[go: up one dir, main page]

EP1971696A1 - Procédé de précipitation de nickel - Google Patents

Procédé de précipitation de nickel

Info

Publication number
EP1971696A1
EP1971696A1 EP07701358A EP07701358A EP1971696A1 EP 1971696 A1 EP1971696 A1 EP 1971696A1 EP 07701358 A EP07701358 A EP 07701358A EP 07701358 A EP07701358 A EP 07701358A EP 1971696 A1 EP1971696 A1 EP 1971696A1
Authority
EP
European Patent Office
Prior art keywords
nickel
sulphide
iron
solution
cobalt
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Withdrawn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
EP07701358A
Other languages
German (de)
English (en)
Other versions
EP1971696A4 (fr
Inventor
Michael Rodriguez
Bruce James Wedderburn
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 AU2006900103A external-priority patent/AU2006900103A0/en
Application filed by Murrin Murrin Operations Pty Ltd filed Critical Murrin Murrin Operations Pty Ltd
Publication of EP1971696A1 publication Critical patent/EP1971696A1/fr
Publication of EP1971696A4 publication Critical patent/EP1971696A4/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Withdrawn legal-status Critical Current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
    • C22B3/20—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
    • 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
    • C22B15/0093—Treating solutions by chemical methods by gases, e.g. hydrogen or hydrogen sulfide
    • 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
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
    • 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 method for the precipitation of nickel. More particularly, the present invention is a hydrometallurgical method for the preferential precipitation of nickel and cobalt sulphides from solutions containing iron and/or chrome. Additionally, the method is intended to substantially avoid the formation of sulphide scale during the precipitation process.
  • Nickel and cobalt are typically recovered from leach solutions by contacting the pregnant liquors with a suitable reductant such as hydrogen sulphide. It is known that iron and chrome will tend to co-precipitate as a sulphide under conventional hydrogen sulphide precipitation conditions. Such co-precipitation is undesirable for the detrimental effect on product quality and the demands placed on downstream processing of the mixed sulphide product.
  • iron is most often rejected as a ferric oxyhydroxide (typically as a goethite) and as a hematite product . In some situations iron is also rejected as a jarosite product.
  • Hematite is the most acceptable iron product for intermediate storage or disposal, because of its high thermodynamic stability, its high density (4.9 to 5.3 g/cm 3 ), its high iron content (60% - 70%) and its low adsorption of water and base metals.
  • the rejection of iron as a hematite product in the high pressure acid leaching processes used for nickel laterites necessitates the use of temperatures in the order of 25O 0 C and pressures in the order of 45 Bar. This process by its very nature involves capital intensive equipment which is itself expensive to maintain and has associated high operating costs.
  • the present method has as one objective thereof to substantially overcome the problem of scaling, whilst also providing the advantage that the incidence of iron sulphide co-precipitation is reduced, or to at least provide a useful alternative to prior art methods.
  • the preceding discussion of the background art is intended to facilitate an understanding of the present invention only. It should be appreciated that the discussion is not an acknowledgement or admission that any of the material referred to was part of the common general knowledge in Australia as at the priority date of the application.
  • the reductant in (i) and (iii) comprises one or more of hydrogen sulphide, sodium hydrogen sulphide, or sulphur dioxide.
  • free acid concentration is preferably within the range of about 0.5 g/L to 3.5 g/L
  • the neutralising agent of step (ii) may comprise any one or more of limestone, lime and calcrete.
  • step (i) preferably occurs at less than about 100 0 C and ambient pressure.
  • the resulting ferric sulphate concentration of the resulting solution of step (iii) is less than about 1 g/L.
  • the oxidation potential of the solution resulting from step (i) through to (vi) is maintained between about 30OmV and 40OmV (measured against a Pt- Ag/AgCI reference electrode) to ensure no oxidation of ferrous sulphate to ferric sulphate occurs.
  • the solution temperature is in the range of about 8O 0 C to 12O 0 C when sulphide seed is added.
  • the concentration of seed in solution is in the range of about 10g/L to 100g/L and the total seed surface area is between about 1 m 2 /L and 10m 2 /L.
  • Hydrogen sulphide overpressure in step (v) and step (vi) is preferably maintained between about 10OkPa and 40OkPa in order to produce the mixed sulphide product.
  • the residence time of step (vi) is between about 0.25 to 4 hours is employed to ensure complete precipitation of the mixed sulphide. Still preferably, the residence is between about 0.5 and 1.5 hours.
  • the concentration of nickel in the leach solution is preferably in the range of about 1 g/L to 50 g/L, and cobalt within about 0.1 g/L to 10 g/L.
  • the concentration of nickel is in the range of about 1 g/L to 10 g/L for a nickel laterite solution, or between about 10 g/L and 50 g/L for a nickel sulphide solution.
  • Cobalt concentrations are preferably within the range of about 0.1 g/L to 2 g/L, and about 2 g/L to 10 g/L respectively.
  • Iron concentration in the leach solution is preferably in the range of about 0.5g/L to 15g/L.
  • Figure 1 is a diagrammatic representation of a flow sheet depicting a method for the precipitation of nickel and cobalt from leach solutions in the presence of iron in accordance with the present invention.
  • FIG. 1 there is shown a hydrometallurgical method 10 for precipitating nickel and cobalt from pregnant leach solutions, also containing iron, obtained from the high pressure acid leach of a nickel laterite ore.
  • the nickel concentration is in the range of 1 g/L to 10 g/L.
  • Cobalt concentrations are within the range of 0.1 g/L to 2 g/L.
  • Iron concentration in the leach solution is in the range of about 0.5-15g/L.
  • Th ⁇ method 10 of the present invention comprises passing such a pregnant leach solution to a pre-reduction step 12 in which hydrogen sulphide gas 13 is sparged through the solution at a temperature of less than 100 0 C. Iron present as ferric sulphate (Fe 2 (SO 4 ) 3 ) is reduced to ferrous sulphate (FeSO 4 ) such that the resulting ferric concentration is less than 1 g/L.
  • the solution from the pre-reduction circuit 12 then undergoes neutralisation 14 using a calcrete slurry to reduce the free acid (FA) concentration to between about 0.5 and 3.5 g/L. It is understood that if the oxidation potential of the solution is not controlled, then ferric can form during neutralisation 14. Consequently, following neutralisation 14 a stream of hydrogen sulphide gas 15 is again passed through the solution from the pre-reduction circuit 12 in an additional reduction step 16, to ensure that the oxidation potential is within the range of about 300 to 400 mV (Pt-Ag/AgCI reference electrode), for example 350-380 mV.
  • a pre-heating step 18 raises the temperature of the solution from the reduction step 16 to between about 80 and 12O 0 C in preparation for a subsequent precipitation step 20.
  • a mixed sulphide seed 21 in the range of 10 g/L to 100 g/L is introduced to the solution prior to the introduction of hydrogen sulphide gas 22.
  • the total seed surface area is between about 1m 2 /L and 10m 2 /L.
  • Hydrogen sulphide gas 22 is introduced at an overpressure of 100-400 kPa to precipitate a mixed sulphide product 24. This is maintained for the duration of the residence time, between about 0.25 to 4 hours, for example 0.5 to 1.5 hours, in order to effect complete conversion to the mixed sulphide product 24.
  • the pre-heating step 18 allows the precipitation step 20 to occur within acceptable commercial parameters by increasing the kinetics of the precipitation reactions and also allows dissolved H 2 S to be driven off.
  • Neutralisation may also be effected using any one of lime, limestone, ammonia or caustic.
  • the mixed sulphide precipitate contains nickel in the range of 50 to 55%, cobalt at 3 to 5% and iron at 1 to 3% wt/wt.
  • Table 1 Composition of Mixed Sulphide Feed Solution 1.
  • Solution 1 proceeded directly to mixed sulphide precipitation, whilst the Eh of Solution 2 was first reduced to 350-380 mV (Pt-Ag/AgCI reference electrode) with H 2 S to ensure all iron in ferric form was converted to ferrous before heating the solution in preparation for sulphide precipitation.
  • the method of the present invention may be applied to the recovery of nickel and cobalt from nickel sulphide leach solutions.
  • the pregnant leach solution have a nickel concentration in the range of about 10 g/L to 50 g/L, and a cobalt concentration of about 2 g/L to 10 g/L.
  • iron concentration is typically in the range of about 0.5 to 15g/L

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (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

L'invention concerne un procédé (10) de récupération de nickel et de cobalt dans des solutions de lixiviation en présence de fer ou de chrome, ledit procédé consistant i) à ajouter un agent (13) de réduction à une solution de lixiviation contenant du nickel, du cobalt et du fer, de manière que toute quantité de fer sous forme de sulfate ferrique soit réduite en sulfate ferreux et/ou toute quantité de chrome hexavalent soit réduite en chrome trivalent; ii) à neutraliser (14) au moins une partie de l'acide libre par ajout d'un agent de neutralisation; ii) à ajouter un agent (15) de réduction afin de garantir que tout le fer présent conserve sa forme ferreuse et/ou le chrome conserve sa forme trivalente; iv) à chauffer la solution avant la précipitation du sulfure mélangé; v) à ajouter un germe (21) de sulfure mélangé et un sulfure d'hydrogène (22) pour réaliser la précipitation (20) du nickel et du cobalt sous la forme d'un produit de sulfure mélangé (24); et (vi) à maintenir ce mélange en présence du sulfure d'hydrogène (22) pendant le temps de séjour nécessaire, afin de permettre la précipitation complète du produit de sulfure mélangé (24).
EP07701358.9A 2006-01-10 2007-01-10 Procédé de précipitation de nickel Withdrawn EP1971696A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2006900103A AU2006900103A0 (en) 2006-01-10 Method for the Precipitation of Nickel
PCT/AU2007/000013 WO2007079531A1 (fr) 2006-01-10 2007-01-10 Procédé de précipitation de nickel

Publications (2)

Publication Number Publication Date
EP1971696A1 true EP1971696A1 (fr) 2008-09-24
EP1971696A4 EP1971696A4 (fr) 2013-09-04

Family

ID=38255905

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07701358.9A Withdrawn EP1971696A4 (fr) 2006-01-10 2007-01-10 Procédé de précipitation de nickel

Country Status (7)

Country Link
EP (1) EP1971696A4 (fr)
AU (1) AU2007204590B2 (fr)
BR (1) BRPI0706851A2 (fr)
CA (1) CA2636378A1 (fr)
RU (1) RU2008126770A (fr)
WO (1) WO2007079531A1 (fr)
ZA (1) ZA200805618B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5245768B2 (ja) * 2008-11-28 2013-07-24 住友金属鉱山株式会社 ニッケル及びコバルトを含む硫化物の製造方法
EP2430201B1 (fr) * 2009-04-30 2018-10-17 World Resources Company Procédé de récupération de métaux et de composés métalliques à partir de minerai extrait et d'autres matières premières sources contenant des métaux
CN111498916B (zh) * 2020-06-03 2022-07-26 中国恩菲工程技术有限公司 红土镍矿制备氢氧化镍钴过程中去除六价铬的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6261527B1 (en) * 1999-11-03 2001-07-17 Bhp Minerals International Inc. Atmospheric leach process for the recovery of nickel and cobalt from limonite and saprolite ores
AUPS201902A0 (en) * 2002-04-29 2002-06-06 Qni Technology Pty Ltd Modified atmospheric leach process for laterite ores
AU2002950815A0 (en) * 2002-08-15 2002-09-12 Wmc Resources Ltd Recovery nickel
JP4525428B2 (ja) * 2004-05-13 2010-08-18 住友金属鉱山株式会社 ニッケル酸化鉱石の湿式製錬方法
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

Also Published As

Publication number Publication date
ZA200805618B (en) 2009-08-26
WO2007079531A1 (fr) 2007-07-19
CA2636378A1 (fr) 2007-07-19
BRPI0706851A2 (pt) 2011-04-12
AU2007204590B2 (en) 2010-07-22
EP1971696A4 (fr) 2013-09-04
RU2008126770A (ru) 2010-02-20
AU2007204590A1 (en) 2007-07-19

Similar Documents

Publication Publication Date Title
AU2007204591B2 (en) Hematite precipitation
US7329396B2 (en) Process for the recovery of value metals from material containing base metal oxides
EP0862659B1 (fr) TECHNIQUE DE RECUPERATION DE NICKEL DANS UN MINERAI LATERITIQUE AU Ni-Fe-Mg A FORTE TENEUR EN MAGNESIUM
AU2007288123B2 (en) Improved hydrometallurgical method for the extraction of nickel from laterite ores
US4097575A (en) Roast-neutralization-leach technique for the treatment of laterite ore
AU2017218246B2 (en) Sulfuration treatment method, sulfide production method, and hydrometallurgical process for nickel oxide ore
CA2799528A1 (fr) Procede permettant de controler la reaction dans une etape de reaction de sulfuration
AU2005248187B2 (en) Method of recovering nickel or cobalt
Hosseini Nasab et al. Selective precipitation of iron from multi-element PLS produced by atmospheric leaching of Ni-Co bearing laterite
EP3252177A1 (fr) Procédé de fusion humide pour minerai d'oxyde de nickel
AU2007204590B2 (en) Method for the precipitation of nickel
AU2008341033B2 (en) Selectively leaching cobalt from lateritic ores
WO2011120127A1 (fr) Lixiviation faiblement acide de nickel et de cobalt à partir de minerais de nickel pauvres contenant du fer
AU2007100742B4 (en) Method for the Precipitation of Nickel
US20100300249A1 (en) Recovering Metal Values from a Leach Residue
AU2017220174B2 (en) Neutralization method and nickel oxide ore hydrometallurgical method
JP7176595B1 (ja) 鉱石スラリーの製造方法、ニッケル酸化鉱石の湿式製錬方法
Hosseini Nasab et al. The effect of inorganic acids on reducing iron impurities during iron-rich laterite ore leaching
US20100300248A1 (en) Recovering Metal Values from a Metalliferrous Material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080630

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL MK

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: MURRIN MURRIN OPERATIONS PTY LTD

RAX Requested extension states of the european patent have changed

Extension state: AL

Payment date: 20080710

Extension state: MK

Payment date: 20080630

A4 Supplementary search report drawn up and despatched

Effective date: 20130806

RIC1 Information provided on ipc code assigned before grant

Ipc: C22B 23/00 20060101ALI20130731BHEP

Ipc: C22B 3/44 20060101ALI20130731BHEP

Ipc: C22B 3/20 20060101AFI20130731BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140304