuellement ajusté en conséquence par addition d'une solution alcaline.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on utilise comme solution alcaline une solution concentrée d'hydroxyde de potassium.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la densité de courant dans l'électrolyse est de 1-20 A/dm2.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la température de l'anolyte est de 20-50°C.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'on fait passer en continu l'anolyte et/ou le catholyte en circuit sur la membrane échangeuse de cations (16).
  8. Procédé selon la revendication 7, caractérisé en ce que la vitesse d'écoulement de l'anolyte est de 1-4 l/min.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la teneur en acide de la solution contenant du rhodium est de 40-80 ml/l d'acide phosphorique concentré et/ou de 25-80 ml/1 d'acide sulfurique.
  10. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'on envoie des solutions contenant du rhodium, ayant une teneur en acide de plus de 80 ml/l, pour abaisser la teneur en acide et/ou pour réduire la teneur en fractions anioniques éventuellement présentes, dans le compartiment cathodique d'une cellule électrolytique supplémentaire, qui est séparé par une membrane échangeuse d'anions du compartiment anodique correspondant, rempli d'une solution aqueuse de sulfate de sodium.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'acide dilué bon conducteur comprend H2SO4, H3PO4, HCl ou HNO3.
  12. Procédé selon la revendication 11, caractérisé en ce que l'acide dilué bon conducteur comprend H2SO4 à 10-20 %.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'on ajuste le pH de l'acide dilué bon conducteur à pH = 0,5, pour permettre une séparation des métaux nobles transportés.
EP99910109A 1998-02-05 1999-02-05 Procede de regeneration electrolytique de solutions de rhodium contaminees Expired - Lifetime EP1051541B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19804534A DE19804534C1 (de) 1998-02-05 1998-02-05 Verfahren zur elektrolytischen Regeneration verunreinigter Rhodiumlösungen
DE19804534 1998-02-05
PCT/DE1999/000316 WO1999040238A2 (fr) 1998-02-05 1999-02-05 Procede de regeneration electrolytique de solutions de rhodium contaminees

Publications (2)

Publication Number Publication Date
EP1051541A2 EP1051541A2 (fr) 2000-11-15
EP1051541B1 true EP1051541B1 (fr) 2001-11-28

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EP99910109A Expired - Lifetime EP1051541B1 (fr) 1998-02-05 1999-02-05 Procede de regeneration electrolytique de solutions de rhodium contaminees

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EP (1) EP1051541B1 (fr)
AT (1) ATE209709T1 (fr)
AU (1) AU2920599A (fr)
DE (2) DE19804534C1 (fr)
WO (1) WO1999040238A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI818791B (zh) * 2022-11-02 2023-10-11 環球晶圓股份有限公司 化學鍍鎳液之處理系統及處理方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB662299A (en) * 1949-07-08 1951-12-05 Mond Nickel Co Ltd A process for the purification of rhodium
US3375179A (en) * 1964-10-29 1968-03-26 Litton Systems Inc Method of anodizing beryllium and product thereof
GB1144716A (en) * 1966-03-29 1969-03-05 Ustav Nerostnych Surovin Method of producing rhodium concentrates
GB1491521A (en) * 1975-01-07 1977-11-09 Swarsab Mining Separation and purification of rhodium
ZA775358B (en) * 1977-09-06 1979-04-25 Nat Inst Metallurg The recovery and purification of rhodium
FR2616810B1 (fr) * 1987-03-25 1989-08-18 Rhone Poulenc Sante Procede electrochimique pour recuperer le rhodium metallique a partir de solutions aqueuses de catalyseurs usages

Also Published As

Publication number Publication date
DE59900461D1 (de) 2002-01-10
ATE209709T1 (de) 2001-12-15
WO1999040238A2 (fr) 1999-08-12
AU2920599A (en) 1999-08-23
DE19804534C1 (de) 1999-06-24
WO1999040238A3 (fr) 1999-09-30
EP1051541A2 (fr) 2000-11-15
HK1034544A1 (en) 2001-10-26

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