EP3426825B1 - Affinage électrolytique d'or brut - Google Patents

Affinage électrolytique d'or brut Download PDF

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Publication number
EP3426825B1
EP3426825B1 EP17713591.0A EP17713591A EP3426825B1 EP 3426825 B1 EP3426825 B1 EP 3426825B1 EP 17713591 A EP17713591 A EP 17713591A EP 3426825 B1 EP3426825 B1 EP 3426825B1
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EP
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Prior art keywords
gold
anode
cathode
raw
electrolyte solution
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EP17713591.0A
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German (de)
English (en)
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EP3426825A1 (fr
Inventor
Thorsten Koras
Revin SHANGULA
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    • 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 invention relates to a process for the electrolytic refining of raw gold.
  • Raw gold Contaminated gold, hereinafter referred to as raw gold, is particularly common in the recycling of electrical and electronic components. Usually, the recycling (fine) gold should be of higher purity than in the present raw gold.
  • Raw gold is a gold alloy that consists of fine gold and admixtures of other metals. In particular, copper and possibly also silver often occur as admixtures.
  • the semi-permeable membrane is impermeable to gold-containing ions, insoluble components and abrasive oxide particles. Fine gold is extracted from the gold-containing ions in the anode-side area by adding bisulfite salts.
  • the electrolytic refining for the extraction of fine gold from raw gold contaminated with accompanying elements takes place in a trough 1/2, which is divided into a first area 1 and a second area 2 by a membrane 3 permeable to certain ions. Each area comprises an electrode A1, K2 and an electrolyte solution E1, E2.
  • Base metals such as copper, nickel, tin and zinc or their compounds are to be considered as accompanying elements; silver, palladium and platinum metals or their compounds are to be considered as precious metals.
  • an electrode A1 made of raw gold acting as an anode, or an anode basket acting as an anode loaded with raw gold scrap, or a contact rod acting as an anode, in contact with raw gold scrap is connected to the positive pole of a voltage source for a direct current circuit.
  • This anode A1 is arranged in an aqueous electrolyte solution E1 containing dissociated hydrochloric acid and / or dissociated chloride salts.
  • the hydrochloric acid concentration of the electrolyte solution E1 is in the range between 5 and 15%.
  • an electrode K2 acting as a cathode is connected to the negative pole of the voltage source and arranged in an aqueous electrolyte solution E2 containing dissociated sulfuric acid and / or dissociated sulfate salts.
  • the sulfuric acid concentration in the electrolyte solution E2 is approx. 10%.
  • the membrane 3 separates the two electrolyte solutions E1 and E2 from one another.
  • the anode which consists of raw gold, is dissolved to form positively charged base metals containing cations and negatively charged gold anions (also called negatively charged gold complex anions).
  • the membrane 3 is permeable only for positively charged cations formed in the first region 1 in the direction of the negative cathode K2 arranged in the second region 2, on which the metal contained in the cations, possibly e.g. Copper precipitates.
  • Negative charged gold-containing anions are enriched in the electrolyte solution E1 in the first region 1.
  • a so-called anode basket made of electrically conductive material loaded with raw gold scrap can also be considered as anode in area 1 in the first process step.
  • the contact between the anode basket and the raw gold scrap must be guaranteed.
  • a contact rod in contact with the Rohgotd scrap can also be used as an anode.
  • the cathodic deposition of simply refined fine gold see Fig. 2 .
  • an electrode K1 ' which acts as cathode and is connected to the negative pole of the voltage source is arranged.
  • an electrode A2 acting as an anode and connected to the positive pole of the current source is arranged in the electrolyte solution E2.
  • the gold is precipitated from the anions originally containing negatively charged gold at the negative cathode K1 in the first region 1 as simply refined fine gold.
  • the simply refined gold has a higher degree of purity than the gold in the raw gold anode A1 or in the raw gold scrap.
  • the electrode K1 coated with simply refined fine gold according to the second process step is connected in the first region 1 as the anode electrode A1 'to the positive pole of the voltage source and in the electrolyte solution containing hydrochloric acid E1 arranged, in the second area 2 an electrode K2 ', which acts as a cathode and is connected to the negative pole of the voltage source, is arranged in the electrolyte solution E2 containing sulfuric acid.
  • the simply refined fine gold adhering to the electrode A1 ' is dissolved to form positively charged base metal-containing cations, such as copper cations, and negatively charged gold-containing anions.
  • the membrane 3 is permeable only for positively charged cations formed in the first region 1 in the direction of the negative cathode K2 'arranged in the second region 2, on which the base metal contained in the cations is deposited.
  • the electrode K1 'acting as a cathode is connected to the negative pole of the voltage source and arranged in the electrolyte solution E1 in the first area 1.
  • the electrode A2 'acting as an anode is connected to the positive pole of the voltage source and arranged in the electrolyte solution E2.
  • the gold from the originally negatively charged gold-containing anions in the first region 1 is deposited on the negative cathode K1 'as double refined fine gold.
  • the double refined gold has a higher degree of purity than the single refined gold.
  • the first to fourth method steps can be followed by further method steps five and six.
  • the fifth process step analogously to the third process step, the double-refined fine gold deposited cathodically in the fifth and sixth process step would be anodically dissolved, and in the sixth process step analogously to the fourth process step, as triple-refined fine gold would be deposited cathodically.
  • PTFE sulfonated tetrafluoroethylene polymer
  • the method according to the invention is carried out at a temperature of approximately 55 degrees Celsius.
  • the gold-dissolving process steps one and three take place at a voltage of 5 to 6 volts with a maximum current of 30 amperes; the gold-depositing process steps two and four at a voltage of 2 to 4 volts and a current of 8 to 20 amps.
  • the silver admixture in the anodic raw gold reacts with the chlorine of hydrochloric acid contained in the electrolyte E1: it forms poorly water-soluble silver chloride, which is particularly reflected as an undesirable solid coating on the raw gold anode or on the raw gold scrap. This coating prevents or limits the contact of the electrolyte E1 with the raw gold anode or with the raw gold scrap and therefore hinders the electrolysis.
  • This brittle coating ensures better contact of the electrolyte E1 with the raw gold anode or with the raw gold scrap and therefore no longer limits the electrolysis process as much as is the case with silver chloride.
  • the electrode A1 made of raw gold or the raw gold scrap (in the anode basket or in contact with the contact rod) is subjected to ultrasound.
  • ultrasonic transducer elements which are mounted in a housing, are used as commercial goods for ultrasound exposure.
  • This housing is coupled via a chamber to the outer wall of the tub 1/2 such that the ultrasonic vibrations emerging from the housing pass through the chamber filled with water or glycerol with as little loss as possible and can strike the anode in the tub 1/2.
  • the wall of the chamber and the tub in the area of the ultrasonic vibrations passing through them consists of a material, preferably of polypropylene, which allows the ultrasound to pass through with as little loss as possible.
  • the frequency of the ultrasonic transducer elements used is 40 KHz. You have no direct contact with the electrolyte.
  • Martin-WALTER Ultrasound Technology AG, Hardstr. 13, D-75334 Straubenhard are used as commercial goods for ultrasound exposure.
  • any insoluble particles such as silver chloride or the particles of the brittle coating detached from the anode by ultrasound are filtered out of the electrolyte solution E1 mixed with hydrochloric acid.
  • This filtering out can be done, for example, by means of a circulation pump.
  • the filter cartridges No. NT 10 "(item no. 11007) from Filtertechnik Jäger GmbH (Siemensstr. 1, D-89264 Hasenhorn), which are available as commercial goods, can be used as filter material. These filter cartridges are only permeable to particles smaller than 5 micrometers.
  • a newly prepared electrolyte solution E1 with predefinable initial proportions of hydrochloric acid and urea (carbonic acid diamide) is used. This can e.g. ensure that the concentration of the chloride ions is the same in the electrolyte E1 containing dissociated hydrochloric acid at the beginning of the first and third process steps. And there are no different dissolution times for the gold resulting from different concentrations.
  • titanium electrodes are used as cathode K2 in method step one and as cathode K2 'in method step.
  • anode A1 in process step three as cathode K1 in process step two, as cathode K1 in process step four, as anode A2 in process step two, as anode A2 in process step four, and as anode in process step one, insofar as it does not itself consist of raw gold, platinum-plated titanium electrodes are used.
  • the anode basket for holding the raw gold scrap consists of a mesh-like mesh made of placed titanium expanded metal.

Claims (6)

  1. Procédé d'obtention d'or fin par affinage électrolytique d'or brut contaminé par des éléments d'accompagnement, l'électrolyse s'effectuant dans une cuve qui est divisée par une membrane (3) perméable à certains ions en une première zone (1) et une deuxième zone (2), chaque zone comprenant une électrode et une solution électrolytique, caractérisé par les étapes de procédé successives suivantes:
    a) la dissolution anodique de l'or brut
    Dans la première zone (1), une électrode (A1) en or brut faisant office d'anode ou une cage anodique chargée de débris d'or brut faisant office d'anode ou une barre de contact en contact avec des débris d'or brut faisant office d'anode est reliée au pôle positif d'une source de tension pour un circuit de courant continu et est disposée dans une solution électrolytique (E1) contenant de l'acide chlorhydrique dissocié et/ou des sels de chlorure dissociés, dans la deuxième zone (2), une électrode (K2) faisant office de cathode est reliée au pôle négatif de la source de tension et est disposée dans une solution électrolytique (E2) contenant de l'acide sulfurique dissocié et/ou des sels de sulfate dissociés, la membrane (3) séparant les deux solutions électrolytiques (E1) et (E2), l'or brut se dissolvant en formant des cations contenant des métaux non précieux chargés positivement tels que des cations de cuivre et des anions contenant de l'or chargés négativement, et la membrane (3) étant perméable seulement pour des cations chargés positivement formés dans la première zone (1) en direction de la cathode négative (K2) disposée dans la deuxième zone (2), sur laquelle se précipite le métal non précieux contenu dans les cations, et la solution électrolytique (E1) étant enrichie dans la première zone (1) avec des anions contenant de l'or chargés négativement;
    b) le dépôt cathodique de l'or fin affiné une fois
    Après dissolution de l'or brut dans la première zone (1) selon l'étape de procédé a), une électrode (K1) faisant office de cathode, reliée au pôle négatif de la source de tension, est disposée dans la première zone (1) dans la solution électrolytique (E1), et une électrode (A2) faisant office d'anode, reliée au pôle positif de la source de courant, est disposée dans la deuxième zone (2) dans la solution électrolytique (E2), l'or se précipitant à partir des anions contenant de l'or, chargés initialement négativement, dans la première zone (1) sur la cathode négative K1 sous forme d'or fin simplement affiné une fois à un degré plus élevé de pureté que le degré de pureté de l'or dans l'anode d'or brut (A1);
    c) la dissolution anodique de l'or fin une fois affiné
    L'électrode (K1) revêtue avec de l'or fin affiné une fois selon l'étape de procédé b) est reliée dans la première zone (1) comme électrode (A1') faisant office d'anode au pôle positif de la source de tension et disposée dans une solution électrolytique (E1) contenant de l'acide chlorhydrique et/ou des sels de chlorure dissociés, alors que, dans la deuxième zone (2), une électrode (K2') faisant office de cathode reliée au pôle négatif de la source de tension est disposée dans une solution électrolytique (E2) contenant de l'acide sulfurique et/ou des sels de sulfate dissociés, l'or fin affiné une fois adhérant à l'électrode (A1') étant dissous en formant des cations contenant des métaux non précieux chargés positivement, tels que des cations de cuivre, et des anions contenant de l'or chargés négativement, et la membrane (3) étant perméable seulement pour les cations chargés positivement formés dans la première zone (1) en direction de la cathode K2' négative disposée dans la deuxième zone (2), sur laquelle se précipite le métal non précieux contenu dans les cations;
    d) le dépôt cathodique de l'or fin affiné deux fois
    Après dissolution de l'or fin affiné une fois selon l'étape de procédé c), une électrode (K1') faisant office de cathode est reliée au pôle négatif de la source de tension et est disposée dans la solution électrolytique (E1) dans la première zone (1), alors que, dans la deuxième zone (2), une électrode (A2') faisant office d'anode est reliée au pôle positif de la source de tension et disposée dans la solution électrolytique (E2), l'or se précipitant à partir des anions contenant de l'or, chargés initialement négativement, dans la première zone (1) sur la cathode négative (K1') sous forme d'or fin affiné deux fois à un degré plus élevé de pureté que le degré de pureté de l'or affiné une fois précipité sur la cathode (K1) dans l'étape de procédé b);
    e) la solution électrolytique (E1) contenant, en plus, de l'urée (carbonyldiamide) au moins dans la première étape de procédé a).
  2. Procédé selon la revendication 1, caractérisé en ce que la membrane (3) se compose de polymère de tétrafluoroéthylène (PTFE) sulfoné comportant des résidus de SO3 chargés négativement.
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que l'électrode (A1) en or brut ou les débris d'or brut dans la cage anodique ou les débris d'or brut en contact avec la barre de contact est/sont soumis(e) aux ultrasons.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que les particules non solubles comme le chlorure d'argent, formées le cas échéant, sont filtrées de la solution électrolytique (E1) mélangée à l'acide chlorhydrique et/ou aux sels de chlorure dissociés.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que, dans les étapes de procédé a) et c), une solution électrolytique (E1) nouvellement constituée comportant des proportions de départ prédéfinies d'acide chlorhydrique et/ou de sels de chlorure dissociés et d'urée (carbonyldiamide) est utilisée pour la dissolution de l'or brut ou fin.
  6. Procédé selon la revendication 1, caractérisé en ce que la cathode (K2) dans l'étape de procédé a) et la cathode (K2') dans l'étape de procédé c) sont fabriquées à partir de titane, en ce que l'anode (A1') dans l'étape de procédé c), la cathode (K1) dans l'étape de procédé b), la cathode (K1') dans l'étape de procédé d), l'anode (A2) dans l'étape de procédé b), l'anode (A2') dans l'étape de procédé d), ainsi que l'anode dans l'étape de procédé a), dans la mesure où elle ne se compose pas elle-même d'or brut, sont fabriquées à partir de titane qui est platiné.
EP17713591.0A 2016-03-09 2017-03-09 Affinage électrolytique d'or brut Active EP3426825B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL17713591T PL3426825T3 (pl) 2016-03-09 2017-03-09 Elektrolityczna rafinacja surowego złota

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016104237.4A DE102016104237A1 (de) 2016-03-09 2016-03-09 Elektrolytische Raffination von Rohgold
PCT/EP2017/055604 WO2017153547A1 (fr) 2016-03-09 2017-03-09 Affinage électrolytique d'or brut

Publications (2)

Publication Number Publication Date
EP3426825A1 EP3426825A1 (fr) 2019-01-16
EP3426825B1 true EP3426825B1 (fr) 2020-05-06

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EP17713591.0A Active EP3426825B1 (fr) 2016-03-09 2017-03-09 Affinage électrolytique d'or brut

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EP (1) EP3426825B1 (fr)
CN (1) CN109312481B (fr)
DE (1) DE102016104237A1 (fr)
EA (1) EA036684B1 (fr)
ES (1) ES2811380T3 (fr)
PL (1) PL3426825T3 (fr)
PT (1) PT3426825T (fr)
WO (1) WO2017153547A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102017216564A1 (de) * 2017-09-19 2019-03-21 Siemens Aktiengesellschaft CO2-freie elektrochemische Herstellung von Metallen und Legierungen davon

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US4437889A (en) * 1981-08-06 1984-03-20 Palacios Mendoza Eliodoro Method of recovering silver from solid and liquid photographic waste
JPS6070196A (ja) * 1983-09-26 1985-04-20 Sumitomo Metal Mining Co Ltd 金電解精製法及びその装置
US4612093A (en) * 1985-05-31 1986-09-16 Shor International Corporation Method and apparatus for purification of gold
JPH0238536A (ja) * 1988-07-29 1990-02-07 Tanaka Kikinzoku Kogyo Kk イリジウム酸性溶液中の貴金属分離法
US5009755A (en) 1990-01-22 1991-04-23 Shor Peter S Refining method
US6896788B2 (en) * 2000-05-22 2005-05-24 Nikko Materials Company, Limited Method of producing a higher-purity metal
CN1208482C (zh) * 2003-04-11 2005-06-29 山东黄金集团有限公司焦家金矿 一种粗金提纯的方法
DE102006056017B4 (de) * 2006-11-23 2016-02-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Rückgewinnung von Edelmetallen
US20110094877A1 (en) * 2007-08-06 2011-04-28 Gomez Rodolfo Antonio M Electrochemical system for metal recovery
CN101705507A (zh) * 2009-11-27 2010-05-12 苏州天地环境科技有限公司 从含氰镀金废液中电解回收金的方法
CN102978658A (zh) * 2011-09-07 2013-03-20 江西铜业股份有限公司 一种阴极金电解精炼工艺
CN102618885B (zh) * 2012-04-13 2014-08-27 陕西黄金集团西安秦金有限责任公司 一种适于高银合质金快速电解精炼的辅助试剂
CN103590071A (zh) * 2013-11-01 2014-02-19 白银有色集团股份有限公司 一种提高金电解精炼工艺中金析出品位的方法

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Also Published As

Publication number Publication date
PT3426825T (pt) 2020-08-20
PL3426825T3 (pl) 2021-04-06
CN109312481A (zh) 2019-02-05
DE102016104237A1 (de) 2017-09-14
EA036684B1 (ru) 2020-12-08
EA201892012A1 (ru) 2019-02-28
WO2017153547A1 (fr) 2017-09-14
CN109312481B (zh) 2020-10-16
ES2811380T3 (es) 2021-03-11
EP3426825A1 (fr) 2019-01-16

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