WO2006029499A1 - Procede permettant de recuperer du nickel et du cobalt a partir de minerais de laterite par combinaison de lixiviation a pression atmospherique et a pression moderee - Google Patents

Procede permettant de recuperer du nickel et du cobalt a partir de minerais de laterite par combinaison de lixiviation a pression atmospherique et a pression moderee Download PDF

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Publication number
WO2006029499A1
WO2006029499A1 PCT/CA2005/000988 CA2005000988W WO2006029499A1 WO 2006029499 A1 WO2006029499 A1 WO 2006029499A1 CA 2005000988 W CA2005000988 W CA 2005000988W WO 2006029499 A1 WO2006029499 A1 WO 2006029499A1
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Prior art keywords
leach
nickel
ore
recited
iron
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PCT/CA2005/000988
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English (en)
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David Neudorf
David A. Huggins
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Skye Resources Inc.
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Priority to BRPI0513652-0A priority Critical patent/BRPI0513652A/pt
Priority to EP05761684A priority patent/EP1778883A4/fr
Priority to JP2007524144A priority patent/JP2008508428A/ja
Priority to AU2005284620A priority patent/AU2005284620A1/en
Priority to CA002572420A priority patent/CA2572420A1/fr
Publication of WO2006029499A1 publication Critical patent/WO2006029499A1/fr

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    • 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
    • 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
    • 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
    • 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
    • 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
    • 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 the hydrometallurgical processing of nickeliferous laterite ore, and in particular to a method for acid leaching both the limonite fraction and the saprolite fraction of such ores in a single process.
  • Laterite ores are formed by the in-situ weathering of nickel- bearing ultramafic rocks near or at the surface of the earth in tropical environments by the action of naturally acidic meteoric waters over geologic time. They consist of a variety of clay, oxide and silicate minerals, some enriched in nickel and/or cobalt, and this distinguishes them from the other major class of nickel ores, the sulfide ores.
  • the latter consist typically of sulfide minerals of iron, nickel and cobalt, often with copper and minor precious metals, and are associated with mafic-ultramafic magmatic intrusions in the earth's crust.
  • the weathering process typically creates a layered deposit, with the products of complete or most extensive weathering occurring near the surface and these grading into the products of lesser degrees of weathering as depth is increased and finally terminating in unweathered rock at some greater depth.
  • the highly weathered layer usually contains most of its contained nickel microscopically distributed within very finely divided goethite particles.
  • Goethite is an oxyhydroxide of ferric iron with the chemical formula
  • FeOOH FeOOH.
  • This layer is usually given the name limonite, and typically contains a high proportion of iron.
  • Cobalt is usually associated with the limonite layer and is usually predominantly associated with oxidized manganese minerals (Mn(III) and/or Mn(IV) containing oxides and hydroxides), often called asbolane or manganese wad.
  • Mn(III) and/or Mn(IV) containing oxides and hydroxides often called asbolane or manganese wad.
  • the lesser weathered layers typically contain increasing proportions of their contained nickel in various magnesium silicate minerals, such as, for example, serpentine.
  • Serpentine is a silicate mineral of magnesium which has the chemical formula 3MgO * 2Si ⁇ 2 * 2H 2 O. It is believed that nickel substitutes for some of the magnesium in serpentine.
  • Magnesium may also be substituted by other divalent metals, for example, ferrous iron (Fe 2+ ).
  • ferrous iron Fe 2+
  • silicate minerals that also host nickel in the incompletely weathered zones.
  • the partially weathered, high-magnesium bearing zone is often given the name saprolite, or garnierite. ("Garnierite" is also used to describe a particular apple-green colored magnesium-nickel silicate mineral of variable composition.)
  • Saprolite 1.2-3.5 % Ni, 0.02-0.07 % Co, 7-20 % Fe, 10-20 %
  • Each zone also contains typically significant concentrations of aluminum, manganese and chromium, as well as trace concentrations of other heavy metals such as copper and zinc in a variety of other minerals.
  • nickel values typically can not be concentrated substantially by physical means, that is, so-called ore dressing techniques, prior to chemical processing to separate the metal values. This renders the processing of laterites expensive, and means to lower the costs of processing laterites have been sought for many decades.
  • HPAL High Pressure Acid Leaching
  • the process utilizes sulfuric acid leaching at high temperature, typically 250 0 C, and high pressure; the associated steam pressure at 250 0 C is approx. 570 psi or 39 atmospheres.
  • high temperature typically 250 0 C
  • high pressure the associated steam pressure at 250 0 C is approx. 570 psi or 39 atmospheres.
  • the nickeliferous minerals in the ore are nearly completely solubilized.
  • the dissolved iron is rapidly precipitated as hematite (Fe ⁇ O ⁇ ) at the high temperature employed because this compound is largely insoluble even in slightly acidic solutions at this temperature.
  • the nickel remains in solution and after cooling, the leach residue containing iron is separated from the nickel-bearing solution by thickening in a series of wash thickeners, a so-called counter-current decantation (CCD) circuit.
  • CCD counter-current decantation
  • a major disadvantage of the HPAL process is that it requires sophisticated high-temperature, high-pressure autoclaves and associated equipment which are expensive, both to install and to maintain.
  • the HPAL process also consumes more sulfuric acid than is required to stoichiometrically dissolve the non-ferrous metals content of the ore because at high temperature most of the sulfate ions provided by sulfuric acid are tied up as bisulfate ions (HSO 4 " ).
  • sulfuric acid (H2SO4) only dissociates to release a single proton (H + ) at high temperature.
  • the bisulfate ions decompose to sulfate (SO 4 2" ) and another proton.
  • the latter proton (acid) is therefore not utilized fully for leaching and results in excess sulfuric acid which must be neutralized, for example with limestone.
  • U.S. Pat. No. 4,097,575 describes an improvement to the HPAL process which constitutes roasting saprolite ore below about 820 0 C in order to render the ore more reactive with sulfuric acid and then using the roaster calcine to neutralize excess acid in the discharge of an autoclave wherein pressure leaching of limonite ore occurs. Nickel contained in the saprolite ore is largely dissolved during this neutralization.
  • U.S. Pat. No. 6,379,636 B2 describes a further improvement to the process described in U.S. Pat. No. 4,097,575 wherein the saprolite roasting step is eliminated and the saprolite in "raw" form is used to neutralize the excess acid in the autoclave discharge solution. In addition, more acid could be added to the discharge to increase the amount of saprolite that could be leached. However, this process still requires the use of expensive autoclaves.
  • the precipitation of iron is as a jarosite compound, which is a thermodynamically unstable compound of iron that decomposes over time to release sulfuric acid, thus causing environmental problems.
  • jarosite is not stated explicitly it would be apparent to one skilled in the art that jarosite will precipitate at the conditions outlined in the examples).
  • Jarosite contains two moles of sulfate for every three moles of iron and thus this compound represents substantial excess consumption of sulfuric acid to provide the necessary sulfate ions.
  • nickel extractions from the ore were apparently relatively low. While extractions were not stated explicitly, based on the nickel content of the residue and the fact that the residue weight must be more than the weight of the original ore because jarosite contains a lower percentage of iron than the original ore and virtually all of the iron remained in the residue, nickel extractions were usually in the 60-65 % range.
  • U.S. Patent Nos. 6,261 ,527 B1 and 6,680,035 B2 describe another atmospheric leaching process in which limonite ore is first "totally" leached with strong sulfuric acid, i.e. both nickel and iron are substantially dissolved from goethite, and then saprolite ore is leached in the resulting limonite leach slurry while simultaneously precipitating iron as jarosite by the addition of a jarosite precipitating agent.
  • This process also has the disadvantage of producing jarosite.
  • WO 03/093517 A1 describes an improvement to this process, which constitutes eliminating the addition of a jarosite-forming ion such as sodium, potassium or ammonium, and causing the iron to precipitate as a compound other than jarosite, such as goethite.
  • the process overcomes the disadvantages of jarosite, but sulfuric acid consumption was 0.59 to 0.87 tonnes per tonne of ore in the examples cited, and was over 0.72 tonnes per tonne of ore in nine of the eleven examples cited.
  • 6,680,035 B2 and WO 03/093517 A1 are based on the fact that goethite is more refractory to acid leaching than typical saprolite minerals, such as serpentine. This has been demonstrated by other researchers (see, for example: John H. Canterford, "Leaching of Some Australian Nickeliferous Laterites with Sulfuric Acid at Atmospheric Pressure," Proc. Australasian Inst. Min. Metall., 265 (1978), 19-26; N. M. Rice and L.W. Strong, "The Leaching of Lateritic Nickel Ores in Hydrochloric Acid," Canadian Metallurgical Quarterly, 13(3)(1974), 485-493; and Figure 5 of U.S. Patent No.
  • Nos. 6,261 ,527 B1 and 6,680,035 B2 and WO 03/093517 A1 is that the leach process is slow. Greater than 10 hours leach retention time is required to complete the reactions. Thus, many large leach reactors are required to carry out the process and this increases the capital and operating costs of the process compared to a leach process which has a much shorter retention time.
  • the atmospheric leach processes described above address the disadvantages of high pressure leaching but have significantly lower nickel extraction (typically 80-85 % for atmospheric leaching versus 90-97 % for high pressure acid leaching).
  • the object of the present invention is to obviate or mitigate the disadvantages of high pressure acid leaching processes while achieving higher and faster recoveries of nickel and cobalt than the known atmospheric leach processes.
  • the present invention provides a process for the efficient leaching of nickel and cobalt from limonite and saprolite ores in two stages, the first stage consisting of mixing and reacting a slurry of the limonite ore with concentrated mineral acid at atmospheric pressure, and the second stage consisting of adding saprolite ore to the resulting leach slurry and then leaching at a moderately elevated temperature and pressure.
  • Iron is efficiently separated from nickel and cobalt in the solid leach residue primarily as an oxide and/or hydroxide of ferric iron other than jarosite.
  • the limonite leach step should be carried out at a temperature close to the boiling point.
  • the quantity of acid added should be approximately that required to stoichiometrically dissolve the soluble non-ferrous metals in the ore as well as the soluble iron, and a small excess of acid may advantageously be used to drive the dissolution reactions.
  • a reductant such as sulfur dioxide or ferrous sulfate, is added to the limonite leach slurry in order to enhance the dissolution of nickel, and particularly cobalt.
  • the temperature should be high enough to achieve a rapid rate of reaction and satisfactory nickel (and cobalt) extraction, but low enough that the resulting working pressure is within the tolerance of a simple, low cost autoclave.
  • the working pressure of the autoclave is approximately equal to the pressure of saturated steam at the working temperature employed. This pressure increases very rapidly with increasing temperature, especially much above about 150 0 C.
  • an appropriate range of temperature for carrying out the second stage of leaching in the present invention is from about 120 to 160 0 C, and the temperature should be kept as low as reasonably possible consistent with good process performance. It has been found that excellent results are achieved, for example, at 150 0 C.
  • the associated pressure at this temperature (approximately 70 psi) is low enough to enable a simple autoclave system to be used for carrying out the leach.
  • an iron-bearing "seed" material is added to the leach slurry at the start of the saprolite pressure leach stage to accelerate the precipitation of dissolved ferric iron and the extraction of remaining nickel and cobalt from the solid phases.
  • the leach solution is preferably neutralized prior to nickel and cobalt recovery.
  • the laterite leaching method of the present invention can surprisingly achieve high levels of nickel extraction while avoiding the high cost of high-pressure autoclaves, and avoiding the production of environmentally unfriendly, high-acid consuming jarosite compounds. While the process does require an autoclave, the operating conditions are relatively benign compared to the high pressure acid leaching processes (nearly ten times or more the operating pressure required for the latter autoclave processes). Consequently, the process of this invention permits much simpler equipment design, and operations and maintenance are also easier than in high pressure acid leach processes.
  • the saprolite leach and iron precipitation reactions occur much faster at moderately elevated temperature and a much shorter leach retention time, compared to the previously described atmospheric leach processes, is required.
  • the autoclave required to carry out the process of the current invention is much smaller than the atmospheric leach reactors required for the processes of U.S. Patent Nos. 6,261 ,527 B1 and 6,680,035 B2 and WO 03/093517 A1.
  • the process of the current invention achieves higher nickel extraction than can be achieved with the aforementioned atmospheric leach processes.
  • the present invention can achieve at least about 90 %, and as high as 95 % or more, nickel extraction and as much as 95 % or more cobalt extraction, with about 5 to 10 % iron extraction.
  • FIG. 1 is a flow sheet showing in simplified form one embodiment of the process of the present invention.
  • FIG. 2 is a flow sheet showing another embodiment of the process of the present invention in which some of the leach residue is recycled in order to provide seed for iron precipitation.
  • a slurry of limonite ore is mixed with a concentrated mineral acid, chosen from the group sulfuric, hydrochloric and nitric, or a mixture of any of these acids, in a suitable device such as a stirred tank reactor, or in the case of continuous processing, a series of stirred tank reactors.
  • a suitable device such as a stirred tank reactor, or in the case of continuous processing, a series of stirred tank reactors.
  • the limonite ore slurry is produced by conventional means, such as screening and pulping the ore in a drum scrubber, which will be apparent to those skilled in the art.
  • the quantity of acid added is approximately that required to stoichiometrically dissolve the soluble non-ferrous metals in the ore as well as the soluble iron, i.e. most of the nickel, cobalt, magnesium, aluminum, copper, zinc, iron present in goethite and other soluble iron hydroxyl-oxide minerals, and a small portion of the chromium, which is usually contained primarily in the relatively insoluble mineral chromite.
  • a small excess of acid may be added to drive the dissolution reactions as far as possible to completion and to ensure maximum extraction of nickel and cobalt from the limonite ore.
  • some of the magnesium and aluminum may be insoluble and this should be taken into account to determine the precise acid addition.
  • the addition of concentrated acid to limonite ore slurry results in the generation of substantial heat, raising the temperature of the mixture as high as the boiling point of the leach solution.
  • the atmospheric limonite leach step is preferably carried out close to the boiling point of the solution to maximize the rates of the leaching reactions and thereby minimize the residence time required to complete the reactions.
  • Additional steam or other energy may be added to the leach reactors in order to maintain the leach temperature as close to the boiling point as possible. It is preferable that the limonite ore slurry density be as high as possible consistent with good mixing in order to minimize the need for additional energy and to minimize the volume of pregnant liquor that needs to be treated subsequently for nickel and cobalt recovery.
  • the limonite ore slurry is leached for sufficient time to complete the reactions. This is typically 1 to 4 hours if the limonite leach is conducted at approx. 95 to 105 0 C.
  • a reductant is added to the limonite leach slurry in order to enhance the dissolution of nickel, and particularly cobalt, from the ore.
  • Most of the cobalt and a smaller proportion of the nickel present in limonite ore is contained typically in a variety of oxidized manganese minerals, referred to collectively as "manganese wad.”
  • Manganese is typically in the tetravalent or trivalent state in these minerals and is refractory to acid leaching unless a reductant is added to cause the manganese to dissolve in the divalent form. The dissolution of manganese is necessary to allow the contained cobalt and nickel to dissolve as well, as will be apparent to those skilled in the art.
  • Suitable reductants include sulfur dioxide (SO 2 ), either as a gas or aqueous solution of SO 2 and ferrous iron, as a soluble salt, e.g. ferrous sulfate, although many other reducing species will also react with oxidized manganese compounds.
  • SO 2 sulfur dioxide
  • ferrous iron as a soluble salt, e.g. ferrous sulfate, although many other reducing species will also react with oxidized manganese compounds.
  • the resulting limonite leach slurry is injected into an autoclave along with the saprolite ore.
  • the saprolite ore typically will be prepared by crushing, grinding and screening or cycloning of the run-of-mine saprolite ore to achieve a particle size that allows the saprolite ore particles to be suspended in the autoclave reactor during the leaching process.
  • the resulting slurry is heated to the desired reaction temperature, for example in the range of 120 to 160 0 C, by any appropriate means, for example by direct injection of intermediate pressure steam into the autoclave, or by direct or indirect steam heating of the leach slurry prior to injection into the autoclave.
  • the autoclave retention time is sufficient to allow most of the iron in solution after the limonite atmospheric leach to hydrolyze and precipitate, and the acid regenerated by iron hydrolysis to react with the saprolite ore, thus extracting most of the contained nickel and cobalt, as well as magnesium and other impurity metals.
  • the nickel extraction obtained in the current process is up to 10 or more percentage points greater than the nickel extraction obtained in the process of WO 03/093517 A1 , using similar acid/ore and saprolite/limonite ratios. This is a very significant advantage of the current process as compared to the processes described in U.S. Patent Nos. 6,261 ,527 B1 and 6,680,035 B2 and WO 03/093517 Al
  • the use of a temperature above the boiling point for the saprolite leaching stage may also provide a higher nickel/iron ratio in solution, which is advantageous with respect to downstream processing of the leach solution. This is because in most cases virtually all iron must be removed from solution before effecting nickel and cobalt recovery. Usually, the residual iron in solution is removed by adding a base, for example calcium carbonate, to the leach slurry and precipitating iron oxyhydroxide compounds. Some nickel will co-precipitate with the iron resulting in losses of the pay metal. The neutralizing agent also represents an additional operating cost of the process.
  • a base for example calcium carbonate
  • a further advantage of the use of higher temperature is an improvement in the solid/liquid separation properties of the final leach slurry, with higher settling rates being achieved with a higher leaching temperature.
  • the leach slurry is subjected to solid/liquid separation by filtration or thickening to produce a pregnant leach solution containing most of the nickel and cobalt contained in the ore and a solid residue containing most of the iron in the ore.
  • thickening is carried out in a series of thickeners with counter-current flow of a wash water stream and the leach slurry in order to wash most of the entrained metal values out of the leach residue, a method called counter-current decantation (CCD).
  • CCD counter-current decantation
  • the pregnant leach solution proceeds to nickel and cobalt recovery by methods known to those skilled in the art, such as solvent extraction, ion exchange, sulfide precipitation using sulfiding agents, e.g. hydrogen sulfide, or hydroxide precipitation, using for example magnesia as the precipitating agent.
  • the nickel and cobalt can also be recovered from the leach slurry without prior solid/liquid separation, using the resin-in-pulp process.
  • an ion exchange resin which extracts nickel and possibly cobalt is added directly to the leach slurry. After the extraction is complete, the resin is separated from the nickel-depleted leach slurry by screening. After washing the resin to remove solids, the nickel can be eluted from the resin with a fresh acid solution.
  • the leach solution may be neutralized with a base, such as calcium carbonate, magnesium oxide, sodium carbonate or the like, to neutralize free acidity remaining from the leach process and precipitate small amounts of ferric iron, aluminum, and chromium, while minimizing co- precipitation of nickel and cobalt.
  • a base such as calcium carbonate, magnesium oxide, sodium carbonate or the like
  • This process may be carried out in a single or multiple steps separated by intermediate solid/liquid separations.
  • the first stage of neutralization may be carried out prior to separating the leach residue from the leach solution.
  • the combined leach and neutralization residue may then be separated from the partially neutralized leach solution by filtration or thickening, as described above.
  • a second stage of neutralization may then still be desirable, depending on the method selected for nickel and cobalt recovery from the pregnant leach solution.
  • the resulting neutralization residue may be separated from the neutralized leach solution by filtration or thickening. This second-stage neutralization residue is ideally returned to the first stage neutralization to re- dissolve any co-precipitated nickel and cobalt.
  • an iron- bearing "seed” material is added to the leach slurry at the start of the saprolite pressure leach stage, as shown in FIG. 2.
  • the purpose is to accelerate the precipitation of dissolved ferric iron and the extraction of remaining nickel and cobalt from the solid phases.
  • the surfaces of the seed particles provide low- activation energy sites for hydrolysis and precipitation of iron, for example as ferric hydroxide, goethite, or hematite.
  • This seed material is ideally a portion of the final leach residue itself, which contains precipitated iron compounds.
  • the following examples illustrate the method of the present invention.
  • the ore used in these examples came from a Central American laterite deposit.
  • the limonite and saprolite fractions of the ore had the compositions given in Table 1.
  • the saprolite ore was crushed and ground to approx. -100 mesh before use in the tests.
  • EXAMPLE 1 An acid solution was prepared by adding 287.6 g of 96 % sulfuric acid and 48.0 g of 37 % HCI (both mineral acids being reagent grade) to 702 mL of water. The acid solution was transferred to a 2- liter cylindrical reaction kettle equipped with a mechanical stirrer, 4 plastic baffles, and a tight-fitting lid equipped with a water condenser open to the atmosphere. The reaction kettle was heated by an external, electrical heating mantle. 381.7 g (wet) of the limonite ore described in Table 1 were added to the acid solution while heating and stirring the mixture. The temperature was controlled at 94 to 105 0 C and the limonite ore was leached for 5 hours.
  • Liquid samples were taken from the leach slurry at 1 , 2 and 5 hours.
  • the leach slurry was transferred to a 2- liter titanium autoclave, along with 344.8 g (wet) of the saprolite ore described in Table 1.
  • the saprolite ore had first been wet ground to approximately -100 mesh and then filtered to form a cake containing 27.5 % moisture.
  • 128.6 g of technical grade hematite also was added to the autoclave to "seed" the precipitation of iron.
  • the autoclave was equipped with a mechanical stirrer, thermocouple, cooling coil and external heating mantle.
  • the leach slurry was heated to 150 0 C and held at that temperature for 2 hours.
  • a sample was removed from the autoclave after 1 hour (6 hours total leach time, including the limonite atmospheric leach).
  • the assays in Table 2 indicate that the nickel and iron in limonite ore were dissolved substantially during the atmospheric leach stage and that 1 hour was sufficient to carry the leaching reactions almost to completion, although the further reduction in free acid at 2 and 5 hours indicates that some further reaction occurred.
  • the 6-hour solution assays (Table 2, 1 hour of pressure leaching) and the final solution assays (Table 3, 2 hours of pressure leaching) indicate that the iron in solution was rapidly hydrolyzed and precipitated at the moderate pressure and temperature conditions in the autoclave, while dissolving most of the nickel contained in the saprolite ore.
  • the final solution nickel and iron assays were significantly higher than the 1-hour solution assays due to substantial evaporation that occurred during vacuum filtration of the final leach liquor.
  • EXAMPLE 2 Another test was carried out similarly to that described in Example 1 with the following exceptions.
  • the limonite ore used had the following composition: 1.55 % Ni, 48.4 % Fe, 0.47 % Mg, and 37.2 % moisture. 398.1 g (wet) of this ore was used in the test, along with 573.7 g water, 288.2 g of 96 % H 2 SO 4 , 46.9 g of 37 % HCI, and 285.7 g of MgSO 4 * 7H2 ⁇ . No hematite seed material was used in the test. The MgSO 4 *7H2 ⁇ was dissolved in the water prior to adding the acid to the solution.
  • the purpose of adding soluble magnesium to the solution was to simulate the recycle of a magnesium-rich solution which would remain after nickel and cobalt recovery from the pregnant leach solution.
  • the atmospheric leach was carried out with a temperature of 96 to 101 0 C. No sample was taken from the autoclave during the pressure leach stage.
  • Example 1 illustrates that seeding is not required to achieve effective iron precipitation. Also, the presence of dissolved magnesium in solution initially does not appear to impact negatively on the extraction of nickel or precipitation of iron.
  • EXAMPLE 3 For comparison, another test was done to simulate the conditions of the process described in WO 03/093517 A1. The atmospheric limonite leaching stage was carried out similarly to the limonite leach stage described in Example 1. 398.1 g (wet) of the same limonite ore used in Example 2 was added to a solution comprised of 719.9 g water, 288.2 g 96 % H 2 SO 4 and 46.9 g of 37 % HCI. Leaching was carried out for 4 hours at 101-104 0 C.
  • EXAMPLE 4 Another test was done to compare the results obtained from using a combination of atmospheric and moderate pressure leaching, as prescribed in the current invention, with the results from using moderate pressure leaching alone.
  • 381.7 g (wet) of the limonite described in Table 1 312.5 g of the ground saprolite at 20.0 % moisture, 734.4 mL of water, 288.3 g of 96 % H 2 SO 4 and 46.8 g of 37 % HCI were charged to a 2-liter titanium autoclave, heated to 150 0 C, and leached for 2 hours. After rapid cooling, the leach slurry was filtered and the leach residue was repulp washed as in the previous examples. The filtrate, wash solution and solid residue were assayed as in the other examples. Metals extractions were calculated based on the solution volumes, residue weight and assays.
  • EXAMPLE 5 The limonite and saprolite fractions of the ore used in this example had the compositions given in Table 9:
  • the saprolite was wet ground to -100 mesh and filtered to produce a filtercake. 262 g (dry basis) of this filtercake was added to the limonite leach slurry, which was then transferred to an autoclave. The autoclave was sealed and heated to 150 0 C, at which temperature leaching was allowed to continue for an additional hour before rapidly cooling the autoclave. The slurry was sampled at the completion of the additional one- hour leach period. The saprolite to limonite ratio was 1.1 and the sulfuric acid addition was 650 kg H 2 SO4 per tonne of ore in this test.
  • Ni, Co, and Mg extractions were calculated using a "silicon-tie" method in which the weight of solid residue was calculated using ore and residue silicon assays on the assumption that none of the silicon leached. These weights and ore and residue assays were then used to calculate extractions.
  • This test differs from Example 1 mainly in that only 4 hours of limonite leaching were employed, sulfur dioxide gas was added during the limonite leach, no seed was added during the saprolite leaching phase, and only one hour of autoclave leaching was used. The results still indicate a very high nickel extraction with minimal iron extraction and very good leaching of cobalt. The latter was due to the efficacy of sulfur dioxide as a reductant for the manganese wad material present in the ore.

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  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé permettant de lixivier des minerais de latérite contenant une limonite et une saprolite. On ajoute suffisamment d'acide minéral à un coulis de limonite qui est lixivié à pression atmosphérique afin de dissoudre la plus grande partie des métaux solubles non ferreux et du fer soluble. Après adjonction de saprolite, le coulis est ensuite lixivié à une température supérieure au point d'ébullition normal et à une pression supérieure à la pression atmosphérique pendant une durée suffisante pour lixivier la plus gande partie du nickel contenu dans la saprolite et pour précipiter la plus grande partie du fer dans une solution. Puis, on réduit la pression du coulis, et on récupère le nickel et/ou le cobalt de la solution de lixiviation par extraction par solvant, traitement de résine en pulpe ou autre échange ionique, par précipitation d'un sulfure ou d'un hydroxyde ou par un autre procédé de récupération.
PCT/CA2005/000988 2004-08-02 2005-06-23 Procede permettant de recuperer du nickel et du cobalt a partir de minerais de laterite par combinaison de lixiviation a pression atmospherique et a pression moderee WO2006029499A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BRPI0513652-0A BRPI0513652A (pt) 2004-08-02 2005-06-23 processo para lixiviar minérios de laterita contendo limonita e saprolita
EP05761684A EP1778883A4 (fr) 2004-08-02 2005-06-23 Procede permettant de recuperer du nickel et du cobalt a partir de minerais de laterite par combinaison de lixiviation a pression atmospherique et a pression moderee
JP2007524144A JP2008508428A (ja) 2004-08-02 2005-06-23 大気圧浸出および中圧浸出の組合せによるラテライト鉱石からのニッケルおよびコバルト回収法
AU2005284620A AU2005284620A1 (en) 2004-08-02 2005-06-23 Method for nickel and cobalt recovery from laterite ores by combination of atmospheric and moderate pressure leaching
CA002572420A CA2572420A1 (fr) 2004-08-02 2005-06-23 Procede permettant de recuperer du nickel et du cobalt a partir de minerais de laterite par combinaison de lixiviation a pression atmospherique et a pression moderee

Applications Claiming Priority (2)

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US59237504P 2004-08-02 2004-08-02
US60/592,375 2004-08-02

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WO2006029499A1 true WO2006029499A1 (fr) 2006-03-23

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PCT/CA2005/000988 WO2006029499A1 (fr) 2004-08-02 2005-06-23 Procede permettant de recuperer du nickel et du cobalt a partir de minerais de laterite par combinaison de lixiviation a pression atmospherique et a pression moderee

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US (1) US20060024224A1 (fr)
EP (1) EP1778883A4 (fr)
JP (1) JP2008508428A (fr)
KR (1) KR20070041770A (fr)
CN (1) CN100402679C (fr)
AU (1) AU2005284620A1 (fr)
BR (1) BRPI0513652A (fr)
CA (1) CA2572420A1 (fr)
GT (1) GT200600110A (fr)
TW (1) TW200607867A (fr)
WO (1) WO2006029499A1 (fr)
ZA (1) ZA200701848B (fr)

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WO2008138039A1 (fr) * 2007-05-14 2008-11-20 Bhp Billiton Ssm Development Pty Ltd Récupération de nickel à partir d'un minerai de latérite à haute teneur de matériaux ferreux
JP2010509497A (ja) * 2006-11-10 2010-03-25 コンパニア バレ ド リオ ドセ イオン交換樹脂を使用してラテライト鉱石からニッケルおよびコバルトを回収するためのプロセス
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WO2007092994A1 (fr) * 2006-02-15 2007-08-23 Andreazza Consulting Pty Ltd Traitement de minerai de laterite
JP2010509497A (ja) * 2006-11-10 2010-03-25 コンパニア バレ ド リオ ドセ イオン交換樹脂を使用してラテライト鉱石からニッケルおよびコバルトを回収するためのプロセス
WO2008138039A1 (fr) * 2007-05-14 2008-11-20 Bhp Billiton Ssm Development Pty Ltd Récupération de nickel à partir d'un minerai de latérite à haute teneur de matériaux ferreux
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ZA200701848B (en) 2008-04-30
KR20070041770A (ko) 2007-04-19
EP1778883A1 (fr) 2007-05-02
US20060024224A1 (en) 2006-02-02
CN100402679C (zh) 2008-07-16
TW200607867A (en) 2006-03-01
CN101001964A (zh) 2007-07-18
CA2572420A1 (fr) 2006-03-23
EP1778883A4 (fr) 2007-08-29
AU2005284620A1 (en) 2006-03-23
JP2008508428A (ja) 2008-03-21
GT200600110A (es) 2006-04-26
BRPI0513652A (pt) 2008-05-13

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