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WO2017117626A1 - Précipitation de nickel et de cobalt - Google Patents

Précipitation de nickel et de cobalt Download PDF

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Publication number
WO2017117626A1
WO2017117626A1 PCT/AU2017/050004 AU2017050004W WO2017117626A1 WO 2017117626 A1 WO2017117626 A1 WO 2017117626A1 AU 2017050004 W AU2017050004 W AU 2017050004W WO 2017117626 A1 WO2017117626 A1 WO 2017117626A1
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Prior art keywords
nickel
cobalt
gypsum
solution
precipitated
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PCT/AU2017/050004
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English (en)
Inventor
Paul Benjamin VOIGT
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Glencore Queensland Ltd
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Glencore Queensland Ltd
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Priority claimed from AU2016900007A external-priority patent/AU2016900007A0/en
Application filed by Glencore Queensland Ltd filed Critical Glencore Queensland Ltd
Publication of WO2017117626A1 publication Critical patent/WO2017117626A1/fr
Anticipated expiration legal-status Critical
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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
    • C22B23/0453—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

Definitions

  • the present invention relates to a process for the precipitation of nickel and/or cobalt from solution.
  • the most common industrial methods for recovery for nickel and cobalt from solution to a saleable form is either as metal or a hydroxide precipitate.
  • processing routes where the nickel and cobalt are precipitated from solution this can be done separately in sequence (to obtain a mainly nickel containing precipitate, such as nickel hydroxide and a mainly cobalt containing precipitate such as cobalt hydroxide) or as a mixed hydroxide precipitate (MHP).
  • MHP mixed hydroxide precipitate
  • the neutralising agent used in this process is magnesia (MgO).
  • Magnesia is an effective precipitation agent since it is cheaper than some neutralising agents like sodium hydroxide, readily available and as the nickel or cobalt is precipitated the magnesium passes from solid to solution meaning there is limited contamination of the final product with the neutralising agent. Magnesia, however is expensive relative to calcium based neutralisation agents such as Lime or Limestone.
  • the current invention reports a similar process where surprisingly, a similar process can be applied to nickel and cobalt to produce a nickel and/or cobalt oxide/hydroxide or a carbonate precipitate.
  • the precipitate type will depend on the operating conditions but for simplicity will be referred to as nickel precipitate or cobalt precipitate or a nickel containing material or a cobalt containing material.
  • the metals can either be precipitated singly, separately, separately in sequence or together as a mixed precipitate.
  • the advantages of this process are use of lime or limestone which is more abundant and significantly cheaper than magnesia. It also prevents magnesium accumulating in the system process water causing solubility limitations and contamination from co-precipitation. In some embodiments, other deleterious elements in solution such as magnesium can remain in solution and not be co-precipitated resulting in a higher grade nickel and/or cobalt precipitate.
  • the solution may also contain one or more of dissolved magnesium, iron, copper, silicon, cadmium and zinc.
  • the process can be used to recover a high grade and saleable precipitate containing nickel and/or cobalt.
  • the present invention provides a method of precipitating a nickel or cobalt containing solid from an acidic solution containing dissolved nickel and/or cobalt comprising: a) contacting the solution with a calcium containing neutralising agent to raise the pH of the solution to 5.0 to 9.0 at a temperature of from 40 to 95 °C to thereby precipitate a solid cobalt containing material and gypsum, and separating the cobalt containing material from the gypsum; or b) contacting the solution with a calcium containing neutralising agent to raise the pH of the solution to 7.0 to 9.0 at a temperature of from 40 to 95 °C to thereby precipitate a solid nickel containing material and gypsum, and separating the nickel containing material from the gypsum; or c) contacting the solution with a calcium containing neutralising agent to raise the pH of the solution to 5.0 to 9.0 at a temperature of from 40 to 95 °C to thereby precipitate a
  • the acidic solution also contains dissolved magnesium and the precipitation step is operated without causing substantial precipitation of magnesium. In this manner, dissolved magnesium stays in solution and does not report to the nickel and/or cobalt precipitate.
  • the precipitation process suitably involves a precipitation step that is operated in a range where nickel and/or cobalt will be precipitated and magnesium will remain in solution.
  • the key operating conditions are pH from 5.0 - 9.0, or 6.0 to 9.0, for cobalt and/or nickel.
  • the pH is from 7.5 to 8.5 or about 7.5, and an operating temperature of from 40 to 95 °C, preferably about 60°C, is used.
  • the calcium containing neutralising agent is suitably in the form of lime (CaO) or hydrated lime (Ca(OH) 2 ).
  • limestone (CaCO 3 ) may be used as the neutralising agent.
  • a mixture of different calcium- containing neutralizing agents may be used.
  • the solution containing dissolved nickel and/or cobalt may also contain other dissolved metals, such as iron, copper, silicon, cadmium and zinc, however other metals may also be present.
  • the process may also include the step of (d) contacting the solution with a calcium containing neutralising agent to raise the pH of the solution to 4.5 to 6.0 at a temperature of from 40 to 95°C to precipitate other metals (Cu and/or Zn) to form a solid Cu and/or Zn containing material and gypsum, and separating the Cu and/or Zn containing material from the gypsum.
  • This step will suitably be conducted before precipitation of nickel and/or cobalt. Removing the dissolved copper and/or zinc from the solution enables the copper and/or zinc to be recovered and sold or processed further to form copper metal and/or zinc metal.
  • this precipitation step may be operated without causing substantial precipitation of magnesium.
  • the precipitated copper and zinc material and precipitated gypsum will normally be separated from the liquor, with the liquor (still containing dissolved nickel and/or cobalt) being sent for further processing to recover nickel and/or cobalt therefrom.
  • the process comprises contacting the solution with a calcium containing neutralising agent to raise the pH of the solution to 5.0 to 9.0, or from 6.0 to 9.0, more preferably 6.5 to 7.5 at a temperature of from 40 to 95°C, preferably about 60°C, to thereby precipitate a solid nickel and/or cobalt containing material and gypsum, in some embodiments without causing substantial precipitation of magnesium, and separating the nickel and/or cobalt containing material from the gypsum.
  • the calcium containing neutralising agent is suitably in the form of lime (CaO) or hydrated lime (Ca(OH) 2 ).
  • Nickel and/or cobalt in solution will be precipitated in the form of nickel oxide and/or cobalt oxide in this embodiment.
  • nickel oxide will be used to refer to a combination of nickel oxide, nickel hydroxide and nickel sulphate since depending on the operating conditions will dictate the proportions of each compound formed.
  • cobalt oxide will be used to refer to a combination of cobalt oxide, cobalt hydroxide and cobalt sulphate since depending on the operating conditions will dictate the proportions of each compound formed.
  • the process involves a precipitation step that is operated in a range where nickel and/or cobalt will be precipitated and, in some embodiments, dissolved magnesium will remain in solution.
  • the operating conditions include pH from 5.0 - 9.0, preferably about 7.5 to about 8.5, and an operating temperature of from 40 to 95 °C, preferably about 60°C.
  • the calcium containing neutralising agent is suitably in the form of lime (CaO) or hydrated lime (Ca(OH) 2 ).
  • the pH of solution containing nickel and/or cobalt is raised, for example by the addition of neutralising agent such as lime, to a pH in the range of 5.0 to 9.0, or from 6.0 to 9.0, to precipitate nickel and/or cobalt as oxide forms and the whole or a major part of lime is converted to gypsum.
  • This stage may be operated successfully at temperature up to boiling points of the solution at atmospheric pressure, preferably in the range of 40 to 95°C.
  • the pulp leaving this stage may be sent to a separation stage with or without solid-liquid separation. In some circumstance, it may be desirable to re-circulate portions of pulp or thickened pulp from this stage to the precipitation stage.
  • the pulp is sent to a separation process in order to separate the nickel and/or cobalt precipitate from gypsum.
  • nickel and/or cobalt precipitate is separated from the gypsum using a flotation step.
  • Flotation is a process for separating finely ground minerals from their associated gangue. This process is usually used to separate one solid from another by using the affinity of air bubbles to solids.
  • nickel and/or cobalt oxide including metal oxides or hydroxides is recovered as flotation concentrate and gypsum is recovered as tailing.
  • Cationic collectors such as dodecylamine hydrochloride, are used as flotation agents.
  • Potassium amyl xanthate or dodecylamine sulphate may be used for this purpose. Any frother could be used, but a Dowfroth 250 was found useful.
  • the flotation process may be operated at ambient temperature and also successfully at temperature up to 90.degree. C. and the pulp from the third stage may be used without any heating or cooling stages.
  • the gypsum from the flotation step can be recycled to either of the leaching or neutralization steps.
  • the precipitation step results in the nickel and/or cobalt precipitate forming a finer fraction of particles and the gypsum forming a coarser fraction of particles.
  • the finer particles (which contain most of the precipitated nickel and/or cobalt) may be separated from the coarser particles (which contain most of the gypsum) using alternative separation techniques. This operation may be used in conjunction with, or as an alternative to, flotation.
  • the sizing separation may be performed by any method, either individually or in combination. For example, sizing may be performed by using one or more of the following techniques: classifier, elutriation, settling, screening, tables, and cyclones.
  • a classifier is a device for subjecting comminuted ore to the action of water either in such a way that a division of the ore particle is made into two or more products according to relative settling powers.
  • Cyclones are devices primarily used for separation of solids from fluids. Cyclones oppose centrifugal forces collinear to fluid drag, substantially at right angles to a rapid carrying current. Since such separation depends on relative particle size and specific gravity, it can be used for separation of solids from each other.
  • the precipitation step results in most of the nickel and/or cobalt precipitate having a particle size of less then 30 ⁇ and most of the gypsum having a particle size of greater than 30 ⁇ m.
  • the particle size of the precipitated gypsum in the precipitated nickel and/or cobalt may be controlled such that the cut point between the coarser particles and the finer particles is different to 30 ⁇ m.
  • most of the gypsum may report to a +50 ⁇ fraction and most of the nickel and/or cobalt precipitate may report to a- 50 ⁇ m fraction.
  • the cut point between the course fraction and the fine fraction is around 20 ⁇ m.
  • Control of the size of the gypsum particles may be achieved by feeding gypsum seed particles to the precipitation stage.
  • the gypsum seed particles may comprise a recycled stream of gypsum fines that are recovered from the precipitation stage (for example, this stream may be obtained by recycling part of the fines stream from the separator that is used to separate the course gypsum particles from the fine particles after the precipitation stage).
  • the recycle ratio can be controlled such that the gypsum particles are not too large to impact the process.
  • the nickel and/or cobalt oxide in the precipitated slurry can be separated from gypsum by a screening technology that uses appropriate sieves.
  • the precipitated slurry is wet-screened with a series of sieves and the undersized materials are collected for the final product.
  • the oversized materials are collected and recycled partly or wholly to the leaching or neutralization step.
  • the oversized materials can be leached with acid, such as sulphuric acid, to dissolve nickel and/or cobalt.
  • the nickel and/or cobalt bearing solution can be recycled to the leaching, neutralization or precipitation stage to recover nickel and/or cobalt.
  • the leached residue can be washed and recovered as pure gypsum.
  • the undersized materials also can be treated further by flotation or granulometric/size separation operation, as described in the previous sections, to increase nickel and/or cobalt grade.
  • the process comprises contacting the solution with a calcium carbonate containing neutralising agent to raise the pH of the solution to 5.0 to 7.5, or from 6.0 to 7.5, preferably 6.5 to 7.5, at a temperature of from 40 to 95 °C preferably about 60°C, to precipitate a solid nickel and/or cobalt containing material and gypsum without causing substantial precipitation of magnesium, and separating the solid nickel and/or cobalt containing material from the gypsum.
  • the calcium containing neutralising agent is suitably limestone (CaCO 3 ) and the nickel and/or cobalt in solution is precipitated as nickel and/or cobalt carbonate.
  • milled limestone is contacted with nickel and/or cobalt sulphate solution at pH 5.0 - 7.0 or 6.0 to 7.0, at a temperature of from 40 to 95 °C, preferably about 60°C.
  • the milled limestone may have a nominal size of less than 100 ⁇ m, such as about 75 ⁇ m .
  • Nickel and/or cobalt carbonate and gypsum will precipitate.
  • the slurry is then passed to a separator to separate the nickel and/or cobalt carbonate and gypsum from the solution.
  • the separator may be a thickener where the overflow (which may contain +30 ⁇ particles that include a significant proportion of the precipitated gypsum and unreacted limestone) is sent forward to nickel and/or cobalt polishing (as not all nickel and/or cobalt may be removed from solution) or for solid/liquid separation.
  • the underflow (which may contain sub 30 ⁇ particles that include a significant proportion of the precipitated nickel and/or cobalt carbonate) from the first thickener may be partly recycled to another reactor or directly to a reaction vessel or thickener, preferably at about 60°C, to contact all or just a portion of the incoming fresh nickel and/or cobalt sulphate stream from the leach process.
  • any unreacted limestone from nickel and/or cobalt precipitation is converted to gypsum.
  • Minimal nickel and/or cobalt would be precipitated from solution at this stage as reaction of unreacted limestone would dominate.
  • the slurry from this stage is sent to a second separator and the liquid stream (overflow), which still contains dissolved nickel and/or cobalt, is sent for nickel and/or cobalt precipitation with limestone.
  • the underflow from the second separator may be sent to nickel and/or cobalt solution polishing to remove any nickel and/or cobalt from solution or may be sent straight to gravity separation where any precipitated nickel and/or cobalt carbonate would report to the fine fraction and the coarse gypsum fraction would be recycled to the process.
  • the concentrate could then be passed to a further separator, such as a thickener and filter.
  • the cake may be washed to remove any magnesium in solution and also remove any nickel and/or cobalt should a nickel and/or cobalt polishing step be excluded.
  • the nickel and/or cobalt polishing step may be conducted by any known method and could be a continuously stirred tank reactor (CSTR) contacting the slurry and hydrated lime at suitable conditions, such as pH 6.5, to precipitate any nickel and/or cobalt, from solution.
  • CSTR continuously stirred tank reactor
  • the precipitation step results in a slurry containing precipitated nickel and/or cobalt carbonate and gypsum being formed.
  • This slurry may be separated into a nickel and/or cobalt carbonate -rich fraction and a gypsum-rich fraction, the gypsum-rich fraction containing precipitated gypsum and unreacted limestone.
  • the nickel and/or cobalt carbonate- rich fraction may comprise fine particles, such as sub 30 ⁇ particles, that include a significant proportion of precipitated nickel and/or cobalt carbonate
  • the gypsum-rich fraction may comprise coarse particles, such as +30 ⁇ particles that include a significant proportion of precipitated gypsum and unreacted limestone.
  • the nickel and/or cobalt carbonate -rich fraction may be sent forward to nickel and/or cobalt polishing (as not all nickel and/or cobalt may be removed from solution) or for solid/liquid separation.
  • the gypsum-rich fraction may be recycled to another reactor or sent directly to a reaction vessel or thickener, preferably at about 60°C, to contact all or a portion of fresh nickel and/or cobalt sulphate stream from a leach process to convert unreacted limestone to gypsum.
  • the resulting slurry may be separated into a liquid stream and a solids stream.
  • the liquid- stream which contains dissolved nickel and/or cobalt, may be sent to nickel and/or cobalt precipitation with limestone and the solids stream may be sent to nickel and/or cobalt solution polishing to remove any nickel and/or cobalt from solution or sent straight to separation where any precipitated nickel and/or cobalt carbonate is separated from precipitated gypsum.
  • the precipitated nickel and/or cobalt carbonate may report to a fine fraction and the precipitated gypsum may report to a coarse fraction.
  • the precipitated gypsum may be recycled to the process.
  • the precipitated nickel and/or cobalt carbonate may be subjected to a liquid/solid separation and the solid may be washed to remove any magnesium in solution.
  • the washed solids may be recovered as a nickel and/or cobalt carbonate concentrate.
  • the particle size of the precipitated gypsum in the precipitated nickel and/or cobalt may be controlled such that the cut point between the coarser particles and the finer particles is different to 30 ⁇ m.
  • most of the gypsum may report to a +50 ⁇ fraction and most of the nickel and/or cobalt precipitate may report to a- 50 ⁇ fraction.
  • the cut point between the course fraction and the fine fraction is around 20 ⁇ . Other size cutpoints may also be used.
  • cobalt and nickel can be precipitated from solution at different pH
  • cobalt would be precipitated first in a pH range of 5.0 to 7.5 at a temperature of around 60°C and nickel would be precipitated second in a slightly higher pH range of 7.0 to 9.0 at a temperature around 60°C.
  • the processing steps described above would be used to recover a final cobalt product.
  • the resulting solution containing nickel would be subjected to a precipitation step to precipitate nickel and the processing steps described above would be used to recover a final nickel product.
  • the fraction containing cobalt and/or nickel containing material may be contacted with an acidic feed solution, such as a fresh acidic feed solution, and held at a pH that is lower than the pH at which the calcium and/or nickel containing material is first precipitated, followed by separating the cobalt and/or nickel containing material from a gypsum containing material.
  • these additional steps can upgrade the cobalt and/or nickel containing material.
  • the cobalt and/or nickel containing material that is recovered as a fine fraction following the initial cobalt and/or nickel precipitation step is contacted with fresh acidic solution and held at a lower pH than the pH used in the initial precipitation step.
  • the cobalt and/or nickel containing material was initially precipitated at pH 8.5 and the cobalt and/or nickel containing material (such as the fine fraction recovered following the initial precipitation step) is contaminated with gypsum/lime/limestone or magnesium, then the cobalt and/or nickel containing material could be contacted with fresh acidic feed solution and held at a lower pH, such as a pH of 7.0, and subsequently treated to separate the solids into a gypsum containing fraction and a cobalt and/or nickel containing fraction. It is in found that this step results in precipitation of more cobalt and/or nickel from the fresh feed solution, re-solubilises some of the precipitated magnesium from the concentrate and allows removal of gypsum to the gypsum containing fraction.
  • a sufficient amount of acidic feed solution is contacted with the cobalt and/or nickel containing material to cause the pH to decrease to the desired level at which unreacted lime or limestone in the cobalt and/or nickel containing material reacts to form additional gypsum, any precipitated magnesium resolubilises and cobalt and/or nickel in the acidic solution precipitates, without requiring the addition of any additional calcium containing material.
  • the pH used in the step of contacting the cobalt and/or nickel containing material with acidic feed solution should be conducted at a pH that is lower than the pH used in the initial precipitation step, the pH range used in the step of contacting the cobalt and/or nickel containing material acidic feed solution should still fall within the pH ranges given in (a), (b) or (c) above.
  • step (a), (b) or (c) may be essentially the same as described in US20140105797 Al (the entire contents of which are herein incorporated by cross reference), such as residence time, seeding of gypsum crystals and separation of nickel and/or cobalt precipitate and gypsum by gravity or by other separation process that separates finer particles from coarser particles.
  • the gypsum fraction from the gravity separation or other separation process may be at least partly recycled to the process.
  • the nickel and or cobalt oxide fraction may be thickened and filtered.
  • the nickel or cobalt carbonate process is a variant again of US20140105797 Al where the process is operated at conditions where cobalt and nickel are precipitated and magnesium is not.
  • the calcium containing neutralising agent is suitably limestone (CaC0 3 ).
  • limestone limestone
  • One possible mechanism that causes this arises where the limestone particle becomes coated in a gypsum layer and remains inert.
  • the other avenue for unreactive limestone is that the driving force for complete reaction is not as high with limestone compared to hydrated lime.
  • the case where gypsum coats the particle can be overcome by regrinding the material to liberate the limestone surfaces but this is not amenable to the process as grinding will break down the gypsum particles potentially rendering them less than 30 ⁇ and reporting to the concentrate but likely interfering with the seeding/gypsum growth cycle.
  • the driving force issue that limits limestone reactivity can be overcome by re-treating the solids with fresh feed.
  • the expression "without causing substantial precipitation of magnesium” should be taken to mean that less than 10% of the magnesium in solution is precipitated, or less then 5% of the magnesium in solution is precipitated, or less than 3% of the magnesium in solution is precipitated, or less then 1% of the magnesium in solution is precipitated.
  • Figure 1 shows the flow sheet of embodiments of the process of the present invention
  • Figure 2 is a process flowsheet of the process used in Example 1 ;
  • Figure 3 shows the nickel and calcium content of the +20 ⁇ m and -20 ⁇ m particle size fractions obtained in example 4.
  • Figure 4 shows the particle size distribution of the particles for the +20 ⁇ m and -20 ⁇ m fractions of the particles precipitated in example 4.
  • the pregnant leach solution containing cobalt and or nickel enters the precipitation process. In industrial practice, this may occur after other metals have been removed, such as copper, zinc, iron, aluminium and manganese.
  • cobalt only will be used although the process can be used for zinc, copper, cobalt and nickel to recover a valuable high grade precipitate.
  • Figure 1 shows cobalt recovery using cobalt precipitation.
  • a pregnant leach solution 1 is fed to precipitation vessel A as described in US20140105797 Al, the entire contents of which are herein incorporated by cross reference.
  • the preferred process conditions are pH 7.5 at 40 - 95°C.
  • lime 4 is added to the liquid.
  • the lime may be hydrated lime (Ca(OH)2) or lime (CaO). Steam may also be required for heating (6 and 7), but if CaO is added, the heat released by the exothermic hydration reaction to form Ca(OH) 2 may be sufficient to heat the solution to the desired temperature. Addition of the lime causes precipitation of cobalt oxide. Gypsum will also be formed.
  • the slurry 3 of liquid and precipitated solids from cobalt oxide precipitation step A and B is sent to a thickener C and the underflow to a cobalt oxide separator E, which suitably may be in the form of a cyclone.
  • the thickener overflow is process water.
  • this separator E the solids are separated into a fine overflow stream (e.g. sub 30 ⁇ particles or sub 20 ⁇ m particles) 21 (which contains approximately 50% cobalt and approximately 2 percent calcium, equating to 95 to 99% recovery of the cobalt oxide) and a coarse underflow stream (e.g. plus 30 ⁇ particles or plus 20 ⁇ particles stream) (which contains approximately 2% cobalt and the bulk of the remainder being gypsum).
  • the cobalt oxide stream 11 is sent to a cobalt oxide filter G and the resulting cake may then be dried further depending on product requirements and put into bags for sale.
  • a flocculating agent may be added. Wash water is used to wash the filter cake to remove any soluble contaminants such as chlorine.
  • Stream 17 is returned to an upstream process with excess acid requiring neutralisation before the cobalt precipitator to re-solubilise any cobalt in this stream as shown by process L which in a cobalt plant may be used to remove iron, aluminium and manganese (FAM).
  • FAM iron, aluminium and manganese
  • Stream 16 is recycled to permit seeding of the gypsum crystal facilitating improved separation of cobalt oxide and gypsum at the cobalt oxide separator. If hydrated lime slurry is used, stream 16 is recycled to the hydrated lime stock tank. If CaO is used, stream 16 is recycled to the cobalt oxide precipitator.
  • the cobalt oxide product may be recycled as well to grow cobalt oxide particle size so that filtration performance is improved but still allowing efficient separation from the gypsum.
  • a solution containing appreciable quantities of both dissolved nickel and dissolved cobalt may be subjected to the present process to form a mixed precipitate containing both nickel and cobalt.
  • the process can be performed sequentially to recover separate cobalt and nickel products when cobalt and nickel are both present in the feed solution.
  • the process can be replicated for copper, zinc and nickel recovery and can also be applied with limestone.
  • Using lime to precipitate metal hydroxides is well known in the industry.
  • the metal hydroxide is precipitated but insoluble gypsum co-product is also precipitated lowering the grade of the final product.
  • the process is controlled such that the gypsum is rendered as a significantly different particle size than the metal hydroxide by seeding and recycling the gypsum.
  • the metal hydroxide reports to the finer fraction (-50 ⁇ m).
  • the two products can be separated with a hydrocyclone with the underflow returning to the process and the overflow reporting to the final product.
  • test conditions were:
  • test conditions were:
  • PT05 and PT06 tests were conducted in the absence of magnesium in solution with and without gypsum seed in the lime slurry.
  • the cobalt grade is high in both tests.
  • PT06 grade is lower due to the contamination from gypsum in the seed material. The full benefit of gypsum recycle is difficult to obtain on this small scale experimentation. While cobalt grade was maximised, the re-dissolution efficiency remained around 90% which is likely to be uneconomic at full scale.
  • PT07 and PT08 showed markedly lower cobalt grade with the presence of magnesium. At pH 8.5 all of the magnesium was precipitated causing contamination of the final concentrate. Temperature did not have an impact of cobalt grade.
  • Table 4 shows that the PT07 and PT08 concentrate samples could be upgraded from 35% to over 45% cobalt. Of particular interest is PT08a where nearly all magnesium is leached out of the concentrate. This has implications for the final circuit design since a two stage contact could be performed to minimise magnesium and maximise cobalt grade. Due to the sample size, the leaching of cobalt in the +20 ⁇ could not be checked.
  • a synthetic acidic feed solution containing 19.0g/L nickel was prepared by mixing nickel sulphate hexahydrate reagent with tap water and then adjusting to pH 4.0 using sulphuric acid.
  • the nickel precipitation test (PT09) was operated at 60°C for a period of 6.17 hours. This was a batch test using a heated 5 L reactor with lime used to control the pH to 9.0. The reactor was started half full with a milk of lime slurry at pH 9.0 and 60°C. The synthetic nickel feed solution was slowly added to the reactor until the pH decreased to 7.0, at which point additional lime was added until pH was 9.0 again. This process was repeated until the reactor was filled. 5.17 hours of the time was used for incremental feed solution addition and another hour was used to allow the system to equilibrate. The final reactor slurry was collected, filtered and assayed for nickel and calcium for mass balance purposes.
  • the collected solids were initially laser sized and then wet screen through a 20 ⁇ screen using processed liquors.
  • the oversize (+20 ⁇ ) and undersize fractions (- 20 ⁇ ) were each laser sized and then assayed for nickel and calcium for mass balance and product evaluation purposes.
  • the totalised mass balance for the tests was 89% and the nickel mass balance was 109%.
  • Lime consumption was 34.3 kg/m 3 of feed (1.81 kg/kg Ni), reported as hydrated lime (Ca(OH) 2 ).
  • the final precipitate from the tests was a green colour, indicative of Ni(OH) 2 .
  • the nickel precipitation test produced a fine product grading 44.6% nickel (by weight) at 98.5% recovery.
  • Table 5 shows the mass balance and assays arising from this test:
  • Table 6 shows data relating to particle size distribution and assays obtained in this example.
  • the -20 ⁇ fraction contained 44.60% by weight nickel, which represents a recovery of 98.5% of the nickel in the feed.
  • the -20 ⁇ fraction contained 5.88% calcium, which represented 19.2% of the calcium added to the precipitation step.
  • the +20 ⁇ fraction contained only 0.60% nickel, which represented 1.5% recovery of the nickel in the feed.
  • the coarse fraction contains 22.3% by weight calcium, which represented 80.8% of the calcium added to the precipitation step.
  • a further experimental run was conducted in which a feed solution containing 20 g/L nickel (as nickel sulphate) dissolved in solution was fed to a precipitation tank.
  • the precipitation tank was operated at pH 9.0, with pH control being achieved by addition of hydrated lime.
  • the operating temperature was 60°C. This resulted in precipitation of particulate material.
  • the particular material was separated into a -20 ⁇ fraction and a +20 ⁇ fraction by screening the particular material on the 20 ⁇ screen.
  • Figure 3 shows the grade of the +20 ⁇ and -20 ⁇ particle size fractions obtained in this example.
  • the minus 20 ⁇ fraction contained 44.6% nickel with a 98.5% recovery of nickel to the -20 ⁇ fraction.
  • the -20 ⁇ fraction contained 4.9% calcium.
  • the +20 ⁇ fraction contained approximately 22% weight calcium and less than 1% by weight nickel.
  • Figure 4 shows the particle size distribution for the +20 ⁇ and the -20 ⁇ fractions obtained in this example.

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Abstract

Cette invention porte sur un procédé de précipitation d'un solide contenant du nickel ou du cobalt à partir d'une solution acide contenant du nickel et/ou du cobalt dissous, comprenant la mise en contact de la solution avec un agent de neutralisation contenant du calcium pour élever le pH de la solution à une valeur de 5.0 à 9.0 à une température de 40 à 95 °C de sorte à entraîner la précipitation d'un matériau solide contenant du cobalt et/ou d'un matériau solide contenant du nickel et d'un gypse et séparer du gypse le matériau solide contenant du cobalt et/ou le matériau solide contenant du nickel. Le matériau solide contenant du cobalt et/ou le matériau solide contenant du nickel peut rapporter à une fraction de particules fines et le gypse peut rapporter à une fraction granulométrique grossière et la matière solide contenant du cobalt et/ou un matériau contenant du nickel solide peut être séparé du gypse en utilisant une technique de séparation de la taille des particules.
PCT/AU2017/050004 2016-01-04 2017-01-04 Précipitation de nickel et de cobalt Ceased WO2017117626A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
AU2016900007 2016-01-04
AU2016900007A AU2016900007A0 (en) 2016-01-04 Precipitation of Nickel and Cobalt
AU2016903088A AU2016903088A0 (en) 2016-08-05 Precipitation of Nickel and Cobalt and/or Lithium
AU2016903088 2016-08-05
AU2016903776 2016-09-20
AU2016903776A AU2016903776A0 (en) 2016-09-20 Precipitation of Nickel and Cobalt and/or Lithium

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WO2017117626A1 true WO2017117626A1 (fr) 2017-07-13

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109354252A (zh) * 2018-11-27 2019-02-19 来宾华锡冶炼有限公司 一种硫酸污水的处理方法
CN114427037A (zh) * 2022-01-06 2022-05-03 中国恩菲工程技术有限公司 从低浓度镍钴溶液中连续化富集镍钴的方法

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US4006215A (en) * 1975-04-02 1977-02-01 The International Nickel Company, Inc. Recovering iron, nickel, or cobalt from sulfate solution
CA1040868A (fr) * 1975-04-02 1978-10-24 Inco Ltd. Recuperation des metaux utiles en solution par neutralisation a l'aide de chaux ou de calcaire
US4201648A (en) * 1978-04-12 1980-05-06 The International Nickel Co., Inc. Nickel recovery from sulfur-deficient mattes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006215A (en) * 1975-04-02 1977-02-01 The International Nickel Company, Inc. Recovering iron, nickel, or cobalt from sulfate solution
CA1040868A (fr) * 1975-04-02 1978-10-24 Inco Ltd. Recuperation des metaux utiles en solution par neutralisation a l'aide de chaux ou de calcaire
US4201648A (en) * 1978-04-12 1980-05-06 The International Nickel Co., Inc. Nickel recovery from sulfur-deficient mattes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109354252A (zh) * 2018-11-27 2019-02-19 来宾华锡冶炼有限公司 一种硫酸污水的处理方法
CN114427037A (zh) * 2022-01-06 2022-05-03 中国恩菲工程技术有限公司 从低浓度镍钴溶液中连续化富集镍钴的方法
CN114427037B (zh) * 2022-01-06 2023-09-29 中国恩菲工程技术有限公司 从低浓度镍钴溶液中连续化富集镍钴的方法

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