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WO2001009399A1 - Recuperation d'argent dans une saumure acide par cementation - Google Patents

Recuperation d'argent dans une saumure acide par cementation Download PDF

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Publication number
WO2001009399A1
WO2001009399A1 PCT/ZA2000/000130 ZA0000130W WO0109399A1 WO 2001009399 A1 WO2001009399 A1 WO 2001009399A1 ZA 0000130 W ZA0000130 W ZA 0000130W WO 0109399 A1 WO0109399 A1 WO 0109399A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
silver
solution
stream
cement
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/ZA2000/000130
Other languages
English (en)
Inventor
Jozef Marie Schaekers
Noelene Ahern
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.)
BHP Billiton SA Ltd
Original Assignee
Billiton SA Ltd
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 Billiton SA Ltd filed Critical Billiton SA Ltd
Priority to AU68049/00A priority Critical patent/AU6804900A/en
Publication of WO2001009399A1 publication Critical patent/WO2001009399A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet 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
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • 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 the recovery of silver from an acidic brine solution
  • Sulfide ions can be used to precipitate silver sulf ⁇ de (1) Disadvantages are that foreign ions are introduced into the system and the resulting silver sulfide product needs further processing
  • Iodide precipitation is fairly effective to recover silver' 2 ', especially if selectivity over copper is required, but again foreign ions are introduced Furthermore the iodide reagent is potentially expensive and the silver iodide product formed needs further processing
  • the invention provides a method of recovering silver from an acidic brine solution which includes the steps of
  • the method may include the step of ensuring, when necessary, that the pH of the solution is at a value of between 0, and 5 Preferably the pH of the solution is between 1 ,5 and 3,0 Thus, where necessary, the method may include the step of
  • step (c) adjusting the pH of the solution prior to, or during, step (a)
  • Step (a) may be carried out in one or in a plurality of stages
  • the silver cement may be separated in any appropriate way but preferably use is made of a liquid/solid separation process At least part of a brine solution which is produced by step (b) may be used to provide at least part of the copper which is required for the cementation step (a)
  • the method thus preferably includes the steps of: (d) splitting the solution which is produced by step (b) into at least first and second streams,
  • step (g) clarifying at least the second stream by removing metallic copper, and (h) using at least the clarified second stream to provide copper (I) for step (a)
  • Step (f) may be preceded by a step of (i) removing impurities from the second stream
  • step (g) the copper solution may be clarified in any appropriate way but preferably use is made of a solid/liquid separation process
  • the method of the invention may include the step of
  • step (j) using metallic copper, which is separated in step (g), in step (f) by adding the metallic copper to the second stream
  • Step (j) may be preceded by the step of
  • Step (k) combining at least part of the first stream with the second stream, obtained after step (i), and reducing the resulting combined stream in step (f)
  • Step (k) may be preceded by the step of
  • Copper may be removed from the first stream, in step (e), in any appropriate way, for example by using sulfide to precipitate copper as copper sulfide
  • the acidic brine solution may arise in different ways and, for example, may arise from the brine leaching of a silver and copper bearing bio-leach residue In this particular case the copper sulfide may be recycled to the biological leaching stage
  • Losses of copper and silver are avoided by recycling the copper sulfide, in the manner indicated but this is not limiting for alternative methods such as solvent extraction, ion exchange and standard cementation techniques can be used to remove the copper
  • silver bearing material which is subjected to brine leaching can be produced in any appropriate way and need not necessarily be produced as a bio-leach residue
  • Such material may for example include concentrates, pressure- leach residues roasted concentrates or anode slimes from electrowinning operations
  • a silver bearing material 10 is subjected to a bio-leaching process 12 to produce a silver and copper bearing residue 14
  • the residue is subjected to a leaching step 16 which involves the addition of a brine solution 18
  • a solid/liquid separation step 19 to produce a silver (I) containing brine solution 20 which contains copper and, possibly other impurities
  • the copper may be present naturally or, as emerges hereinafter may be added
  • the pH of the bnne solution 20 is of the order of 2,0
  • the pH of the brine solution is adjusted in a step 22 so that it lies between 0 1 and 5,0 and, preferably, is between 1 ,5 and 3,0
  • the solution 20 is then subjected to a cementation process 24 which involves the cementation of silver (I) in the solution by copper (I) (block 26)
  • a cementation process 24 which involves the cementation of silver (I) in the solution by copper (I) (block 26)
  • Ag * + Cu * Ag° + Cu 2*
  • the solution should be maintained between ambient and 90°C and preferably is between ambient and 50°C
  • the cementation process may be carried out for up to two hours but normally from twenty to forty minutes is adequate Atmospheric pressure may prevail during the cementation step
  • the cementation step 24 can be done in a single stage or in a number of stages with multiple additions of copper (I).
  • the cementation step produces a slurry 28 which is then subjected to a liquid/solid separation step 30 to produce silver cement 32 and a substantially silver-free brine solution 34
  • the silver cement 32 may be treated as required to recover silver products.
  • the silver cement may contain some copper contamination if conditions are such that some disproportio ⁇ ation of copper (I) to copper metal and copper (II) occurs.
  • composition of the slurry 28 is substantially the same as of the solution 20, but with most of the silver removed and higher copper levels
  • the solution 34 is, as indicated in the flow chart, split into a first stream 34A and a second stream 34B
  • the ratio of the split depends on the amount of copper (I) which is required for the cementation step 24 and the amount of copper (I) which is expected to be produced by oxidation of metallic copper by oxidants other than copper (II), eg. iron (III).
  • the first stream 34A may include from 20 to 80% of the solution 34 but normally from 35 to 65% of the solution is adequate
  • the first stream 34A undergoes a copper removal step 36 of any appropriate type
  • sulfide 38 to precipitate copper as copper sulfide 40 which can then be recycled to a sulfide oxidation stage for example the biological leaching step 12 (in the case in which use is previously made of the biological leaching step)
  • a substantially copper-free brine solution 42 is produced This solution may be subjected to a stage 44 for the removal of impurities 46
  • the solution 42 contains the impurities that were present in the original brine solution 20 and the step 44 is used to remove most impurities besides elements like the alkaline metals Further impurity removal treatment such as jarosite precipitation or the introduction of a bleed stream 48 may be resorted to if such elements become problematic
  • the brine solution produced after removal of the impurities 46 carries the reference numeral 50
  • the second stream 34B of the solution 34 undergoes an optional impurity removal stage 52 for the removal of impurities 54
  • the stage 52 may make use of precipitation, solvent extraction or ion exchange techniques depending on the nature of the impurities Possibly problematic impurities are removed except copper and a limited amount of ferric iron
  • the resulting copper (II) solution 56 is then combined with the solution 50 and the copper (II) in the combined solution is reduced to copper (I) in a step 58 by the addition of metallic copper 60 to produce copper (I) (62)
  • the copper (I) solution 62 is clarified by subjecting the solution to a solid/liquid separation stage 64 wherein excess metallic copper 60 is separated from the solution 62.
  • the resulting clarified copper (I) solution 26 is used in the cementation reaction 24
  • the production of copper (I) should be carried out at temperatures between ambient and 90°C, typically between ambient and 50°C
  • the pH of the solution should be maintained between 0 1 and 3,0 and preferably lies between 0,5 and 1 ,5 Up to four hours may be required for the reaction but typically less than one hour is adequate
  • the chloride content of the solution should be between 20 and 200 g/l depending on the chloride concentration in the brine feed stream 20
  • the brine solution 20 should contain 20 - 200 g/l chloride ions and some silver (I), from 1 ppm to saturation levels Other elements that may be tolerated in the bnne solution are
  • Non-oxidising anio ⁇ s and non-precipitating anions with respect to Cu * and Ag ⁇ such as oxidised sulfur species (sulfates, thiosulfate, thionates, etc), acetates and short chain carboxylates can also be tolerated
  • oxidising anions such as chromates and sulfites
  • impurities are not expected to be present in any significant quantity due to their reduction during reduction of copper (II) and hence can be tolerated
  • the list of impurities is not comprehensive and moderate levels of most impurities that do not affect the stability of copper (I) and do not cause precipitation of silver or copper are expected to be acceptable

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Cette invention concerne une technique d'extraction d'argent dans une saumure acide produite par lessivage d'un résidu de biolixiviation d'argent et de cuivre. Selon ce procédé, on ajoute du cuivre à la solution pour déplacer l'argent (1) et produire une suspension dont on extraie l'argent sous forme de dépôt par une opération de séparation des liquides et des solides.
PCT/ZA2000/000130 1999-08-02 2000-08-02 Recuperation d'argent dans une saumure acide par cementation Ceased WO2001009399A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU68049/00A AU6804900A (en) 1999-08-02 2000-08-02 Silver recovery from acidic brine solution by cementation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA99/4930 1999-08-02
ZA994930 1999-08-02

Publications (1)

Publication Number Publication Date
WO2001009399A1 true WO2001009399A1 (fr) 2001-02-08

Family

ID=25587837

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ZA2000/000130 Ceased WO2001009399A1 (fr) 1999-08-02 2000-08-02 Recuperation d'argent dans une saumure acide par cementation

Country Status (3)

Country Link
AU (1) AU6804900A (fr)
PE (1) PE20010614A1 (fr)
WO (1) WO2001009399A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2304095A1 (es) * 2003-09-23 2008-09-01 Outokumpu Technology Oyj Metodo para el tratamiento de lodos anodicos.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB644585A (en) * 1946-11-26 1950-10-11 United States Radium Corp Radioactive metal products and method for making the same
US4124379A (en) * 1977-01-17 1978-11-07 Cyprus Metallurgical Processes Corporation Recovery of silver from cuprous chloride solutions by amalgamation
US4874429A (en) * 1986-10-31 1989-10-17 Austria Metall Aktiengesellschaft Hydrometallurgical process for the recovery of silver from copper electrolysis anode sludge
JPH02294495A (ja) * 1989-05-09 1990-12-05 Dowa Mining Co Ltd 超高純度銅を得るための浄液および電解法
JPH03223429A (ja) * 1990-01-26 1991-10-02 Tanaka Kikinzoku Kogyo Kk 銀含有硝酸液からの銀の回収方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB644585A (en) * 1946-11-26 1950-10-11 United States Radium Corp Radioactive metal products and method for making the same
US4124379A (en) * 1977-01-17 1978-11-07 Cyprus Metallurgical Processes Corporation Recovery of silver from cuprous chloride solutions by amalgamation
US4874429A (en) * 1986-10-31 1989-10-17 Austria Metall Aktiengesellschaft Hydrometallurgical process for the recovery of silver from copper electrolysis anode sludge
JPH02294495A (ja) * 1989-05-09 1990-12-05 Dowa Mining Co Ltd 超高純度銅を得るための浄液および電解法
JPH03223429A (ja) * 1990-01-26 1991-10-02 Tanaka Kikinzoku Kogyo Kk 銀含有硝酸液からの銀の回収方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 015, no. 068 (C - 0807) 18 February 1991 (1991-02-18) *
PATENT ABSTRACTS OF JAPAN vol. 015, no. 508 (C - 0897) 24 December 1991 (1991-12-24) *
PUVVADA G ET AL: "THE CEMENTATION OF AG(I) IONS FROM SODIUM CHLORIDE SOLUTIONS ONTO A ROTATING COPPER DISC", HYDROMETALLURGY,NL,ELSEVIER SCIENTIFIC PUBLISHING CY. AMSTERDAM, vol. 37, no. 2, 1 February 1995 (1995-02-01), pages 193 - 206, XP000501465, ISSN: 0304-386X *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2304095A1 (es) * 2003-09-23 2008-09-01 Outokumpu Technology Oyj Metodo para el tratamiento de lodos anodicos.
ES2304095B2 (es) * 2003-09-23 2009-04-01 Outokumpu Technology Oyj Metodo para el tratamiento de lodos anodicos.

Also Published As

Publication number Publication date
PE20010614A1 (es) 2001-05-25
AU6804900A (en) 2001-02-19

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