WO2006013568A2 - Procede de recuperation de metaux precieux provenant de dechets electroniques faisant appel a une technique hydrometallurgique - Google Patents

Procede de recuperation de metaux precieux provenant de dechets electroniques faisant appel a une technique hydrometallurgique Download PDF

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Publication number
WO2006013568A2
WO2006013568A2 PCT/IL2005/000836 IL2005000836W WO2006013568A2 WO 2006013568 A2 WO2006013568 A2 WO 2006013568A2 IL 2005000836 W IL2005000836 W IL 2005000836W WO 2006013568 A2 WO2006013568 A2 WO 2006013568A2
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Prior art keywords
solution
ions
concentration
halogen
dust
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PCT/IL2005/000836
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English (en)
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WO2006013568A3 (fr
Inventor
Vladimir Kogan
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Berg Recycling Industries Ltd.
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Publication of WO2006013568A2 publication Critical patent/WO2006013568A2/fr
Publication of WO2006013568A3 publication Critical patent/WO2006013568A3/fr

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Classifications

    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • 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
    • C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/28—Amines
    • C22B3/282—Aliphatic amines
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to extraction of precious metals from scrap or from mineral earth, in particular to the extraction of such metals from natural sources as well as from scrape of electronic circuits, computer scrap and catalysts.
  • Precious metals which are non-ferrous metals such as gold and platinum group metals (PMG' s) exist in many industrial products, such as electronic scrap (electrical/electronic equipment), printed circuit boards and relay scrap.
  • Gold, silver and palladium are frequently used for electroplating of connectors and contacts because they have excellent corrosion resistance and high electrical conductivity.
  • silver and gold are used in hybrid links and solders.
  • Such metals also exist in vehicles exhaust catalysts. Merely discarding old printed circuits, old computers or vehicle's exhaust catalysts poses an environmental problem. Furthermore, it results in a raise in their price.
  • Electronic scrap is composed of plastics (30%), refractory oxides (30%), and metals (40%).
  • the metals are found in many electronic components such as edge connectors, integrated circuits, and transistors.
  • the amounts of the metals are the following (wt.%): 0.02-0.05 Au, 0.1-0.2 Ag, 0.01-0.005 Pd, 14-18 Cu 5 1-2 Ni, 4-6 Sn, 2-4 Pb, 5-8 Al and 1-3 Fe.
  • the physical forms of these precious metals may be plated gold or palladium on copper laminate and plated gold or silver on nickel or iron.
  • the main economic driving force for the recycling of electronic scrap is the recovery of precious metals, particularly gold and palladium.
  • Environmental considerations are another, very important consideration in electronic scrap recycling.
  • the disposal of obsolete electronic equipment is a problem of considerable magnitude. Treating these wastes in a way that does not harm the environment is a complex process due to the heterogeneous composition of the obsolete equipment.
  • Electronic scrap is recycled using mechanical, hydrometallurgical, and
  • the mechanical processing of scrap is usually used as a pre-treatment and its main purpose is to separate compounds and components from the initial scrap.
  • Such processing is done by comminuting the scrap, classification, and separation (by differences of density, weight, size, magnetic properties, etc.) of the different compounds included in the wastes.
  • the resulting fraction is, in general, already enriched in a certain material that can be separated from the main stream.
  • concentrate and wastes can be further refined by air/or hydraulic classification and density separation.
  • HNO 3 H 2 SO 4 exists as a liquid up to 24O 0 C.
  • the chemistry involved in such processes are reduction and oxidation of the metals in order to extract them and bring them into solution.
  • the main steps in hydrometallurgical processing consist of a series of acid or caustic beads of finely divided solid material.
  • the solutions are then subjected to separation procedures such as electrowinning, solvent extraction, precipitation, cementation, ion exchange, filtration and distillation to isolate and concentrate the metals of interest.
  • Cyanide pressure leaching was examined (CM. Madelines et al, Hydrometallurgy, 35: (1994)) for recovering silver, gold and palladium from precious metals containing scrap.
  • the remarkable success of cyanide as lixiviate for gold is due to the enormous stability of the dicyanoaurate ion.
  • the high concentration of copper in initial raw material might interfere with the selective recovery of silver, gold and palladium.
  • cyanide process where substantial care is needed to prevent evolution of the hazardous HCN gas and destruction of the remaining cyanide in the waste solution.
  • halogen ions such as bromide or iodide
  • nitrogen oxide generated from the pressure leading process are continuously converted from respectively, to bromide or iodide and to nitrate, which are the major reagents for the production of copper and gold ions in the leaching solution.
  • pressure leaching is expensive and can render the process complicated with respect to materials and handling.
  • F. Solomon in U.S. Patent 4,997,532 (1989) suggested a process based on treating precious metal-bearing scrap with a polar organic solvent where bromine is dissolved to form non-aqueous precious metals complexes.
  • the organic solvent is subjected to electrolysis to recover the extracted metals.
  • This process is not suitable for use with combined scraped metal second material. This is because highly flight of polar organic solvent at temperature 80-90 0 C which the optimal condition of platinum and rhodium dissolution in bromine/bromide system.
  • polar organic solvent so possess necessary selectivity in liquid- liquid extraction process by respective precious metals recovering from leaching solution, containing also copper, metal, iron, zinc, etc.
  • the present invention is based on the fact that a novel approach to extract non-ferrous precious metals from mineral earth, mineral materials, and scraped metal second source including electrical and electronic scrap as well as catalysts, was developed.
  • the process of the present invention allows for a high percentage of separate recovery of platinoids, gold and silver into solution, requiring a relatively small amount of reagent.
  • the approach is based on the use of two complexing agents, an aqueous agent in combination with an organic agent.
  • the present invention is directed to a method for recovering non- ferrous precious metals from raw material such as mineral earth and scrap of electronic appliances and catalysts.
  • the raw material is initially (a) mechanically crushed and shredded to obtain dust containing fine particles which is further processed by the steps of:
  • HX and alkali metal halogen to achieve appropriate X " concentration, adding an organic extracting and complexing agent in the form of triisobutylphosphinesulfoxide in (RO) 3 PO, R being C 3- i 0 -alkyl, and C 9- i 7 -hydrocarbon and further adding an oxidizing agent capable of transmitting halogen ions into free halogen, heating, cooling and separating the phases, wherein from the organic phase are obtained by sedimentation essentially all of the platinum present in the dust.
  • the dust is obtained from a cyclone system
  • the strong acid is a H 2 SO 4
  • the halogen used is bromine or chloride, most preferably bromine.
  • the oxidizing agent should be a strong agent capable of converting halogen ions into basic halogen.
  • Such an oxidizing agent may be H 2 O 2 or MnO 2 .
  • the combined organic extracting and complexing agents are added in a form supported by macro-pore matrix, most preferably polypropylene.
  • the method of the present invention concerns recovering of precious, non- ferrous metals from raw material.
  • the raw materials are preferably from electrical and electronic scrap, catalysts or from mineral earth.
  • electronic scrap are electronic circuits such as printed circuits, computer scrap such as boards and screens, catalysts are catalytic converters, and homogeneous and heterogeneous catalysts, mineral earth are minerals of natural source which include the various non-ferrous precious metals.
  • the method according to the present invention employs hydrometallurgical techniques, use of liquid reagents for treating and reducing of ores. Prior to commencing the hydrometallurgical process the raw material is processed by an initial mechanical processing to yield a fraction of fine particles.
  • the processing comprises shredding the scrap, desk vibration separator, dust extraction system to obtain three separate groups differing in their particle size and density.
  • the first group has a high density typically above 8 gr/c 3 and this fraction contains mainly copper concentrate bearing non-ferrous precious metals.
  • the second group has a density of less than 1.5 gr/c containing mainly plastic, rubber and residues of metals. These two fractions are removed where a third group containing dust from cyclone system containing fine particles is further processed according to the present invention. Mineral earth ores are directly subjected to the hydrometallurgical process.
  • the process employs a complexation/oxidation leaching process where the concentration of the oxidized metals in the leach media is continuously increased through the use of acid mixtures both aqueous and organic solution for achieving precious metal oxidation.
  • the initial raw material is first subjected to a mechanical/or chemical enrichment obtaining concentrates of precious metals including platinum group metals (PGM' s), gold and silver.
  • PGM' s platinum group metals
  • the obtained concentrate is then treated in an aqueous solution containing halogen ions in an amount sufficient for forming in the system complex anions of silver, gold and PGM' s as M +11 X p p" ⁇ .
  • an oxidizing agent which is able to transfer free halogen ions (e.g. Cl “ , Br “ , I “ ) into the neutral free halogen (e.g. Cl 2 , Br 2 or I 2 ) in the leach liquor.
  • the oxidizing agent may be any strong agent capable of converting 2X " to X 2 where non- limiting examples of such an oxidizing agent are H 2 O 2 , MnO 2; KMnO 4 and chromates.
  • the extraction process is carried stepwise, recovering in each step a different type of precious metal or a mixture of two metals.
  • a continuous one-pot process is carried resulting in a fortified mixture of all precious metals.
  • the scrap is initially mechanically crushed resulting in three separate groups differing in their particle size and density where the third group containing dust from cyclone system containing fine particles is further processed according to the present invention.
  • HX is hydrochloric acid solution, where a solution containing 50-200 gr/L HCl and 250-320 gr/L MgCl 2 at the temperature of 85-110°C for about 1.5-3 hours followed by filtration.
  • the solution contains aluminum, tin and lead.
  • the obtained solid residue is cleaned, and further treated with a strong acid such as hydrosulfuric acid solution, containing 50-200 gr/L H 2 SO 4 and 150-250 gr/L MgCl 2 .
  • the pulp (solution) is now brought to the desired redox-potential in the range of 450-550 mV, by the addition to the pulp of 50% solution of hydrogen peroxide at a temperature of 60-80 0 C.
  • the solution is agitated until the majority of copper, nickel and zinc are removed.
  • the pulp obtained is mixed with 20-50% solution of tributylphosphate in kerosene where the aqueous phase to organic phase ratio is 20-50:1.
  • the combined phases having a redox-potential 850-950 mV are further vigorously agitated at a temperature not exceeding 30-40 0 C, until complete dissolution of gold is achieved where the gold is now in the organic solvent.
  • Phase separation yields the gold as powder.
  • the residual solid is transferred into a water solution with pH 0.5-1.5 obtained by the addition of HBr or HCl, where bromide ions are additionally introduced in the form of CaBr 2 until the total concentration of bromide ions is 150-250 gr/L Br " .
  • the obtained pulp is mixed with 2-20% solution of trioctylamine in kerosene and with intensive stirring of the said pulp, a solution comprising an oxidant is added.
  • the oxidant is hydrogen peroxide
  • a solution of 50% hydrogen peroxide is added setting the redox-potential of the system at a level of 680-870 mV where the temperature is kept at a range of about 50-60 0 C.
  • the organic phase is separated and palladium is recovered from the organic phase by sedimentation using Zn in acidic medium.
  • the acidic medium is preferably, HCl (50gr/liter), however, also H 2 SO 4 or any other acid may yield similar results.
  • the obtained solid residue is cleaned and transferred into the water solution having an HBr or HCl concentration of between 20 to 30 gr/liter, followed by the addition of bromide ions in the form of CaBr 2 or NaBr in order to obtain a total concentration 80-120 gr/L Br " .
  • the obtained pulp is further mixed with 10-20% solution of the tertiary aliphatic amine, preferably, triisobutylphosphinesulfoxide in tributylphosphate and kerosene.
  • a solution of a strong oxidizing agent such as MnO 2 or H 2 O 2 is added.
  • Preferably 50% hydrogen peroxide is added to the aqueous/organic slurry while vigorous agitating the pulp is continued providing a redox-potential to the system at an optimal level of 800-950 mV where the temperature is kept such that it does not exceed 80-95 0 C.
  • the agitation is continued where all platinum is in the organic phase.
  • the organic phase is separated and platinum is recovered from the organic phase by sedimentation using Zn in acidic medium.
  • the acidic medium is preferably HCl (50 gr/liter), however, also H 2 SO 4 or any other acid may yield similar results. It may be noted that according to the present invention, all the precious metals are extracted from the aqueous phase into the organic phase from which they are easily obtained.
  • the temperature, concentration of bromide ions and bromine, the redox-potetnial of the solution and the pH of the leach solution are important and should be maintained carefully.
  • the pulp is transferred from the reactor and filtered.
  • the solid residue is washed thoroughly and the washed material is combined with the mother solution.
  • the platinum group metals (PGM' s), gold and silver which are in the organic solution, can then be recovered from using known methods.
  • HX halogen
  • MgX 2 halogen
  • the solid residue is then mixed with 50-100 gr/L hydrosulfuric solution, containing 180-320 gr/L MgCl 2 in 60-80 gr/L bromide-ions in the form of NaBr.
  • a solution comprising 5.0% trioctylamine in tributylphosphate and kerosene at the ratio of aqueous phase to organic phase 100-200:1 is added to the above slurry, followed by the addition of a strong oxidizing agent such as MnO 2 or H 2 O 2 .
  • a strong oxidizing agent such as MnO 2 or H 2 O 2 .
  • 50% solution of hydrogen peroxide is added resulting in the formation of a system having a redox-potential of 650-870 mv.
  • silver, gold, palladium and platinum sequentially precipitate in the form of powders of the respective precious metals, where the mother liquor is returned to fresh scarp material processing.
  • EXAMPLE 1 15 Kg of original computer scrap with initial metal content, wt. %: 17.85
  • the first fraction, weighted 4.18 kg is copper concentrate with following composition, wt. %: 54.5 Cu, 5.74 Fe, 4.66 Ni, 1.62 Al, 1.34 Sn, 2.9 Zn, 0.81 Pb, 0.27 Ag, 0.0645 Au, 0.042 Pd other plastic, rubber, glass, humidity.
  • This particular fraction comprising a copper concentrate bearing precious metals can be sent direct to copper refinery.
  • the second fraction weighted 8.12 kg, contained essential amount of plastic, rubber and only 5.64% Al, 1.43% Fe, 0.49% Ni, 6.9% Sn, 2.1.% Zn, 2.28% Cu, 5.66 Pb.
  • the third fraction is dust from cyclone system, weighted 2.56 kg, with total content, wt., %: 6.78 Cu, 7.20 Al, 6.87 Sn, 0.98 Zn, 5.23 Pb, 0.295 Ag, 0.106 Au, 0.0769 Pd, 0.00269 Pt and 78.46 plastic, rubber, humidity.
  • the third fraction is most suitable for recovering the precious metals, was processed by a hydrometallurigical technique.
  • the processing of the dust product was performed in a 20 L Pyrex round-bottomed flask placed in a thermostatically controlled water bath. The flask was installed with mechanical stirrer and fitted with Pyrex condenser, thermometer, electrodes for pH and Eh measurement, and three tubes for addition 40% solution of NaOH or 20% solution of hydrobromic acid and 50% hydrogen peroxide solution.
  • first leach solution 5.3L of 32% hydrochloric acid solution which is 120% of stochiometric amount required to complete the dissolution of aluminum, tin, lead, and zinc was mixed with a prepared 500 gr/L solution of magnesium chloride, and the mixture was poured into a flask. 2.65 Kg of dust product (third fraction) was added to the solution and the slurry was stirred. The first leaching process was conducted for 3 hours at temperature 95 0 C. During this period 98% of aluminum, 96% of tin, 98.6% of lead and 92% of zinc were extracted in each solution. The leaching residue was filtered, washed and then transferred to begin a second stage of processing.
  • the solid residue was treated with 8 L of hydrosulfuric acid solution, containing 60gr/L H 2 SO 4 and 150gr/L MgCl 2 .
  • the redox-potential of the leach system near 45OmV was adjusted by adding to the pulp a solution of 50% solution of hydrogen peroxide.
  • the second leach procedure was performed for a period of 3 hours at a temperature of 65°C. In result more than 92% of the copper and 94% of the nickel originally present were dissolved by this procedure.
  • the solid residue was filtered, washed and in order to recover the precious metals present therein was treated with 3L of acidic sodium bromide solution containing 10 gr/L hydrobromic acid and 80 gr/L bromide ions.
  • the solid residue was transferred into a water solution with pH 0.8, achieved by the addition of HBr, and to the said solution bromide ions were introduced in the form of CaBr 2 until the total concentration of bromide ions is 180 gr/L Br ' .
  • the obtained pulp is further mixed with 10% solution of trioctylamine in kerosene and with intensive stirring of the pulp it was further treated by 50% H 2 O 2 providing redox-potential of the system at the level of 750 mV and the temperature not more than 60 0 C.
  • the pulp was stirred for 2 hours, where all the palladium was transferred to the organic solution.
  • the organic phase is separated and palladium is recovered from the organic phase by sedimentation using Zn in acidic medium.
  • H 2 SO 4 or any other acid may yield similar results.
  • the residual solid was further processed in order to selective recover platinum.
  • the residual solid was washed and transferred into a water solution, containing 50gr/L HBr and 100gr/L CaBr 2 .
  • To the obtained pulp were added a 5% solution of the triisobutylphosphinesulphoxide in tributylphosphate and kerosene and while the pulp is vigorously stirred, there was added rapidly a solution of 50% solution of H 2 O 2 providing a redox-potential of the system at the level of 850 mV and the temperature not more than 75 0 C. Stirring was continued where all the platinum is transferred to the organic solution and recovered by evaporation of the solvent.
  • the processing of the dust product was performed in 20 L Pyrex round-bottomed flask placed in a thermostatically controlled water bath. The flask was installed with mechanical stirrer (turbine type) and fitted with Pyrex condenser, thermometer, electrode for Eh measurement and a tube for addition 50% hydrogen peroxide solution.
  • a 1.5 kg of dust product was added to 6.0 L of hydrochloric solution, containing 180gr/L HCl and 250gr/L MgCl 2 and then the slurry was stirred.
  • the first leaching process was conducted for 3 hrs at temperature 80-95 0 C. During this period 98% of aluminum, 94% of tin, 96% of lead and 94% of zinc were extracted in each solution.
  • the leaching residue was filtered and then transferred to thermostatically flask for a second stage of processing. To recover copper, the solid residue was treated with 4.6 L of hydrosulfuric acid solution, containing 50 gr/L H 2 SO 4 and 200 gr/L MgCl 2 .
  • the redox-potential of the leach system near 550 mv was adjusted by adding to the stirred pulp a solution of 50% solution of hydrogen peroxide.
  • the second leach procedure was performed for a period of 2.5 hrs. at a temperature 80 0 C. In result more than 96% of copper and 98% of nickel were dissolved by this procedure.
  • the solid residue was filtered, washed and in order to combine recovering of precious metals was placed in the thermostatically flask, 3 L of acidic sodium bromide solution containing 30 gr/L HCl and 180 gr/L bromide-ions were added.
  • a 1.46 kg mixed spent catalytic converters sample was found to have 0.08% platinum, 0.04% palladium and 0.008% rhodium by mass. It was treated with 6 L of acidic sodium bromide solution containing 60 gr/L HCl and 220 gr/L bromide-ions. To the obtained pulp were added 60 mL 8% solution of triisobutylphosphinesulfoxide in tributylphosphate and kerosene. The three components organic solvent was supported by 300 gr. macro pore polypropylene granules and during intensive stirring of the pulp it was further treated by 50% hydrogen peroxide solution providing the redox-potential of the system at about 870 mv and the temperature not more than 60 0 C. The pulp was stirred for 3 hrs where more than 94% platinum, 96% palladium and 94% rhodium were recovered by supported organic solvent.
  • An oxidizing agent 20% concentrate of manganese dioxide, was added providing the redox-potential of the system at a level of more than about 850 mv and the temperature not more than 60 0 C.
  • the pulp was stirred for 6 hrs where more than 92% platinum, 94% palladium and 96% gold were extracted by supported organic solvent.
  • EXAMPLE 5 A 1.5kg of complex gold bearing concentrate composed of pyrite and stibnite was treated in condition of proposed process. It was leached with 6 L of acidic sodium bromide solution containing 60gr/L HCI and 220gr/L bromide- ions. To the obtained pulp were added 140 mL of supported liquid membrane (SLM) in form of 12.8% solution of triisobutylphosphinesulfoxide in tributylphosphate and kerosene. 160gr of Celgard-2500, a micro porous polypropylene film, was used as the solid support for the liquid organic solvent and the pulp stirred vigorously.
  • SLM supported liquid membrane
  • An oxidizing agent 20% concentrate of manganese dioxide, was added providing the redox-potential of the system at a level of more than about 850mv and the temperature not more than 30-40 0 C.
  • the pulp was stirred for 6hrs where more than 92% gold were extracted by supported organic solvent.

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Abstract

L'invention concerne un procédé hydrométallurgique pour extraire des métaux précieux non ferreux provenant de déchets électroniques, de terre minérale et de matières minérales.
PCT/IL2005/000836 2004-08-04 2005-08-04 Procede de recuperation de metaux precieux provenant de dechets electroniques faisant appel a une technique hydrometallurgique WO2006013568A2 (fr)

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IL16334204 2004-08-04
IL163342 2004-08-04

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WO2006013568A3 WO2006013568A3 (fr) 2006-05-04

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WO2013152424A1 (fr) * 2012-04-09 2013-10-17 Process Research Ortech Inc. Procédé aux chlorures pour la lixiviation d'or
WO2015175251A1 (fr) * 2014-05-12 2015-11-19 Summit Mining International Inc. Procédé de lixiviation de saumure pour la récupération de métaux de valeur à partir de matériaux oxydés
US9215813B2 (en) 2010-04-15 2015-12-15 Advanced Technology Materials, Inc. Method for recycling of obsolete printed circuit boards
US9221114B2 (en) 2011-12-15 2015-12-29 Advanced Technology Materials, Inc. Apparatus and method for stripping solder metals during the recycling of waste electrical and electronic equipment
EP2606158A4 (fr) * 2010-08-20 2017-04-26 Entegris Inc. Processus responsable permettant de récupérer les métaux précieux et les métaux de base à partir de déchet électronique
US9777346B2 (en) 2015-09-03 2017-10-03 Battelle Energy Alliance, Llc Methods for recovering metals from electronic waste, and related systems
US11408053B2 (en) 2015-04-21 2022-08-09 Excir Works Corp. Methods for selective leaching and extraction of precious metals in organic solvents
US20220349023A1 (en) * 2021-05-03 2022-11-03 Phoenix Tailings Inc. Noble metal extraction method and apparatus
CN116652204A (zh) * 2023-07-28 2023-08-29 长春黄金研究院有限公司 球形金粉及其制备方法
WO2024038414A1 (fr) 2022-08-19 2024-02-22 Tübi̇tak Système hybride de membrane et de réduction cathodique pour enrichissement et récupération de rhodium

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD137601A1 (de) * 1978-07-05 1979-09-12 Sigrid Herrmann Verfahren zur abtrennung von palladium und gold aus platin und platinmetallschrott
US4378275A (en) * 1981-12-03 1983-03-29 Saudi-Sudanese Red Sea Joint Commission Metal sulphide extraction
US5304359A (en) * 1992-03-03 1994-04-19 Bhp Minerals International Inc. Dissolution of platinum group metals from materials containing said metals

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS526307A (en) * 1975-06-30 1977-01-18 Kuronieegeru Herumuuto Method of extracting noble and base metals from ore
JPS5278702A (en) * 1975-12-26 1977-07-02 Nissan Motor Co Ltd Extraction of noble metal from wast catalyzer
JPS61235520A (ja) * 1985-04-11 1986-10-20 Nippon Mining Co Ltd 貴金属の浸出方法
RU2151209C1 (ru) * 1998-03-05 2000-06-20 Институт физиологически активных веществ РАН Способ экстракционного разделения платины и палладия

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD137601A1 (de) * 1978-07-05 1979-09-12 Sigrid Herrmann Verfahren zur abtrennung von palladium und gold aus platin und platinmetallschrott
US4378275A (en) * 1981-12-03 1983-03-29 Saudi-Sudanese Red Sea Joint Commission Metal sulphide extraction
US5304359A (en) * 1992-03-03 1994-04-19 Bhp Minerals International Inc. Dissolution of platinum group metals from materials containing said metals

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 197709 Derwent Publications Ltd., London, GB; Class M25, AN 1977-15312Y XP002361814 & JP 52 006307 A (KRONJEGEL H) 18 January 1977 (1977-01-18) *
DATABASE WPI Section Ch, Week 197733 Derwent Publications Ltd., London, GB; Class J01, AN 1977-58204Y XP002361816 & JP 52 078702 A (NISSAN MOTOR CO LTD) 2 July 1977 (1977-07-02) *
DATABASE WPI Section Ch, Week 200034 Derwent Publications Ltd., London, GB; Class J01, AN 2000-389723 XP002361815 & JP 11 290604 A (ISUKURA SANGYO KK) 26 October 1999 (1999-10-26) *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 080 (C-409), 11 March 1987 (1987-03-11) & JP 61 235520 A (NIPPON MINING CO LTD), 20 October 1986 (1986-10-20) *

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US9221114B2 (en) 2011-12-15 2015-12-29 Advanced Technology Materials, Inc. Apparatus and method for stripping solder metals during the recycling of waste electrical and electronic equipment
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US20220349023A1 (en) * 2021-05-03 2022-11-03 Phoenix Tailings Inc. Noble metal extraction method and apparatus
US11649524B2 (en) * 2021-05-03 2023-05-16 Phoenix Tailings Inc. Noble metal extraction method and apparatus
WO2024038414A1 (fr) 2022-08-19 2024-02-22 Tübi̇tak Système hybride de membrane et de réduction cathodique pour enrichissement et récupération de rhodium
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