WO1992002648A1 - Procede d'extraction de metaux precieux de residus de lessivage - Google Patents

Procede d'extraction de metaux precieux de residus de lessivage Download PDF

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Publication number
WO1992002648A1
WO1992002648A1 PCT/AU1991/000333 AU9100333W WO9202648A1 WO 1992002648 A1 WO1992002648 A1 WO 1992002648A1 AU 9100333 W AU9100333 W AU 9100333W WO 9202648 A1 WO9202648 A1 WO 9202648A1
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WO
WIPO (PCT)
Prior art keywords
valuable metals
leach
accordance
residue
metals
Prior art date
Application number
PCT/AU1991/000333
Other languages
English (en)
Inventor
Roger Leo Player
Steven Paul Matthew
Jorma Matti Ilmari Tuppurainen
Original Assignee
Mount Isa Mines Limited
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 Mount Isa Mines Limited filed Critical Mount Isa Mines Limited
Priority to AU82897/91A priority Critical patent/AU650471B2/en
Publication of WO1992002648A1 publication Critical patent/WO1992002648A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/04Obtaining noble metals by wet processes
    • C22B11/042Recovery of noble metals from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/02Obtaining lead by dry processes
    • C22B13/025Recovery from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/16Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention relates to a method of extracting valuable metals from leach residues and in particular to a method of extracting valuable metals from leach residues of lead and silver.
  • Lead and silver leach residues are an end product of conventional electrolytic zinc refining techniques. It is known that several metals including lead and silver pass through the refining stage to the residue and those metals are not easily recoverable by conventional processes. Presently, the residues are recycled several times by conventional refining techniques and some metal recovery is evident but there is a proportion of lead and silver metal which is not recoverable. Further, the metal content in the residue is so high that the residue is often not safe for disposal. There are also a number of trace metals in the residue and .these ' metals are not recoverable by conventional methods. The trace metals are commercially valuable and some metals such as Ge and In have application in the semiconductor market. It would therefore be of commercial value to recover the metals from the residue.
  • the leach residue is fed continuously and the fume is acid-leached.
  • the leach residue to be treated contains silver, lead, zinc and other metals, all of which substantially revert to fume leaving a slag substantially low in lead, suitable for disposal.
  • the leach residue feeds are in an unneutralized state and may be highly acidic and in yet a further preferred embodiment the residues are lead and silver residues that have been filtered.
  • Valuable metals recovered may include Ag, Pb, Zn, Cd and electronic metals, by which is meant germanium, indium and gallium.
  • the preferred operating temperature is between 1200 to 1220°C, temperatures at which the process was stable and the slags were fluid.
  • the preferred composition of the disposable slag is 0.45% Pb, 0.65% Zn, 350 ppm Ag, 10 ppm Ge, 220 ppm Ga, 10 ppm In, less than 10 ppm Cd, 10 ppm Bi, 10 ppm As and 40 ppm Sb as the aforementioned slag composition meets the West German standard for disposal as Group S solid waste.
  • extraction rates to the fume of valuable metals from unneutralized leach residues will be at least 90% Ag, 98% Pb, 90% Zn, 10% Ga, 99% In and 99% Cd and greater than or equal to 80% Ge. Preferably, 98% Ge.
  • This fume leach residue is then smelted under reducing conditions to produce crude lead and silver together with a low lead slag suitable for disposal.
  • the reducing conditions referred to preferably includes a lance positioned under the surface of the furnace slag wherein enriched air or oxygen and a stoichiometric excess of oil or hydrocarbon gas is fed to the furnace slag.
  • Figure 1 is a process flow sheet of smelting residues in accordance with the present invention.
  • a Pb-Ag leach residue is combined with an iron oxide based flux and coal for reduction and mixed in a pug mill with sufficient water to form a moist agglomerate.
  • This mix constitutes the feedstock and is fed to an ISASMELT furnace by conveyor and dropped directly into a molten slag bath.
  • ISASMELT is a trade mark of Mount Isa Mines.
  • the feedstock may be dried and injected into the bath down the lance.
  • the ISASMELT process is based on submerged gas injection into melts via a top entry submerged SIROSMELT (trade mark) lance to produce turbulent baths in which high intensity smelting or reduction reactions can occur.
  • Heat is supplied by natural gas and combustion air injected down the lance.
  • the slag is tapped continuously or batchwise for disposal.
  • Air or oxygen is injected into the stream of vapours exiting the furnace to oxidize sulphur and to oxidize the metal vapour to metal oxides.
  • the furnace offgas is cooled with spray water and the fume containing valuable metals is collected in a baghouse. The fume from this smelting stage is leached to extract the zinc, cadium and electronic metals for recovery as sulphates.
  • the residue from this leach contains the lead and silver and is smelted via the ISASMELT battery paste process referred to above to produce lead and silver bullion.
  • the battery paste process is operationally similar to the method of smelting the Pb-Ag leach residue feed described above.
  • the fume leach residue is combined with coal for reduction and mixed with sufficient water to form a moist agglomerate.
  • This feedstock is fed to an ISASMELT furnace and dropped directly into the molten slag bath. Heat is supplied by natural gas and combustion air injected down a lance.
  • the lead and silver product is removed as the metal by tapping from the furnace as bullion.
  • the low lead slag resulting from battery paste process is a suitable starting bath for the method of present invention, thereby enabling a direct changeover between the two methods.
  • the slag is batch reduced to produce a disposable low lead slag and smelting of the leach residue feed restarted.
  • a 150 g/1 sulphuric acid leach at 60 ⁇ C gave extractions (metal in solution as a percentage of the metal in the fume) from the fume of > 99% Zn, > 80% Ge, 90% Ga, 85% In and > 99% C (see Table 1). Less than 0.1% of Pb and Ag was extracted.
  • Testwork on Pb-Ag leach residue feed was carried out in a 250Kg Isasmelt furnace.
  • the furnace had an internal diameter of 380mm and was 1.5m high. It was lined with chrome-magnesite refractories. Air and oil were injected into a bath through a 30mm nominal bore lance. Feed was added via a variable speed conveyor and dropped directly into the molten slag bath. The offgases passed through an evaporative gas cooler and were cleaned in .a reverse pulse baghouse.
  • the leach residue feed was mixed with converter slag as a flux and coal for reduction then pelletised prior to each run.
  • 50 kg of slag from previous runs was melted in the furnace to form a starting-bath.
  • the wet residue was then fed continuously to the furnace at a controlled rate and smelted. Oil was used as fuel. Normal air and air enriched to 30 and 35% oxygen were used, with 30% O enrichment giving optimum conditions. Slag samples were taken periodically from the furnace during each run and the fume rates were measured at the baghouse.
  • the Pb-Ag leach residue feed was smelted under reducing conditions in an attempt to produce a disposable slag.
  • This approach maximised the fuming rate and resulted in a leachable fume containing the valuable metals in a single continuous process.
  • reduction smelting was stable and easily controlled, with fluid slags and high fuming rates under a range of operating conditions. All the valuable metals except gallium were extracted into the fume for further recovery and the slag was suitable for disposal.
  • Metal extractions increased with temperature and coal rate. Silver extractions in particular were highly dependent upon temperature and coal rate. Gallium extractions were low under all conditions. Optimum operating conditions were temperatures in the range from 1200 to 1220°C and a coal rate of 40 to 50% by weight of dry residue. The slag composition and metal extractions under such optimum conditions are summarized in Table 1. The projected metal extractions for the proposed plant are also given in Table 1. Example 2
  • Granulated slag samples from five runs were leached according to the West German standard method for "Group S", for determining suitability for disposal as solid waste.
  • Leaching testwork on the fume was carried out under a range of conditions.
  • a 4 hour sulphuric acid leach at 70 g/1 acid strength and 60°C gave a recovery of 95% Zn and 90% Cd from the fume.
  • Increasing acid strength to 110 g/1 recovered 70% of Ge and 25% Ga content of the fume.
  • a sulphuric acid leach at 150 g/1 acid strength and 60°C gave recoveries from the fume of >99% Zn, >80% Ge, 90% Ga, 85% In, and >99% Cd under these conditions.
  • Less than 0.1% of the lead and silver were mobilised and the rest of the lead and silver remained in the fume leach residue after extraction.
  • the smelting rate to treat 40,000 dry tonnes per annum, lead-silver leach residue feed is expected to be 7 tph (dry weight) of the leach residue for 65% of the operating time and 20 tph (dry weight) of the fume leach residue for 5% of the operating time.
  • the separate steps may be carried out on an alternating basis in an Isasmelt furnace preferably of dimensions 2m inside diameter. It is envisaged that over a two week period, the leach residue feed would be treated continuously for a period of 13 days and the resulting fume leach residue on the remaining day.
  • the afterburning prevents condensation of molten elemental sulphur over the surface of the fume particles.
  • 3 tph residue is 7 Nm /s, injection-plus ingress air.
  • the furnace offtake is maintained below 1250°C by 3.6 1/s spray cooling water injected into the offtake.
  • the SO ? content during the afterburning step is low at 1.7% dry basis. It is envisaged that cheaper gas handling systems may prove feasible depending on process changes such as higher slag temperature and reduced coal consumption or reduction by natural gas.
  • ISASMELT VESSEL (2m ID Refractory lined, with water cooled copper top) 1 400 000 GAS COOLER (Refractory lined, including sprays etc.) 1 200 000 LANCE HANDLING 100 000 STRUCTURAL STEEL 400 000 FOUNDATIONS 200 000 CONTROL ROOM 75 000
  • PROCESS AIR BLOWER 850 kW
  • PROCESS GAS BAGHOUSE including bags
  • 500 000 PROCESS GAS FAN 200 000 CHAIN CONVEYOR 100 000
  • Scale up to a production plant is based,on reduction smelting of un-neutralized Pb-Ag leach residue feed at 7 tph (dry wt) for 65% of the time and smelting the fume leach residue at 20 tph (dry wt) for 5% of the time.
  • the maximum smelting rate used during the 250 kg testwork was 80 dry kg residue per hour. Scaling up, this indicates that a furnace of 2.0 m internal diameter is required to smelt 7 dry tph leach residue.
  • This furnace will also enable treatment of the leach residue at 20 dry tph using air enriched to 30% 0 2 and natural gas as fuel.
  • the oil consumption during reduction smelting at 1200 to 1220°C was 300 g oil/dry kg residue at 30% 0 2 , after correcting for furnace heat losses. This is equivalent to a heat requirement 5.2 MJ/dry kg residue on the proposed plant, i.e., when fluxing at 25% haematite, or 10 MW at 7 tph residue.
  • the furnace heat losses on the proposed plant are estimated to be a maximum of 1 MW, giving a total heat load of 11 MW at 7 tph residue.
  • the natural gas required to supply this heat at 1220°C, 90% combustion stoichiometry and 30% 0 ? is 0.65 Nm 3 /s.
  • the air rate at this fuel consumption is 3.8 Nm /s and the oxygen rate is 0.5 NmVs (i.e., 60 tpd) to give 30% 0 2 .
  • the air supply pressure for low pressure lances is 150 kPa, supplied from a single stage blower.
  • the oxygen supply pressure is also 150 kPa.
  • the oil consumption during smelting at 1000°C was 75 g oil/dry kg fume, after correcting for furnace heat losses. Considering the higher water content of the fume after leaching, it is estimated that this is equivalent to a heat requirement of 2.0 MJ/dry kg residue on the proposed plant, or 12 MW at 20 tph residue, with 10% fuming which is recycled. Including furnace heat losses, the total heat load is 13 MW.
  • the natural gas required to supply this heat 1000°C, 95% stoichiometry and 30% 0 2 is 0.60 Nm 2 /s.
  • the air rate at this fuel consumption is 3.7 Nm 2 /s and the oxygen rate is 0.5 NrnVs.
  • the reduction coal rate required to give high metal extractions and a disposable slag during reduction smelting of the leach residue in the testwork was 45% by weight of dry residue; i.e., 2.0 tph fixed carbon for reduction at 7 tph residue. This is equivalent to a coal rate of 2.9 tph for coal containing 70% fixed carbon on the proposed plant.
  • acceptable slag compositions for the process lie in the range 45 to 55% Fe), 30 to 40% (SiO + Al O ) with a maximum of 6% Al O , and 10 to 20% (CaO + MgO) with a maximum of 3% MgO.
  • the holding capacity of a 2 m internal diameter furnace will allow 2 hours operation between slag taps when smelting the leach residue.
  • This slag may be either granulated or cast for disposal depending upon the requirements.
  • the time between crude lead taps when smelting the leach residue will also be 2 hours.
  • Lances are constructed out of schedule 40 mild steel pipe with a stainless steel tip and an internal swirler. They wear by gradual thinning of the tip, and when approximately 300 mm has been worn off another length of stainless steel is rewelded on to the end to form a new tip. Lance lives currently average 100 hours operating time. Similar lives are expected when smelting Pb-Ag leach residues.
  • the furnace is lined with chrome-magnesite wear bricks. Based on known refractory lives, a minimum period of one year is expected between rebricks.
  • a moist agglomerate feedstock is used giving good hygiene.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Manufacture And Refinement Of Metals (AREA)

Abstract

Procédé d'extraction de métaux précieux de résidus de lessivage contenant ces métaux, ledit procédé consistant à: 1) alimenter un four en résidu de lessivage, 2) faire fondre le résidu de lessivage au moyen d'une lance immergée dans des conditions de réduction, 3) récupérer une proportion importante des métaux précieux à partir du four sous forme de fumées, et 4) lessiver les fumées pour en extraire les métaux solubles.
PCT/AU1991/000333 1990-07-27 1991-07-26 Procede d'extraction de metaux precieux de residus de lessivage WO1992002648A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU82897/91A AU650471B2 (en) 1990-07-27 1991-07-26 Method of extracting valuable metals from leach residues

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPK1444 1990-07-27
AUPK144490 1990-07-27

Publications (1)

Publication Number Publication Date
WO1992002648A1 true WO1992002648A1 (fr) 1992-02-20

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Application Number Title Priority Date Filing Date
PCT/AU1991/000333 WO1992002648A1 (fr) 1990-07-27 1991-07-26 Procede d'extraction de metaux precieux de residus de lessivage

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DE (1) DE4191864T1 (fr)
WO (1) WO1992002648A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0489083A1 (fr) * 1989-08-24 1992-06-10 Ausmelt Pty Ltd Traitement par fusion de dechets metallurgiques contenant des composes de fer et des elements toxiques.
EP0581995A1 (fr) 1992-08-07 1994-02-09 Arnotech Consulting AG Récupération de matériaux de valeur
FR2828924A1 (fr) 2001-08-27 2003-02-28 Coflexip Conduite flexible pour le transport d'un fluide

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292283A (en) * 1977-10-27 1981-09-29 Klockner-Humboldt-Deutz Ag Method for the recovery of zinc
US4606760A (en) * 1985-05-03 1986-08-19 Huron Valley Steel Corp. Method and apparatus for simultaneously separating volatile and non-volatile metals
AU6152786A (en) * 1985-08-16 1987-02-19 Ausmelt Pty Ltd Recovery of zinc, plus silver and lead, as a fume by lancing
US4655437A (en) * 1985-05-03 1987-04-07 Huron Valley Steel Corp. Apparatus for simultaneously separating volatile and non-volatile metals
AU6109490A (en) * 1985-08-16 1990-11-22 Ausmelt Pty Ltd Recovery of metal values from metal bearing materials
AU6274290A (en) * 1989-08-24 1991-04-03 Ausmelt Pty Ltd Smelting of metallurgical waste materials containing iron compounds and toxic elements

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292283A (en) * 1977-10-27 1981-09-29 Klockner-Humboldt-Deutz Ag Method for the recovery of zinc
US4606760A (en) * 1985-05-03 1986-08-19 Huron Valley Steel Corp. Method and apparatus for simultaneously separating volatile and non-volatile metals
US4655437A (en) * 1985-05-03 1987-04-07 Huron Valley Steel Corp. Apparatus for simultaneously separating volatile and non-volatile metals
AU6152786A (en) * 1985-08-16 1987-02-19 Ausmelt Pty Ltd Recovery of zinc, plus silver and lead, as a fume by lancing
AU6109490A (en) * 1985-08-16 1990-11-22 Ausmelt Pty Ltd Recovery of metal values from metal bearing materials
AU6274290A (en) * 1989-08-24 1991-04-03 Ausmelt Pty Ltd Smelting of metallurgical waste materials containing iron compounds and toxic elements

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0489083A1 (fr) * 1989-08-24 1992-06-10 Ausmelt Pty Ltd Traitement par fusion de dechets metallurgiques contenant des composes de fer et des elements toxiques.
EP0489083A4 (fr) * 1989-08-24 1994-01-19 Ausmelt Pty. Ltd.
EP0581995A1 (fr) 1992-08-07 1994-02-09 Arnotech Consulting AG Récupération de matériaux de valeur
FR2828924A1 (fr) 2001-08-27 2003-02-28 Coflexip Conduite flexible pour le transport d'un fluide

Also Published As

Publication number Publication date
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