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WO2025073525A1 - Procédé et appareil de lixiviation de nickel - Google Patents

Procédé et appareil de lixiviation de nickel Download PDF

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Publication number
WO2025073525A1
WO2025073525A1 PCT/EP2024/076629 EP2024076629W WO2025073525A1 WO 2025073525 A1 WO2025073525 A1 WO 2025073525A1 EP 2024076629 W EP2024076629 W EP 2024076629W WO 2025073525 A1 WO2025073525 A1 WO 2025073525A1
Authority
WO
WIPO (PCT)
Prior art keywords
leach solution
oxidising agent
aqueous leach
dissolution
nickel
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.)
Pending
Application number
PCT/EP2024/076629
Other languages
English (en)
Inventor
Ole Morten DOTTERUD
Martin STORM LARSEN
Elke Willam Thisted
Therese STALLEMO BJERLAND
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.)
Glencore Nikkelverk AS
Original Assignee
Glencore Nikkelverk AS
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
Application filed by Glencore Nikkelverk AS filed Critical Glencore Nikkelverk AS
Publication of WO2025073525A1 publication Critical patent/WO2025073525A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0207—Control systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/028—Flow sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B3/02—Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching

Definitions

  • Nickel mainly occurs in the nature as nickel lateritic ores or as sulphide nickel ores which are extracted and chemically reduced by various hydrometallurgical and/or pyrometallurgical processes to (metallurgical grade) elementary nickel or ferronickel.
  • metallurgical grade nickel has often too high impurity levels to be acceptable for use in electroplating/electroless plating or as raw material for the manufacturing of cathodes for LIBs and need to be refined.
  • Nickel sulphate solutions may be produced by leaching nickel metal in an aqueous leaching agent comprising sulphuric acid and usually an oxidizing agent to speed up the dissolution rate.
  • Bilczuk et al. (2016) [Ref. 2] has studied the dissolution rates of nickel metal in sulphuric acid as a function of temperature, sulphuric acid concentration, and three different oxidant types, oxygen gas, ferric sulphate and hydrogen peroxide.
  • the study observed different kinetic regimes depending on the oxidant used for the dissolution of nickel and concluded that the order of reactivity of the different oxidants used in this work was:
  • this may be obtained by providing a mathematical relation describing the above described onset-level of hydrogen peroxide/oxidising agent causing the surface passivation effect as a function of acid strength, more or less continuously measuring the real content/concentration of sulphuric acid and of hydrogen peroxide/oxidising agent being present in the aqueous leach agent, applying the real content/concentration of sulphuric acid to define a set value, being somewhat less than the onset-level (to avoid triggering the formation of a surface passivation of the nickel), of the content/concentration of hydrogen peroxide/- oxi dising agent to be present in the aqueous leach agent, and then applying a regulation algorithm to regulate the flow volume of hydrogen peroxide/oxidising agent being introduced to the aqueous leach solution to minimise the deviation between the real value and the set value of the hydrogen peroxide/oxidising agent content.
  • the invention has been described in light of hydrogen peroxide as the oxidising agent, it is believed that a similar surface passivation
  • the method further comprises:
  • the term “more or less continuously regulating the addition of oxidising agent to the aqueous leach solution” as used herein encompasses either fully continuous regulation of the feeding rate of oxidising agent or intermittent regulations/corrections of the feeding rate made at regular intervals of time.
  • the regulation of the feeding rate is made at time intervals being in the range of from 5 seconds to 15 minutes, preferably from 10 seconds to 10 minutes, more preferably from 15 seconds to 5 minutes, and most preferably from 30 seconds to 2 minutes.
  • pre-specified rest content of sulphuric acid refers to a parameter which may be applied to terminate the leach process.
  • the battery industry often specifies the acceptable maximum content of unreacted sulphuric acid in the nickel sulphate solution.
  • the present method according to the invention may be made to automatically endure until the leach process has consumed sufficient amounts of the (initially supplied) sulphuric acid to obtain a remaining content of unreacted acid being on or below this maximum allowable content.
  • the amount or strength of the sulphuric acid in the “virgin” leach solution depends on the battery industry’s specification of the acceptable maximum content of unreacted sulphuric acid and the requested level of dissolved nickel in the pregnant leach solution/battery grade nickel sulphate solution.
  • a typical example of dissolved nickel contents in battery grade nickel sulphate solutions is from 10 to 200 g/1, more preferably from 50 to 150 g/1, and most preferably from 80 to 120 g/1 Ni 2+ ions per litre pregnant leach solution/battery grade nickel sulphate solution.
  • the initial sulphuric acid contents/acid strengths in the “virgin” leach solution will typically be in the range from about 20 g/1 to 400 g/1.
  • the determination of the required initial sulphuric acid contents/acid strengths in the “virgin” leach solution to arrive at a pregnant leach solution containing a specific nickel ion content and maximum amount of unreacted sulphuric acid is a matter of simple stoichiometric considerations and calculations within basal common general knowledge in the field and needs no further description.
  • onset-level, Conset, of oxidising agent content in the aqueous leach solution causing a nickel surface passivation effect refers to the content (concentration) of oxidising agent in the aqueous leach solution at which the leach rate of the nickel is observed to drop rapidly, (probably) due to the surface passivation effect described above caused by formation of a layer of NiO on the surface of the nickel.
  • concentration concentration of oxidising agent in the aqueous leach solution at which the leach rate of the nickel is observed to drop rapidly, (probably) due to the surface passivation effect described above caused by formation of a layer of NiO on the surface of the nickel.
  • this onset-level is dependent on the acid strength of the aqueous leach solution, and both the acid and oxidising agent are consumed during a leach, it would be practical to have a mathematical relation describing this onset-level for all relevant acid strengths (ranges of acid content, pH-ranges) to provide the actual onset-level of oxidising agent at given (e.g. measured) acid content/ strength in the aqueous leach solution in a method for regulating the content of oxidising agent and preventing adding so much oxidising agent to trigger this surface passivation effect of the nickel.
  • the person skilled in the art may derive a mathematical relation describing the onset level of oxidising agent over a representative range of acids strengths at given leach temperatures by performing a curve fitting using linear or non-linear regression analysis of literature reported data of the onset level of oxidising agent.
  • Representative range of acids strengths relates to the range of acid strengths being actual for the intended leach process from the initial “virgin” leach solution to the final pregnant leach solution, which may be determined as discussed above.
  • the oxidising agent may advantageously be oxygen, ozone or hydrogen peroxide, preferably hydrogen peroxide.
  • the container 100 is made of a metal, preferably a stainless- steel alloy. However, any material having the mechanical strength to carry and hold the solid to be dissolved and the aqueous leach solution may be applied.
  • the inner wall of the container 100 may be lined with a corrosion resistant lining, such as e.g. a rubber, a polyethylene, a polytetrafluoroethylene, or a vinyl ester.
  • enriching means an increase in the concentration of the solute/dissolved nickel sulphate in the aqueous leach solution caused by the leach/dissolution of the nickel metal.
  • pregnant or rich aqueous leach solution means an aqueous leach solution having a high concentration of dissolved nickel sulphate, typically at a concentration level being acceptable as the intended nickel sulphate product.
  • lean aqueous leach solution as used herein means an aqueous leach solution containing no or only a relatively small concentration of dissolved nickel sulphate.
  • the dissolution reactor may further comprise:
  • a second dissolution chamber 201-2 comprising a lower inlet second 202-2 for an aqueous leach solution, an upper inlet 203-2 for nickel, and an outlet 204-2, for aqueous leach solution located below the inlet 203-2 and above the second inlet 202-2, and
  • the outlet 204-1 of the first dissolution chamber 201-1 is connected to the second inlet 202-2 of the second dissolution chamber 201-2, and
  • the process plant according to the third aspect of the invention may further comprise a series of four, five, six, seven or eight dissolution chamber, each having a lower inlet for a aqueous leach solution, an upper inlet for solid compound, and an outlet for aqueous leach solution located below the inlet and above the inlet as described above, and which is serially interconnected by having the outlet of each dissolution chamber except the last of the series connected to the inlet of the next dissolution chamber, and where the inlet of the first dissolution chamber of the series is connected to the first liquid conduit and the outlet of the last dissolution chamber of the series is connected to the second liquid conduit.
  • Figure 1 is a diagram presenting empirically determined onset-levels of hydrogen peroxide over a range of acid strengths given as pH causing a surface passivation of nickel in an aqueous leach solution comprising sulphuric acid and hydrogen peroxide.
  • Figure 2 is similar diagram as given in figure 1, but which also presents an example of the maximum level of hydrogen peroxide to be obtained by the regulation method according to the present invention.
  • Figure 6 is a drawing schematically illustrating another example embodiment of a process plant according to the third aspect of the invention utilising one dissolution chamber and two storage containers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Automation & Control Theory (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

La présente invention concerne un procédé et un appareil pour optimiser le taux de dissolution de nickel dans une solution de lixiviation aqueuse comprenant de l'acide sulfurique et un agent oxydant, l'optimisation étant obtenue en fournissant une relation mathématique décrivant un niveau initial de teneur en agent oxydant dans la solution de lixiviation aqueuse provoquant un effet de passivation de surface de nickel, puis en régulant l'ajout d'agent oxydant à la solution de lixiviation aqueuse pour que le niveau soit proche, mais quelque peu inférieur au niveau initial de l'agent oxydant pendant le processus de lixiviation.
PCT/EP2024/076629 2023-10-02 2024-09-23 Procédé et appareil de lixiviation de nickel Pending WO2025073525A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20231053 2023-10-02
NO20231053A NO20231053A1 (en) 2023-10-02 2023-10-02 Method and apparatus for leaching nickel

Publications (1)

Publication Number Publication Date
WO2025073525A1 true WO2025073525A1 (fr) 2025-04-10

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PCT/EP2024/076629 Pending WO2025073525A1 (fr) 2023-10-02 2024-09-23 Procédé et appareil de lixiviation de nickel

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WO (1) WO2025073525A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1460402A (en) * 1974-02-05 1977-01-06 Imetal Method of reclaiming nickel values from a ferro-nickel alloy
WO2013077296A1 (fr) 2011-11-22 2013-05-30 住友金属鉱山株式会社 Procédé de fabrication de sulfate de nickel de haute pureté
WO2019090389A1 (fr) 2017-11-10 2019-05-16 Bhp Billiton Nickel West Pty Ltd Production de sulfate de nickel de pureté élevée
CN110735041A (zh) 2019-08-28 2020-01-31 广西银亿高新技术研发有限公司 一种循环催化氧化酸浸难溶金属废料的工艺方法
CN111689530A (zh) * 2020-05-25 2020-09-22 荆门市格林美新材料有限公司 一种硫酸镍溶液的生产方法和装置
EP3967661A1 (fr) 2020-09-09 2022-03-16 Northvolt AB Procédé de préparation de solutions de sulfate de métal de qualité de batterie
CA3231411A1 (fr) * 2021-09-10 2023-03-16 Hirofumi Shouji Procede de traitement d'un alliage
WO2023066656A1 (fr) * 2021-10-22 2023-04-27 Basf Se Procédés et systèmes de production d'un produit de sulfate de nickel
NO20220405A1 (en) 2022-04-01 2023-10-02 Glencore Nikkelverk As Continuous dissolution reactor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITBO20110573A1 (it) * 2011-10-06 2013-04-07 Marchi & Brevetti Interprise S R L Con Unico Soci Dispositivo e metodo per la dissoluzione di una sostanza chimica solida in acqua
JP7183765B2 (ja) * 2018-12-20 2022-12-06 住友金属鉱山株式会社 硫酸ニッケル溶液の製造方法および製造装置
JP7415221B2 (ja) * 2019-11-18 2024-01-17 住友金属鉱山株式会社 硫酸ニッケル溶液の製造装置および製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1460402A (en) * 1974-02-05 1977-01-06 Imetal Method of reclaiming nickel values from a ferro-nickel alloy
WO2013077296A1 (fr) 2011-11-22 2013-05-30 住友金属鉱山株式会社 Procédé de fabrication de sulfate de nickel de haute pureté
WO2019090389A1 (fr) 2017-11-10 2019-05-16 Bhp Billiton Nickel West Pty Ltd Production de sulfate de nickel de pureté élevée
CN110735041A (zh) 2019-08-28 2020-01-31 广西银亿高新技术研发有限公司 一种循环催化氧化酸浸难溶金属废料的工艺方法
CN111689530A (zh) * 2020-05-25 2020-09-22 荆门市格林美新材料有限公司 一种硫酸镍溶液的生产方法和装置
EP3967661A1 (fr) 2020-09-09 2022-03-16 Northvolt AB Procédé de préparation de solutions de sulfate de métal de qualité de batterie
CA3231411A1 (fr) * 2021-09-10 2023-03-16 Hirofumi Shouji Procede de traitement d'un alliage
WO2023066656A1 (fr) * 2021-10-22 2023-04-27 Basf Se Procédés et systèmes de production d'un produit de sulfate de nickel
NO20220405A1 (en) 2022-04-01 2023-10-02 Glencore Nikkelverk As Continuous dissolution reactor

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Abeggs Handbuch", 1939
ABEGG ET AL.: "Handbuch der Anorganischen Chemie", NATURE, vol. 140, no. 1081, 1937, pages 358, Retrieved from the Internet <URL:https://doi.org/10.1038/1401081a0>
BILCZUK DARIO ET AL: "Kinetic study of the dissolution of metallic nickel in sulphuric acid solutions in the presence of different oxidants", CANADIAN JOURNAL OF CHEMICAL ENGINEERING, vol. 94, no. 10, 5 August 2016 (2016-08-05), Hoboken, USA, pages 1872 - 1879, XP055949572, ISSN: 0008-4034, DOI: 10.1002/cjce.22576 *
BILCZUK ET AL.: "Kinetic study of the dissolution of metallic nickel in sulphuric acid solutions in the presence of different oxidants", THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, vol. 94, October 2016 (2016-10-01), pages 1872 - 1879, XP055949572, Retrieved from the Internet <URL:https://doi.org/10.1002/cjce.22576> DOI: 10.1002/cjce.22576
JENSSEN ET AL.: "The Minerals, Metals & Materials Series", SPRINGER, article "Filtration Properties of Ferric Hydroxide Precipitate in Nickel Production"

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