WO2009039580A1 - Stabilisation de sulfates métalliques - Google Patents

Stabilisation de sulfates métalliques Download PDF

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Publication number
WO2009039580A1
WO2009039580A1 PCT/AU2008/001431 AU2008001431W WO2009039580A1 WO 2009039580 A1 WO2009039580 A1 WO 2009039580A1 AU 2008001431 W AU2008001431 W AU 2008001431W WO 2009039580 A1 WO2009039580 A1 WO 2009039580A1
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WO
WIPO (PCT)
Prior art keywords
metal sulfate
process according
product
crystals
magnesium
Prior art date
Application number
PCT/AU2008/001431
Other languages
English (en)
Inventor
Eric Girvan Roche
John Baines
Original Assignee
Bhp Billiton Ssm Development 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 AU2007905265A external-priority patent/AU2007905265A0/en
Application filed by Bhp Billiton Ssm Development Pty Ltd filed Critical Bhp Billiton Ssm Development Pty Ltd
Publication of WO2009039580A1 publication Critical patent/WO2009039580A1/fr

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
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/96—Methods for the preparation of sulfates in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/40—Magnesium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B9/00—Magnesium cements or similar cements
    • C04B9/04—Magnesium cements containing sulfates, nitrates, phosphates or fluorides
    • 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
    • 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
    • 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 process for stabilising metal sulfates that may be present in a brine solution in a metal recovery process.
  • the invention is particularly applicable to the stabilising magnesium sulfate crystals, that may have been salted out of the final brine from a nickel and/or cobalt recovery process. It is also applicable to stabilising other metal sulfates that may be present in such solution, such as iron sulfate and manganese sulfate, or metal sulfate salts sourced from another source.
  • the stabilised metal sulfate product will be a solidified compound which will exhibit good stability to water and is dense and geotechnically stable.
  • Laterite ores include both a high magnesium content saprolite component, and a low magnesium content limonite component.
  • nickel and cobalt are recovered from laterite ore by high pressure acid leach processes where the nickel and cobalt are leached from the ore with sulfuric acid. Following the addition of magnesium oxide, the nickel and cobalt are recovered as a mixed nickel and cobalt hydroxide precipitate.
  • metals for example magnesium, ferric iron, ferrous iron, aluminium, chromium and manganese may also be discarded, or metals from other sources such as any magnesium solubilised from magnesium oxide, that may be used in the process, is also discarded as waste.
  • the dissolved metals generally report to brine associated with the refinery as metal sulfates or metal chloride brine.
  • a solution that includes magnesium sulfate for example the brine solution from a laterite ore leaching process, is bled from the circuit and stored in evaporation ponds where the magnesium precipitates due to evaporation.
  • the water balances in these circuits are maintained with "fresh" make-up water. While this method is acceptable in arid regions it is not suitable for areas where there is a high net positive rainfall. Hence an alternative method for rejecting magnesium from solution and fixing it into an environmentally suitable product is required.
  • the current process for rejecting magnesium from solution in areas of high rainfall is to increase the solution pH with lime to precipitate magnesium producing a residue containing gypsum and magnesium hydroxide.
  • the lime consumption and disposal requirements add significantly to project costs and can result in the project becoming uneconomical.
  • alternative options for rejecting magnesium from solution need to be developed to improve the economics for processing tropical laterites/saprolites.
  • the present invention aims to provide a process where magnesium sulfate in solution, for example magnesium sulfate that is the waste product of a nickel and/or cobalt recovery process, is converted to a stable, environmentally suitable end product
  • the present invention provides a process for the stabilisation of a crystallised metal sulfate product.
  • the process is particularly applicable to stabilising magnesium sulfate crystals that have been recovered from the brine solution that is generally regarded as waste from nickel and/or recovery processes. It is also applicable to stabilising other sulfates that may be present, such as iron sulfate and manganese sulfate.
  • a stabilising compound such as lime (slaked or unslaked lime)
  • crystallised metal sulfates by adding a sub-stoichiometric amount of a stabilising compound, such as lime (slaked or unslaked lime) to crystallised metal sulfates, that a stable solid may be formed that is environmentally suitable for disposal.
  • the stable product is rock-like, has low porosity and has substantially lower solubility in water than crystallised metal sulfates, and so can be readily used as landfill.
  • a process for producing a stable solid metal sulfate product including the steps of: a) providing a source of crystallised metal sulfate; b) adding a sub-stoichiometric amount of a stabilising compound to the crystallised metal sulfate to form a paste or slurry like intermediate product; and c) allowing the paste or slurry like product to solidify.
  • the present invention is particularly applicable to providing a stable solid metal sulfate where the metal sulfate is derived from a nickel and/or cobalt recovery process although the process is not restricted to this embodiment.
  • the metal sulfate may have been derived from the metal sulfates that are present in waste brine that result from a nickel and/or cobalt recovery process.
  • the process is particularly applicable to processing waste brine that may result from the sulfuric acid leaching of nickel and/or cobalt containing laterite ores.
  • a process for producing a stable metal sulfate product from a metal sulfate waste material in a nickel and/or cobalt recovery process including the steps of: a) providing a source of metal sulfate crystals that have been derived from part of a nickel and/or cobalt recovery process; b) adding a sub-stoichiometric amount of a stabilising compound to the metal sulfate crystals to form a paste or slurry like intermediate product; and c) allowing the paste or slurry like product to solidify.
  • the metal sulfate crystals have been derived from the brine solution associated with a nickel and/or cobalt recovery process from the sulfuric acid leaching of nickel and/or cobalt containing laterite ores.
  • the stabilising compound may be selected from calcium oxide, calcium carbonate, calcium hydroxide, magnesium oxide, magnesium carbonate, magnesium hydroxide, calcium silicate or sodium silicate, but calcium oxide and calcium hydroxide are preferred.
  • a small amount of water or brine may be added to the metal sulfate/stabilising compound mix to aid homogenous mixing, so that a paste or slurry like intermediate product is produced.
  • the water may also be available from the hydrated form of the metal sulfate crystals.
  • This paste or slurry like intermediate product may be pumped or transported to an empoundment such as a pit, where it is allowed to solidify.
  • the water or brine may be sourced from recycled process water and may include one or more of raw brine, fresh water, the solution produced by crystallising out the metal sulfate from a source of brine, or an intermediate leach solution in the nickel and/or cobalt recovery process.
  • the amount of stabilising compound added may be any suitable amount to form a paste or slurry like consistency, but preferably it is in an amount of 0.1 to 0.9, preferably 0.2 to 0.7 stoichiometric ratio with respect to the metal sulfate.
  • the source of the crystallised metal sulfate may be from any source, but in one preferred embodiment, it may be sourced by crystallising the metal sulfate that remains in the brine solution following a nickel and/or cobalt recovery process.
  • the metal sulfate may exist in such solutions as a hydrated product.
  • the process may be applicable to processing a number of metal sulfates that may be present in such brine solutions
  • the process is particularly applicable to the processing of hydrated crystallised sulfates, such as monohydrated or heptahydrated magnesium sulfate, monohydrated or heptahydrated iron sulfate, or x hydrated manganese sulfates where x is between 1 and 6.
  • the metal sulfates may be crystallised by any manner, including an evaporative crystallisation step.
  • crystallisation may be achieved by using a concentrated sulfuric acid, which is added to the brine to salt out solid crystalline metal sulfate. Further concentrated sulfuric acid may be added to dehydrate the metal sulfate crystals to produce a solid, substantially dehydrated crystalline metal sulfate product.
  • a detailed description of this process as applied to crystallising magnesium sulfate is published in application PCT/AU2006/001984 in the name of BHP Billiton SSM Development Pty Ltd, the entire content of which is incorporated herein by reference.
  • the metal sulfate may be crystallised by using waste heat from other parts of a nickel and/or cobalt recovery process, in order to evaporate much of the water, producing a hot concentrated solution of the metal sulfate, which upon cooling, crystallises out of the solution as crystallised metal sulfates.
  • the process of the present invention provides processing magnesium sulfate that is present in the brine solution following a nickel and/or cobalt recovery process.
  • crystallised magnesium sulfate that has been sourced from a brine solution is mixed with a sub-stoichiometric amount of the stabilising compound together with an amount of water and/or brine to aid in homogenous mixing of the stabilising compound and magnesium sulfate crystals.
  • This forms a slurry or paste like intermediate product.
  • the resultant slurry or paste may be pumped to a pit or suitable empoundment and allowed to solidify in the pit to form a solid stable product.
  • Figure 1 shows a possible flowsheet for the leaching of a nickel or laterite ore.
  • Figures 2 and 3 show the result of mixing monohydrated MgSO 4 crystals with CaO or Ca(OH) 2 .
  • Figures 4 to 9 show the result of hydrated MgSO 4 mixed with CaO or Ca(OH) 2 compared with monohydrated MgSO 4 mixed with CaO or Ca(OH) 2 and water.
  • Figure 1 illustrates a possible flowsheet where a nickel laterite ore is leached with sulfuric acid (1 ).
  • the leachate will include dissolved metals from the ore, including dissolved magnesium, ferric iron, ferrous iron, aluminium, chromium and manganese together with the desired nickel and cobalt ions.
  • the pH of the leach liquor may be raised by the addition of a neutralising agent such as limestone (2) in order to precipitate out some of the unwanted products. Iron and aluminium will precipitate out and the iron and aluminium products are discarded as residue (3).
  • a neutralising agent such as limestone (2)
  • Nickel and cobalt may then be recovered by precipitating the nickel and cobalt as a mixed hydroxide product (for example by the addition of magnesium oxide) or as a mixed sulfide product (for example by the addition of hydrogen sulfide) (4) and (5).
  • a mixed hydroxide product for example by the addition of magnesium oxide
  • a mixed sulfide product for example by the addition of hydrogen sulfide
  • the resultant brine solution that remains following the precipitation of both wanted and unwanted metals will retain metal sulfates, in particular magnesium sulfates, but may also include other sulfates such as iron and manganese sulfates.
  • the magnesium sulfates are crystallised from the brine solution (6) and will generally form a hydrated salt, such as the magnesium sulfate heptahydrate (7) following a solid/liquid separation step to remove the solid magnesium sulfate salt from the resultant solution.
  • the resultant solution (12) may be recycled to the nickel recovery process as required.
  • calcium oxide (8) is combined with the magnesium sulfate crystals together with additional water (9) if required, in order to form a paste or slurry like material (10).
  • This paste or slurry like material may be transported, such as by pump, to long term storage (11 ), such as a clay-lined storage pit.
  • long term storage the slurry or paste like composition will set to a rock-like product having low porosity and a substantially reduced solubility in water than the crystallised metal sulfates.
  • the stabilised magnesium sulfate product may be used for other purposes, such as landfill, and is geotechnically stable. That is, it exhibits considerable strength, weight bearing ability and is resistant to extreme climatic events such as flooding, unlike for example disposal dams containing lime based precipitate sludges.
  • Table 1 presents the stoichiometric ratios of mixtures between lime powders (burnt and hydrated) and mono hydrated lime crystals for this section of work. Note that additional water was not added to create a paste.
  • Table 2 shows the amount of water added to mixtures of 15g of MgSO 4 -H 2 O crystals and 50% stoichiometric ratio of lime powder (burnt and hydrated). As the water was added, comments were made on its consistency, and then more water was added until a paste was finally made. These final pastes were labelled (samples 15 and 16) and packed in a mould to wait and see if it set as a solid "concrete-like" product.
  • Table 3 presents the stoichiometric ratios of mixtures between lime powders (burnt and hydrated) and hepta hydrated lime crystals. Note that additional water was not added to create a paste.
  • the hepta-hyd rated MgSO 4 crystals appear to have provided enough water to initially create a paste and then dry into a competent solid when mixed with both burnt and hydrated lime. This result was the same irrespective of whether burnt lime (CaO) or hydrated lime (Ca(OH) 2 ) was used.
  • the solid products are shown in Figure 6 and Figure 7.
  • a cement-like product can be formed from both monohydrated and hepta hydrated MgSO 4 crystals using considerably less than a 100% stoichiometric ratio of lime
  • the solid product can be generated using as little as 30% stoichiometric ratio of lime addition with respect to MgSO 4 . It is postulated that the solid is created by binding un-reacted magnesium sulfate crystals with Mg(OH) 2 and gypsum that is formed from the reaction of slaked lime with MgSO 4 and water.
  • the physical competency of the solid product is dependent upon the amount and consistency of reacted product in the solid. With optimum combination of ingredients the solid product is dense, exhibits low porosity, and is very hard. • For the stoichiometric ratios of lime addition described, the solid product exhibits very delayed solubility in water, with the amount redissolving decreasing with increased lime addition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé de fabrication de produit de sulfate métallique stable. Ce procédé comprend les étapes qui consistent : a) à utiliser une source de cristaux de sulfate métallique; b) à ajouter une dose sous-stoechiométrique d'un composé de stabilisation aux cristaux de sulfate métallique afin que soit formé un produit intermédiaire de type pâte ou boue; et c) à amener le produit de type pâte ou boue à se solidifier.
PCT/AU2008/001431 2007-09-26 2008-09-26 Stabilisation de sulfates métalliques WO2009039580A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2007905265A AU2007905265A0 (en) 2007-09-26 Stabilisation of Metal Sulfates
AU2007905265 2007-09-26

Publications (1)

Publication Number Publication Date
WO2009039580A1 true WO2009039580A1 (fr) 2009-04-02

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PCT/AU2008/001431 WO2009039580A1 (fr) 2007-09-26 2008-09-26 Stabilisation de sulfates métalliques

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4298379A (en) * 1980-01-31 1981-11-03 The Hanna Mining Company Production of high purity and high surface area magnesium oxide
WO2006043158A1 (fr) * 2004-10-21 2006-04-27 Anglo Operations Limited Procede de lixiviation en presence d'acide hydrochlorique pour la recuperation d'un metal de valeur a partir d'un minerai
WO2006081605A1 (fr) * 2005-02-01 2006-08-10 Bhp Billiton Ssm Technology Pty Ltd Processus de production d'oxyde de magnesium
CA2521817A1 (fr) * 2005-09-30 2007-03-30 Bhp Billiton Innovation Pty Ltd Methode de lixiviation atmospherique de minerai lateritique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4298379A (en) * 1980-01-31 1981-11-03 The Hanna Mining Company Production of high purity and high surface area magnesium oxide
WO2006043158A1 (fr) * 2004-10-21 2006-04-27 Anglo Operations Limited Procede de lixiviation en presence d'acide hydrochlorique pour la recuperation d'un metal de valeur a partir d'un minerai
WO2006081605A1 (fr) * 2005-02-01 2006-08-10 Bhp Billiton Ssm Technology Pty Ltd Processus de production d'oxyde de magnesium
CA2521817A1 (fr) * 2005-09-30 2007-03-30 Bhp Billiton Innovation Pty Ltd Methode de lixiviation atmospherique de minerai lateritique

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