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WO2023213919A1 - Procédé de lixiviation oxydante d'un métal - Google Patents

Procédé de lixiviation oxydante d'un métal Download PDF

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Publication number
WO2023213919A1
WO2023213919A1 PCT/EP2023/061744 EP2023061744W WO2023213919A1 WO 2023213919 A1 WO2023213919 A1 WO 2023213919A1 EP 2023061744 W EP2023061744 W EP 2023061744W WO 2023213919 A1 WO2023213919 A1 WO 2023213919A1
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WIPO (PCT)
Prior art keywords
process according
hydrochloric acid
solution
metal
chloride solution
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PCT/EP2023/061744
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English (en)
Inventor
Bart KLAASEN
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Umicore NV SA
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Umicore NV SA
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Priority to EP23725583.1A priority Critical patent/EP4519468A1/fr
Publication of WO2023213919A1 publication Critical patent/WO2023213919A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/08—Halides; Oxyhalides
    • C01G51/085—Chlorides; Oxychlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/08—Halides; Oxyhalides
    • C01G53/09—Chlorides; Oxychlorides
    • 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
    • C22B23/0423—Halogenated acids or salts thereof

Definitions

  • the present invention relates to processes for manufacturing a metal chloride, specifically nickel chloride, cobalt chloride and manganese chloride.
  • Nickel is an important industrial metal which finds primarily applications in stainless steel production, nonferrous corrosion-resistant alloys, electroplating, alloy steel. High purity nickel is essential for developing different applications. Nickel having a purity above 98% can be obtained from refining nickel ore resources such as nickel sulphide ore and nickel oxide ore. Often, these ores also comprise an amount of iron.
  • This process is also known as oxidative leaching of Ni metal, a process which is highly exothermic (-440 kJ/mol).
  • cobalt chloride may be prepared in a similar manner.
  • WO 2011/114000 Al discloses a hydrometallurgical method of processing nickel containing raw material.
  • the raw material is leached in chloride-based leaching media in a process integrated with chlorine-alkali electrolysis, solvent extraction and electrowinning process stages for producing metallic nickel.
  • the solvent extraction stage comprises a nickel solvent extraction stage, where nickel is extracted from an aqueous solution containing high concentration of chloride.
  • the electrolyte in the electrowinning stage is a sulphate containing aqueous liquid.
  • Nickel leaching processes as above often require further purification steps.
  • CN 109 518 006 A reports on a removal method of trace cobalt in a nickel chloride solution.
  • a solution obtained through 99.95% nickel board electro-dissolution is adopted as the nickel chloride solution or a commercially available pure nickel chloride crystal is used for preparing the nickel chloride solution; the nickel chloride solution is subjected to extraction deep purification through an extraction agent Cyanex272 matched with solvent oil with the proper proportion, and cobalt, copper and iron are removed.
  • the pure nickel chloride solution After impurity removal, the pure nickel chloride solution is obtained, the content of cobalt is reduced to 0.001 g/L, meanwhile, the content of copper and iron is reduced to 0.0001 g/L, and the aim of removing three impurity elements in one working procedure is achieved.
  • the method is applied to the high-purity nickel production, the purity of the obtained nickel plate product is 99.999%, the contents of the cobalt and the copper are both smaller than 1 ppm, the content of iron is smaller than 2 ppm.
  • the nickel chloride solution obtained after impurity removal can meet the need of preparing high-purity nickel and other high-purity nickel products.
  • novel processes are in demand to provide new processes which allow for ease of operation, high throughput, and optimized use of reactants. Such processes should further be safe and easy to operate, the product quality should be high and consistent, and the processes should be easily performed at large scale.
  • the current invention provides a solution for at least one of the above-mentioned problems by providing a continuous process for the oxidative leaching of Ni, Co and/or Mn.
  • the process is performed under continuous flow conditions in a column reactor, and also preferably the acid concentration in the oxidative leaching solution is substantially depleted.
  • the acid in the oxidative leaching solution is depleted to the extent that the temperature of the obtained metal chloride solution increased to a temperature close to but below the boiling point of the solution.
  • the inventors have found that under such conditions, the conversion rate of the metal to the metal chloride is maximized, and accordingly also the capacity of the column.
  • the inventive process is schematically shown in Figure 1.
  • Figure 1 shows schematically a process according to the invention in a column reactor.
  • Figure 2 shows the dissolution rate for nickel (Y-axis, kg/h) in an oxidative leaching process according to the inventive process, as a function of the average acid concentration (X-axis, g/L chloride acid, calculated as the average of CHA, i and CHA, O) at a constant volumetric flow rate through a column.
  • a compartment refers to one or more than one compartment.
  • “About” as used herein referring to a measurable value such as a parameter, an amount, a temporal duration, and the like, is meant to encompass variations of +/- 20% or less, preferably +/-10% or less, more preferably +/-5% or less, even more preferably +/-1% or less, and still more preferably +/-0.1% or less of and from the specified value, in so far such variations are appropriate to perform in the disclosed invention.
  • the value to which the modifier "about” refers is itself also specifically disclosed.
  • continuous process is to be considered as a process in which the produced solution has a substantially constant composition.
  • a continuous process is a process in which the produced solution has a constant composition within the range of what are considered normal process variations.
  • liquid reagents which are fed to the reactor have a fixed composition under normal process conditions.
  • the produced solution has a composition whereby the concentration of each ingredient is within the range of +/-20% or less, preferably +/-10% or less, more preferably +/-5% or less, even more preferably +/-3% or less of its average concentration.
  • the present invention provides a continuous process which operates under steady-state conditions.
  • hydrochloric acid and hydrogen peroxide are fed to the process according to the present invention at a substantially constant concentration and flow rate.
  • Ni metal may be fed to the process intermittently or gradually.
  • the present invention provides a continuous process wherein the bed volume of metal particles containing nickel is controlled in a column reactor within the range of +/-20% or less, preferably +/-10% or less, more preferably +/-5% or less, even more preferably +/- 3% or less of its average bed volume.
  • concentrated metal chloride solution is to be considered as synonymous to the term "metal chloride solution having a metal content of at least 60 g metal/L,” optionally comprising further contents, such as hydrochloric acid in an amount of less than 30 g/L HCI, preferably less than 20 g/l and more preferably less than 10 g/L.
  • said metal chloride solution has a metal content of at least 60 g metal/L, and preferably at least 80 g metal/L.
  • Said metal chloride solution preferably has a content of metal chloride below the saturation point of metal chloride at the processing temperature, i.e. at a temperature of about 90°C or of about 95°C.
  • said metal chloride solution has a metal content between 80 and 200 g metal/L, preferably between 90 and 175 g metal/L and more preferably between 100 and 150 g metal/L.
  • said metal chloride solution obtained from the oxidative leaching reaction is a metal chloride solution having a metal content of between 110 and 140 g/L, more preferably between 120 and 140 g/L, and most preferably said metal chloride solution having a metal content of about 130 g/L.
  • the present invention provides a process, preferably a continuous process, for the preparation of a metal chloride solution in a column reactor by oxidative leaching of metal particles.
  • the process is a continuous process for the preparation of Ni, Co and/or Mn chloride solutions in a column reactor.
  • said metal particles comprise Ni, Co and/or Mn, more preferably Ni and/or Co, respectively.
  • said Ni, Co and/or Mn particles are provided in high purity, i.e., a purity above 98 at.%, preferably above 99 at.% and most preferably above 99.5 at.%, whereby purity is expressed as the total content of Ni, Co and Mn relative to the total weight of the particles.
  • the content of impurities, i.e. elements different from Ni, Co and Mn is less than 2 at.%, relative to the total atomic content of said particles, preferably less than 1 at.% and more preferably less than 0.5 at.%.
  • the column reactor has a feed section at the bottom of said reactor, an outflow or overflow section at the upper end or top end of said reactor, and a reaction section between said feed section and said overflow section. Said process comprises the steps of: i. feeding metal particles containing nickel, cobalt and/or manganese to the reaction section of said column reactor; ii.
  • the process according to the first aspect of the invention is a continuous process.
  • the process according to the first aspect of the invention is applied for preparing a concentrated metal chloride solution.
  • the process is typically performed under continuous flow conditions in a column reactor and in that the acid in the oxidative leaching solution is substantially depleted after passage through the column reactor.
  • steps ii. and iii. are typically performed under continuous flow conditions, while step i. can be performed under continuous flow conditions or can be performed gradually or intermittently.
  • the acid in the oxidative leaching solution is depleted to the extent that the temperature of the obtained metal chloride solution increased to a temperature just below the boiling point of the solution, and to ensure that the capacity of the column is maximized for a targeted acid concentration in the metal chloride solution at the top of the reactor.
  • the inventors have found that under such conditions, the conversion of Ni, Co and/or Mn to the respective nickel, cobalt and/or manganese chloride is maximized, and accordingly also the capacity of the column is maximized.
  • the depletion of hydrochloric acid over the column reactor is expressed by the ratio of the hydrochloric acid concentration (CHA,O) of the metal chloride solution obtained in step ii. to the hydrochloric acid concentration (CHA ) of said oxidative leach solution which is fed to the reactor.
  • the inventors recommend that said ratio is maintained at a value between 0.90 and 0.01, preferably between 0.70 and 0.01, preferably between 0.50 and 0.02, and more preferably between 0.45 and 0.10. Most preferably, said ratio is about 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, or any value there in between. In the context of the present invention, this ratio is referred to as "acid ratio.”
  • Figure 1 shows schematically a process according to the invention in a column reactor.
  • a desired, i.e., a sufficiently low, acid ratio can be managed by maintaining a sufficiently low flow rate of the oxidative leach solution through the column reactor.
  • the inventors have found that the process in the column reactor is more easily controlled at lower flow rates for the oxidative leach solution through said column reactor. Maintaining a sufficiently low flow rate of said oxidative leach solution results in the depletion of hydrochloric acid at the top of said column reactor.
  • a sufficiently low flow rate of said oxidative leach solution to said column reactor allows to control the leaching reaction such that the temperature of the metal chloride solution at the top of the column reactor remains below the boiling point of the solution, while the inlet temperature can be kept moderate to low.
  • a sufficiently low flow rate allows to control the progress of the leaching reaction to ensure complete consumption of the oxidizing agent and is preferably managed to result in a temperature at the top of the column which is just below the boiling point of the solution.
  • the inventors realized that operating the process in the column reactor at a sufficiently low flow rate, results in a higher average acid concentration in the column reactor, and consequently a faster conversion of metallic Ni, Co and/or Mn to NiCIz, C0CI2, and/or MnCh, respectively.
  • Figure 2 shows the dissolution rate for nickel (Y-axis, kg/h) in an oxidative leaching process according to the inventive process, as a function of the average acid concentration (X-axis, g/L hydrochloric acid, calculated as the average of CHA, i and CHA, 0) at a constant volumetric flow rate through the column.
  • the results show that the nickel dissolution rate increases with higher average acid concentration in the column.
  • a maximum capacity for a continuous process can be obtained at maximum consumption of the acid over the column, provided that the temperature at the top of the column reactor is controlled to a temperature below the boiling temperature of the nickel chloride solution.
  • the present invention provides a process according to the first aspect, whereby, on a macroscopic scale, a ID flow profile is maintained throughout the column.
  • the present invention provides a process according to the first aspect, whereby the acid ratio, i.e., the ratio of the hydrochloric acid concentration (CHA,O) of said nickel chloride solution obtained from the column reactor to the hydrochloric acid concentration (CHA ) of the oxidative leach solution, which is fed to the column reactor, is lower than 0.70, lower than 0.65, lower than 0.60, lower than 0.55, or even lower than 0.50.
  • said ratio is between 0.5 and 0.1.
  • said ratio is lower than 0.45 and even lower than 0.40.
  • said ratio is higher than 0.05.
  • said ratio is about 0.10, about 0.15, about 0.20, about 0.25, about 0.30, about 0.35, or any value there in between.
  • the present invention provides a process according to the first aspect, whereby the difference A ac in acid concentration CHA, i and CHA, 0 is at least 5 g/L hydrochloric acid and at most 50 g/L hydrochloric acid, preferably at least 10 g/L hydrochloric acid and at most 30 g/L hydrochloric acid.
  • said difference Aac in acid concentration is at least 12 g/L or at least 15 g/L and more preferably at least 20 g/L.
  • said difference A ac in acid concentration is at most 50 g/L or at most 40 g/L and more preferably at most 30 g/L.
  • said difference Aac in acid concentration is about 14 g/L, 16 g/L, 18 g/L, 20 g/L, 22 g/L, 25 g/L, or any value there in between.
  • the present invention provides a process according to the first aspect, whereby said metal chloride is nickel chloride and whereby the nickel chloride solution has a nickel content of between 80 and 250 g Ni/L, preferably between 120 and 225 g Ni/L and more preferably between 150 and 200 g Ni/L.
  • said nickel chloride solution obtained from the oxidative leaching reaction has a nickel content of between 160 and 190 g/L, more preferably between 170 and 180 g/L.
  • the oxidative leaching process i.e., the column reactor, is controlled to ensure that the nickel chloride solution obtained from said column reactor has a residual chloric acid content (CHA,O) of between 1 g/L and 20 g/L.
  • the residual amount of hydrochloric acid in said nickel chloride solution is between 2 g/L and 15 g/L, more preferably between 2 g/L and 10 g/L, and most preferably the residual amount of hydrochloric acid is about 5 g/L, 6 g/L, 7 g/L, 8 g/L, 9 g/L or 10 g/L, or any value there in between.
  • the present invention provides a process according to the first aspect, whereby said metal chloride is cobalt chloride and whereby the cobalt chloride solution has a cobalt content of between 80 and 250 g Co/L, preferably between 120 and 225 g Co/L and more preferably between 150 and 200 g Co/L.
  • said cobalt chloride solution obtained from the oxidative leaching reaction has a cobalt content of between 160 and 190 g/L, more preferably between 170 and 180 g/L.
  • the oxidative leaching process i.e., the column reactor
  • the cobalt chloride solution obtained from said column reactor has a residual chloric acid content (CHA,O) of between 1 g/L and 20 g/L.
  • CHAI residual chloric acid content
  • Leaching to a lower residual hydrochloric acid content ensures that hydrochloric acid is used economically in the process.
  • the residual amount of hydrochloric acid in said cobalt chloride solution is between 2 g/L and 15 g/L, more preferably between 2 g/L and 10 g/L, and most preferably the residual amount of hydrochloric acid is about 5 g/L, 6 g/L, 7 g/L, 8 g/L, 9 g/L or 10 g/L, or any value there in between.
  • the present invention provides a process according to the first aspect, whereby said metal chloride is manganese chloride and whereby the manganese chloride solution has a manganese content of between 80 and 250 g Mn/L, preferably between 120 and 225 g Mn/L and more preferably between 150 and 190 g Mn/L.
  • said manganese chloride solution obtained from the oxidative leaching reaction has a manganese content of between 150 and 180 g/L, more preferably between 160 and 170 g/L.
  • the oxidative leaching process i.e., the column reactor
  • the oxidative leaching process is controlled to ensure that the manganese chloride solution obtained from said column reactor has a residual chloric acid content (CHA,O) of between 1 g/L and 20 g/L.
  • CHAI residual chloric acid content
  • Leaching to a lower residual hydrochloric acid content ensures that hydrochloric acid is used economically in the process.
  • the residual amount of hydrochloric acid in said manganese chloride solution is between 2 g/L and 15 g/L, more preferably between 2 g/L and 10 g/L, and most preferably the residual amount of hydrochloric acid is about 5 g/L, 6 g/L, 7 g/L, 8 g/L, 9 g/L or 10 g/L, or any value there in between.
  • the present invention provides a process according to the first aspect, whereby said oxidative leach solution is fed to said reactor, i.e., said column reactor, at a temperature above 20°C, preferably above 30°C, preferably above 40°C and more preferably above 50°C.
  • said oxidative leach solution is fed to said reactor at a temperature of 50 to 90°C, preferably at a temperature between 55°C and 80°C, more preferably at a temperature of about 65°C. It is advantageous to provide a cooler oxidative leach solution to the column, to allow for a higher concentration of acid. Such a higher concentration of acid would allow for a higher conversion of metallic Ni, Co and/or Mn and thus a higher capacity of the process.
  • a desired temperature e.g., 65°C
  • hydrochloric acid and/or hydrogen peroxide at room temperature
  • the present invention provides a process according to the first aspect, whereby said metal chloride solution is removed from said reactor at a temperature below the boiling temperature of said metal chloride solution, preferably at a temperature of 90°C to 107°C, more preferably at a temperature between 95°C and 105°C.
  • said metal chloride solution which is evacuated from the reactor has a temperature of 95°C to 101°C, such as 96°C, 97°C, 98°C,99°C or
  • the present invention provides a process according to the first aspect, whereby a first fraction ⁇ pi of said metal chloride solution is cooled from a temperature above 90°C to a temperature below 75°C, and whereby said fraction ⁇ pi is mixed with hydrochloric acid and hydrogen peroxide in water to form an oxidative leach solution, prior to feeding said oxidative leach solution to said reactor.
  • said first fraction ⁇ pi is cooled from a temperature above 95°C to a temperature below 70°C, more preferably from a temperature above 97°C to a temperature below 65°C.
  • Cooling may proceed in a heat exchanger such as a plate heat exchanger, a shell- and-tube heat exchanger, or in a reactor with cooling means.
  • said heat exchanger consists of a reactor with cooling means.
  • Such reactors additionally allow for buffering a volume of said first fraction ⁇ pi.
  • hydrochloric acid and/or hydrogen peroxide can be pre-heated with the heat which is recovered from the heat exchanger.
  • the process conditions according to the inventive process ensure that a constant temperature of the metal chloride solution at the top of the column reactor is realized, which allows for a straightforward cooling process.
  • the present invention provides a process according to the first aspect, whereby a first fraction ⁇ pi of said metal chloride solution is mixed with hydrochloric acid and/or hydrogen peroxide to form an oxidative leach solution, prior to feeding said oxidative leach solution to said reactor.
  • the volumetric ratio of said first fraction ⁇ pi to the total volume of said metal chloride solution is between 0.70 and 0.98, preferably between 0.75 and 0.95, more preferably between 0.85 and 0.94 and most preferably is equal to 0.86, 0.88, 0.90, 0.91, 0.92, 0.93, or any value there in between.
  • the present invention provides a process according to the first aspect, whereby heat recovered from the cooling step of said first fraction ⁇ pi is, at least in part, used for heating the oxidative feed solution and/or the content of said reactor to a temperature of between 55°C and 75°C, preferably to a temperature between 60°C and 70°C, most preferably at a temperature of about 65°C.
  • the present invention provides a process according to the first aspect, whereby a second fraction ⁇ p2 of said metal chloride solution is subjected to a purification step to reduce the concentration of one or more impurities in said second fraction ⁇ p2, whereby said impurities comprise one or more selected from the list comprising Cu, Zn, Fe, Al, F, C, Ca, Si, P, S, As, Cd, Sb and Mg.
  • a base is added to said second fraction ⁇ p2 of said nickel chloride solution to react with the residual amount of hydrochloric acid present in said metal chloride solution, prior to subjecting said second fraction to a further purification step, whereby said base is selected from the group consisting of potassium hydroxide, potassium carbonate, nickel hydroxide, nickel carbonate, cobalt hydroxide, cobalt carbonate, manganese hydroxide, manganese carbonate, ammonium carbonate, ammonium hydroxide, calcium hydroxide, calcium carbonate, sodium hydroxide, sodium carbonate, lithium hydroxide, lithium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, or a combination of two or more of the aforementioned.
  • said base is added until the pH of the metal chloride solution is between 1 and 5, preferably between 2 and 4, and more preferably between 2.5 and 3.8.
  • the present invention provides a process according to the first aspect, whereby said metal particles comprise nickel in an amount of at least 97 wt.%, relative to the total weight of said metal particles, preferably at least 98 wt.% and more preferably at least 99 wt.%. Said metal particles may further contain Co in an amount of up to 1 wt.%. Preferably said metal particles contain Ni in an amount of at least 99.5 wt.%.
  • the Ni metal feed preferably comprises highly pure Ni metal, having a purity of typically 99.97+ %, 99.98+ %, or even 99.99+ %.
  • Ni metal may be fed to the reactor in the form of Ni cut cathode metal, having a size of typically l"xl", 2"x2" or 4"x4", a shredded or cut full plate cathode metal obtained from an electrowinning process; Ni metal rounds; or Ni pellets, balls having diameter of about 0.5 cm.
  • the present invention provides a process according to the first aspect, whereby said metal particles comprise cobalt in an amount of at least 97 wt.%, relative to the total weight of said metal particles, preferably at least 98 wt.% and more preferably at least 99 wt.%.
  • Said metal particles may further contain Ni in an amount of up to 1 wt.%.
  • Preferably said metal particles contain cobalt in an amount of at least 99.5 wt.%.
  • the cobalt metal feed preferably comprises highly pure cobalt metal, having a purity of typically 99.97+ %, 99.98+ %, or even 99.99+ %.
  • the Co metal may be fed to the reactor in the form of Co cut cathode metal, having a size of typically l"xl", 2"x2" or 4"x4", a shredded or cut full plate cathode metal obtained from an electrowinning process; Co metal rounds; or Co pellets, balls having diameter of about 0.5 cm.
  • the present invention provides a process according to the first aspect, whereby said metal particles comprise nickel, cobalt and/or manganese, and optionally iron and/or copper, whereby the total weight of nickel, cobalt, manganese, and if present iron and copper is at least 97 wt.%, relative to the total weight of all metallic substances in said metal particles, preferably at least 98 wt.% and more preferably at least 99 wt.%.
  • said metal particles contain nickel, cobalt, manganese, iron and/or copper in an amount of at least 99.5 wt.%.
  • Hydrogen peroxide used in the process is typically a 30 to 60 wt.%, such as 50 wt.% solution in water and hydrochloric acid has a concentration up to 38 wt.% in water, preferably between 30 and 38 wt.%, and more preferably a 36 wt.% concentration in water.
  • Any water used in the process may be high purity water, such as demineralized water or RO water.
  • the present invention provides a process according to the first aspect, whereby said oxidative leach solution which is fed to the reactor comprises hydrochloric acid in an amount of 10 to 100 g/L, preferably in an amount of 15 to 60 g/L.
  • said oxidative leach solution comprises hydrochloric acid in an amount of 15 to 45 g/L, more preferably in an amount of 20 g/L to 35 g/L.
  • the present invention provides a process according to the first aspect, whereby said oxidative leach solution comprises hydrogen peroxide in an amount of 2 to 25 g/L, preferably 5 to 20 g/L, and more preferably in an amount of 8 to 15 g/L.
  • the present invention provides a process according to the first aspect, whereby hydrogen peroxide is present in the oxidative leach solution which is fed to the column reactor in a sub-stoichiometric amount relative to the amount of hydrochloric acid present in said oxidative leach solution.
  • the oxidative leach solution may comprise 0.4 mol/L hydrogen peroxide and 1.0 mol/L hydrochloric acid.
  • the molar ratio of hydrogen peroxide to hydrochloric acid in the oxidative leach solution which is fed to the column reactor is between 1.2 and 2.0, preferably between 1.6 and 2.0, and more preferably is about 1.8.
  • Processes according to the invention allow to operate with a sub-stoichiometric amount of hydrogen peroxide which ensures complete consumption of hydrogen peroxide, whereby a residual amount of hydrochloric acid in the formed metal chloride solution is allowed.
  • the present invention provides a process according to the first aspect, whereby hydrochloric acid and hydrogen peroxide are present in a stoichiometric amount in said oxidative leach solution.
  • the molar ratio of hydrochloric acid to hydrogen peroxide is between 2: 1 and 2: 1.2, more preferably between 2.0: 1.0 and 2: 1.1.
  • An excess of hydrogen peroxide supports further depletion of the hydrochloric acid.
  • An excess of hydrogen peroxide ensures that hydrogen peroxide is not the rate limiting factor for the process. Excess hydrogen peroxide can be recovered from the column reactor effluent.
  • the present invention provides a process according to the first aspect, whereby a gaseous atmosphere in the overflow section of said column reactor is circulated through a scrubber.
  • a gaseous atmosphere in the overflow section of said column reactor is circulated through a scrubber.
  • said scrubber is cooled.
  • said scrubber and circulation reactor are integrated in one single unit.
  • said circulation reactor is maintained at a temperature between 50°C and 70°C, preferably at a temperature of about 60°C or about 65°C. Lower temperatures favour the efficiency of the scrubbing operation.
  • the present invention provides a process according to the first aspect, whereby said oxidative leach solution is contacted with said metal particles at atmospheric pressure, i.e., 1 bar, or at an under-pressure of less than 0.5 bar, preferably less than 0.2 bar, and more preferably less than 0.1 bar.
  • said oxidative leach solution is contacted with said metal particles under an atmosphere of oxygen, air or oxygen-enriched air.
  • the gaseous atmosphere in the overflow section is flushed with an inert gas, such as N2. This allows for a straightforward removal of hydrogen gas, in case hydrogen gas is formed in the column reactor.
  • the present invention provides a process according to the first aspect, whereby the gaseous atmosphere in the overflow section is treated in a scrubber to remove water and any hydrogen that may have formed.
  • the present invention provides a process according to the first aspect, whereby a bed volume consisting of said metal particles in the column reactor has a diameter Db and a height Hb, whereby the ratio of said height to said diameter Hb: Db is between 0.8 to 9, preferably between 1 and 5.
  • the height and diameter of said bed volume are maintained substantially constant throughout the process.
  • the inventive process proceeds in a column.
  • the term “column” is to be considered equivalent to the term “column reactor”, “packed bed” or “packed bed reactor”, “tower” or “tower reactor” and refers to a column reactor having a substantially cylindrical form having an internal diameter D and a height H.
  • the column reactor consists of a vertically arranged cylindrical column and is arranged to operate without mechanical agitation, preferably in the upflow mode, i.e., fluid flow from bottom to top of the column.
  • the column reactor is further characterized by (i) a feed section at the bottom of said cylindrical reactor for feeding liquid reagents such as an aqueous solution comprising hydrochloric acid and hydrogen peroxide; (ii) a top section or an overflow section at the upper part or top end of the column reactor, at the opposite side of the feed section, characterized by an effluent for collecting the overflowing metal chloride solution; (iii) a middle section or a reaction section in the middle of said cylindrical reactor, where the leaching reaction proceeds.
  • Metal particles comprising nickel, cobalt and/or manganese are preferably fed at the top of the reactor and may be dosed gradually or intermittently to form a bed of metal particles on a support in said column reactor.
  • Said column reactor preferably comprises a support above the feed section for supporting a solid reagent such as a reagent metal, Ni, Co and/or Mn.
  • Said support consists of a grid for supporting the reagent metal.
  • the column reactor is preferably equipped with means to feed a solid reagent such as the reagent metal to the reaction zone of the column reactor.
  • the column reactor is preferably also equipped with means for radially and uniformly distributing the oxidative leach solution in the feed section of the column reactor.
  • the solid reagent can be dosed on the support by introduction of the reagent metal at the top of the reactor, or at any position above the support.
  • the overflow zone is provided with an outlet to receive a metal chloride solution via an overflow mechanism.
  • the present invention provides a process according to the first aspect of the invention, whereby a liquid volume consisting of said oxidative leach solution in said column reactor has a diameter DL and a height HL, whereby the ratio of said height to said diameter HL: DL is between 1.0 and 10.0, preferably between 1.5 and 8.0, more preferably between 2.0 and 5.0 and most preferably about 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5.0, or any value there in between.
  • a proper geometry of the liquid volume in the column reactor ensures that a 1-dimensional flow can be obtained throughout the column; and that small metallic particles resulting from reacted metallic feed particles are not upwardly entrained with the metal chloride solution resulting from the oxidative leaching reaction, thereby entraining unreacted metal particles and thereby contaminating the obtained metal chloride solution, as well as lowering the efficiency of the process.
  • said column reactor is cylindrically shaped and has an internal diameter D and a height H, whereby the ratio of said height H to said diameter D is significantly higher than 1, such as between 1.0 and 10.0, preferably between 1.5 and 8.0, more preferably between 2.0 and 5.0 and most preferably about 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5.0, or any value there in between.
  • a proper geometry of the column reactor, especially a sufficiently high ratio H : D ensures that a 1-dimen- sional flow can be obtained throughout the column.
  • the present invention provides a process according to the first aspect of the invention, whereby said oxidative leach solution comprising hydrochloric acid and hydrogen peroxide in water is fed in step ii. via a bottom section of said column reactor to said reaction section, and whereby said metal chloride solution is evacuated in step iii. via a top section of said column reactor from said reaction section.
  • said metal particles are fed via a top section of said column reactor to the reaction zone. Said metal particles may be fed continuously or intermittently, preferably intermittently.
  • said reaction zone may also incorporate a mechanical impeller, i.e. an impeller that is attached to a motor by means of a rod for the purpose of solely mixing liquid reagents.
  • a static mixer is used.
  • the reaction zone comprises a plurality of vertical baffles placed diametrically opposite to each other and placed at a position between said inlet nozzles and the said impeller such that at least one baffle is placed on diametrically opposite ends of the reactor walls.
  • the impeller and the vertical baffles help in micro-level mixing of the reactants.
  • the impeller improves reactor kinetics.
  • the vertical baffles contribute towards ensuring the maximum mixing of the reactants within the reaction zone.
  • the placement of the vertical baffles ensures that the reaction is limited to the reaction zone and does not extend into the zones above the reaction zone.
  • said reactor has a calming zone above the reaction zone.
  • the calming zone has a tubular structure with a constant cross section, preferably equal to that of said reaction zone, or with a widening cross section whereby the diameter of said cross section is larger than the cross section of the reaction zone.
  • the calming zone is in fluid communication with said reaction zone and has the reaction zone at its distal end and the overflow zone at its proximal end.
  • the function of the calming zone is to achieve a non-turbulent liquid flow in which unreacted metal fines adapt a nonfluidised condition. This allows the unreacted or insufficiently reacted metal particles to return to the reaction zone.
  • the calming zone may comprise a plurality of horizontal baffles placed in the central, proximal, and distal parts of the calming zone.
  • at least two of the provided horizontal baffles may be downward type of baffles with a centre flow aperture adapted to slow down the speed of the reactant mixture.
  • the provided central horizontal baffle is a conical type baffle with annular flow. In this embodiment, the placement of the horizontal baffles creates a curved flow path that allows for particles of a large size to settle down, while at the same time, allowing the upward flowing mixture to travel smoothly into the overflow zone.
  • the overflow zone has a tubular structure, with a cross section equal to that of the calming zone and the reaction zone, and is placed at the proximal end of the reactor.
  • the overflow zone is provided with an outlet to receive the formed nickel sulphate solution.
  • Figure 1 shows schematically a process according to the invention in a column reactor.
  • the column reactor has an internal diameter D and a height H, whereby the ratio H :D is about 3.35. Before mixing said fraction ⁇ pi with hydrochloric acid and hydrogen peroxide, said fraction ⁇ pi is cooled from a temperature of about 97°C to a temperature of about 70°C.
  • the oxidative leach solution prepared accordingly has a temperature of about 66°C and has a hydrochloric acid content of about 26 g/L and is fed via a feed section to the reaction zone of the column reactor.
  • the reaction zone comprises Ni metal cut cathodes having a dimension of about 2" by 2" and having a nickel content of 99.97%.
  • the metal particles containing nickel are intermittently fed on the support plate above the reactor feed section; metal particles feed omitted in Figure 1.
  • the Ni metal is provided in a bed, said bed having a bed volume characterized by a height and diameter, whereby the ratio of said height to said diameter is about 3.
  • a nickel chloride solution N is formed having a residual amount of hydrochloric acid CSA,O of about 7 g/L.
  • the ratio of concentration of hydrochloric acid in the effluent vs. the concentration of hydrochloric acid in the feed solution is about 0.22. Due to the exothermic nature of the reaction, the temperature To of the nickel chloride solution N at the top of the column is about 97°C.
  • a first fraction ⁇ pi of the nickel chloride solution N is cooled from a temperature of about 97°C to a temperature of about 70°C, and subsequently mixed with the mixture of hydrochloric acid A and hydrogen peroxide P in water.
  • a second fraction ⁇ p2 of said nickel chloride solution N is further processed to a pH of about 3.0 and is subsequently processed to eliminate impurities. Gases which may have formed in the atmosphere at the top of the column reactor are treated in a scrubbing unit.
  • Example 1 The process according to Example 1 is repeated, whereby the nickel feed is replaced by a cobalt feed consisting of Co metal cut cathodes having a dimension of about 1" by 1" and having a cobalt content of 99.9% to yield a high purity cobalt chloride solution.
  • Example 2 The process according to Example 1 is repeated, whereby the nickel feed is replaced by a nickel-cobalt feed consisting of about 60 at.% Ni, 25 at.% Co and 7 at.% Mn, 3 at.% Cu and 5 at.% Fe.
  • the metal feed consists of granulated metal particles.

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Abstract

La présente invention concerne un procédé de préparation d'une solution de chlorure de nickel dans un réacteur à colonne, des particules métalliques contenant du nickel et/ou du cobalt étant mises à réagir avec une solution de lixiviation oxydante comprenant de l'acide chlorhydrique et du peroxyde d'hydrogène dans de l'eau et l'acide contenu dans la solution de lixiviation oxydante étant sensiblement appauvri.
PCT/EP2023/061744 2022-05-05 2023-05-04 Procédé de lixiviation oxydante d'un métal Ceased WO2023213919A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3656940A (en) * 1968-06-21 1972-04-18 Nickel Le Process for the purification of nickel containing solutions
US4016054A (en) * 1974-07-10 1977-04-05 Imetal Hydrometallurgical treatment process for extracting constituent metal values from ferro-nickel
US5104445A (en) * 1987-07-31 1992-04-14 Chevron Research & Technology Co. Process for recovering metals from refractory ores
WO2011114000A1 (fr) 2010-03-18 2011-09-22 Outotec Oyj Procédé de traitement de matériau brut nickélifère
CN107447107A (zh) * 2017-08-23 2017-12-08 中南大学 一种富贵锑控电位分离并回收贱金属的方法
CN109518006A (zh) 2018-10-30 2019-03-26 金川集团股份有限公司 一种氯化镍溶液中微量钴的去除方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3656940A (en) * 1968-06-21 1972-04-18 Nickel Le Process for the purification of nickel containing solutions
US4016054A (en) * 1974-07-10 1977-04-05 Imetal Hydrometallurgical treatment process for extracting constituent metal values from ferro-nickel
US5104445A (en) * 1987-07-31 1992-04-14 Chevron Research & Technology Co. Process for recovering metals from refractory ores
WO2011114000A1 (fr) 2010-03-18 2011-09-22 Outotec Oyj Procédé de traitement de matériau brut nickélifère
CN107447107A (zh) * 2017-08-23 2017-12-08 中南大学 一种富贵锑控电位分离并回收贱金属的方法
CN109518006A (zh) 2018-10-30 2019-03-26 金川集团股份有限公司 一种氯化镍溶液中微量钴的去除方法

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