EP3749792B1 - Alliages de métaux précieux et d'étain et leur traitement hydrométallurgique - Google Patents

Alliages de métaux précieux et d'étain et leur traitement hydrométallurgique Download PDF

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Publication number
EP3749792B1
EP3749792B1 EP18753327.8A EP18753327A EP3749792B1 EP 3749792 B1 EP3749792 B1 EP 3749792B1 EP 18753327 A EP18753327 A EP 18753327A EP 3749792 B1 EP3749792 B1 EP 3749792B1
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Prior art keywords
noble metal
metal
tin
weight
tin alloy
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German (de)
English (en)
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EP3749792A1 (fr
Inventor
Christoph Röhlich
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Heraeus Deutschland GmbH and Co KG
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Heraeus Deutschland GmbH and Co KG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent
    • 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
    • C22B11/042—Recovery of noble metals from waste materials
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/0438—Nitric acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C22C11/04—Alloys based on lead with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
    • C22C3/005—Separation of the constituents of alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

Definitions

  • the invention relates to a method for hydrometallurgical processing of certain alloys consisting of (i) gold and / or platinum, (ii) palladium, silver and / or copper, (iii) tin and optionally (iv) one or more other elements with a certain gold and / or platinum: tin weight ratio.
  • Gold, platinum, palladium and silver are precious metals; copper and tin are non-precious metals.
  • Gold and / or platinum on the one hand and alloys containing palladium, silver and / or copper on the other hand, for example gold-silver alloys such as Dore metal, are usually processed hydrometallurgically by first treating them with nitric acid in a first step, The metals palladium, silver and copper, which are less noble than gold and platinum, go into solution as nitrate. Gold or platinum in the remaining residue can be brought into solution in a subsequent step with a medium comprising hydrochloric acid and a suitable oxidizing agent as tetrachlorogoldic or hexachloroplatinic acid. If said alloys also contain tin, this separation process can often not be carried out without further ado.
  • the problems described can surprisingly be avoided as soon as the aforementioned noble metal-tin alloys in particular have a certain gold and / or platinum: tin weight ratio. It is assumed that in the course of the aforementioned separation process not tin dioxide is formed, but an alloy comprising tin, gold and / or platinum, which cannot be attacked by nitric acid alone, which in the subsequent step is formed with the medium comprising hydrochloric acid and a suitable oxidizing agent of hexachlorotin acid and tetrachloroauric acid and / or hexachloroplatinic acid can be brought into solution.
  • the noble metal-tin alloy is specifically selected in process step (a1) or specifically produced in process step (a2) such that it is preferably made up of constituents (i) 0.45 to 25% by weight 3 to 20% by weight of at least one metal A selected from the group consisting of gold and platinum, (ii) 35 to 99.2% by weight, preferably 40 to 95% by weight, of at least one metal B selected from the group consisting of palladium, silver and copper, (iii) 0.3 to 30% by weight, preferably 2 to 17.5% by weight tin and (iv) 0 to 50% by weight of at least one of gold, platinum, Palladium, silver, copper and tin of various elements is composed of 100% by weight and at the same time has a metal A: tin weight ratio of 0.7: 1, preferably in the range from 1: 1 to 10: 1. It is clear to the person skilled in the art that the metal A: tin weight ratio in view of the weight / quantity ratios of the constituents (i) to (iv)
  • the noble metal-tin alloy preferably consists of (i) 3 to 20% by weight of at least one metal A selected from the group consisting of gold and platinum, (ii) 40 to 95% by weight of at least one metal B selected from Group consisting of palladium, silver and copper, (iii) 2 to 17.5% by weight of tin and (iv) 0 to 50% by weight of at least one of gold, platinum, Palladium, silver, copper and tin of various elements with a metal A: tin weight ratio in the range from 1: 1 to 10: 1.
  • noble metal-tin alloy or alloys composed as mentioned above are noble metal-tin alloys composed essential to the invention, also referred to herein as “noble metal-tin alloy of the type essential to the invention” or “the noble metal-tin alloy” .
  • the composition of the noble metal-tin alloy, which is essential to the invention, evidently forms an essential prerequisite for a successful and uncomplicated implementation of the method according to the invention while avoiding the aforementioned problems with solid-liquid separation.
  • the noble metal-tin alloy is specifically selected, in particular from noble metal-tin alloys.
  • the targeted selection takes place in such a way that the aforementioned conditions essential to the invention with regard to composition and, associated therewith, also the metal A: tin weight ratio are met.
  • the noble metal-tin alloy of the type that is essential to the invention can therefore already be present in its finished form and processed hydrometallurgically in process steps (b) to (d).
  • the noble metal-tin alloy is first specifically produced in such a way that the above-mentioned conditions essential to the invention with regard to composition and, consequently, also the metal A: tin weight ratio are met.
  • the noble metal-tin alloy can be produced by alloying the metals or elements that make it up. From the overall context of the present patent application, however, it becomes clear to the person skilled in the art that the noble metal-tin alloy is generally preferably not produced directly by alloying the metals or elements that make it up.
  • the noble metal-tin alloy can be specifically produced in process step (a2) according to one of the following procedures (a2-1) to (a2-5) known per se to the person skilled in the art.
  • the person skilled in the art knows how to skillfully select and combine the starting materials according to type and quantity in each case in order to arrive at a noble metal-tin alloy of the type essential to the invention.
  • the procedure (a2-1) comprises or consists in melting down at least one valuable material to be recycled with the formation of a multiphase system comprising a lower one Phase made of molten noble metal-tin alloy of the type essential to the invention and an upper phase made of molten slag with lower density, optionally with the addition of collector metal and / or slag former and / or reducing agent, and separating the upper phase from the lower phase using the difference in density , followed by cooling and solidifying the separated melts, and collecting the solidified precious metal-tin alloy.
  • the valuable material to be recycled can be a single valuable material or a mixture of different valuable materials.
  • the at least one valuable material to be recycled can also comprise at least one different substance in addition to noble metal and base metal, the latter in particular selected from inorganic refractory materials, ie inorganic non-metallic at high temperatures, for example in the range of 200 to 650 ° C, physically and chemically not or practically not changing materials.
  • inorganic refractory materials include silica, alumina, calcium oxide, iron oxide, calcium sulfate, calcium phosphate and tin dioxide.
  • the at least one substance different from noble metal and non-noble metal can, for example, be or have been a component, possibly the sole component of ceramic filter materials, blasting media, abrasives and / or inorganic carrier materials, for example catalyst carrier materials.
  • the at least one valuable material to be recycled can come from one or more different sources. It can be mine concentrate and / or one or more wastes or waste mixtures. Examples of waste types include waste from jewelry production, waste from the dental sector, electronic scrap, precious metal scrap, precious metal-containing waste from precious metal processing companies, precious metal waste, used precious metal catalysts, precious metal catalyst dusts, precious metal-containing slag, precious metal dross, precious metal-containing and optionally dried sludge, for example from electrical refining and spoil from precious metal mines.
  • the procedure (a2-2) comprises or consists in treating a molten alloy different from the noble metal-tin alloy of the type that is essential to the invention with an oxidizing agent such as, in particular, oxygen, with the formation of a multiphase system comprising a lower phase of molten noble metal-tin alloy of the type essential to the invention and an upper phase of molten slag with lower density, in which oxidation products are found, optionally with the addition of collector metal and / or slag-forming, and separating the upper phase from the lower phase using the difference in density, followed by cooling and solidifying of the separated melts, and collecting the solidified precious metal-tin alloy.
  • an oxidizing agent such as, in particular, oxygen
  • Procedure (a2-3) comprises or consists in alloying at least two different alloys, optionally with the addition of at least one element, for example metal, to form a noble metal-tin alloy of the type that is essential to the invention.
  • the at least two different alloys can be at least two different noble metal-tin alloys of the type essential to the invention or at least two noble metal-tin alloys different from each other and of the type essential to the invention or at least one noble metal-tin alloy from The type essential to the invention and at least one noble metal-tin alloy different from the type essential to the invention.
  • at least one of the at least two different alloys is not a noble metal-tin alloy. Frequently, none of the at least two different alloys is a noble metal-tin alloy.
  • the procedure (a2-4) comprises or consists in alloying at least one element, for example a metal, to form an alloy with the formation of a noble metal-tin alloy of the type that is essential to the invention.
  • the alloy undergoing alloying can itself be a noble metal-tin alloy of the type that is essential to the invention; in general, however, it is not a noble metal-tin alloy of the composite type that is essential to the invention.
  • the procedure (a2-5) comprises or consists in distilling off tin, for example excess tin, from an alloy, optionally with the assistance of a vacuum or under reduced pressure with the formation of a noble metal-tin alloy of the essential elements of the invention Type.
  • the alloy experiencing the distillation of tin can itself be a noble metal-tin alloy of the type that is essential to the invention; in general, however, it is not a noble metal-tin alloy of the composite type that is essential to the invention.
  • step (b) of the method according to the invention nitric acid-soluble or the nitric acid-soluble components of the noble metal-tin alloy specifically selected in step (a1) or specifically produced in step (a2) are mixed with nitric acid to form a nitric acid solution comprising the at least a metal B dissolved as dissolved nitrate and an undissolved residue.
  • the nitric acid used in step (b) has an oxidizing effect and has a concentration, for example, in the range from 10 to 67% by weight.
  • Step (b) can be carried out at temperatures, for example, in the range from 20 ° C. to the boiling point.
  • the aforementioned formation of voluminous, finely particulate and possibly gel-like tin dioxide does not occur.
  • the undissolved residue comprising gold or platinum does not require any additional chemical treatment or separation step before process step (d) is carried out. Obviously, the undissolved residue is not associated with troublesome tin dioxide or at least essentially does not contain any such or is free of it.
  • step (c) of the process according to the invention the undissolved residue formed in step (b) is separated off from the nitric acid solution.
  • Customary solid-liquid separation processes known to the person skilled in the art can be used, for example decanting, siphoning, filtering or suitable combinations of such separation processes.
  • step (c) does not require any additional chemical treatment or separation step before carrying out process step (d).
  • step (d) of the process according to the invention the undissolved residue separated from the nitric acid solution in step (c) is dissolved in a medium comprising hydrochloric acid and at least one oxidizing agent.
  • a solution comprising hexachloroauric acid and tetrachloroauric acid or hexachloroplatinic acid and hexachloroplatinic acid or hexachlorotin acid and tetrachloroauric acid and hexachloroplatinic acid can be formed.
  • the hydrochloric acid used in step (d) has a concentration, for example in the range from 3 to 12 mol / L.
  • the at least one oxidizing agent can in particular be selected from the group consisting of nitric acid, chlorates, nitrates, bromates, iodates, chlorites, bromites, iodites, hypochlorites, hypobromites, hypoiodites, perchlorates, ozone, ozonides, superoxides, oxygen, chlorine, bromine, iodine , Peroxo compounds, permanganates and chromates.
  • Step (d) can be carried out at temperatures, for example, in the range from 20 ° C. to the boiling point.
  • Alloys with the composition given in the table below were mixed with 4 ml of 53% strength by weight nitric acid per gram of alloy and carefully heated from room temperature to 100 ° C. with stirring. The alloys partially dissolved with the formation of a black to shiny metallic residue and NOx gas. The absence of NOx development signaled the end of the dissolution reaction (duration between 2 and 7 hours). After cooling, the respective mixture obtained could be filtered within a period of 10 to 60 minutes and the residue washed out several times with water.
  • the washed-out residue was either treated with aqua regia (mixture of 75 ml of 10M hydrochloric acid and 25 ml of 53% strength by weight nitric acid) or made up to a total volume of 100 ml with 6M hydrochloric acid.
  • the mixture was heated to 80 ° C. with stirring and, if this had not yet happened, 53% strength by weight nitric acid was added until no further change in the reaction mixture and no further NOx formation could be seen was (10 to 20 ml of the 53 wt .-% nitric acid).
  • the residue dissolved to form a yellow to orange colored clear solution.
  • Alloys with the composition given in the table below were mixed with 4 ml of 53% strength by weight nitric acid per gram of alloy and carefully heated from room temperature to 100 ° C. with stirring. The alloys partially dissolved with formation a purple voluminous residue and NOx gas. The absence of NOx development signaled the end of the dissolution reaction (duration between 2 and 7 hours). After cooling, the respective mixture obtained could be filtered within a period of 10 to 60 minutes and the residue washed out several times with water.
  • the purple color of the residue indicated the formation of Au particles in a tin dioxide matrix ("Cassius' gold purple”).
  • a phase analysis on a sample of the residue by means of X-ray diffractometry showed tin dioxide as the main phase.
  • the washed-out residue was made up to 200 ml with 6M hydrochloric acid, heated to 80 ° C. with stirring, and either 4.5M sodium chlorate solution or 53% strength by weight nitric acid were added dropwise until the redox potential of the mixture was> 900mV vs. Ag / AgCl -Standard electrode was. The mixture turned from purple to yellow and a milky suspension formed.
  • the mixture was allowed to cool and filtered through a blue band paper filter. In no case was a clear filtrate obtained, since fine white particles penetrated the filter. The filtration was slow and in no case could it be carried out within a period of less than 6 hours. Sometimes the mixture formed a stable suspension with a gel-like to slimy consistency, which clogged the filter and did not allow solid / liquid separation.
  • a metal button with the composition 18 wt.% Cu, 26 wt.% Sn, 49 wt.% Ag, 0.7 wt.% Au, 0.35 wt.% Pd, 1.7 wt. -% Pb, 2.4% by weight Bi, 1% by weight Zn, 0.3% by weight Fe, 0.13% by weight Ni, 0.12% by weight Co; Weight ratio Au: Sn 0.027: 1.
  • the metal button was divided and a fragment of approx.
  • the mixture was stirred at room temperature overnight, then at 100 ° C. for an additional 3 hours. At first a reaction could still be seen after heating, then no more. It was allowed to cool while stirring. The supernatant solution was filtered through a blue band filter. The residues were placed directly in a beaker and made up to approx. 100 ml with 6M hydrochloric acid. 4.5M sodium chlorate solution was added dropwise at 60 ° C. with stirring. After adding 0.2 ml, the mixture had changed color from purple to milky yellow. A total of 1 mL of sodium chlorate solution was added in each case. The mixture was stirred for 1.5 hours, then the excess chlorate was boiled off and the solution was allowed to cool. The mixtures were filtered, and again a white precipitate was observed in each case, which was so fine that it penetrated through the filter.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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Claims (11)

  1. Procédé de traitement hydrométallurgique d'un alliage de métal noble et d'étain composé (i) de 0,45 à 25% en poids d'au moins un métal A sélectionné dans le groupe composé d'or et de platine, (ii) de 35% à 99,2% en poids d'au moins un métal B sélectionné dans le groupe composé de palladium, d'argent et de cuivre, (iii) de 0,3 à 30% en poids d'étain et (iv) de 0 à 50% en poids d'au moins un élément différent de l'or, de la platine, du palladium, de l'argent, du cuivre et de l'étain avec un métal A : rapport pondéral d'étain ≥ 0,7 : 1, comprenant les étapes suivantes :
    (a1) sélection ciblée de l'alliage de métal noble et d'étain
    ou
    (a2) fabrication ciblée de l'alliage de métal noble et d'étain,
    (b) dissolution de composants de l'alliage de métal noble et d'étain, solubles dans l'acide nitrique, avec de l'acide nitrique pour former une solution d'acide nitrique comprenant au moins un métal B comme nitrate dissous et un résidu non dissous,
    (c) séparation du résidu non dissous de la solution d'acide nitrique et
    (d) dissolution du résidu séparé dans un milieu contenant de l'acide chlorhydrique et au moins un agent oxydant.
  2. Procédé selon la revendication n°1, dans lequel l'alliage de métal noble et d'étain est composé (i) de 3 à 20% en poids d'au moins un métal A sélectionné dans le groupe composé d'or et de platine, (ii) de 40% à 95% en poids d'au moins un métal B sélectionné dans le groupe composé de palladium, d'argent et de cuivre, (iii) de 2 à 17,5% en poids d'étain et (iv) de 0 à 50% en poids d'au moins un élément différent de l'or, de la platine, du palladium, de l'argent, du cuivre et de l'étain avec un métal A : rapport pondéral d'étain compris entre 1 : 1 et 10 : 1.
  3. Procédé selon la revendication n°1 ou n°2, dans lequel l'étape (a2) est sélectionnée à partir de l'une des procédures (a2-1) - (a2-5) :
    - procédure (a2-1) comprenant la fusion d'au moins un matériau à recycler pour former un système à plusieurs phases comportant une phase inférieure à partir de l'alliage de métal noble et d'étain fondu et une phase supérieure à partir de scories fondues avec une densité plus faible, le cas échéant en ajoutant du métal de collecte et/ou des scorifiants et/ou des agents réducteurs, ainsi que la séparation de la phase supérieure et de la phase inférieure en exploitant une différence de densité, suivie du refroidissement et de la solidification de la fusion séparée, et la prise de l'alliage de métal noble et d'étain solidifié.
    - procédure (a2-2) comprenant le traitement d'un alliage fondu, différent de l'alliage de métal noble et d'étain, avec un agent oxydant pour former un système à plusieurs phases comportant une phase inférieure à partir de l'alliage de métal noble et d'étain fondu et une phase supérieure à partir de scories fondues avec une densité plus faible, dans laquelle se retrouvent des produits oxydants formés, le cas échéant en ajoutant du métal de collecte et/ou des scorifiants, ainsi que la séparation de la phase supérieure et de la phase inférieure en exploitant une différence de densité, suivie du refroidissement et de la solidification de la fusion séparée, et la prise de l'alliage de métal noble et d'étain solidifié.
    - procédure (a2-3) comprenant l'alliage d'au moins deux alliages différents l'un de l'autre, le cas échéant en ajoutant au moins un élément pour former l'alliage de métal noble et d'étain.
    - procédure (a2-4) comprenant l'ajout d'au moins un élément à un alliage pour former l'alliage de métal noble et d'étain.
    - procédure (a2-5) comprenant la distillation de l'étain à partir d'un alliage pour former l'alliage de métal noble et d'étain.
  4. Procédé selon la revendication n°3, dans lequel le matériau à recycler ou au moins un matériau à recycler est composé, outre le métal noble et le métal commun, d'au moins une substance différente de ceux-ci.
  5. Procédé selon la revendication n°4, dans lequel la substance différente du métal noble et du métal commun ou au moins une substance différente du métal noble et du métal commun est sélectionnée dans le groupe de matières inorganiques réfractaires.
  6. Procédé selon la revendication n°5, dans lequel le groupe de matières inorganiques réfractaires est composé de dioxyde de silicium, d'alumine, d'oxyde de calcium, d'oxyde de fer, de sulfate de calcium, de phosphate de calcium et de dioxyde d'étain.
  7. Procédé selon la revendication n°4, dans lequel la substance différente du métal noble et du métal commun ou au moins une substance différente du métal noble et du métal commun est un composant des matériaux de filtrage céramique, des agents de grenaillage, des matériaux abrasifs et/ou des matériaux supports inorganiques.
  8. Procédé selon la revendication n°3, dans lequel la matière à recycler ou au moins une matière à recycler est sélectionnée dans le groupe composé de concentrés miniers, de déchets et de mélanges de déchets, le ou les déchets étant sélectionnés dans le groupe composé de déchets provenant de la fabrication de bijoux, de déchets provenant du secteur dentaire, de déchets électroniques, de déchets de métal noble, de déchets contenant du métal noble issu d'entreprises transformant le métal noble, de détritus de métal noble, de catalyseurs en métal noble usagés, de poussières de catalyseurs en métal noble, de scories contenant du métal noble, de débris contenant du métal noble, de boues contenant du métal noble et, le cas échéant, séchées ainsi que de déblais issus de mines de métal noble.
  9. Procédé selon l'une des revendications précédentes, dans lequel l'acide nitrique utilisé dans l'étape (b) présente une concentration comprise 10 et 67% en poids.
  10. Procédé selon l'une des revendications précédentes, dans lequel l'acide chlorhydrique utilisé dans l'étape (d) présente une concentration comprise 3 et 12 mol/l.
  11. Procédé selon l'une des revendications précédentes, dans lequel l'agent oxydant utilisé dans l'étape (d) ou au moins un agent oxydant utilisé dans l'étape (d) est sélectionné dans le groupe composé d'acide nitrique, de chlorates, de nitrates, de bromates, d'iodates, de chlorites, de bromites, d'iodites, d'hypochlorites, d'hypobromites, d'hypoiodites, de perchlorates, d'ozone, d'ozonides, de superoxydes, d'oxygène, de chlore, de brome, d'iode, de composés peroxo, de permanganates et de chromates.
EP18753327.8A 2018-02-09 2018-07-30 Alliages de métaux précieux et d'étain et leur traitement hydrométallurgique Active EP3749792B1 (fr)

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EP18155948 2018-02-09
PCT/EP2018/070531 WO2019154530A1 (fr) 2018-02-09 2018-07-30 Procédé de traitement hydro-métallurgique d'un alliage de métal précieux - étain

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EP3749792B1 true EP3749792B1 (fr) 2021-06-09

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US (1) US20210071284A1 (fr)
EP (1) EP3749792B1 (fr)
CN (1) CN111630193B (fr)
TW (1) TWI685571B (fr)
WO (1) WO2019154530A1 (fr)
ZA (1) ZA202004852B (fr)

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CN114807624B (zh) * 2022-04-07 2023-10-13 北京电子科技职业学院 一种抗氧化耐磨贵金属首饰的制备装置及方法

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CN105886769B (zh) * 2015-01-26 2018-11-13 昆明冶金高等专科学校 一种硝酸溶解多金属合金物料集贵金属的方法
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TW201934765A (zh) 2019-09-01
WO2019154530A1 (fr) 2019-08-15
CN111630193B (zh) 2022-05-03
CN111630193A (zh) 2020-09-04

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