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WO2019090389A1 - Production de sulfate de nickel de pureté élevée - Google Patents

Production de sulfate de nickel de pureté élevée Download PDF

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Publication number
WO2019090389A1
WO2019090389A1 PCT/AU2018/051203 AU2018051203W WO2019090389A1 WO 2019090389 A1 WO2019090389 A1 WO 2019090389A1 AU 2018051203 W AU2018051203 W AU 2018051203W WO 2019090389 A1 WO2019090389 A1 WO 2019090389A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
solution
nickel sulfate
resin
loading
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AU2018/051203
Other languages
English (en)
Inventor
Richard Clout
John Stewart
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BHP Nickel West Pty Ltd
Original Assignee
BHP Billiton Nickel West 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 AU2017904565A external-priority patent/AU2017904565A0/en
Application filed by BHP Billiton Nickel West Pty Ltd filed Critical BHP Billiton Nickel West Pty Ltd
Priority to AU2018363879A priority Critical patent/AU2018363879B2/en
Publication of WO2019090389A1 publication Critical patent/WO2019090389A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C22B23/0407—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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/10—Sulfates
    • 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
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt

Definitions

  • the Invention relates to a process for the production of high purity nickel sulfate from a nickel powder leach In sulfuric acid.
  • Nickel sulfate b used In electroplating and electro less plating as well as being a material for secondary batteries. There Is a need for high purity nickel sulfate that is substantially free of impurities including copper, iron and cobalt for such uses.
  • the invention provides a process for producing high purity nickel sulfate, preferably having a purity of 299.8%, more preferably 299.98%, suitable for use In a battery or nickel plating, comprising the step of:
  • nickel sulfate solution selectively removing non-nickel metal impurities from a nickel sulfate solution, preferably a sub-saturated acidic nickel sulfate solution for example obtained from nickel powder, by Ion exchange using a nickel pre-loaded Ion exchange (IX) resin which adsorbs non-nickel metal Impurities from the solution to form a substantially non-nlckel metal Impurities free nickel sulfate solution from which the high purity nickel sulfate can be recovered.
  • the nickel sulfate solution comprises trace amounts of non-nickel metal impurities.
  • the nickel sulfate solution is a sub-saturated nickel sulfate solution.
  • the nickel sulfate solution is non-nickel metal impurity depleted sub- saturated nickel sulfate solution.
  • the nickel sulfate solution is acidic.
  • the nickel sulfate solution is an acidic non-nickel metal impurity depleted sub-saturated nickel sulfate solution which comprises trace amounts of non-nickel metal impurities.
  • the step of selectively removing the trace amounts of non-nickel metal impurities involves buffering the nickel sulfate solution prior to ion exchange (IX) with one or more basic nickel compounds to a pH optimised for selectivity and stability of non-nickel metal impurity loading onto the nickel pre-loaded ion exchange resin.
  • IX ion exchange
  • the process further comprises the step of recovering the high purity nickel sulfate from the substantially non-nickel metal impurities free nickel sulfate solution, preferably in the form of crystalline alpha nickel sulfate hexahydrate.
  • the nickel sulfate solution is an acidic sub-saturated nickel sulfate solution
  • the method comprises prior to the selective removal step, the additional steps of:
  • non-nickel metal depleted nickel sulfate solution comprising a sub- saturated concentration of nickel sulfate and trace amounts of one or more non-nickel metal impurities.
  • the process is preferably a batch process, comprising the steps of:
  • selective removal of the trace amounts of non-nickel metal impurities involves buffering the acidic sub-saturated non-nickel metal depleted nickel sulfate solution prior to ion exchange (IX) with one or more basic nickel compounds to a pH optimised for selectivity and stability of non-nickel metal impurity loading onto a nickel pre-loaded ion exchange resin.
  • IX ion exchange
  • the invention provides a process, preferably a batch process, for leaching nickel sulfate from nickel powder comprising the steps of:
  • step (ii) separating the acidic sub-saturated nickel sulfate solution from the unleached nickel powder to provide a discharge solution which is a substantially solid-free acidic sub- saturated nickel sulfate solution; and optionally repeating steps (i) and (ii) one or more times, wherein the one or more additional leaching steps (i) are carried out with sulfuric acid, preferably using the unleached nickel solid separated in step (ii).
  • the acidic sub-saturated solution of dissolved nickel sulfate and one or more non-nickel metal impurities, together with unleached nickel powder is a pregnant leach solution.
  • the pregnant leach solution is a solution is a solution of metal laden water generated from stockpile leaching and heap leaching for example.
  • a pregnant leach solution is an acidic solution and may comprise one or more organic and/or inorganic acids.
  • the process is carried out as a batch process.
  • non-nickel metal impurities are co-leached by the acid, together with the nickel sulfate.
  • the one or more non-nickel metal impurities include one or more of Ca, Al, Na, P, Si, K, Mg, Mn, Se, Cr, Co, Fe, Cu, Zn, As, Ru, Pb, Hr, Pd, Ag, Cd, Sb, Ir, Pt, Au and Bi.
  • the most significant impurities tend to be varying amounts of Co, Cu, Cr, K, Ca, Na, Zn and/or Fe.
  • the impurities in most appreciable quantities are usually Co, Cu and/or Fe.
  • various metal oxidation states species can be present in the leach solution, for example, iron can be present in the ferric or ferrous form.
  • the sulfuric acid used in the process for leaching is prepared using demineralised water. This is thought to reduce the contaminant burden to impurities arising from sulfuric acid leaching of nickel powder. This means that metal contaminants that are found in mains water are avoided.
  • the nickel powder for leaching may be provided directly from a nickel powder leach plant.
  • the nickel sulfate process is carried out in proximity to a nickel powder leach plant.
  • the raw material nickel powder can conveniently been provided to the nickel sulfate processing plant directly from the discharge of wet metals driers in the nickel powder leach plant.
  • the nickel powder raw material can be provided by transport from an alternative source; however, this would be expected to add to the overall processing cost.
  • the nickel powder used in the process described has an average particle size of from about 1 micron to about 1200 microns, more preferably from 10 microns to about 1000 microns, more preferably still from about 100 microns to about 900 microns. In some embodiment, it is believed that coarser particles leach more slowly such that there is a preference for less coarse particles where faster leaching is desirable.
  • the nickel powder raw material may have a purity of from about 98% to about 100%. However, the nickel powder preferably has a purity of ⁇ 99.8% nickel. Such nickel powder may be obtainable by any industrial process capable of generating nickel powder having such purity. One example of a suitable process is nickel powder production from a process involving hydrogen pressure reduction.
  • the leaching process is carried out at a temperature of from about 50 °C to about 100 °C, most preferably from about 70 °C to about 95 °C, most preferably still at about 80 °C.
  • the process temperature is achieved and/or maintained by steam heating, for example, by a steam heating coil provided in the leach tank. Steam may be conveniently provided from a close by refinery.
  • a sub-saturated nickel sulfate solution comprises dissolved nickel in a concentration which is about 70%to about 99% of the theoretical nickel sulfate saturation concentration under the particular leaching conditions used.
  • Preferred sub-saturated solutions are of from about 90% to about 98% nickel sulfate, more preferred sub-saturated solutions are of from about 92% to about 97%, with solutions of about 95% of the theoretical nickel sulfate saturation concentration being most preferred.
  • the pregnant leach solution is a sub- saturated nickel sulfate solution that comprises dissolved nickel in a concentration that is about 70% to about 99%, more preferably from about 92% to about 97%, most preferably about 95% of the theoretical nickel sulfate saturation concentration.
  • the sub- saturated nickel sulfate solution is acidic.
  • the degree of nickel sulfate saturation in the leach solution is dependent on factors including the pH of the acid used, the temperature of the leach solution and/or the rate of evaporation from the leaching solution.
  • the leaching sulfuric acid concentration and/or the process temperature may be controlled to in order to produce a discharge solution which is sub-saturated at about 95% of the saturation limit of nickel sulfate at under the processing conditions used.
  • a nickel sulfate saturation of about 95% is readily achievable using an optimised acid concentration and processing conditions as described herein.
  • operating close to saturation, particularly at higher temperatures, for example, 80°C minimises evaporation duty in downstream process crystallisation stages, and eliminates the need for a pre-evaporator reducing capital and processing costs.
  • the initial concentration of sulfuric acid used in leaching step (i) is from about 150 g/L and about 350 g/L, more preferably from about 200 g/L and about 300g/L, more preferably still from about 250 g/L to about 290g/L, most preferably about 280 g/L (which corresponds to about 150 ml/L of sulfuric acid/water).
  • nickel powder is preferably provided/maintained at a loading of between about 850 g/L and 1200 g/L, more preferably, from about 950 g/L to about 1100 g/L, most preferably about 1000 g/L (mass of nickel per litre of sulfuric acid).
  • the nickel in the sulfuric acid has a pulp density, that is amount of solids in a pulp of nickel in acid, in the range of about 500 to about 1500 g/l, more preferably from about 600 to about 200 g/L, more preferably still from about 750 g/L to about 850 g/L, with a particularly preferred pulp density being about 800 g/L, for example at a pH of between about 0 and about 3.5.
  • the process occurs at about atmospheric pressure or at a positive gauge pressure.
  • at least leaching step (i) may be carried out at about atmospheric pressure or more preferably at a positive gauge pressure.
  • step (i) the nickel solid and sulfuric acid are agitated.
  • the leaching and/or separation may be carried out under aeration, for example, under a compressed air atmosphere, for example, having a flow rate of about 0.1 to about 9.5 L min, more preferably 1 - 5 L min, most preferably about 1 L min.
  • aeration for example, under a compressed air atmosphere, for example, having a flow rate of about 0.1 to about 9.5 L min, more preferably 1 - 5 L min, most preferably about 1 L min.
  • Lower flow rates, for example, ⁇ 3.5 L min are preferred as higher flow rates tend to result in increasing amounts of evaporation of the leaching acid which results in premature saturation of nickel sulfate in the discharge solution.
  • the process is carried out anaerobically, for example using N 2 sparging.
  • the process desirably further comprises the step of removing the evolved hydrogen gas, for example, by flushing the local environment around the leaching location with steam, for example, a snuffing steam, and/or by operating the leaching process at a positive gauge pressure to prevent air ingress. It will be understood that the flush is maintained in the vicinity of at least the leach tank vapour space.
  • a preferred steam flush is a steam/air mixture comprising from about 50% to about 90% steam.
  • a steam flush providing a minimum of 70 vol% steam atmosphere is particularly desirable.
  • the process further comprises the step of scrubbing the hydrogen steam flush off gas generated to remove acid mist and particulates prior to atmospheric discharge.
  • the process includes the step of carrying out at least the leaching step under a nitrogen blanket to prevent a potentially explosive hydrogen/air mixture forming.
  • the separating step 0 and/or additional bulk impurity removal steps also described herein can further be carried out using a steam flush and/or under a nitrogen blanket to minimise the risk of formation of an explosive environment.
  • the unleached solid nickel is separated from the sub-saturated pregnant leach solution, for example, by filtering or by decanting.
  • Decanting is a particularly preferred separation method as conveniently leaves the unreached nickel in place for easy commencement of a subsequent leach batch where fresh acid is simply to be added in the next batch.
  • discharge solution decanting takes place after a suitable period for settling has elapsed. Completion of the leaching step can be identified by observation that the pregnant leach solution has a predetermined pH, or that the leaching step has been allowed to process for a predetermined period of time.
  • step (i) is allowed to proceed until the pregnant leach solution has a pH of from about 0 to about 4, more preferably a pH of about 1 to about 3.5, most preferably a pH of about 3.
  • the leaching step (i) may proceed for a period of from about 2 to about 30 hours, more preferably from about 8 to about 24 hours, more preferably still from about 9 to about 12 hours, most preferably for about 10 hours.
  • the pregnant leach solution comprises from about 130 g/L to about 210 g/L nickel, more preferably from about 1 0 g/L to about 200 g/L nickel, more preferably still from about 150 g/L to about 195 g/L nickel, and most preferably about 192 g/L.
  • a solution pH 3 generally corresponds to a nickel sulfate solution concentration of 192 g/L. Terminating the leaching process at about pH 3 is preferred as it provides a balance between (i) terminating at a lower pH, but requiring a much great amount of neutralisation agent to neutralise the excess free acid, and (ii) terminating at a higher pH, which means the reaction is far slower and would take much longer and so would require increased capital for larger reaction tanks where the total process throughput is fixed.
  • the term about represents a plus/minus deviation on a value corresponding to 1% in the context of pH measurements and 5% of concentration values.
  • the method further comprises the step of removing the bulk non- nickel metal impurities from the discharge solution.
  • the process further comprises the steps of:
  • non-nickel metal impurity-depleted discharge solution comprising a sub-saturated solution of nickel sulfate and trace amounts of the one or more non-nickel metal impurities.
  • the precipitation step may include the step of oxidising one or more non- nickel metal impurities in the discharge solution. Such an oxidation step is preferably carried out prior to the precipitation step. Oxidation of one or more of the metal impurities can assist in formation of metal species which precipitate at a more desirable pH, for example, the pH of operation. For example, oxidation converts iron from ferrous to ferric whereby ferric hydroxide and other impurities can be more conveniently precipitated at about pH 5.
  • the precipitated non-nickel metal impurities comprise non-nickel metal hydroxides which are formed when the pH of the discharge solution is sufficiently increased to a level where such hydroxides can form.
  • the sulfuric acid may comprise one or more oxidising agents, for example, oxygen, preferably supplied by sparging the sulfuric acid with air.
  • an oxidising agent preferably it comprises a source of oxygen, for example, air, such as an air sparge.
  • air can be sparged through the discharge solution.
  • the precipitating step can be executed by increasing the pH of the discharge solution to a pH of about 3 to about 7, preferably to a pH of about 4.5 to about 5.5, more preferably to a pH of about 5.
  • a particularly preferred precipitation pH is about 5.
  • the pH of the discharge solution may be increased by the addition of one or more basic compounds, preferably one or more basic nickel compounds, most preferably nickel hydroxide.
  • Nickel hydroxide is suitable to raise the pH of the acidic sub-saturated solution (e.g. a pregnant leach solution) or the discharge solution to about pH 5 to about pH 5.5, with reasonable neutralisation kinetics and efficiency. This is achievable with sufficient leach residence time.
  • alkali bases in particular, sodium or potassium hydroxide bases are avoided as these bases typically leads to alkali contamination in the final product which can be burdensome to remove.
  • the process further includes the step of separating the non-nickel metal impurities precipitate from the discharge solution to form a non-nickel metal impurity-depleted discharge solution.
  • the non-nickel metal impurity-depleted discharge solution is a non-nickel metal hydroxide-depleted discharge solution.
  • Means for separation include any suitable separation means, for example, decanting, centrifuging or filtering.
  • the non-nickel metal impurity- depleted discharge solution is filtered to remove any remaining solids prior to storage in the ion exchange (IX) feed tank and/or prior to ion exchange (IX).
  • the non-nickel metal impurity-depleted discharge solution is held in the ion exchange (IX) feed tank prior to the ion exchange processing.
  • filter sludge recovered from filtering is preferably transferred to a refinery final thickener for further processing or disposal.
  • the discharge solution has a pH of from about 3 to about 7, more preferably about 4 to 6, most preferably a pH of about 5.
  • the bulk impurity removal process is associated the additional step of acid mist scrubbing to scrub off or remove any hydrogen gas evolved at this stage of the process.
  • this scrubbing step is completely separate to the off-gas scrubbing used during leaching thereby ensuring hydrogen and oxygen do not mix in corresponding off-gas scrubbers.
  • the steps of the bulk impurity removal process may be carried out by flushing the local environment around the leaching location with snuffing steam and/or a positive gauge pressure to prevent air ingress as described above. If necessary, the bulk impurity removal process may also include the step of carrying out the leaching step under a nitrogen blanket to prevent the hydrogen mixing with air to form an explosive environment as described above.
  • the invention provides a process for producing high purity nickel suitable for use in battery manufacture or nickel plating, preferably having a purity of >99.98% nickel sulfate, comprising the steps of:
  • the invention provides a process for producing a high purity nickel sulfate solution suitable for crystallisation of high purity, preferably >99.98% purity nickel sulfate hexahydrate, comprising the steps of:
  • a nickel sulfate solution preferably being a substantially solid-free acidic sub-saturated nickel sulfate solution, comprising dissolved nickel sulfate and one or more non-nickel metal impurities, preferably a pregnant leach solution, more preferably obtainable by a process as defined in any one of claims 5 to 19;
  • the nickel sulfate solution is an acidic sub-saturated nickel sulfate, more preferably an acidic sub-saturated non-nickel metal impurity-depleted discharge solution, more particularly, such as one which has been subjected to a bulk non-nickel metal impurity removal process as described herein.
  • the nickel sulfate solution is a pregnant leach solution which may be obtainable by the leaching processes described herein.
  • the nickel sulfate solution from which the non-nickel metal impurities are removed is a subsaturated nickel sulfate solution, preferably having a nickel concentration of about 100 g/L to about 215 g/L nickel.
  • the sub-saturated nickel sulfate solution has an initial concentration of nickel in the range of from about 130 g L to about 210 g/L nickel, more preferably from about 150 g/L to about 200 g/L nickel, more preferably still from about 175 g/L to about 195 g/L nickel, and most preferably about 190 g/L.
  • the non-nickel metal impurities are present, for example, in trace amounts, particularly if the nickel sulfate solution has been subject to a bulk non-nickel metal impurity removal process.
  • the non-nickel metal impurities include divalent metal cations, for example, divalent cobalt, iron and/or copper ions, preferably cobalt ions.
  • the non-nickel metal impurities in the nickel sulfate solution are selectively retained by the resin in exchange for pre-loaded nickel and/or hydrogen ions.
  • the subjecting step includes the step of buffering the nickel sulfate solution prior to ion exchange (IX) with one or more basic nickel compounds, preferably to a pH optimised for selectivity and stability of non-nickel metal impurity loading onto the nickel preloaded ion exchange resin.
  • a preferred amount of nickel hydroxide is sufficient to neutralise acid released by the resin in exchange for nickel during nickel preloading so that the pH of the pre-IX and post-IX solutions are substantially equivalent, preferably within 10% of the relevant pH unit.
  • the precise optimised pH may depend on factors including the chemistry of the resin used but will be readily be determinable as shown in the examples provided herein.
  • the nickel sulfate solution has an initial pH of pH ⁇ 6, preferably a pH of from about 4.5 to about 6, more preferably, a pH of about 5 to about 5.5, most preferably, a pH of about 5.
  • the nickel sulfate solution has a final pH of pH ⁇ 6, preferably a pH of from about 4.5 to about 6, more preferably, a pH of about 5 to about 5.5, most preferably, a pH of about 5.
  • the first and one or more additional rounds of ion exchange are carried out at a temperature of from about 50 °C to about 95 °C, more preferably from about 70 °C to about 90 °C, most preferably at about 80°C.
  • the resin is capable of extracting metal ions from solution. More suitably still, the resin is capable of selective removal of metal ions from solution. Selective removal means one or more metal ions are removed from the solution in preference to different metal ions which remain in solution at a given pH/operating conditions.
  • the resin is a cation exchange resin.
  • the resin may be comprised of one or more polymers based on at least one monovinylaromatic compound and/or at least one polyvinylaromatic compound. It is preferable when chelating resins for the purposes of the invention are polymers composed of for example, styrene, divinylbenzene and ethylstyrene.
  • the resin is preferably in bead form.
  • the resin is a macroporous crosslinked polystyrene based resin, which is preferably acidic or otherwise capable of extracting metal ions from solution such as the nickel sulfate solutions, as described herein.
  • the resin is a metal chelating resin which comprises one or more metal chelating functional groups.
  • the resin comprises organophosphorus functional groups which are capable of selectively complexing with certain metal ions, for example, under certain pH conditions. Desirably such functional groups include phosphoric, phosphonic or phosphinic acid based functional groups.
  • An example of a phosphoric acid based resin is one comprising di-2-ethylhexyl-phosphat (D2EHPA) functional groups (Lewatit VP OC 1026®).
  • An example of a phosphonic acid based resin is one comprising aminomethyl phosphonic acid functional groups (Lewatit TP-260®).
  • An example of a phosphinic acid based resin is one comprising bis-(2,4,4-trimethylpentyl-) phosphinic acid functional groups (Lewatit TP-272®).
  • the resin is not a TP-207 resin.
  • the resin is provided in two or more columns arranged in a lead/lag configuration, whereby the lag column can act as (i) a polishing column when the impurity breakthrough of the lead column becomes undesirably, or as a new lead column where the original led column is subject to regeneration thereafter becoming the lag column.
  • the first IX discharge solution is transferred to a crystallisation plant.
  • Control of solution pH is critical to the optimum selectively and efficiency of the ion exchange resin.
  • Increasing the pH of the preloading feed solution typically results in increased nickel loading. However, if the pH is too high, undesirable species precipitation may occur and/or impurity loading may cease or decrease to unacceptably low levels.
  • fresh and preloaded resin has available hydrogen ions for exchange with suitable metal ions. As the hydrogen ion exchange reaction releases two hydrogen ions for each divalent metal (II) ion taken up by the resin, the acidity of
  • discharge/effluent from the ion exchange column tends towards increased acidity over time such that the equilibrium pH tends to be greater than the initial pH.
  • a pronounced increase in acidity may be undesirable as this may have a negative effect on the resin's ability to selectively uptake the non-nickel metal impurities, for example, cobalt in the case where a TP272 resin is used and/or may inhibit nickel preloading/uptake by the resin.
  • the pre-loading step involves introducing nickel ions to the resin in fresh form (protonated) under conditions whereby hydrogen ions on the fresh resin are exchanged for the introduced nickel ions.
  • the nickel ions are typically provided in the form of a nickel pre-load solution.
  • the process for selectively removing non-nickel metal impurities from a nickel sulfate solution further comprises the step of preloading the resin of the first round of ion exchange (IX) with nickel ions.
  • IX ion exchange
  • one or more buffering agents can be used to control the pH at a value that ensures impurity, particularly Co impurity, loading stability and optimum selectively.
  • the ion exchange process includes the step of buffering the acidity of the solution passing through the ion exchange resin which increases with time.
  • nickel hydroxide as base/buffer advantageously avoids pH decrease during ion exchange avoids and avoids the introduction of alkali or ammonium contaminant during pH adjustment.
  • ammoniacal nickel complexes is avoided during the pre-loading by avoiding ammonia pH adjustment; avoiding formation of nickel hydroxide precipitates at higher pH (pH > 6); minimising degradation and loss of resin functional groups by operating at relatively low pH ⁇ 6; and providing for minimum washing requirements.
  • the resin of the first round of ion exchange is preloaded with nickel using a nickel pre-loading feed solution, which is preferably a portion of the first IX discharge solution, or an alternative source of filtered clean nickel sulfate solution, preferably in the presence of nickel hydroxide for pH adjustment buffering.
  • a nickel pre-loading feed solution which is preferably a portion of the first IX discharge solution, or an alternative source of filtered clean nickel sulfate solution, preferably in the presence of nickel hydroxide for pH adjustment buffering.
  • the pH of the pre-loading feed solution may be buffered/increased to a desired pH by the addition of one or more basic compounds, preferably basic nickel compounds, most preferably nickel hydroxide.
  • Nickel hydroxide is suitable to raise the pH of an acidic sub-saturated nickel sulfate solution to from about pH 5 to about pH 5.5. At higher pH, the nickel and/or other species may begin to precipitate.
  • the resin is pre-loaded using clean nickel sulfate in the presence of nickel hydroxide for pH adjustment buffering.
  • the preloading feed solution pH is from about pH 4.5 to about pH 6, more preferably from about pH 4.0 to about pH 5. In this latter pH range minimal nickel precipitation occurred while maximising nickel loading onto resin.
  • the preferred preloading feed pH is from about 4.5 to about 6, more preferably from 4.5 to about 5.5, most preferably the preloading feed pH is about 5.
  • alkali bases such as sodium hydroxide, potassium hydroxide or ammonium hydroxide bases are avoided as the may lead to contamination in the final nickel sulfate product
  • the pre-loading step involves introducing a clean nickel sulfate solution substantially free of non-nickel metal impurities.
  • the resin may be preloaded using an alternative source of filtered clean nickel sulfate solution.
  • the process involves the step of filtering the first IX discharge solution or alternative source of solution prior to preloading. Filtering prior to preloading advantageously removes residual solids, for example, resin particles.
  • the nickel pre-loading is maximised using a maximum strength nickel pre- loading feed, preferably, a maximum strength clean nickel sulfate solution as described herein.
  • the nickel pre-loading feed solution has an initial concentration of nickel in the range of from about 130 g/L to about 210 g/L nickel, more preferably from about 150 g/L to about 200 g/L nickel, more preferably still from about 175 g/L to about 195 g/L nickel, and most preferably about 190 g/L.
  • the nickel hydroxide base is generated from a portion of the IX purified clean nickel sulfate solution, which is the first IX discharge solution.
  • the clean nickel sulfate solution substantially free of non-nickel metal impurities may be a portion of the first IX discharge solution as described above.
  • the nickel hydroxide could be produced from a bleed of a nickel powder refinery process, for example, a Sherritt Gordon Process, via ammonia steam stripping process to generate nickel hydroxide.
  • the amount of nickel hydroxide provided is sufficient to neutralise acid released by the resin in exchange for nickel during nickel preloading.
  • a preferred amount of nickel hydroxide is one that can substantially stabilise the pH pre-loading feed solution such that the pH of the solution a column of resin is substantially the same as the pH of the solution discharging from the column of resin.
  • the preferred preloading feed pH is from about 4.5 to about 6, more preferably from 4.5 to about 5.5, most preferably the preloading feed pH is about 5.
  • using a pre-loading feed having a pH greater than about 5.5 tends to adversely affect Co impurity removal by the column.
  • the process for selectively removing non-nickel metal impurities from a nickel sulfate solution further comprises the step of generating the nickel hydroxide for pH adjustment/buffering from clean nickel sulfate solution.
  • the process further comprises subjecting the first IX discharge solution to a second round of ion exchange using nickel preloaded resin to provide a second IX discharge solution being a polished IX discharge solution.
  • the second round of ion exchange may be used where impurity break through is observed in the first IX discharge solution.
  • the process further comprises the step of regenerating the resin used in ion exchange, preferably on observation that (i) loading of substantially all of the non-nickel metal impurities onto the resin has been achieved or (ii) break through of the non-nickel metal impurity in the first IX discharge solution.
  • cobalt breakthrough in the IX column discharge solution can signify that resin regeneration or replacement is required.
  • the method further comprises the step of replacing or regenerating the resin used in the ion exchange rounds.
  • the requirement for replacement or regeneration of the resin may be determined for example on observation that loading of substantially all of the non-nickel metal impurities onto the resin has been achieved and/or that the non-nickel metal impurity concentration begins to increase in the first IX discharge solution.
  • regenerating resin which has been used in ion exchange involves the steps of:
  • pre-loading the resin with nickel by flushing the resin with a nickel pre-loading feed solution wherein the pre-loading exchanges at least a portion of the hydrogen ions loaded onto the resin for nickel ions in the nickel pre-load feed, thereby loading nickel ions onto the resin to provide resin in nickel pre-loaded form.
  • step (iv) is carried out as described above.
  • nickel pre-loading feed solution has a pH about pH 4.5 to about pH 6, more preferably from about pH 4.0 to about pH 5. In this latter pH range minimal nickel precipitation occurred while maximising nickel loading onto resin.
  • the nickel pre-loading feed solution is a clean nickel sulfate solution, more preferably being a portion of the first IX discharge solution. It should be understood that the clean nickel sulfate solution and the first IX discharge solution described herein is an acidic sub-saturated nickel sulfate solution, preferable obtainable by a leaching process as described herein.
  • the nickel pre-loading feed solution further comprises a buffering amount of nickel hydroxide.
  • a buffering amount of nickel hydroxide is one which is sufficient to optimise for selectivity and stability of non-nickel metal impurity loading onto the nickel pre-loaded ion exchange resin
  • the nickel pre-loading feed solution comprising nickel sulfate and/or nickel hydroxide is preferably filtered prior to the pre-loading step.
  • a slightly acidic pH for the wash for example, a pH of about 3 to about 6, more preferably from about 4 to about 5, avoids dissolution of the active resin component which would lead to a loss of ion exchange capacity.
  • a pH of about 4 to about 5 is particularly suitable to preserve the resin.
  • the wash sulfuric acid may be recycled to a leach acid solution for reuse.
  • the strip solution comprising the removed impurities is transferred to a waste collection tank.
  • the clean nickel sulfate solution preferably being the first IX discharge solution, is crystallised to form high purity nickel sulfate crystals, preferably, nickel sulfate hexahydrate crystals, for example, in the alpha form.
  • the sub-saturated nickel sulfate solution is an acidic pregnant leach solution, for example, obtainable from a nickel sulfate leaching process as defined herein, and which has been subjected to bulk impurity removal and trace impurity removal via ion exchange as described herein.
  • the clean nickel sulfate solution may be filtered prior to crystallisation.
  • the invention provides a process for producing high purity nickel suitable for use in battery manufacture or nickel plating, preferably having a purity of ⁇ 99.98% nickel sulfate, comprising the steps of:
  • the process further comprises the optional step of oxidising non-nickel metal impurities in the sub-saturated nickel sulfate solution prior to the step of raising the pH of the sub-saturated nickel sulfate solution to induce precipitation of insoluble non-nickel metal impurities.
  • the insoluble precipitate is formed by increasing the pH of the discharge solution to a pH of about 3 to about 7, preferably to a pH of about 4.5 to about 5.5, more preferably to a pH of about 5, and separating the precipitate to form a non-nickel metal impurities depleted, preferably a non-nickel metal hydroxides-depleted sub-saturated nickel sulfate solution and which has been subjected to bulk impurity removal and trace impurity removal via ion exchange as described herein.
  • the clean nickel sulfate solution may be filtered prior to crystallisation.
  • recovering step (iv) involves crystallising the non-nickel metal impurity depleted sub-saturated nickel sulfate solution to form high purity nickel sulfate crystals, preferably nickel sulfate hexahydrate crystals, more preferably alpha nickel sulfate hexahydrate crystals.
  • Crystalline alpha nickel sulfate hexahydrate is particularly desirable as it is the industry standard for applications such as battery manufacture and nickel plating, including electroless and electoplating.
  • the sub-saturated nickel sulfate solution is an acidic pregnant leach solution, for example, obtainable by leaching nickel powder in sulfuric acid, for example, by a process as defined herein.
  • the selectively removal step (iii) is an ion exchange process as defined herein.
  • the crystallising step is carried out at a temperature of from about 45 °C to about 65 °C, preferably from about 50 °C to about 60 °C, most preferably at about 53°C and/or under a pressure of about 10 kPa absolute, preferably forming alpha crystalline nickel sulfate hexahydrate.
  • the crystallising step is carried out in an evaporative crystalliser, for example, a mechanical vapour recompression type crystalliser, preferably a draft tube baffle crystalliser.
  • an evaporative crystalliser for example, a mechanical vapour recompression type crystalliser, preferably a draft tube baffle crystalliser.
  • the process further comprises the step of separating the crystals from the nickel sulfate solution, for example, dewatering using a filter, centrifuge or cyclone.
  • the process further comprises the step of drying the crystals to provide dry high purity nickel sulfate hexahydrate, for example, in a fluid bed dryer.
  • the invention provides a processing plant capable of producing high purity ( ⁇ 99.8%, more preferably ⁇ 99.98%) nickel sulfate from nickel powder comprising:
  • an acidic nickel leach module for generating sub-saturated pregnant leach solution comprising nickel sulfate and non-nickel metal impurities, preferably configured for batch leaching;
  • a bulk non-nickel metal impurity removal module for precipitating the bulk of the non-nickel metal impurities, preferably configured to oxidise oxidisable non-nickel metal impurities in the pregnant leach solution;
  • a trace non-nickel metal impurity ion exchange removal module for removing trace amounts of non- nickel metal impurity to form a purified sub-saturated nickel sulfate solution substantially free of non-nickel metal impurity, preferably configured for one or more rounds of ion exchange in lead/lag configuration; and optionally,
  • a nickel sulfate crystallisation module for crystallisation of high purity nickel sulfate crystals from the purified sub-saturated nickel sulfate solution substantially free of non-nickel metal impurity, preferably configured to crystallise alpha-nickel sulfate hexahydrate.
  • the plant further comprises a nickel hydroxide formation module for preparation of nickel hydroxide for use as an acid neutraliser and/or as a pH buffer in the production of the high purity nickel sulfate, wherein the nickel hydroxide formation module is in communication with the bulk non-nickel metal impurity removal module and/or the trace non-nickel metal impurity ion exchange removal module for providing nickel hydroxide solution thereto.
  • a nickel hydroxide formation module for preparation of nickel hydroxide for use as an acid neutraliser and/or as a pH buffer in the production of the high purity nickel sulfate, wherein the nickel hydroxide formation module is in communication with the bulk non-nickel metal impurity removal module and/or the trace non-nickel metal impurity ion exchange removal module for providing nickel hydroxide solution thereto.
  • the nickel hydroxide formation module comprises a closed circuit for forming a nickel hydroxide solution such that ammonia and/or NaOH used for neutralisation and pH adjustment during nickel hydroxide preparation is isolated from the bulk non-nickel metal impurity removal module and/or the trace non-nickel metal impurity ion exchange removal module thereby avoiding contamination of nickel sulfate solutions.
  • the bulk non-nickel metal impurity oxidiser module is in communication with a source of oxidant, for example, air, and a source of nickel hydroxide acid neutraliser and/or as a pH buffer preferably from the nickel hydroxide formation module as described herein.
  • a source of oxidant for example, air
  • a source of nickel hydroxide acid neutraliser and/or as a pH buffer preferably from the nickel hydroxide formation module as described herein.
  • the plant further comprise a hydrogen gas mitigation module associated with at least module (i) and/or module (ii) for management of hydrogen gas evolved during processing.
  • the hydrogen gas mitigation module comprises a source of a steam flush for management of hydrogen evolved during the process.
  • the hydrogen gas mitigation module is configured to generate and maintain a steam flush comprising about 70 vol% steam.
  • the hydrogen gas mitigation module comprises a scrubber for scrubbing acidic mist from the off gas prior to venting to the atmosphere.
  • the hydrogen gas mitigation module further comprises means for processing nickel leaching under a positive gauge pressure to prevent air ingress.
  • the hydrogen gas mitigation module further comprises a means for providing a blanket of nitrogen gas over at least module (i) and/or module 0 to assist in the prevention of the formation of a potentially explosive hydrogen/air mixture.
  • the plant is configured to provide sulfuric acid from a refinery to the plant, wherein the plant is configured to provide sulfuric acid to the acidic nickel leach module for leaching nickel sulfate from nickel powder and/or sulfuric acid ion exchange removal module for ion-exchange stripping during regeneration.
  • the plant is provided with a means for producing and/or providing demineralised water which is used to prepared required acid dilutions and wash for the ion exchange steps.
  • the plant further comprises a nickel sulfate dewatering module for removing the bulk of solute from nickel sulfate crystals downstream of the nickel sulfate crystallisation module.
  • the plant further comprises a nickel sulfate crystal dryer module to dry the crystals to a high purity nickel sulfate hexahydrate product in powder form.
  • the plant further comprises a high purity nickel sulfate product packaging module.
  • the plant is configured to recycle condensates from one or more plant modules, for example, heating coils in the leaching module, the product dryer module, and/or the crystallisation module for reuse.
  • plant modules for example, heating coils in the leaching module, the product dryer module, and/or the crystallisation module for reuse.
  • the plant further includes one or more off-gas scrubbers, for example, associated with the acidic nickel leach module, the bulk non-nickel metal impurity oxidiser module and/or the bulk non-nickel metal impurity removal module for capture of gases and the nickel sulfate crystallisation module to capture nickel sulfate dust.
  • one or more off-gas scrubbers for example, associated with the acidic nickel leach module, the bulk non-nickel metal impurity oxidiser module and/or the bulk non-nickel metal impurity removal module for capture of gases and the nickel sulfate crystallisation module to capture nickel sulfate dust.
  • the invention provides for a use of nickel hydroxide as an acid neutraliser and/or a pH buffer in a process for preparing high purity nickel sulfate, preferably having a purity of >99.8%, more preferably ⁇ 99.98% nickel sulfate suitable for use in battery manufacture or nickel plating including electroplating and electroless plating.
  • the invention provides for a use of nickel hydroxide as an acid neutraliser and/or a pH buffer in an ion exchange purification process for selective removal of non-nickel metal impurities from a nickel sulfate solution, preferable an acidic sub-saturated nickel sulfate solution, more preferably, an acidic sub-saturated nickel sulfate solution from which bulk non-nickel metal impurities have been removed.
  • the invention provides for a use of nickel hydroxide as an acid neutraliser and/or a pH buffer in nickel sulfate solution, preferable an acidic sub-saturated nickel sulfate solution to precipitate non-nickel metal impurities in as insoluble non-nickel metal impurities, for example, non-nickel metal hydroxides.
  • the invention provides for a use of a nickel pre-loaded ion exchange resin to selectively remove non-nickel metal impurities from a nickel sulfate solution, preferable an acidic sub-saturated nickel sulfate solution, more preferably, an acidic sub- saturated nickel sulfate solution from which bulk non-nickel metal impurities have been removed.
  • the resin is a phosphoric acid, a phosphonic acid or phosphinic acid resin.
  • the invention provides for a use of a nitrogen gas blanket to prevent formation of explosive air and hydrogen mixtures over an acidic nickel leach evolving hydrogen.
  • the invention provides for a use of a sub-saturated nickel sulfate solution in a process for the preparation of high purity nickel sulfate, preferably having a purity of >99.8%, more preferably ⁇ 99.98% nickel sulfate, and preferably wherein the sub-saturated nickel sulfate solution is a pregnant leach solution, for example, obtainable by a process according to the invention.
  • the invention provides for high purity nickel sulfate obtainable by a process according to the invention.
  • the invention provides for a use of high purity nickel sulfate as defined in herein in the manufacture of an energy storage device, for example, a battery or capacitor and/or in a nickel plating process including electroplating and electroless plating.
  • the invention provides for an energy storage device, for example, a battery or capacitor, comprising nickel sulfate obtainable by a process according to the invention.
  • the invention provides for a product comprising plated nickel derived from comprising nickel sulfate obtainable by a process according to the invention.
  • Figure 1 illustrates a process flow diagram for an exemplary embodiment of the production of high purity of nickel sulfate as described herein;
  • FIG. 1 illustrates the particle size distribution (PSD) of the nickel powder sample used in the bench scale experiments
  • Figure 3(A) - (G) illustrate the results of bench scale experiments relating to the effect of pulp density on leaching;
  • A Effect of pulp density on nickel powder dissolution in tests maintained at pH 0 and 1. Tests were maintained at 80 °C, with a compressed air aeration rate of 5 L/min. All tests were operated for a period of 10 hours;
  • B Impact of Pulp density on leaching rate at pH 1 , 80°C;
  • C Comparison of Nickel concentration for tests operated under anaerobic conditions at 290 g/L sulfuric acid, 80 °C;
  • D Impact of Pulp density on
  • Figure 4(A) - (D) illustrate the results of bench scale experiments relating to the effect of pH on leaching;
  • A Effect of operational pH on nickel powder dissolution. Tests were maintained at 80 °C, with a compressed air aeration rate of 5 L/min. All tests were operated for a period of 10 hours with 1000 g/L nickel powder present;
  • B Comparison of simple free hydrogen ion concentration and total nickel dissolution;
  • C Comparison of total nickel dissolved and total sulfuric acid added over all 31 tests, excluding anomalies of tests 7, 8 and 12;
  • D Aerobic Impact of Leaching Time on pH;
  • Figure 5(A) - (C) illustrate the results of bench scale experiments relating to effect of aeration rate on leaching;
  • A Impact of aeration rate and nitrogen on nickel powder dissolution at 80 °C, 1000 g/L nickel powder and pH 1.0. Red data point is N 2 -sparged test;
  • B Impact of aeration rate on measured solution evaporation;
  • C Effect of Aeration rate on Ni Extraction Rate;
  • Figure 6(A) - (E) illustrate the results of bench scale experiments relating to effect of pH on impurity leaching;
  • A Comparison of pH;
  • B Comparison of free acidity;
  • C Comparison of
  • Figure 7(A) & (B) illustrate the results of bench scale experiments relating to effect of temperature on leaching;
  • Figure 8(A) - (G) illustrate the results of bench scale experiments relating to batch acid leaching;
  • A Impact of acid loading on nickel powder dissolution at 80 °C with 1000 g/L nickel and 5 L min aeration.
  • B Neutralisation with time for acid loading tests at 80 and 100 °C;
  • C Nickel concentration over time during tests operated under near-optimal conditions.
  • D Solution pH over time in near optimal tests. Tests were operated at 80 °C, 1000 g/L nickel and 1 L min aeration;
  • E Aerobic Batch Acid Addition Ni Extraction Rate;
  • F Impact of acid loading on nickel extraction rate;
  • G Batch acid addition pH profile;
  • Figure 9(A) - (H) illustrate the results of bench scale experiments relating to the effect of acid concentration on impurity leaching for Co, F, Cr, K, Ca, Na, Cu, Zn respectively;
  • Figure 10 illustrates a comparison of iron, copper and zinc concentrations to pH. Note that Cu and Zn are reported in ⁇ g/L (ppb), Fe reported in mg/L (ppm);
  • Figure 11(A) & (B) illustrate the results of bench scale experiments relating to the effect of agitation on leaching;
  • Figure 12(A) - (E) illustrates a schematic of the IX process of the invention and results of bench scale experiments relating to the effect of preloading of resin on IX;
  • A schematic of the IX process of the invention;
  • B pH isotherms with fresh TP272 without pH control showing the effect of utilizing the ion exchange resin TP 272 without pre-loading;
  • C Ni pre-loading with Ni sulphate solution (initial 20 g/L Ni);
  • D Ni loading pH profile with various nickel concentration in the feed solutions (80 °C);
  • E Ni pre-loading kinetics for pH 5 and 6 at 80 °C;
  • Figure 13(A) - ( ) illustrates the results of bench scale experiments relating to the effect of non-preloaded resin and comparison to nickel pre-loaded resin;
  • A Comparison of initial solution pH with final pH after equilibrium loading;
  • B Metal loading (%) pH isotherms with fresh TP 272 vs. final pH without pH control;
  • C Metal loading (mg/g resin) pH isotherms with fresh TP 272 vs.
  • Figure 14(A) - (D) illustrates (A) pH isotherm profile for TP 272; (B) pH isotherm profile for Cyanex 272 resin;
  • Figure 15(A) - (D) illustrates the results of bench scale experiments relating to cobalt stripping kinetics;
  • A Ni and Co loading (mg/g) vs. loading time;
  • B Ni and Co loading (%) vs. loading time;
  • C Mass balance of Ni and Co loading;
  • D Metal stripping (%) vs. stripping time;
  • Figure 16 illustrates the results of bench scale experiments relating to the effect of pH (H 2 SO 4 concentration) on % metal stripping
  • Figure 17(A) - (H) illustrates the results of bench scale experiments relating to the results based on air dry mass;
  • Figure 18 illustrates the results of bench scale experiments relating to the total exchange capacity vs. stability test cycles
  • Figure 19(A) - (E) illustrates the results of bench scale experiments relating to the variation of exchange capacity;
  • A Metal loadings on the resin vs. cycles;
  • B Co behaviour in the stability tests;
  • C Ni behaviour in the stability tests;
  • D Fe behaviour in the stability tests;
  • FIG. 20(A) - 20(E) illustrates the results of bench scale experiments relating to the effect of consecutive loading and sampling;
  • E Metal mass loading vs. pH with TP 207;
  • Figure 21(A) & (B) illustrates the results of bench scale experiments relating to the loading kinetics with TP 207;
  • Figure 22(A) - 22(D) illustrates the results of bench scale experiments relating to loading distribution isotherms for TP 207;
  • A Metal loading (%) vs. solution / resin ratios;
  • B Raffinate metal concentration with solution / resin ratios;
  • C Metal loading at various A/ Resin (TP 207) ratios;
  • D Fe distribution isotherm with resin TP 207;
  • Figure 23 illustrates the results of bench scale experiments relating to the elution of TP In particular to elution acidity isotherms with TP 207;
  • Figure 24(A) - 24(C) illustrates the results of bench scale experiments relating to IX -
  • Amberiite IRC 748 resin (A) Metal loading efficiency vs. pH with IRC 748 resins; (B) Raffinate metals vs. pH with IRC 748 resin; (C) Metal loadings on resin vs. pH with IRC 748 resin;
  • Figure 25 illustrates the results of bench scale experiments relating to IX -Purolite;
  • Figure 26(A) - 26(C) illustrates the results of bench scale experiments relating to SX
  • Figure 27(A) & 27(B) illustrates the results of bench scale experiments relating to column loading tests;
  • Figure 28 illustrates the results of bench scale experiments relating to
  • Figure 29 illustrates the results of bench scale experiments relating to the effect of column washing in particular a column Co loading washing profile
  • Figure 30 illustrates the results of bench scale experiments relating to column washing in particular the elution profile at different acidities (H 2 SO 4 concentrations).
  • Figure 31 illustrates the results of bench scale experiments relating to column elution washing;
  • Figure 32(A) - 32(E) illustrates the results of bench scale experiments relating to the effect of column tests; (A) breakthrough point of TP 272 resin; (B) cobalt breakthrough curve comparison.
  • Nickel powder 100 is leached in a batch process in a nickel leach module A.
  • Nickel leach module A comprises one or more leach acid solution preparation tanks 110, preferably a plurality of tanks, which are in fluid communication with the following sources of consumables: a source of steam and/or nitrogen gas 150, a source of sulfuric acid 130, a source of demineralised water 120 for diluting the sulfuric acid to a desired concentration, and a source of nickel powder 100, for example directly from a nearby nickel powder refinery.
  • the tanks are adapted to include a source of steam for heating, for example, indirect steam heating via heating coils associated with the tanks 110. Agitation is provided by the leach acid solution preparation tank agitators (not shown) which are associated with the tanks 110.
  • the nickel leach module A also comprises a leach gas scrubber 170 for scrubbing hydrogen evolved from leaching from the vapour spaces about the tanks 110.
  • the leach gas scrubber 170 is configured to vent scrubbed off-gas 160 to the atmosphere.
  • the bulk impurity removal module B comprises one or more solution aeration vessels 190 which is in communication a source of oxygen/air 200 for sparging into the vessels 190 to convert iron impurity in the discharge solution 140 from the ferrous to ferric oxidation state.
  • the aeration vessels 190 are in fluid communication with a source of a nickel hydroxide slurry 390 which is generated in a nickel hydroxide preparation module C.
  • the aeration vessels 190 are equipped with separate acid mist scrubber (not shown) to the leach tanks 110 to ensure hydrogen and oxygen do not mix in the off-gas scrubbers.
  • the scrubber is configured to vent scrubbed off-gas 220 to the atmosphere.
  • the vessels are in
  • the polishing filters 230 are ideally configured to operate in a duty/standby arrangement, and can be equipped with a backwash cycle and a solution filter sludge tank (not shown) and transfer pump (not shown).
  • Module B further comprises an IX feed tank (not shown) for holding filtered non-nickel metal impurity depleted discharge solution 250 before IX.
  • This module comprises one or more ion exchange (IX) columns 270 which ideally are arranged in a lead/lag configuration.
  • a third column (not shown) may be provided off-line for regeneration which includes washing, stripping and pre-loading.
  • the fourth column (not shown) may be installed as a spare.
  • the columns will be loaded with suitable resin.
  • An ion exchange discharge tank (not shown) is included in module C for holding resultant first IX discharge solution which is a clean nickel sulfate solution 310 substantially free of non-nickel metal impurities.
  • the tank is associated with one or more ion exchange discharge polishing filters 400 for removing any carry-over resin or solids from the IX columns 270.
  • a crystalliser plant feed tank (not shown) holds filtered clean nickel sulfate solution 420 and is in fluid communication with the crystalliser 450 of a crystalliser plant E.
  • the fluid line between the one or more ion exchange discharge polishing filters 400 and the crystalliser 450 configured to divert a small portion of the filtered clean nickel sulfate solution 420, a nickel hydroxide preparation module B and to an ion exchange nickel preload tank (not shown) to be held until IX column 270 regeneration is required.
  • the IX columns 270 adapted to be in fluid communication with a source of acid, demineralised water and nickel preload solution from the nickel hydroxide preparation module B as well as an ion exchange waste tank (not shown).
  • the one or more ion exchange discharge polishing filters 400 are in fluid
  • Nickel powder 100 is leached in a batch process in a nickel leach module A which comprises one or more leach acid solution preparation tanks 110, preferably a plurality of tanks.
  • the nickel powder 100 may be provided to the nickel powder leach plant A from a discharge of wet metals driers in a nickel leach plant before the powder is either packaged or converted in to briquettes.
  • the batch process begins with the transfer of nickel powder 100 to the tanks 110.
  • the target concentration of nickel powder in solution is 1000 g/L. This is a significant excess in the amount of nickel than that stoichiometrically needed for the reaction, to ensure high reaction kinetics. Typically only approximately 10% of the nickel powder in the tanks 110 reacts during the batch cycle. The reaction proceeds are per the equation below.
  • sulfuric acid 130 is continuously mixed with demineralised water 120 to generate acid of a target concentration.
  • the acid dilution is exothermic and this step must be operated with caution.
  • the tanks 110 are then fed with a batch make-up of sulfuric acid solution 130 at a sulfuric acid concentration of approximately 280 g/L.
  • the sulfuric acid solution 130 is transferred to the batch leach tanks 110 on demand using an acid solution pump (not shown).
  • This acid concentration is controlled by addition of demineralised water 120 in order to have the discharge solution 140 at 95% of the saturation limit of nickel sulphate at 80°C.
  • the demineralized water 120 for acid dilution may be supplied by hydrogen plant demineralized water pumps (not shown).
  • the leaching process evolves hydrogen.
  • the vapour space about the leach acid solution preparation tanks 110 is flushed with flush steam 150 and the tanks are preferably operated at a positive pressure to prevent ingress air.
  • the flush steam (snuffing steam) 150 ideally maintains a minimum 70 vol% steam atmosphere in the vapour space about the tanks 110.
  • the resultant hydrogen containing off- gas 160 is processed by a leach off-gas scrubber 170 which captures acid mist and particulates before the scrubbed off-gas 180 is discharged via a stack (not shown).
  • vapour space about the tanks 110 which are connected to a source of nitrogen can be flooded with nitrogen 150 to form a nitrogen blanket which can prevent the formation of an explosive environment.
  • the residual acid concentration in the tanks 110 correlates to approximately pH 3, and the nickel sulfate in solution concentration
  • the terminal nickel strength is determined by the amount of acid added to the batch (as there is a vast excess of nickel).
  • the decision to terminate the reaction at pH 3 is a trade-off between (i) terminating at a lower pH, but requiring a much increased amount of nickel hydroxide 390 to neutralise the excess free acid, and (ii) terminating at a higher pH, meaning the reaction takes much longer and so would require increased capital for the larger reaction tank 110, given total throughput is fixed.
  • the leach discharge solution 140 is decanted from the tanks 110 via a leach decant pump (not shown). Un-leached solids remain in the heel of the leach tanks 110 and are reprocessed in the next batch of the leach cycle.
  • the leach discharge solution 140 from the batch leaching process carried out in module A is discharged to a solution surge tank (not shown), which stores the discharge solution 140 thereby providing a flow buffer between the batch upstream (module A) and continuous downstream processes (modules B to E).
  • the leach discharge solution 140 is then fed to one or more solution aeration vessels 190 provided in a bulk impurity removal module B, where oxygen/air 200 is sparged into the vessels 190 to convert iron impurity in the discharge solution 140 from the ferrous to ferric oxidation state.
  • Bulk iron and other impurities are then precipitated by the addition of a nickel hydroxide slurry 390 which is generated from a nickel hydroxide preparation module B. Addition of the nickel hydroxide slurry 390 raises the leach discharge solution 140 to about pH 5. At this pH, residual bulk iron in the discharge solution 140 precipitates as ferric hydroxide.
  • the aeration vessels 190 have their own separate acid mist scrubber (not shown) to the leach tanks 110 to ensure hydrogen and oxygen do not mix in the off-gas scrubbers. After scrubbing, generated off-gas 220 is vented to the atmosphere.
  • the impurity depleted solution 210 then filtered in one or more solution polishing filters 230 to remove any solids (ferric hydroxide, residual nickel powder and other precipitate material if present) in solution which generates a filtered non-nickel metal impurity depleted discharge solution 250 in preparation for ion exchange which occurs in ion exchange module C.
  • the polishing filters 230 are ideally configured to operate in a duty/standby arrangement, and can be equipped with a backwash cycle and a solution filter sludge tank (not shown) and transfer pump (not shown).
  • the filtered non-nickel metal impurity depleted discharge solution 250 is then fed into an IX feed tank (not shown) to await IX.
  • the sludge 260 from the polishing filters 230 can be transferred to a refinery final thickener for disposal.
  • the filtered non-nickel metal impurity depleted discharge solution 250 from the IX feed tank (not shown) is fed to one or more ion exchange (IX) columns 270 located in ion exchange module C to primarily remove cobalt and any remaining trace impurities from the filtered impurity depleted solution 250.
  • the IX columns 270 can be arranged in a lead/lag configuration, with the filtered non-nickel metal impurity depleted discharge solution 250 entering an IX column 270 with partially loaded resin first (lead) before proceeding to an IX column 270 with fresh resin (lag).
  • a third column (not shown) may be provided off-line for regeneration which includes washing, stripping and pre-loading.
  • the fourth column (not shown) may be installed as a spare. The columns will be loaded with suitable resin.
  • Cobalt and other impurities are loaded onto the resin from the filtered non-nickel metal impurity depleted discharge solution 250, with a resultant first IX discharge solution which is a clean nickel sulfate solution 310 substantially free of non-nickel metal impurities discharging to the ion exchange discharge tank (not shown).
  • the clean nickel sulfate solution 310 is then fed to one or more ion exchange discharge polishing filters 400 to remove any carry-over resin or solids from the IX columns 270 which can be removed from the filters as sludge 440.
  • the filtered clean nickel sulfate solution 420 is then held in a crystalliser plant feed tank (not shown) before being pumped to the crystalliser plant E.
  • a small portion of the filtered clean nickel sulfate solution 420, diverted filtered clean nickel sulfate solution 430 is transferred to a nickel hydroxide preparation module B, or to an ion exchange nickel preload tank (not shown) to be held until IX column 270 regeneration is required.
  • the lead column 270 is subjected to a regeneration cycle once the cobalt loading is achieved and the lead column first IX discharge solution cobalt concentration begins to increase.
  • An exemplary regeneration cycle consists of the following steps as shown in Table 2:
  • slightly acidic water (pH 4-5) wash solution (not shown) are used to wash the resin to flush out any entrained nickel solution.
  • the wash solution is prepared by mixing sulfuric acid with demineralized water 280. If the resin is exposed to neutral or alkaline water, the active resin component may be dissolved leading to a loss of ion exchange capacity.
  • the slightly acidic water (pH 4-5) wash solution avoids this problem, particularly for TP 272.
  • the IX waste 330 from the washing and other regeneration reagents may be collected in an IX waste tank (not shown) and pumped to the leach acid solution preparation tanks for re-use.
  • reagent stream 290 provide an approximately 1.5 - 2.0 M sulfuric acid solution which is prepared in a mixing tank (not shown) and pumped for several bed volumes through the IX column 270, stripping off cobalt and other impurities into the stripping waste solution 330.
  • the stripping process loads protons (H+ ions) onto the resin.
  • the strip IX waste 330 is sent to the IX waste collection tank (not shown).
  • An additional wash stage of several bed volumes of demineralised water 280 is then used to wash excess sulfuric acid from the column and is also sent to the IX waste collection tank (not shown).
  • nickel preload solution 300 is first pumped through a filter (not shown) to remove undissolved solids and then onto the IX column 270 and the effluent 320 from the pre-load phase is then pumped back into the pre-load recirculation tank 340.
  • the resin in the IX column 270 exchanges protons (H+ ions) on the resin with nickel ions from the diverted filtered clean nickel sulfate solution 430.
  • This exchange reaction results in increased acidity which is immediately neutralised by the buffered nickel preload solution 300. If this acidity is not neutralised, the pH of the recirculating solution drops and the pre-loading reaction stops.
  • the nickel preloaded column 270 is not washed after pre-loading as it contains diverted filtered clean nickel sulfate solution 430.
  • the filtered clean nickel sulfate solution 420 then proceeds to a nickel sulfate hexahydrate crystallising, dewatering and drying module E.
  • a crystalliser 450 ideally a draft tube baffle (DTB) type crystalliser is chosen over other crystalliser vessel configurations (e.g. Forced Circulation, Oslo) to ensure good product crystal size to allow easy dewatering and washing and to minimise fines during product handling.
  • the crystalliser 450 operates at about 53°C and/or a vacuum of around 10 kPa to produce alpha form nickel sulfate hexahydrate crystals which are the industry standard.
  • the crystalliser module E performs the following functions: (i) blending of filtered clean nickel sulfate solution 420 with centrate stream 510 and other minor streams in the fines recirculation pump (not shown), this includes a bleed pump (not shown) and pipeline (not shown) to control any impurity build up in the crystalliser 450, and (ii) fines destruction in the crystalliser heater (not shown).
  • a two-stage mechanical vapour recompression (MVR) type evaporative crystalliser operating at 53°C is preferably used to produce nickel sulphate hexahydrate.
  • An MVR supplies energy to the crystalliser 450 via electricity over steam as this minimises the opex for the unit, and reduces load on the plant's steam boiler.
  • a cooling water cooled surface condenser (not shown) is provided prior to a vacuum pump (not shown) which is suitable to maintain the preferred operating vacuum.
  • a nickel sulphate hexahydrate crystal slurry 470 generated in the crystalliser 450 is pumped to dewatering cyclone (not shown), with cyclone underflow reporting to a centrifuge 480 for further dewatering.
  • the centrate generated 510 is sent to the crystalliser 450 for blending with filtered clean nickel sulfate solution 420.
  • Centrifuge solids (dewatered) 500 are transferred to a fluid-bed dryer 520 to produce a dry nickel sulfate product 530 which is ready for bagging.
  • the fluid-bed dryer 520 includes an off-gas scrubber 570 for capture of any nickel sulfate dust 540 whereby scrubbed air/gas 560 is vented to the atmosphere. Collected dust 550 is returned to the crystalliser 450 for further processing.
  • the nickel hydroxide slurry 380 is generated from the diverted filtered clean nickel sulfate solution 430 which is pumped from the crystalliser feed tank(not shown) to one or more nickel hydroxide precipitation tanks 340. Sufficient sodium hydroxide 350 is added to allow the precipitation of nickel hydroxide to occur. The resultant nickel hydroxide slurry 380 from each precipitation tank 340 is then pumped to a nickel hydroxide filter (not shown) which captures solid nickel hydroxide.
  • the filtered nickel hydroxide solids (not shown) are washed with demineralised water 360 to remove entrained sodium, with the captured nickel hydroxide solids (not shown) being discharged to a repulp tank (not shown) and the filtrate collected in a nickel hydroxide filter filtrate tank (not shown).
  • the nickel hydroxide filter filtrate tank can be being returned (not shown) to a refinery.
  • the filtered nickel hydroxide solids (not shown) are repulped with diverted filtered clean nickel sulfate solution 430 and a diverted portion of the repulped nickel hydroxide slurry 390 is pumped to the aeration vessels tanks 190 of module B for pH adjustment for metal hydroxide precipitation.
  • a second diverted portion of the nickel hydroxide slurry 380 is pumped to the ion exchange preload recirculation tank (not shown) where it is mixed with diverted filtered clean nickel sulfate solution 430 and is then sent to the ion exchange column 270 for nickel pre-loading as the pH buffered pre-load solution 300.
  • the pH buffered pre-load solution 300 is pumped via a preload solution filter (not shown) to remove any fine nickel hydroxide solids prior to being sent to the ion exchange column 270.
  • a portion of the diverted portion of the repulped nickel hydroxide slurry 390 is pumped to the aeration vessels 190 for pH adjustment and in order to prevent contaminant build-up.
  • Sodium hydroxide 350 may be supplied from a refinery directly to the nickel hydroxide preparation area D, where it is used to precipitate the nickel hydroxide in the pre- load recirculation tanks 340. Detailed description of the invention
  • the flowsheet to produce high purity nickel sulfate is shown in Figure 1.
  • a corresponding bench scale test program was split into three parts (i) nickel powder leach in sulfuric acid (ii) neutralization and nickel hydroxide production, and (iii) ion exchange for impurity removal by IX before crystallisation.
  • An objective of the powder leach bench scale work was to determine the optimum leaching conditions of nickel powder in sulfuric acid as well as to determine the deportment of impurities in the leach.
  • several flowsheets were considered including anaerobic and aerobic leaching of nickel powder in sulfuric acid on a continuous or batch basis.
  • the work was also to evaluate the chemistry and kinetics of nickel powder vat leaching using various anaerobic and aerobic leach conditions, for example sulfuric acid and oxidant (oxygen supplied as air) concentrations, solid :liquid ratios, and temperatures.
  • Nickel leaching behaviour was generally similar in all tests (i.e. the majority of nickel was leached over the first 10 hours) (Figure 3C).
  • the repeated 1000 g/L test demonstrated quicker rates of nickel powder dissolution (based on solution assay) (Figure 3F), with pH neutralisation behaviour matching this ( Figure 3D).
  • Tests at 800 and 1000 g/L demonstrated spurious results, with the nickel powder mass measured after leach tests indicating that only 118 and 151 g of powder was dissolved which is well under the theoretical quantity of nickel expected to be solubilised in the presence of 290 g of sulfuric acid.
  • the particle size distribution of nickel used was assessed to determine if the varying results could be attributed to discrepancies in surface area.
  • pulp density does not significantly affect: the nickel leaching behaviour under anaerobic, acid loaded (290 g) conditions ( Figure 3F), the nickel extraction rate (Figure 3G) or the neutralization rate (Figure 3D) between a pulp density of 700 - 1300 g L.
  • tests 7 and 8 were observed to have impellor corrosion, evidenced by elevated iron concentrations in solution (8.6 and 4.9 g/L).
  • Test 12 was operated with an excess of sulfuric acid over a period of 31 hours. In this case, the reaction between sulfuric acid and nickel powder would have been impacted by the solution nickel concentration reaching saturation, precluding full reaction between the acid and the nickel powder by precipitation of nickel sulfate.
  • the leach pH has a strong influence on the rate of reaction. The highest rate of reaction was pH 0 achieving 174.9 g/L Ni in 10 hours ( Figure 4D).
  • Dissolved oxygen is beneficial to the nickel dissolution reaction (see Equation 1), but not essential. 1.0 L min of air is entirely adequate under these conditions. It can be seen that without air, the rate of reaction is much slower. It should be noted that despite air being added, hydrogen gas was detected in the off-gas from the reactor. This indicated that although air was being added, all of the dissolution of nickel does not occur via the oxidative mechanism (Equation 2) whereby some nickel dissolves via the anaerobic mechanism (Equation 1) that produces hydrogen.
  • the evaporation rate at 80 °C is positively correlated with the air flow rate (Figure 5B).
  • High air flow rates contribute to reaching nickel saturation sooner by evaporative concentration, which hinders further nickel dissolution. This is believed to have contributed to the reduced nickel extraction at the highest air flow rate.
  • Example 4 batch acid loading: impact on nickel dissolution and solution
  • tests 28 150 mis, 276 g acid
  • 29 180 mis, 331.2 g acid
  • 30 200 mis, 368 g acid
  • Tests 28, 29 and 30 were performed with 150 mis (276 g acid), 180 mis (331.2 g acid) and 200 mis (368 g acid) up-front acid loading respectively, and aeration rates of 1 L/min, 1000 g/L pulp density and a temperature of 80 °C.
  • Tests 28, 29 & 30 had corresponding nickel powder dissolutions of 168.3, 186.6 and 194.9 g, respectively.
  • nickel concentrations in solution approaching saturation would result in dissolution rates decreasing and becoming dependent on precipitation of nickel sulfate in the system.
  • the test operated with batch loading of 150 mL (276 g acid) sulfuric acid exceeded a pH of 5 within a period of 8 hours ( Figure 8D).
  • Figure 8B In general it was possible to achieve the target nickel strength within 10 hours ( Figure 8B).
  • the initial rate of reaction was accelerated compared to the test conducted at pH 0.
  • the terminal nickel strength correlated well with the
  • Figure 8B shows the reaction pH verses time.
  • the higher acid dosages 180 mL (331.2 g acid) and 200 mL (368 g acid)
  • pH 1 reached pH 1 after 25 hours (Figure 8D).
  • Tests were then conducted anaerobically (1 L min nitrogen) with varying amounts of acid addition.
  • the terminal nickel strength was a function of the initial acid added. Typically the majority of the nickel had dissolved within five to ten hours. However, the pH generally required up to 24-26 hours to achieve pH 3 (Figure 8G).
  • the impurity suite consisted of Ca, Al, Na, P, Si, K, Mg, Mn, Se, Cr, Co, Fe, Cu, Zn, As, Ru, Pb, Hr, Pd, Ag, Cd, Sb, Ir, Pt, Au, and Bi. Of these elements, only Cr, Co, Fe, K and Na exceeded 5 ppm in the final liquors ( Figure 9A - 9H). Ca and Na were leached almost instantaneously from the nickel powder, possibly originating from surface contaminants on the powder itself.
  • Fe(lll) typically starts to form precipitates at pH above 3 in sulfuric acid. Fe(ll) is stable up to approximately circum-neutral pH (pH 6-7). Copper and zinc values were low throughout the experiment (ppb). Concentrations decreased markedly in test 28 when the pH increased above 5, likely to be indicative of the formation and consequent precipitation of these metals as hydroxides ( Figure 10).
  • test 31 a final impurity test was performed using a fresh batch of nickel powder under the optimum condition established above. The nickel powder was riffled using a virgin plastic riffle, the stirrer for the test was freshly coated with Halar®, and the pH probe was excluded from the test to minimise potential sources of impurity ingression. The test was performed with 150 mL (276 g acid), of 'plant' sulfuric acid. Feed and residue samples were assayed in duplicate, but showed no significant variation. The levels of impurities in this duplicate test were
  • Example 6 impact ofimpellor agitation rate under acid loaded anaerobic conditions
  • Impellor agitation rate was assessed (under anaerobic, acid loaded conditions (290 g/L). Impellor agitation rates were 50, 75, 100 and 150 % of the requirement to completely suspend 1000 g of nickel powder in 1 L of sulfuric acid solution. Nickel leaching and pH behaviour was consistent across tests, with minor variations measured in nickel leaching ( Figure 11 A) and pH ( Figure 11B) behaviour. The test at 75 % agitation demonstrated slightly quicker nickel leaching and pH neutralisation behaviour, and the test at 50 %. Tests indicated that impellor agitation speed within the range tested had minimal impact on nickel powder dissolution.
  • Lock cycle tests are being considered to determine: if the leaching rate remains constant across multiple cycles with the same starting sample of nickel powder; if the average particle size across each cycle changes; and if impurities accumulate over time due to a leaching-precipitation mechanism.
  • nickel powder 168 g was dissolved and leach solution neutralised in 7 hours when operated with 150 mL (276 g acid) of plant acid at 80°C, pulp density of 1000 g/L and an aeration rate of 1 L/min compressed air.
  • the nickel concentration in solution reached 175.9 g/L (indicative of evaporation).
  • Chromium, cobalt and iron impurities increased following the same general trend as nickel. Iron, copper and zinc impurities in solution decreased (precipitated) as the solution pH increased above 5.
  • Nickel dissolution increased to 186.6 and 194.9 g, respectively in the presence of 180 mL (331.2 g acid) and 200 mL (368 g acid) of plant acid. However, in these tests complete neutralisation was not achieved. In experiments operated for 25 hours, solutions became saturated with nickel sulfate, inhibiting further neutralisation. Evaporation rates increased with respect to aeration rate and temperature. At a temperature of 80 °C, aeration rates of 1 , 2.5, 5 and 10 L/min compressed air had evaporation rates of 31.1 , 25.8, 14.3 and 10.9 mL/hr respectively. Increases in temperature also impacted evaporation rates, with evaporation rates reaching up to 51 mL/min at 100 °C.
  • Pulp density between 800-1200 g/L did not impact nickel dissolution kinetics. At pulp densities of 600 and 700 g/L, nickel powder dissolution was decreased relative to comparative tests.
  • Aeration rates of compressed air between 1-5 L min had negligible impact on total nickel powder dissolution.
  • 10 L/min only 98.9 g of nickel was powder was leached compared to 112.7-117.8 g in comparable tests.
  • the higher evaporation rate at 10 L/min may have reduced dissolution rates as the solution approached nickel saturation.
  • the commercial ion exchange resin TP 272 is a macroporous solvent impregnated resin which contains Cyanex 272.
  • Solution pH is a crucial parameter for selectivity and efficiency of ion exchange.
  • a challenging issue associated with use of conventional base reagents NaOH or ammonia solutions to control pH is the contamination of the nickel sulfate product.
  • the process herein relies on (i) neutralisation of the pregnant leach solution with nickel hydroxide thereby avoiding contamination of the nickel sulfate solution, and (ii) pre-loading of the ion exchange resin with nickel sulfate solution, for example, from the purification circuit together with nickel hydroxide for pH adjustment to ensure ion exchange selectivity and efficiency, if needed.
  • Nickel pre-loading was proposed to be a critical step to provide a mechanism for obtaining stable pH to ensure efficient loading of Co impurity in this investigation.
  • the objectives were (i) to establish the pH profile and range for Ni pre-loading, (ii) to test the effect of nickel concentration of feed PLS on loading efficiency, and (iii) to determine type of reagents for neutralisation and ranges of pH for loading.
  • nickel hydroxide prepared was tested as a desirable neutralisation base reagent.
  • the scheme of nickel pre-loading is shown in Figure 12A consists of: (i) pre-loading nickel onto resin, using either a Co/Ni effluent bleed or a purified Ni effluent bleed, with solution adjustment by nickel hydroxide Ni(OH) 2 , and if needed, ammonia or NaOH, followed by a resin wash to remove impurities, and (ii) displacement of the loaded nickel by cobalt impurity, in a cobalt loading step, followed by elution to regenerate the resin for recycle and re-pre-loading.
  • Use of closed circuit allows for isolated use of ammonia or NaOH for neutralisation and pH adjustment without product contamination.
  • ion exchange (IX) stages are operated at 80 °C with a nickel liquor which is close to saturation to reduce the capital cost of a preferred downstream crystallisation step.
  • Tests include: pre-loading and replacement tests, shake out tests, resin stability tests at 80 °C , isotherm tests, and mini-column tests. The chemical stability of the resin at elevated temperature is also studied.
  • Nickel pre-loading tests were conducted using synthetic PLS prepared by using AR grade nickel sulfate.
  • the pre-loading pH isotherm tests were carried out at solid to liquid (S/L) ratio of 10 g / 40 mL (1 :4) in a 100 mL hexagonal glass jar immersed in a temperature controlled oil bath using hot plate with magnetic stirrer. The solution temperature was maintained at 80 ⁇ 1 °C during the tests.
  • the aqueous solution pH was adjusted with ammonia or sulfuric acid solutions.
  • the system was equilibrated at each pH point for 5 minutes and the mixture was sampled at 0.5 pH intervals over a pH range of 3.0 - 7.5. The pH readings were recorded at each sampling point and used for the construction of pH isotherm graphs.
  • the slurry mixture was quickly separated using vacuum filtration with 0.45 ⁇ m sieve to avoid crystallisation due to lower temperature.
  • the aqueous solution was diluted 4 or 5 times for assay and the resin was stripped with 2 sulfuric acid solution for assay.
  • Cobalt loading pH isotherms experiments Cobalt impurity loading distribution isotherms were prepared using air-dried Ni preloaded resin at initial solution pH 4.6 and various S/L ratios in a 100 mL hexagonal glass jar shaking in an incubator shaker. The solution temperature was maintained at 80 ⁇ 1 °C during the tests. Each pH point test was separately performed with the PLS of different initial pH, which was adjusted with nickel hydroxide solid and sulfuric acid solution up to pH about 5.
  • the mixtures were mixed by shaking for 1 - 2 hours until the final equilibrium pH. The final pH was recorded and adjusted if needed. The slurry mixture was quickly separated using vacuum filtration with 0.45 ⁇ sieve. The aqueous solution was diluted 4 or 5 times for assay and the resin was stripped with sulfuric acid solution for assay.
  • the maximum loading of cobalt on the TP 272 resin was investigated.
  • a Langmuir isotherm model was used to fit the data and the maximum loading of the resin was calculated at about 11.5 mg Co/g wsr resin.
  • the equivalent loading is 6 g Co/L wet saturated resin.
  • the loading is lower than the maximum rated capacity of the resin (11 g/L Co) due to the high concentration of nickel and low concentration of cobalt in solution.
  • the extraction kinetics tests were carried out with air-dried Ni pre-loaded resin at initial aqueous pH 5.0 and S/L ratio of 1 g / 40 mL in a 100 mL hexagonal glass jar immersed in a temperature controlled oil bath. The solution temperature was maintained at 80 ⁇ 1 °C during the tests. The extraction kinetics tests were performed at 0.5, 1 , 2, 5, 10 and 30 minutes. Timer was started when the resin was added to the solution with stirring. The mixing was stopped at the required time, final pH was recorded and the slurry was quickly separated. The aqueous solution was diluted 4 or 5 times for assay and the resin was stripped with sulfuric acid solution for assay.
  • Tests were conducted using different strength sulfuric acid solutions to strip the loaded metals. Stripping acidity isotherm tests were conducted with the Co loaded resin samples which were mixed with different concentrations of sulfuric acid solution at a S/L ratio of 1 g / 10 mL and 80 ⁇ 1 °C for 0.5 hour. The tests were carried out in a 100 mL hexagonal jar in an incubator shaker. The slurry mixture was quickly filtered using vacuum filtration with 0.45 ⁇ sieve. The aqueous solution was sent for assay and the resin was stripped with sulfuric acid solution for assay.
  • the stripping kinetics tests were carried out with air-dried cobalt loaded resin and 1.5 M H 2 SO 4 at a S/L ratio of 2 g / 10 mL in a 100 mL hexagonal glass jar immersed in a temperature controlled oil bath. The solution temperature was maintained at 80 ⁇ 1 °C during the tests. The stripping kinetics tests were performed at 0.5, 1 , 2, 5, 10, 30 and 60 minutes. Timer was started when the resin was added to the stirred solution. The mixing was stopped at a required time and the slurry was quickly separated. The aqueous solution was sent for assay and the resin was stripped with sulfuric acid solution for assay.
  • the concentration of iron in the strip solution was lower than the ICP-OES detection limit and therefore was not reported. It was shown that cobalt could not be selectively stripped from the resin as the nickel stripped at a lower pH (1 M, 95% Ni removal vs 1.5 M 95% Co removal).
  • the full scale plant design will use an acid strip solution concentration of about 1.5 M - about 2 M sulfuric acid.
  • the resin Ni preloading, Co loading and elution were conducted with a total of 20 cycles over 4 weeks. Aqueous and resin samples was taken from each cycle to determine metal loadings and resin exchange capacity overtime. The tests were conducted in a 500 mL Schott bottle in an incubator shaker at 80 °C. One cycle of the test consisted of nickel preloading, loaded resin washing, cobalt loading, and cobalt loaded resin washing, loaded resin elution, and eluted resin washing.
  • the nickel preloading test was performed with the synthetic solution containing 190 g/L Ni at a S/L ratio of 50 g / 200 mL with constant shaking for 1 hour.
  • Nickel hydroxide powder (4 - 5 g) was also added to the solution to obtain solution pH 5 - 5.5.
  • the resin was then filtered and washed three times with deionised water (200 mL) for 10 minutes with shaking.
  • the cobalt loading test was conducted with synthetic solution (200 mL) containing target 190 g L Ni, 185 mg/L Co, 11 mg/L Fe and 4 mg/L Cu. The mixture was mixed by shaking for 20 hours. At the end, the solution pH was recorded and resin was filtered. The cobalt loaded resin was then washed three times with deionised water (200 mL) for 10 minutes with shaking.
  • the cobalt elution test was conducted with 2 sulfuric acid solution (200 mL). The mixture was mixed with shaking for 1 hour. The stripped resin was washed three times with deionised water (200 mL) for 10 minutes shaking times each time.
  • the exchange capacity measurement was conducted with sodium hydroxide solution and titrated with sulfuric acid solution. Air dried eluted resin from each cycle (0.3 - 0.5 g) was mixed with 0.196 M or 0.0196 sodium hydroxide solution (50 mL) at 50 °C in an incubator shaker for 12 hours (overnight). The supernatant (5 or 10 mL) was titrated with standard sulfuric acid solution to phenolphthalein end point. The amount of sulfuric acid usage was recorded for calculation of the total exchange capacity (Figure 18). Column design and set up
  • Ion exchange test work was conducted to assess the ability of the commercial resin TP 272 to selectively remove iron, copper and cobalt from leach PLS.
  • the ion exchange columns were constructed using water jacket condensers. Hot water from water baths was circulated through water jacket. The column size in diameter varies slightly from column to column and top to bottom. The measurement data for Column 1 are given in Table 6, indicating that the size is in the range of 140 - 150 mL and 145 mL on average.
  • the column was packed with Lewatit TP 272 resin ( ⁇ 145 mL / 64.5 g).
  • the leach feed solution was first heated up and pumped from the bottom of the condenser with the flow rate of 2 or 5 bed volume (BV). The outlet solution was collected in a 2 L plastic bottle. The solution pH was recorded and sample was taken at each BV.
  • the nickel hydroxide preparation was conducted in a 3 L beaker on a hot plate with magnetic stirrer. Nickel sulfate hexahydrate (1 kg) was dissolved in 2.0 L deionised water. Temperature was maintained at 40 °C initially. Concentrated ammonia solution (25% v/v) was used to adjust the pH to around pH 8. The solution colour turned blue and some nickel hydroxide powder was observed. The temperature was increased to 80 °C with constant stirring overnight. The nickel hydroxide powder was filtered using vacuum filtration. The blue colour filtrate was further mixed with stirring at 80 °C to produce more nickel hydroxide powder. The filtered nickel hydroxide powder was washed three times with deionised water to about pH 6.5 and left air dried before use. Table 4 Conditions for preparation of nickel hydroxide.
  • Ni content was calculated to about 92% with about 8% other components such as water and nickel sulfate.
  • Nickel pre-loading pH isotherms were carried out with Ni sulfate solutions of different Ni concentrations (20, 48, 100, 145 g/L Ni) were conducted in a continuous pH adjustment and sampling of resin for assay of Ni loading at each equilibrium pH. The procedures are detailed in experimental section.
  • Ni loading curves with other feed Ni concentrations are compared in Figure 12D.
  • the loading of Ni generally increased with solution pH.
  • a significant increase of Ni loading was observed with a higher Ni feed concentration (145 g/L Ni) along the pH range tested.
  • the precipitation of Ni may occur at a higher pH, which would also depend on the feed Ni concentration.
  • the nickel preloading kinetics tests were carried out with fresh resin at initial solution pH of 5.0 or 6.0 and S/L ratio of 17.5 g / 70 mL in a 100 mL hexagonal glass jar immersed in temperature controlled oil bath. The solution temperature was maintained at 80 ⁇ 1 ° C during the tests. The Ni preloading kinetics tests were performed at 0.5, 1 , 2, 5, 10 and 30 minutes. Timer was started when the resin was added to the stirred aqueous solution. The samples were taken at the required time and the slurry was quickly separated. The aqueous solution was diluted 4 or 5 times for assay and the resin was stripped with sulfuric acid solution for assay.
  • Nickel loading was very fast (Figure 12E), approaching equilibrium within one minute using both pH 5 and 6 feed nickel sulfate solution. The loadings then varied slightly over time which could be caused by variation of pH and other conditions. The final Ni loading at 30 minutes with pH 5 feed was slightly lower than that with pH 6 feed, though the pH 5 feed Ni concentration was about doubled that of the pH 6 feed. This was consistent to the observations for the effect of pH and Ni concentration on Ni pre-loading as discussed above. D: Summary ofNi pre-loading findings The optimum pre-loading pH was determined to be about pH 4.5 to about 5 as minimal nickel precipitation occurred while maximizing nickel loading.
  • Ni pre-loading for subsequent cobalt loading and stability tests: using synthetic Ni sulfate solution of 190 g/L Ni for Ni pre-loading which is required to stabilise the increase in discharge solution pH.
  • the bleed of the purified nickel sulfate stream within the circuit can be employed for solution making which can be used in multi cycles under optimum pH in the range of Ni concentrations up to more than times dilutions, and using only nickel hydroxide, Ni(OH) 2 , for pH adjustment to highest achievable pH in the range of pH 5 - 6 for reasonable nickel loading efficiency.
  • Nickel hydroxide (Ni(OH) 2 ) can be used for pH adjustment to about pH 4.5 - 6, particularly pH 5, with reasonable loading capacity, indicating Ni(OH) 2 can be used as neutralisation reagent in Ni pre-loading.
  • the resin was bulk pre-loaded using pH 5 feed nickel sulfate with nickel hydroxide used as the neutralisation reagent to take the feed solution to pH 5, if necessary.
  • HA is an acidic extractant, i.e. the active phosphinic acid functional group, for example, in TP 272.
  • the metal loading isotherms against the final equilibrium pH values were plotted in Figure 13B for percent loading efficiency and Figure 13C for metal loading per gram of resin.
  • Ni and Co might also be affected by the variations of their concentrations in the feed. This mainly resulted from the neutralisation with nickel hydroxide and filtration of unreacted fines, during which some loss of metals by possible crystallisation of nickel sulfate at decreased temperature, though an effort was made to shorten filtration time and drop in temperature.
  • the selectivity of Co over Ni expressed by separation factor SF(Co/Ni), increased from 236 at pH 4.2 to 880 at pH 4.4, and then decreased to 120 at pH 5.1. This is generally related to the competing loading at higher pH range.
  • the pH of maximum selectivity at about 4.5 agreed with that observed for the solvent extraction with Cyanex 272.
  • Ni pre-loaded resin provides mechanisms of displacement loadings, including displacement of other metal ions of higher affinity (e.g. Fe 3 *, Cu 2+ and Co 24 ), by metal ion complexes (e.g. bisulphate), and by metal ions including Ni 2+ species.
  • metal ions of higher affinity e.g. Fe 3 *, Cu 2+ and Co 24
  • metal ion complexes e.g. bisulphate
  • metal ions including Ni 2+ species e.g. bisulphate
  • Ni pre-loaded resin stabilised solution pH with a tendency of a slight pH increase after re-equilibrium.
  • the results proved that Ni pre-loading effects stable pH and warrants efficient Co loading at a desired pH range.
  • Ni loading in competing with Co became significant at a higher pH > 5, and there was an optimum pH for Co loading, which shifted slightly with different pre-loaded resin systems in the range of pH 4.5 - 5.
  • the following conditions for further tests were used: pre-loading TP 272 with nickel sulfate solution of 180 g/L at about pH 5 using the prepared nickel hydroxide for pH adjustment, and adjusting pH of synthetic PLS with the prepared nickel hydroxide to close to pH 5 (4.6 - 5).
  • Elution acidity profile was shown in Figure 15. Stripping of >90% Ni and Co occurred at 1.0 M H 2 SO 4 and 1.5 H 2 SO 4 , respectively. Near complete stripping of Cu occurred at 2M H 2 SO 4 . As little Fe was loaded, the stripping of Fe could not assessed. From solvent extraction experience using Cyanex272 with the same function group as Lewatit TP 272, both Ni and Co are easy to strip with much lower acidity. The different behaviour of Ni and Co stripping in terms of high acidity requirement from the loaded TP 272 resin could be attributed to the requirement for high acidity, i.e. strong driving force, to minimise concentration gradient for mass transfer and diffusion of the reactant into the internal micro structure sites and reaction products away from the sites.
  • Air dried resin was used for the distribution isotherm tests with original assay data (shaded) in Table 10 and Table 11), and mass balance data in Table 12.
  • Metal loading curves are shown in Figure 17A for loading efficiency (%) and in Figure 17B for mass loading (mg/g resin).
  • Raffinate metals and Co distribution curve are shown in Figure 17C and Figure 17D, respectively.
  • Ni loading remained high at 31 ⁇ 4 mg/g over the whole R/S ranges examined ( Figure 17B).
  • the selectivity, measured by separation factor (SF) of Co over Ni peaked at a lower range of R/S ratio ( Figure 17A), but the Ni/Co loading ratio on the resin increased linearly with increase in the R/S ratio ( Figure 17B).
  • Raffinate Cu decreased to below 1 mg/L with increased R/S ratios, while raffinate Fe unexpectedly remained high in the range of 7 - 12 mg/L.
  • Assay of Fe by ICP-AES appeared to be less affected by the high nickel sulfate matrix. However, assay errors by ICP-AES could be larger than ICP-MS.
  • the Langmuir adsorption model assumes that molecules are adsorbed at a fixed number of well-defined sites, each of which can only hold one molecule and no transmigration of adsorbate in the plane of the surface. These sites are also assumed to be energetically equivalent and distant to each other so that there are no interactions between molecules adsorbed to adjacent sites.
  • the linear form of the Langmuir isotherm is represented by the following equation:
  • Qe is the amount adsorbed (mg/g)
  • Ce is the equilibrium concentration of the adsorbate ions (mg/L)
  • Qs and K are Langmuir constants related to maximum adsorption capacity (monolayer capacity) (mg/g) and energy of adsorption (L/mg), respectively.
  • a plot of Ce/Qs versus Ce should indicate a straight line of slope 1/Qs and an intercept of 1/Qs-K.
  • Freundlich isotherm is an empirical equation that encompasses the heterogeneity of sites and the exponential distribution of sites and their energies.
  • KF and n are Freundlich constants related to adsorption capacity and adsorption intensity, respectively.
  • Data for Langmuir and Freundlich isotherms are given in Table 14 and shown in Figure 17F - 17H respectively.
  • the monolayer loading capacity on dry resin mass was derived through fitting Langmuir isotherm model at about 11.5 mg/g by taking 6 points as the linear part, and about 13.2 mg/g by taking 8 points as the linear part (Table 14 and
  • the vendor recommended maximum operating temperature for the TP 272 resin is 60°C compared to the leach PLS temperature of 80°C.
  • Degradation of the resin can either be mechanical degradation of the resin or loss in total ion exchange capacity.
  • the extractant can dissolve in the PLS and be removed from the resin.
  • the breakthrough point of the column was set at 30 BVs/hr which corresponded to a raffinate concentration of 20 mg/L Co.
  • the solution was re-passed through a polishing column which produced a raffinate with 1 - 2 mg/L Co, suitable for crystallisation.
  • Tests using Lewatit TP 207 was mainly aimed at removal of Fe and Cu impurities, and behaviours of Co and Ni. The test results are described below.
  • Metal loading efficiency (%) based on resin stripping assays and feed PLS, raffinate metal concentrations, and metal loadings on resin versus pH are shown in Figure 20C, Figure 20D and Figure 20E, respectively.
  • the behaviours of Ni, Co and Cu in these tests were essentially similar to those observed for the consecutive loading and sampling above: dominant Ni loading ( ⁇ 150 mg/g Ni) with low loading of Fe and Cu, and little co-loading of Co.
  • the behaviour of Fe was different.
  • the level of Fe remained at about 10 mg L in the raffinate. This may suggest that neutralisation with nickel hydroxide promote the precipitation of Fe.
  • the metal accountabilities were reasonably good (Table 22).
  • Example 14 Other resins / SX systems
  • Amberlite IRC 748 has the same function group as Lewatit MonoPlus TP 207. pH isotherms were conducted to provide a reference. Conditions of loading distribution isotherms with TP 207 are given in Table 26, and results are shown in Figures 24A to 24C. The results and finding are summarised as follows: Loading behaviour with IRC 748 essentially similar to TP 207, with dominant Ni loading and minor Co loading. Fe decreased from feed ⁇ 12 mg/L to about 2 mg/L in the raffinate, but the loading tended to decrease at pH > 4.0. Cu decreased from feed about 4 mg/L to below 1 mg/L and remained low in raffinate, corresponding to low and constant loading over the pH range.
  • Purolite S910 is amidoxime chelating resin. Metal pH isotherms were conducted for comparison with TP 272. Conditions of loading distribution isotherms with TP 207 are given in Table 27, and results are shown in Figure 25. The resin showed more selective and efficient for loading Cu over other metals.
  • a primary (lead) column (Column 1) was constructed and went through all the running steps, including Ni pre-loading, preload-wash, Co loading and load-wash, elution and elution- wash. Other two columns were similarly constructed and used for simulating polishing (lag) column, and for testing the effect of pH on loading efficiency and selectivity. The results are briefly summarised in the following sections.
  • Test conditions for Column 1 are summarised in Table 31 , involving all running steps.
  • raffinate Co was about 1% at beginning of 1 BV, and consistently increased almost linearly, if some new consecutive running points around 28 BV was excluded. This agreed with the observations from batch Co distribution isotherms regarding lower efficiency of the system with TP 272 and the PLS containing high Ni sulfate for low raffinate Co. About 10 mg/L Co ( ⁇ 7% breakthrough of the feed 136 mg/L Co) occurred at about 30 BV. The raffinate below 10% breakthrough were used as the feed for polishing running. The cobalt loading approached saturation at about 62 - 72 BV with loading about 11 mg/g Co on the air dry resin basis, while Ni loading is 27 - 35 mg/g (Figure 27B).
  • Polishing loading was carried out using the raffinate of Column 1 ( ⁇ 6 % breakthrough) as the feed. ICP-MS assay results are given in Table 33 and shown in Figure 28. With 3 different feed solutions (raffinate from different runs of Column 1) and 3 different flow rates (5, 2, 0.8 BV/h), the polishing resulted in the raffinate Co levels remaining in the range of 1 - 2 mg/L Co. The effect of flow rate or the extended residence time on the polishing was not very significant. The rate of mass transfer and diffusion may become slow at low flow rate, which needs further optimisation in large scale and is expected to be improved at a large scale.

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Abstract

L'invention concerne un procédé pour la production de sulfate de nickel de pureté élevée, ayant de préférence une pureté ≥ 99,8 %, plus préférablement ≥ 99,98 %, approprié pour être utilisé en fabrication de batteries ou en nickelage. Le procédé comprend l'élimination sélective d'impuretés métalliques qui ne sont pas du nickel d'une solution de sulfate de nickel, de préférence d'une solution de sulfate de nickel sous-saturée, obtenue par exemple à partir de poudre de nickel, par échange d'ions à l'aide d'une résine échangeuse d'ions préalablement chargée de nickel (IX) qui adsorbe les impuretés métalliques qui ne sont pas du nickel à partir de la solution pour former une solution de sulfate de nickel pratiquement exempte d'impuretés métalliques qui ne sont pas du nickel à partir de laquelle le sulfate de nickel de pureté élevée peut être récupéré. Le sulfate de nickel récupéré peut être cristallisé pour extraire le produit de pureté élevée.
PCT/AU2018/051203 2017-11-10 2018-11-08 Production de sulfate de nickel de pureté élevée Ceased WO2019090389A1 (fr)

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CN111392783A (zh) * 2020-03-26 2020-07-10 吉林吉恩镍业股份有限公司 一种从高酸含铁、钒硫酸镍溶液中去除钒离子的方法
CN113149091A (zh) * 2021-05-26 2021-07-23 广东佳纳能源科技有限公司 一种电池级镍盐及其制备方法
WO2022099422A1 (fr) * 2020-11-12 2022-05-19 Hatch Ltd. Processus et procédés de production de sulfates de métal
CN114517263A (zh) * 2022-02-21 2022-05-20 中南大学 一种从含镍废弃电容材料提取回收镍与制备镍产品的方法
WO2023006929A1 (fr) * 2021-07-30 2023-02-02 Basf Se Procédés et systèmes de production d'un produit de sulfate de nickel
KR102527172B1 (ko) * 2023-01-11 2023-05-02 고려아연 주식회사 니켈 전해 캐소드로부터 이차전지용 황산니켈 용액의 제조 방법
WO2023099424A1 (fr) 2021-11-30 2023-06-08 Umicore Procédé d'élimination de fer et de cuivre à partir d'une solution à l'aide de réactifs métalliques
JP2023532847A (ja) * 2020-07-10 2023-08-01 ノースボルト・エービー 結晶化金属硫酸塩を製造するための処理及び方法
CN117735630A (zh) * 2023-12-27 2024-03-22 南京霖厚环保科技有限公司 一种硫酸镍溶液去除锌杂质的方法
US20240228321A1 (en) * 2023-01-11 2024-07-11 Korea Zinc Co., Ltd. Method for producing nickel sulfate solution for secondary battery from nickel cathode
CN118350514A (zh) * 2024-06-18 2024-07-16 一夫科技股份有限公司 结合纯度检测的碳酸锂生产管理方法及系统
RU2825429C1 (ru) * 2023-01-11 2024-08-26 Корея Цинк Ко., Лтд. Способ получения раствора сульфата никеля для вторичной батареи из никелевых катодов
WO2025073525A1 (fr) 2023-10-02 2025-04-10 Glencore Nikkelverk As Procédé et appareil de lixiviation de nickel
ES2985641R1 (es) * 2021-08-25 2025-10-24 Guangdong Brunp Recycling Technology Co Ltd Metodo para preparar sulfato de niquel a partir de ferroniquel

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Cited By (24)

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CN111392783B (zh) * 2020-03-26 2022-08-05 吉林吉恩镍业股份有限公司 一种从高酸含铁、钒硫酸镍溶液中去除钒离子的方法
CN111392783A (zh) * 2020-03-26 2020-07-10 吉林吉恩镍业股份有限公司 一种从高酸含铁、钒硫酸镍溶液中去除钒离子的方法
JP2023532847A (ja) * 2020-07-10 2023-08-01 ノースボルト・エービー 結晶化金属硫酸塩を製造するための処理及び方法
US12281027B2 (en) 2020-11-12 2025-04-22 Hatch Ltd. Processes for crystallizing metal sulfates and methods for producing crystallized metal sulfates
WO2022099422A1 (fr) * 2020-11-12 2022-05-19 Hatch Ltd. Processus et procédés de production de sulfates de métal
CN113149091A (zh) * 2021-05-26 2021-07-23 广东佳纳能源科技有限公司 一种电池级镍盐及其制备方法
WO2023006929A1 (fr) * 2021-07-30 2023-02-02 Basf Se Procédés et systèmes de production d'un produit de sulfate de nickel
MA63870B1 (fr) * 2021-07-30 2025-02-28 Basf Se Procédés et systèmes de production d'un produit de sulfate de nickel
ES2985641R1 (es) * 2021-08-25 2025-10-24 Guangdong Brunp Recycling Technology Co Ltd Metodo para preparar sulfato de niquel a partir de ferroniquel
CN118451206A (zh) * 2021-11-30 2024-08-06 尤米科尔公司 使用金属试剂从溶液中除去铁和铜的方法
WO2023099424A1 (fr) 2021-11-30 2023-06-08 Umicore Procédé d'élimination de fer et de cuivre à partir d'une solution à l'aide de réactifs métalliques
WO2023099401A1 (fr) 2021-11-30 2023-06-08 Umicore Lixiviation sélective
CN114517263A (zh) * 2022-02-21 2022-05-20 中南大学 一种从含镍废弃电容材料提取回收镍与制备镍产品的方法
CN114517263B (zh) * 2022-02-21 2023-07-21 中南大学 一种从含镍废弃电容材料提取回收镍与制备镍产品的方法
KR102527172B1 (ko) * 2023-01-11 2023-05-02 고려아연 주식회사 니켈 전해 캐소드로부터 이차전지용 황산니켈 용액의 제조 방법
AU2023222908B2 (en) * 2023-01-11 2024-08-22 Kemco Method for producing nickel sulfate solution for secondary battery from nickel cathode
RU2825429C1 (ru) * 2023-01-11 2024-08-26 Корея Цинк Ко., Лтд. Способ получения раствора сульфата никеля для вторичной батареи из никелевых катодов
US20240228321A1 (en) * 2023-01-11 2024-07-11 Korea Zinc Co., Ltd. Method for producing nickel sulfate solution for secondary battery from nickel cathode
US12258282B2 (en) * 2023-01-11 2025-03-25 Korea Zinc Co., Ltd. Method for producing nickel sulfate solution for secondary battery from nickel cathode
WO2023243832A1 (fr) * 2023-01-11 2023-12-21 고려아연 주식회사 Méthode de production d'une solution de sulfate de nickel pour batterie secondaire à partir d'une cathode au nickel
EP4442649A4 (fr) * 2023-01-11 2025-10-29 Korea Zinc Co Ltd Méthode de production d'une solution de sulfate de nickel pour batterie secondaire à partir d'une cathode au nickel
WO2025073525A1 (fr) 2023-10-02 2025-04-10 Glencore Nikkelverk As Procédé et appareil de lixiviation de nickel
CN117735630A (zh) * 2023-12-27 2024-03-22 南京霖厚环保科技有限公司 一种硫酸镍溶液去除锌杂质的方法
CN118350514A (zh) * 2024-06-18 2024-07-16 一夫科技股份有限公司 结合纯度检测的碳酸锂生产管理方法及系统

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