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EP2326737A1 - Procédé hydrométallurgique permettant de lixivier des métaux de base - Google Patents

Procédé hydrométallurgique permettant de lixivier des métaux de base

Info

Publication number
EP2326737A1
EP2326737A1 EP09813904A EP09813904A EP2326737A1 EP 2326737 A1 EP2326737 A1 EP 2326737A1 EP 09813904 A EP09813904 A EP 09813904A EP 09813904 A EP09813904 A EP 09813904A EP 2326737 A1 EP2326737 A1 EP 2326737A1
Authority
EP
European Patent Office
Prior art keywords
hydrometallurgical method
acid
concentrate
range
nickel
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.)
Withdrawn
Application number
EP09813904A
Other languages
German (de)
English (en)
Inventor
John O'callaghan
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.)
Murrin Murrin Operations Pty Ltd
Original Assignee
Murrin Murrin Operations Pty 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
Priority claimed from AU2008904868A external-priority patent/AU2008904868A0/en
Application filed by Murrin Murrin Operations Pty Ltd filed Critical Murrin Murrin Operations Pty Ltd
Publication of EP2326737A1 publication Critical patent/EP2326737A1/fr
Withdrawn legal-status Critical Current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
    • 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
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • 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 a hydrometallurgical method for leaching base metals. More particularly, the method of the present invention is intended to provide a single process capable of use in the leaching of nickel from a variety of nickel ore compositions.
  • HPAL High Pressure Acid Leach
  • ORP oxidation reduction potential
  • Non-smeltable nickel sulphides are typically unsuitable for smelting as they generally contain high quantities of magnesium (Mg), often in the form of magnesia (MgO). If the MgO content of the slag produced in smelting is too high, it becomes very viscous and can be difficult to remove from the furnace. Further, these ores contain arsenic at levels which render them generally unsuitable to pyrometallurgical treatment due to the potential health and safety issues.
  • Mg magnesium
  • MgO magnesia
  • Australian Innovation Patent 2008100563 addresses the treatment of sulphide ores and/or concentrates in a high pressure acid leach (HPAL) circuit by combining the sulphide ore or concentrate with a HPAL feed comprising oxide ore material and, importantly, adding an oxidant to the HPAL circuit.
  • HPAL high pressure acid leach
  • the present method has as one object thereof to substantially overcome problems associated with the prior art, or to at least provide a useful alternative to those prior art methods.
  • the presence of some ferric iron is maintained by the acid dissolution of hematite at one or more points in the PAL circuit.
  • the free acid concentration measured in the autoclave discharge liquor (after cooling) is preferably within the range of about 10 to 80 g/L.
  • the free acid concentration measured in the cooled autoclave discharge is preferably within the range of about 30 to 60 g//L.
  • the sulphide ore or concentrate is preferably a nickel sulphide ore or concentrate.
  • the oxide ore material comprises a nickel oxide ore or nickel laterite.
  • the sulphide ore or concentrate may comprise a smeltable sulphide ore or concentrate, a non-smeltable ore or concentrate, or a blend thereof.
  • the PAL circuit may preferably comprise a plurality of autoclaves arranged in parallel.
  • the at least one autoclave is preferably operated within the temperature range of about 200 0 C to 27O 0 C
  • the at least one autoclave is operated within the temperature range of about 23O 0 C to 26O 0 C.
  • the pressure of within the autoclave is preferably maintained within the range of about 350OkPa to 650OkPa.
  • the pressure within the autoclave is maintained within the range of 400OkPa to 550OkPa.
  • the oxide ore material preferably has an iron content within the range of about 10% to 50%. More preferably, iron content in the oxide ore material is preferably within the range of about 15% to 50%.
  • the ferric iron concentration in the autoclave is preferably at least about 0.02 g/L.
  • the ferric iron concentration in the autoclave is preferably at least about 0.1 g/L.
  • acid is provided in the form of one or more of a pregnant leach solution (PLS) exiting an atmospheric leach circuit, or an aqueous acid solution comprising acid and water, or concentrated acid.
  • PLS pregnant leach solution
  • aqueous acid solution comprising acid and water, or concentrated acid.
  • acid levels may be supplemented by the addition of aqueous acid solution.
  • the acid is sulphuric acid.
  • the sulphide ore or concentrate preferably has a nickel content within the range of about 2% to 30%.
  • the sulphide ore or concentrate and has a nickel content within the range of about 5% to 20%.
  • the sulphide ore or concentrate preferably comprises about 1 % to 30% (w/w) of the slurry.
  • the sulphide ore or concentrate preferably comprises about 1% to 20% (w/w) of the slurry.
  • the oxide ore preferably has a nickel content within the range of about 0.5% to 3%.
  • the oxide ore has a nickel content within the range of about 0.9% to 2%.
  • the residence time within the autoclave is preferably within the range of about 15 to 120 minutes. More preferably, the residence' time within the autoclave is within the range of about 30 to 90 minutes.
  • the base metals may include but is not limited to, any one or more of nickel, copper and zinc.
  • the oxidation/reduction potential (ORP) of the cooled autoclave discharge is within the range of about 250 to 90OmV (measured against an Ag/AgCI reference).
  • the ORP of the cooled autoclave discharge is within the range of about 300 to 500 mV (Ag/AgCI reference).
  • the PAL circuit is in the form of a high pressure acid leach circuit (HPAL).
  • HPAL high pressure acid leach circuit
  • the acid concentration in the slurry is sufficient to ensure some iron remains in its oxidised (ferric) form in the presence of the nickel sulphide ore or concentrate.
  • FIG. 1 is a diagrammatic representation of a flow sheet depicting a hydrometallurgical method for leaching nickel in accordance with the present invention.
  • FIG. 1 there is shown a hydrometallurgical method 10 for the leaching of base metals in accordance with the present invention.
  • a sulphide ore for example a nickel sulphide ore 12, comprising a smeltable sulphide ore or non-smeltable ore, or a blend thereof, undergoes a concentration step 14 to produce a nickel sulphide concentrate 16.
  • the nickel sulphide concentrate 16 having a nickel content within the range of about 2% to 30%, for example about 5% to 20%, is then combined with an oxide ore, for example a nickel oxide or nickel laterite ore 18, together with water and/or acid 19, to form a slurry 20.
  • the acid 19 may comprise a pregnant leach solution (PLS) exiting an atmospheric leach, for example a heap leach, or an aqueous acid solution comprising acid and water, or it may comprise concentrated acid, for example sulphuric acid.
  • PLS pregnant leach solution
  • the content of nickel within the nickel laterite ore 18 is within the range of about 0.5% to 3%, for example 0.9% to 2%.
  • the nickel sulphide ore 12 or concentrate 16 and nickel laterite ore 18 are combined such that the nickel sulphide ore 12 or concentrate 16 comprises about 1 % to 30% of the slurry 20, for example 1 % to 20%.
  • the slurry 20 is then directed to an autoclave 22 of a pressure acid leach circuit, for example a high pressure acid leach (HPAL) circuit.
  • the HPAL circuit may comprise a plurality of autoclaves arranged in parallel.
  • the slurry 20, is then leached in the autoclave 22 at a temperature within the range of about 200 0 C to 27O 0 C, for example, about 230 0 C to 26O 0 C and a pressure within the range of about 350OkPa to 650OkPa, for example about 4000kpa to 550OkPa, for a residence time within the range of about 15 to 120 minutes, for example, 30 to 90 minutes.
  • the free acid concentration within the autoclave 22 is sufficient to ensure that the ferric iron in solution remains at or above at least about 0.02 g/L, for example at least about 0.1 g/L.
  • the resulting autoclave discharge liquor 24 exiting the autoclave 22 is then subjected to known recovery processes. It will be noted that the process of the present invention does not require the addition of an oxidant. This is because provided the free acid levels are within the range of about 10 to 80g/L as measured in the cooled autoclave discharge liquor, for example about 30 to 60 g/L, the ferric iron concentration can be maintained, albeit at low concentrations. This is understood to result from the dissolution of hematite (which is precipitated from solution under autoclave conditions), in the presence of acid.
  • ferric iron Small quantities of ferric iron (as low as about 0.02g/L) remain in solution, and this has been found to be sufficient to oxidise sulphide in the ore to sulphate. Thus, as the ferric iron is consumed, more ferric is subsequently generated by the dissolution of hematite. It is important to note that unlike previous processes, the process of the present invention does not require ORP to be controlled. Again, this results as provided there is sufficient acid present, the ferric iron will be present and oxidising conditions maintained.
  • the sulphide ore 12 need not necessarily undergo a concentration step 14 in order to be utilised in the method of the present invention. It is also understood that the sulphide ore 12 or concentrate 16, and the oxide ore 18 could be added directly to the autoclave 22, together with water and/or acid 19 without the requirement of blending first.
  • the process of the present invention helps to overcome the problems associated with treating sulphide ores having high Mg content, which can cause problems in pyrometallugical methods.
  • Leaching experiments were conducted using a vertical reactor constructed from Grade 705 Zirconium and fitted with a titanium grade 2 dip tube to which was attached a porous 4842 moel temperature controller via electrical elements housed within a stainless steel enclosure and electrically switched water stream passing through a serpentine cooling coil. Agitation was provided by a magnetically driven twin impeller.
  • Slurry feeds were made up from 577g ore, 1100 g tap water and 51.25 g ferrous sulphate heptahydrate. These were charged to the reactor, the head space displaced 3-4 times to an overpressure of 10OkPa with industrial nitrogen to minimise oxidation of ferrous ion and heating applied to bring the mixture to the acid addition temperature of 235 0 C.
  • the required acid charge was injected using excess pressure supplied from a cylinder of industrial nitrogen using an actuated valve system.
  • the amounts of acid used were targeted to leave i) 30-40g/L free acid and ii) 50-60 g/L free acid, in the final liquors.
  • Sulphuric acid was also added such that the concentration was 22 g/L in the synthetic liquor, in order to obtain a target free acidity of 30 g/L after ferric iron hydrolysis.
  • the Oxidation/Reduction potential (ORP) measurement was made at room temperature within 15 minutes of taking the sample using a TPS smartChem-pH-mV-Temperature meter with platinum electrode (Ag/AgCI, saturated KCI reference) calibrated against a fresh mixture of ZoBell's solution (Eh 236 mV at 22 0 C).
  • the ferrous iron content of the liquor was determined by titrating 10 mL aliquots, to which was added 10 mL of 50:30 sulphuric: phosphoric acid mixture and 4-5 drops of barium diphenylamine sulphonate indicator, against 0.05N potassium dichromate solution.
  • the ferrous iron concentrations in the final HPAL liquors are approximately half of those in the feed slurry, consistent with oxidation by manganese in the smectite/saprolite ore.
  • the change in ORP is approximately 30 mV when the final acidity changes from about 40 g/L to about 85 g/L.
  • the higher ORP at higher acidity is consistent with the presence of greater amounts of ferric iron arising from the acid dissolution of hematite.
  • the nickel sulphide ore composition is provided in Table 5 below:
  • sulphide ores and concentrates can be processed in a HPAL circuit without the need to add further oxidant to the system.
  • the acid levels are maintained at a suitable level, low levels of ferric iron remain in solution. These low levels of ferric iron concentration are sufficient to provide oxidising conditions within the autoclave sufficient to oxidise the sulphide content.
  • Oxidising conditions in the autoclave also minimises damage to the autoclave lining as a result of the reduction of titanium dioxide.
  • Table 7 provides a sample of plant data for a leaching trial conducted and good extractions obtained. Importantly, it should be noted that it was anticipated that extractions would drop slightly if ORP increased. Therefore, if an increase in ORP was observed at any time, additional acid was added to compensate and to ensure extraction levels were maintained.

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

Abstract

La présente invention porte sur un procédé hydrométallurgique permettant de lixivier des métaux de base et comprenant les étapes consistant à : i) combiner un matériau de minerai oxydé avec un minerai sulfuré ou un concentré sulfuré en présence d'un acide pour former une pâte; et ii) lixivier la pâte dans un circuit de lixiviation acide sous pression (PAL) pour produire une liqueur résiduelle stérile lixiviée, la concentration d'acide dans la pâte étant suffisante pour garantir que fer reste sous sa forme oxydée (ferrique) en présence du minerai sulfuré ou du concentré sulfuré.
EP09813904A 2008-09-19 2009-09-18 Procédé hydrométallurgique permettant de lixivier des métaux de base Withdrawn EP2326737A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2008904868A AU2008904868A0 (en) 2008-09-19 A Hydrometallurgical Methods for Leaching Base Metals
PCT/AU2009/001245 WO2010031137A1 (fr) 2008-09-19 2009-09-18 Procédé hydrométallurgique permettant de lixivier des métaux de base

Publications (1)

Publication Number Publication Date
EP2326737A1 true EP2326737A1 (fr) 2011-06-01

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP09813904A Withdrawn EP2326737A1 (fr) 2008-09-19 2009-09-18 Procédé hydrométallurgique permettant de lixivier des métaux de base

Country Status (5)

Country Link
EP (1) EP2326737A1 (fr)
AU (1) AU2009295281B2 (fr)
BR (1) BRPI0913728A2 (fr)
CA (1) CA2737324A1 (fr)
WO (1) WO2010031137A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012065222A1 (fr) * 2010-11-19 2012-05-24 Murrin Murrin Operations Pty Ltd Procédé pour la lixiviation d'un sulfure métallique
US12286686B2 (en) 2021-02-24 2025-04-29 Sherritt International Corporation Co-processing of copper sulphide concentrate with nickel laterite ore

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPM790894A0 (en) * 1994-09-05 1994-09-29 Western Mining Corporation Limited Mineral processing
JP3790152B2 (ja) * 2001-11-14 2006-06-28 日鉱金属株式会社 硫化銅鉱石からの銅の浸出方法
CN1465723A (zh) * 2002-06-23 2004-01-07 唐尚文 氧化锰矿和硫化锌(或硫化铅)精矿在稀酸中直接、同时浸出的方法
CN102586624A (zh) * 2004-11-17 2012-07-18 Bhp比利通Ssm开发有限公司 相继或同时浸取含有镍和钴的矿石
US7387767B2 (en) * 2005-04-07 2008-06-17 Dynatec Corporation Recovery of nickel, cobalt, iron, silica, zinc and copper from laterite ore by sulfuric acid leaching
WO2007095689A1 (fr) * 2006-02-24 2007-08-30 Murrin Murrin Operations Pty Ltd Precipitation d'hematite a haute temperature et haute pression
AU2008100563C4 (en) * 2008-06-13 2010-02-18 Murrin Murrin Operations Pty Ltd Method for the Recovery of Nickel from Ores
AU2008101213B8 (en) * 2008-09-10 2010-04-29 Murrin Murrin Operations Pty Ltd Method for Leaching Nickel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010031137A1 *

Also Published As

Publication number Publication date
BRPI0913728A2 (pt) 2015-10-13
AU2009295281A1 (en) 2010-03-25
AU2009295281B2 (en) 2015-03-26
CA2737324A1 (fr) 2010-03-25
WO2010031137A1 (fr) 2010-03-25

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