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WO1993004208A1 - Procede de recuperation de cuivre - Google Patents

Procede de recuperation de cuivre Download PDF

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Publication number
WO1993004208A1
WO1993004208A1 PCT/US1992/006408 US9206408W WO9304208A1 WO 1993004208 A1 WO1993004208 A1 WO 1993004208A1 US 9206408 W US9206408 W US 9206408W WO 9304208 A1 WO9304208 A1 WO 9304208A1
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WO
WIPO (PCT)
Prior art keywords
copper
solution
aqueous
leach
pregnant
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.)
Ceased
Application number
PCT/US1992/006408
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English (en)
Inventor
Joseph M. Sierakoski
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.)
Henkel Corp
Original Assignee
Henkel Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Priority to FI940526A priority Critical patent/FI940526L/fi
Priority to EP92917245A priority patent/EP0599911A1/fr
Priority to JP5504319A priority patent/JPH06509845A/ja
Priority to AU24144/92A priority patent/AU668358B2/en
Priority to BR9206321A priority patent/BR9206321A/pt
Publication of WO1993004208A1 publication Critical patent/WO1993004208A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • 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
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • 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
    • C22B3/306—Ketones or aldehydes
    • 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

  • This invention relates to a process for the recovery of copper from chalcocite concentrates by a process of partial leaching of the concentrate and extraction of the resulting aqueous ammoniacal leach solution.
  • U.S. Patent 4, 563,256 describes a solvent extraction process for the recovery of zinc values from ammoniacal solutions, which may also contain copper values, employing various oximes as the extractants.
  • U.S Patent 2,727,818 describes a method of leaching copper sulfide materials with ammoniacal leach solutions, indicating that the first Cu from Cu 2 S (chalcocite) dissolves without dissolution of sulfur, and the Cu from CuS (covellite) dissolves only when its sulfur also dissolves. No solvent extraction is discussed.
  • SUBSTITUTESHEET liquid ion exchange process for recovery of metals, such as nickel or copper, from aqueous solutions containing the metal values, including aqueous ammoniacal solutions.
  • FIG. 1 is a diagrammatic flow chart illustrating a partial leaching of a copper concentrate and a liquid-liquid extraction of the copper values from the resulting leach solution, followed by recovery of the copper, either in the form of copper sulfate crystals or as cathode copper by electrowinning.
  • ammonia recovery is simplified as, in the solvent extraction using the reagents employed in the present invention, ammonia is automatically regenerated during extraction and is simply recycled back via the raffinate for further leaching. Since the sulfur is not converted to sulfate in the partial leaching of the present invention, the sulfur, which remains in the leach residue, is concentrated by flotation and is removed to a smelting process as shown in Figure 1, where sulfuric acid may conveniently and efficiently be produced.
  • a chalcocite concentrate is subjected to a partial leaching with ammonia and ammonium sulfate solution. While ammonium sulfate is preferred in order to maintain the sulfate matrix throughout the system and ensure consistent quality of product, other ammonium compounds, such as the carbonate, nitrate and chloride may be employed; however, these may require specialized equipment or additional processing stages.
  • Chalcocite concentrate is typically composed of about 75-90% chalcocite (Cu 2 S) , though some may contain in excess of 90%, with the remainder being substantially covellite (CuS) , with trace amounts of chalcopyrite (CuFeS 2 ) or other forms of copper.
  • the chalcocite concentrate is contacted with ammonium sulfate solution and free ammonia, preferably in the form of ammonium hydroxide, with agitation to form a slurry which may range from about 10% to about 75% solids, typically about 30-60%, with 35-50% being preferred.
  • the higher the percent solids attained the smaller the size of the leaching vessel which is required and the higher the concentration of the copper contained in the aqueous phase.
  • the leaching is conducted at a pH in the range of about 8.5 to 11 to produce cupric ammonium sulfate and is conducted at ambient temperature and pressure, until the remaining copper is present as covellite (CuS) .
  • CuS covellite
  • the chalcocite (Cu 2 S) is leached so as to remove sufficient copper (half of the Cu 2 ) to leave a residue comprised substantially of CuS (covellite) .
  • elevated temperature and pressure may be employed, if desired, or where specialized ambient conditions exist, such as extreme cold conditions. Since the sulfur is not being converted to sulfate, no oxygen is required, however, air may be sparged into the leach vessel which tends to expedite the dissolution
  • Leach retention time is dependent on the desired percentage of copper to be solubilized, however, typically 30 to 90 minutes is generally sufficient to solubilize 20-35% of the total copper contained in the form of chalcocite, using an air sparge at typical ambient temperatures and pressures, i.e. 20-23 degrees Centigrade and atmospheric pressure.
  • the leaching should not substantially exceed the conversion of the chalcocite to covellite, e.g. removal of one part of copper from chalcocite compound which contains 2 parts of copper.
  • the resulting covellite is leached in the present process, there would occur an oxidation of the contained sulfur to sulfate, which is to be avoided or minimized in the present invention, since with any increase in sulfate, it is then required to incorporate a sulfate bleed stream and a subsequent make-up of ammonia lost in the form of ammonium sulfate. Desirably the only losses of ammonia in the process of the present invention will be only a small amount contained in the solids which is lost in the solid/liquid separation step shown in the flow diagram of Figure 1.
  • the leaching is preferably conducted in a continuous fashion with the original concentrate entering the first stage of leach and mixing with the raffinate from the subsequent extraction step.
  • Anhydrous ammonia or ammonium hydroxide is added as needed to maintain a leach pH between about 8.5-11.
  • Ammonium sulfate should be maintained at a level of at least the stoichiometric quantity required to solubilize the desired amount of copper contained in the concentrate.
  • the ammonium sulfate is maintained at a level slightly in excess of the stoichiometric amount, typically at about 10-20% excess, and preferably at about 15% excess. This amount of excess will ensure the amount of copper desired to be
  • the leach slurry is discharged from the leaching vessel and a liquid/solid separation is performed, which may be simple decantation or a filtration step.
  • the solids are preferably washed with water, and/or ammonia water solution, free of copper to remove any copper in solution entrained in the solids.
  • the washed and filtered solids may be subjected to flotation, to produce a new copper concentrate, composed primarily of covellite, CuS.
  • the new covellite sulfide concentrate will contain a higher fuel value for subsequent pyrometallurgical treatment than the original chalcocite concentrate in regard to the copper-sulfur ratio therein.
  • any precious metals such as silver or gold, or other sulfide minerals, such as molybdenite, which were initially present will also be found in the new flotation concentrate, from which they may be further processed and recovered.
  • the copper pregnant leach solution, along with the washing solutions from washing of the solids as described above, will then be sent to the extraction stage of the process, preferably after clarification to remove any fine solids which may be present from the previous step. Such clarification is preferably carried out by filtration.
  • the pregnant copper leach solution which now will contain from about 15-100 grams per liter (g/1) copper, typically about 30-40 g/1, at about pH 9 to 10 is contacted with a water-immiscible, organic solvent solution of an extractant compound having a high copper loading, low ammonia loading, capacity so as to result in a transfer of the copper to the organic solvent solution which forms an organic phase substantially immiscible with the aqueous copper pregnant leach solution.
  • the extraction stage is shown as a single
  • the extraction would be carried out in a continuous countercurrent process, typically employing up to three extraction stages, in a series of mixer-settler units in which the outlet of a mixer continuously feeds a large settling tank where the organic solvent (organic phase) , now containing the copper extractant complex in solution is separated from the depleted aqueous solution (aqueous phase) .
  • This part of the process is referred to as the phase separation.
  • the extraction process is repeated through two or more mixer-settler units in order to more completely extract the copper.
  • the copper pregnant leach solution will be introduced to the first mixer-settler unit extraction stage (often designated E-l) where it is contacted with the organic phase exiting from the second mixer-settler extraction stage (often designated E-2) , thereby involving a countercurrent flow of the organic phase and the aqueous copper solution phase.
  • the aqueous phase from the first extraction unit (E-l) is introduced into the second mixer-settler extraction unit (E-2) , which contact the incoming organic phase, recycled from the stripping stage of the process.
  • the copper loaded organic phase exits E-l and is introduced to a washing step prior to stripping of the copper from the organic phase.
  • the aqueous raffinate (ammonia and ammonium sulfate solution) from the extraction (unit E-2) now substantially barren of copper, typically containing less than 1 g/1 (and preferably about 0.1 g/1) is recycled to the leach step and solids wash steps earlier described.
  • the washing step may consist of only one stage or, as in the case of the extraction step, may consist of more than one.
  • the purpose of the washing step is primarily to remove any entrained, or chemically loaded, ammonia solution which may have been loaded into the organic phase along with the copper. If significantly low ammonia loading extractant compounds are employed, so that no significant amounts of ammonia are loaded
  • the washing step may be omitted and is thus an optional step. It is however preferred that at least one water washing step, pH controlled at a pH of 6-7 with a suitable pH adjusting acid, be employed to conserve ammonia and to minimize contamination of stripping agent employed in the next step of the process. If washing is employed after separation of the aqueous washing phase from the organic phase, the resulting aqueous solution from the washing is returned to the leaching step, while the copper loaded organic phase is then contacted with a stripping agent to form the stripping stage of the process. Again the stripping step may be carried out in a single stage or, as in the case of the extraction step, may typically be carried out countercurrently in more stages or units, i.e.
  • the stripping if carried out in two units, has the loaded organic phase introduced into the first stripping unit (S-l) , where it contacts the stripping agent (preferably sulfuric acid) exiting from the second stripping unit (S-2) , again a countercurrent processing.
  • Sulfuric acid solution containing about 60-180 g/1 sulfuric acid is the preferred stripping agent, as it permits the subsequent recovery of the copper either in the form of copper sulfate crystals or by electrowinning to cathode copper.
  • Other inorganic mineral acids may be employed as stripping agents, such as hydrochloric acid or nitric acid, however such may require other recovery methods or specialized handling equipment.
  • the stripped organic, now substantially barren of the copper and typically containing less than 1 g/1 copper will exit unit S-2 and be introduced to the unit E-2 of the extraction step.
  • the copper in the acidic stripping solution, now containing the copper in a concentrated amount, about 50- 60 g/1, and typically about 50 g/1, is then recovered in conventional manner either by crystallization or electrowinning, as shown in Figure 1.
  • electrowinning the preferred recovery method, cathode copper is recovered as electrolytic copper at a 99.99%+ copper.
  • the spent electrolyte, after deposition of the cathode copper, is then returned to stripping unit S-2.
  • the amount of copper present in the spent electrolyte may be relatively high, though lower than the 50 g/1 in the solution from the stripping step, and typically may contain from about 20-30 g/1 copper. If recovery is by crystallization, the copper is recovered in the form of copper sulfate crystals, which will typically require the introduction of some water to provide the water of hydration for copper sulfate crystals.
  • the spent solution from the crystallization, aqueous sulfuric acid will be recycled to the stripping step, into unit S-2.
  • the copper pregnant leach solution from which the copper is to be recovered by extraction will contain about 15-100 g/1 copper, and typically about 30-40 g/1 copper at pH about 8.5-11.
  • the extraction compounds for use in the practice of this invention on these leach solutions are those which will load, i.e. at least about 15 g/1, or extract, copper to a high degree, from high ammonia concentration solutions preferablywithout significant loading of ammonia.
  • Such compounds, which are preferred for use as an extractant reagent in the present invention because of their low ammonia loading properties are certain beta-diketones such as those described in U. S. Patents 4,065,502 and 4,015,980.
  • One such extractant found to be particularly suitable for use in the present invention is l-phenyl-3- heptyl-l,3-propanedione, available commercially from Henkel Corporation as LIX R 54.
  • Other beta-diketone compounds which may be employed are defined by the following formula:
  • R is phenyl or alkyl substituted phenyl
  • R' is alkyl, alkyl substituted phenyl or chloro substituted phenyl and R"
  • SHEET iU B? ⁇ y ⁇ 5 is H or CN with the provisos that (1) when R is phenyl, R' is a branched chain alkyl group of at least seven carbon atoms and (2) when R is alkyl substituted phenyl, the number of carbon atoms in the alkyl substituent is at least 7 and at least one such alkyl substituent is a branched chain.
  • R is desirably monoalkyl substituted and preferably contains 9 or more carbon atoms.
  • the various alkyl groups are preferably free from substitution and contain less than 20 carbon atoms. Further when R 1 is alkyl, the carbon alpha to the carbonyl group is desirably not tertiary.
  • R" is H
  • R 1 is a branched 7, 8, 9, 12, or 17 carbon chain or a chlorophenyl or short chain (1-5 carbon) alkyl substituted phenyl
  • R is phenyl or a 7, 8, 9, or 12 carbon alkyl substituted phenyl group.
  • beta-diketone compounds are preferred for use in the present invention as the water insoluble extractant compounds because of their low ammonia loading properties
  • other water insoluble copper loading extractants capable of loading copper from aqueous ammoniacal solutions may be employed. With such other reagents it may however, be necessary to include additional treatment of the organic phase because of ammonia loading, before stripping and recycling of materials in the continuous process.
  • R 1 is a saturated aliphatic group of 1-25 carbon atoms or an ethylenically unsaturated aliphatic group of 3-25 carbon atoms or -OR 3 , where R 3 is a saturated or ethylenically unsaturated group as defined above, a is an integer of 0, 1, 2, 3 or 4 and R 2 is H or a saturated or ethylenically unsaturated group as defined above, with the proviso that the total number of carbon atoms in R 1 and R 2 is from 3-25, or phenyl or R 4 substituted phenyl where R 4 is a saturated or ethylenically unsaturated group as defined above which may be the same or different from R 1 .
  • Illustrative of some of the oxime compounds are 5-heptyl salicylaldoxime, 5-octyl salicylaldoxime, 5-nonyl salicylaldoxime, 5-dodecyl salicylaldoxime, 5-nony1-2-hydroxyacetophenoneoxime, 5-nonyl- 2-hydroxyacetophenone oxime, 2-hydroxy-5-nonyl benzophenone oxime and 2-hydroxy-5-dodecyl benzophenone oxime. While it is preferred that a single extractant compound be employed, mixtures of extractants may be employed to meet particular system requirements.
  • essentially water-immiscible liquid hydrocarbon solvents can be used in the copper recovery process of the present invention. These include aliphatic and aromatic hydrocarbons such as kerosenes, benzene, toluene, xylene and the like. A choice of essentially water-immiscible liquid hydrocarbon solvents, or mixtures thereof for commercial operations will depend on a number of factors, including the plant design of the solvent extraction plant
  • the preferred solvents for use in the recovery process of the present invention are the aliphatic and aromatic hydrocarbons having flash points of 130 degrees Fahrenheit and higher, and preferably at least 150 , and solubilities in water of less than 0.1% by weight.
  • the solvents are essentially chemically inert.
  • Representative commercial available solvents are Chevron ion exchange solvent (available from Standard Oil of California, having a flash point 195 F, Escaid 100 and 110
  • the organic solvent solutions will preferably contain from about 0.005 up to about 75% by weight of the oxime compounds, which typically will be employed at about 10-15%.
  • the beta- diketone compound it may be used in an amount approaching 100% solids, but typically will be employed at about 20-30% by weight.
  • volume ratios of the organic:aqueous (0:A) phase will vary widely since the contacting of any quantity of the diketone organic solution with the copper containing aqueous leach solution will result in extraction of the copper values into the organic phase.
  • the organic:aqueous phase ratios for extraction are preferably in the range of about 50:1 to 1:50.
  • the organic:aqueous stripping medium phase ratio will preferably be in the range of about 1:2 to 20:1.
  • the extracting and stripping are normally conducted at ambient temperatures and pressures, although higher and/or lower temperatures and/or pressures are entirely operable. While the entire proces can be carried out as a batch operation, as described earlier, most advantageously the entire process is carried out continuously with the various solutions or streams being recycled to the various operations in the process for recovery of the copper, including the leaching, extraction and stripping steps.
  • the extractant reagent should be soluble in the organic water-immiscible solvent.
  • solubility modifiers include long chain (6-30 carbon) aliphatic alcohols or esters, such as n-hexanol, n-2-ethylhexanol, isodecanol, dodecanol, tridecanol, hexadecanol, octadecanol, isohexadecanol, 2- (1,3,3-trimethyl butyl)-5,7,7-trimethyl octanol and 2,2,4- trimethyl-l,3-pentanediol mono- or di- isobutyrate; long chain alkyl phenols, such as heptylphenol, octylphenol,nonylphenol and dodecylphenol; and organo-phosphorus compounds, such as tri-
  • the dry concentrate (350 grams) was slurried in a baffled, one liter beaker with 525 milliliters (mis) of ammonia sulfate and ammonium hydroxide solution.
  • the ammonium sulfate concentration was 150 grams/liter (g/1) as ammonium sulfate and the ammonium hydroxide concentration was 25 g/1 as ammonium hydroxide.
  • the pH of the ammonium sulfate-ammoniu hydroxide mixture was 9.5.
  • the slurry was agitated with a six vaned, single shrouded impeller to keep the solids suspended in the liquid phase for the duration of the leaching phase. Air was sparged through a glass frit to add some air to the
  • SUBSTITUTESHEET slurry and expedite the leaching of the copper.
  • the test was conducted at ambient temperature, about 23 C. , and ambient pressure. Ammonium hydroxide was added as necessary to maintain a pH range of 9.3-9.8 for the duration of the leaching activity.
  • the concentrate was leached in the described fashion for 90 minutes.
  • the unleached copper solids were filtered and washed with distilled water to recover essentially all of the dissolved copper.
  • the filtrate was collected as pregnant leach solution with some wash water and a second volume that was essentially wash water with some contained copper in solution.
  • the higher grade filtrate has a volume of 780 mis and contained 20.3 g/1.
  • the weaker wash solution had a volume of 490 mis and contained 0.93 g/1 copper.
  • the washed solids from the leaching stage were treated by flotation to produce a second copper concentrate. The solids were slurried with tap water and the pH was adjusted with calcium oxide to pH 10.5 prior to flotation.
  • the float was conducted at about 11% solids and Aerofloat 208 Promoter (sodium diethyl and sodium di-secondary butyl dithiophosphate) was used at 0.15 pounds per ton as collector. Dowfroth 250 was used as a frother and the dosage was also 0.15 pounds per ton. Flotation time was 10 minutes and a new concentrate and tailings were produced. The concentrate (305.1 grams) contained 26.85% copper and the tailings (24.3 grams) contained 22.0% copper. The new concentrate is suitable for processing at a smelter.
  • Aerofloat 208 Promoter sodium diethyl and sodium di-secondary butyl dithiophosphate
  • the higher grade filtrate which contained about 20 g/1 copper was used as the aqueous feed to solvent extraction.
  • the organic extractant was l-phenyl-3-heptyl-l.3-propanedione
  • cupric ammonium sulfate was adjusted to pH 9.5 and containing 20.1 g/1 copper. This solution was contacted with the mixed kerosene-diketone
  • SUBSTITUTE SHEET organic solution at an organic to aqueous ratio of 1:1 in a separatory funnel for 10 minutes.
  • the volumes used were 500 mis of aqueous and 500 mis of organic.
  • the solutions were allowed to separate and analyzed for copper.
  • the copper loaded organic contained 15.0 g/1 and the aqueous or raffinate contained 5.1 g/1 copper
  • the copper loaded organic phase was contacted with a synthetic spent electrolyte containing 30.3 g/1 copper and 170 g/1 sulfuric acid at an organic to aqueous ratio of 1:1 for 10 minutes.
  • the phases were allowed to separate and then analyzed for copper.
  • the stripped organic contained 0.08 g/1 copper and the rich electrolyte contained 44.8 g/1 copper.
  • the stripped organic was then contacted with the aqueous raffinate (5.1 g/1 copper) from the first contact to extract additional copper.
  • the second contact was also for 10 minutes and the two phases were analyzed after separation.
  • the second loaded organic contained 5.02 g/1 copper and the final aqueous raffinate contained 0.35 g/1 copper.
  • the copper may be removed from the rich electrolyte by electrowinning or copper sulfate crystallization.

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Abstract

Procédé amélioré de récupération du cuivre contenu dans un concentré de sulfure de cuivre, la calchocite, et consistant à lessiver partiellement le concentré de calchocite au moyen d'une solution ammoniacale aqueuse telle que l'ammoniaque et le sulfate d'ammonium, sans qu'il se produise de lessivage sensible de soufre ou de conversion en sulfate, et à extraire le cuivre de la solution ammoniacale aqueuse de lessivage partiel obtenue à l'aide d'un produit d'extraction insoluble dans l'eau, de préférence la bêta-dicétone, qui présente une capacité de charge de cuivre élevée, une capacité de charge d'ammoniaque faible, et qui est généralement dissous dans un solvant organique non miscible dans l'eau.
PCT/US1992/006408 1991-08-14 1992-08-06 Procede de recuperation de cuivre Ceased WO1993004208A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
FI940526A FI940526L (fi) 1991-08-14 1992-08-06 Kuparin talteenottomenetelmä
EP92917245A EP0599911A1 (fr) 1991-08-14 1992-08-06 Procede de recuperation de cuivre
JP5504319A JPH06509845A (ja) 1991-08-14 1992-08-06 銅の回収方法
AU24144/92A AU668358B2 (en) 1991-08-14 1992-08-06 Copper recovery process
BR9206321A BR9206321A (pt) 1991-08-14 1992-08-06 Processo para recuperar cobre de um concentrado de calcocita.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US74502891A 1991-08-14 1991-08-14
US745,028 1991-08-14

Publications (1)

Publication Number Publication Date
WO1993004208A1 true WO1993004208A1 (fr) 1993-03-04

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PCT/US1992/006408 Ceased WO1993004208A1 (fr) 1991-08-14 1992-08-06 Procede de recuperation de cuivre

Country Status (10)

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EP (1) EP0599911A1 (fr)
JP (1) JPH06509845A (fr)
AU (1) AU668358B2 (fr)
BR (1) BR9206321A (fr)
CA (1) CA2115160A1 (fr)
FI (1) FI940526L (fr)
MX (1) MX9204666A (fr)
WO (1) WO1993004208A1 (fr)
ZA (1) ZA925990B (fr)
ZM (1) ZM4092A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996017095A1 (fr) * 1994-11-30 1996-06-06 Alliedsignal Inc. Utilisation d'une matrice reticulee impregnee de dissolvant pour la recuperation du metal
WO1997004140A1 (fr) * 1995-07-14 1997-02-06 Consejo Superior Investigaciones Cientificas (Csic) Procede hydrometallurgique pour la recuperation de cuivre contenu dans des materiaux metalliques oxydes
EP0879301A4 (fr) * 1996-02-06 1999-04-14 Henkel Corp Beta-dicetones ameliorees pour l'extraction de cuivre contenu dans des solutions aqueuses ammoniacales
US6107523A (en) * 1997-01-08 2000-08-22 Henkel Corporation Beta-diketones for the extraction of copper from aqueous ammoniacal solutions
AU734689B2 (en) * 1996-12-23 2001-06-21 Cognis Ip Management Gmbh Improvement in the process of recovery of metals
EP1170389A3 (fr) * 1996-02-06 2002-07-03 Henkel Corporation Composés améliorés du type beta-dicétone pour l'extraction du cuivre à partir de solutions ammoniacales
ES2206004A1 (es) * 1998-07-24 2004-05-01 Western Metals Copper Limited Proceso de minerales de sulfuro de cobre.
WO2012107116A1 (fr) * 2010-12-06 2012-08-16 Abb Research Ltd Procédé chimique permettant de supprimer du sulfure de cuivre (cu2s) déposé sur un matériau à base de cellulose dans un transformateur à l'aide d'un agent complexant du cuivre
US20120219478A1 (en) * 2011-02-25 2012-08-30 Cognis Ip Management Gmbh Methods Of Metal Extraction From Ammoniacal Solutions Using Oximes
CN105316490A (zh) * 2015-11-13 2016-02-10 武汉工程大学 循环利用硫酸铵从硫化铜矿中湿法提铜的工艺方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR9206321A (pt) * 1991-08-14 1995-04-11 Henkel Corp Processo para recuperar cobre de um concentrado de calcocita.
US5936129A (en) * 1997-02-21 1999-08-10 Henkel Corporation Process for making sterically-hindered β-diketones
WO1999001420A1 (fr) * 1997-07-03 1999-01-14 Taito Co., Ltd. Procede de preparation de derives d'acide 2-aminomalonique, et intermediaires utilises dans ce procede
JP4356869B2 (ja) * 2002-03-27 2009-11-04 株式会社神戸製鋼所 銅合金中の晶・析出物の抽出分離方法およびこれに用いる抽出分離用液
FI118648B (fi) * 2005-02-14 2008-01-31 Outotec Oyj Menetelmä kuparipitoisten materiaalien käsittelemiseksi
CN101905909A (zh) * 2010-08-20 2010-12-08 重庆浩康医药化工有限公司 复配铜萃取剂

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WO1996017095A1 (fr) * 1994-11-30 1996-06-06 Alliedsignal Inc. Utilisation d'une matrice reticulee impregnee de dissolvant pour la recuperation du metal
US5578217A (en) * 1994-11-30 1996-11-26 Alliedsignal Inc. Use a solvent impregnated crosslinked matrix for metal recovery
WO1997004140A1 (fr) * 1995-07-14 1997-02-06 Consejo Superior Investigaciones Cientificas (Csic) Procede hydrometallurgique pour la recuperation de cuivre contenu dans des materiaux metalliques oxydes
EP0879301A4 (fr) * 1996-02-06 1999-04-14 Henkel Corp Beta-dicetones ameliorees pour l'extraction de cuivre contenu dans des solutions aqueuses ammoniacales
EP1170389A3 (fr) * 1996-02-06 2002-07-03 Henkel Corporation Composés améliorés du type beta-dicétone pour l'extraction du cuivre à partir de solutions ammoniacales
AU734689B2 (en) * 1996-12-23 2001-06-21 Cognis Ip Management Gmbh Improvement in the process of recovery of metals
US6107523A (en) * 1997-01-08 2000-08-22 Henkel Corporation Beta-diketones for the extraction of copper from aqueous ammoniacal solutions
ES2206004A1 (es) * 1998-07-24 2004-05-01 Western Metals Copper Limited Proceso de minerales de sulfuro de cobre.
WO2012107116A1 (fr) * 2010-12-06 2012-08-16 Abb Research Ltd Procédé chimique permettant de supprimer du sulfure de cuivre (cu2s) déposé sur un matériau à base de cellulose dans un transformateur à l'aide d'un agent complexant du cuivre
US20120219478A1 (en) * 2011-02-25 2012-08-30 Cognis Ip Management Gmbh Methods Of Metal Extraction From Ammoniacal Solutions Using Oximes
US8435466B2 (en) * 2011-02-25 2013-05-07 Basf Corporation Methods of metal extraction from ammoniacal solutions using oximes
US8460623B2 (en) 2011-02-25 2013-06-11 Cognis Ip Management Gmbh Methods of metal extraction using oximes
US8475748B2 (en) 2011-02-25 2013-07-02 Cognis Ip Management Gmbh Metal solvent extraction reagents and use thereof
US8529850B2 (en) 2011-02-25 2013-09-10 Cognis Ip Management Gmbh Compositions and methods of using a ketoxime in a metal solvent
US8945490B2 (en) 2011-02-25 2015-02-03 Basf Se Methods of metal extraction using oximes
US8986633B2 (en) 2011-02-25 2015-03-24 Basf Se Compositions and methods of using a ketoxime in a metal solvent extraction reagent
CN105316490A (zh) * 2015-11-13 2016-02-10 武汉工程大学 循环利用硫酸铵从硫化铜矿中湿法提铜的工艺方法

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JPH06509845A (ja) 1994-11-02
AU668358B2 (en) 1996-05-02
BR9206321A (pt) 1995-04-11
FI940526A0 (fi) 1994-02-04
AU2414492A (en) 1993-03-16
FI940526A7 (fi) 1994-02-04
FI940526L (fi) 1994-02-04
EP0599911A1 (fr) 1994-06-08
MX9204666A (es) 1993-02-01
ZM4092A1 (en) 1994-05-25
CA2115160A1 (fr) 1993-03-04

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