[go: up one dir, main page]

WO2025000491A1 - Procédé d'amélioration de la qualité de l'hydroxyde de nickel-cobalt - Google Patents

Procédé d'amélioration de la qualité de l'hydroxyde de nickel-cobalt Download PDF

Info

Publication number
WO2025000491A1
WO2025000491A1 PCT/CN2023/105022 CN2023105022W WO2025000491A1 WO 2025000491 A1 WO2025000491 A1 WO 2025000491A1 CN 2023105022 W CN2023105022 W CN 2023105022W WO 2025000491 A1 WO2025000491 A1 WO 2025000491A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
manganese
cobalt
quality
improving
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/CN2023/105022
Other languages
English (en)
Chinese (zh)
Inventor
许开华
刘维
张坤
彭亚光
金国泉
刘文泽
许鹏云
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.)
Pt Gem Indonesia New Energy Materials
Pt Qmb New Energy Materials
GEM Co Ltd Korea
Original Assignee
Pt Gem Indonesia New Energy Materials
Pt Qmb New Energy Materials
GEM Co Ltd Korea
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 Pt Gem Indonesia New Energy Materials, Pt Qmb New Energy Materials, GEM Co Ltd Korea filed Critical Pt Gem Indonesia New Energy Materials
Priority to PCT/CN2023/105022 priority Critical patent/WO2025000491A1/fr
Priority to CN202380009962.0A priority patent/CN117083248A/zh
Publication of WO2025000491A1 publication Critical patent/WO2025000491A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to the field of hydrometallurgy, and in particular to a method for improving the quality of nickel cobalt hydroxide.
  • patent CN104140130B discloses a nickel-cobalt hydroxide product and its preparation method.
  • the core idea is to use sodium hydroxide as a precipitant to precipitate nickel-cobalt hydroxide, then carry out an alkali-transfer process, and continuously circulate alkali-transfer and crystal return.
  • the alkali-transfer process will lead to local over-alkali, producing high-valent manganese oxides (such as manganese dioxide, manganese tetraoxide, etc.).
  • Patent CN114854987B discloses a nickel-cobalt precipitation method for a laterite nickel ore acid leaching solution for removing iron and aluminum. The core idea is to add a reducing agent before precipitating nickel and cobalt to keep the solution in a reducing atmosphere, thereby preventing manganese from being oxidized into high-price insoluble oxides during the over-alkali process.
  • the purpose of the present invention is to overcome the above technical deficiencies, provide a method for improving the quality of nickel cobalt hydroxide, and solve the technical problems of nickel cobalt hydroxide production cost and high manganese content in the prior art.
  • the present invention provides a technical solution for improving the quality of nickel cobalt hydroxide, which comprises the following steps: S1, the liquid after iron and aluminum removal is treated with a mixture of SO2 and air to remove manganese, A manganese oxide product and a first manganese-removed liquid are obtained; S2, a precipitant A is added to the first manganese-removed liquid to carry out a one-stage nickel-cobalt precipitation reaction, and after dense separation, an underflow and a first overflow are obtained, and the underflow is divided into two parts, a first underflow and a second underflow, wherein the first underflow is washed and filtered to obtain a nickel-cobalt hydroxide product; S3, the first overflow is subjected to a two-stage nickel-cobalt precipitation reaction, and the reactants of the second stage nickel-cobalt precipitation are densely separated to obtain a third underflow and a second overflow; S4, the second overflow is first mixed
  • the beneficial effects of the present invention include:
  • the present invention after removing iron and aluminum, sulfur dioxide and air are directly used to oxidize manganese in the liquid after removing iron and aluminum, and the manganese is directly converted into manganese oxides such as manganese dioxide, so that manganese is removed first and the cost of continuously adding a reducing agent is saved; the liquid after removing manganese is treated to form an alkali-transforming crystal slurry, which itself contains less manganese and will not produce insoluble and non-reactive manganese oxides due to the problem of excessive alkali, thereby reducing the manganese content in the nickel cobalt hydroxide product and improving the quality of the nickel cobalt hydroxide product.
  • Fig. 1 is a process flow chart of the present invention
  • FIG. 2 is a process flow chart of the present invention using two manganese removal processes.
  • the present invention provides a method for improving the quality of nickel cobalt hydroxide, which is applicable to the hydrometallurgical process of preparing nickel cobalt precipitates, and specifically comprises the following steps:
  • the liquid after iron and aluminum removal first undergoes a manganese removal process: SO2 produced by the sulfuric acid plant is mixed with air, and the manganese in the liquid after iron and aluminum removal is oxidized and removed within the pH range of 4-5 to obtain a manganese oxide product and the first liquid after manganese removal.
  • the first overflow undergoes a second-stage nickel-cobalt precipitation reaction, and the reactants of the second-stage nickel-cobalt precipitation undergo a dense separation to obtain a third underflow and a second overflow; the third underflow enters a neutralization stage for cyclic leaching;
  • the second bottom flow is used as a seed to go to the seed tank; the second overflow and the precipitant B are first mixed to perform a mixed alkali-transfer reaction, and then enter the seed tank together with the second bottom flow to obtain an alkali-transfer slurry, and the alkali-transfer slurry returns to a nickel-cobalt precipitation reaction tank for a nickel-cobalt precipitation reaction.
  • the iron-aluminum-removed liquid in step S1 is an iron-aluminum-removed solution of laterite nickel ore acid leaching, which mainly contains components such as 2.5-6 g/L nickel, 0.1-0.5 g/L cobalt, 1-4 g/L manganese, and 3-15 g/L magnesium.
  • step S1 the pH value is adjusted to 4-5 by using sodium hydroxide.
  • the mixing volume ratio of SO2 to air in step S1 is 1:(20-100), preferably 1:(20-50).
  • the manganese removal rate is controlled at 10-50%, more preferably 30-40%, to avoid excessive manganese removal and loss of more nickel and cobalt.
  • step S2 the precipitant A is added only when the nickel-cobalt precipitation reaction is first performed; the ratio of the total molar amount of nickel and cobalt in the first manganese-removed liquid to the molar amount of OH - in the precipitant A is 1:(1.4-2.4), preferably 1:(1.8-2).
  • the separation ratio of the first underflow and the second underflow in step S2 is: 1:(1-10), more preferably 1:(2-10), and most preferably 1:(6-8).
  • the second-stage nickel-cobalt precipitation reaction in step S3 specifically includes: adding lime milk to the first overflow to adjust the pH to 7.8-8.
  • step S4 the ratio of the molar amount of Mg 2+ in the second overflow to the total molar amount of nickel and cobalt in the first manganese-removed liquid is controlled to be (0.6-1.2):1, more preferably 0.8-0.9:1.
  • the precipitant B is sodium hydroxide
  • the ratio of the total molar amount of nickel and cobalt in the first manganese-removed liquid (the first-stage nickel-cobalt precipitation feed) to the molar amount of OH - in the precipitant B is 1:(1.4-2.2), and more preferably 1:(1.6-1.8).
  • step S4 the second overflow is subjected to a manganese removal process to obtain a manganese oxide product and a second manganese-removed liquid, and the second manganese-removed liquid is mixed with a precipitant B to perform a alkali conversion reaction instead of the second overflow.
  • the manganese in the second manganese-removed liquid is further reduced relative to the second overflow, and is substantially completely removed.
  • the present invention first uses a mixture of SO2 and air to oxidize the manganese in the liquid after iron and aluminum removal into manganese oxides such as manganese dioxide, thereby removing manganese;
  • a precipitant A is added to carry out a two-stage nickel-cobalt precipitation reaction, and OH - is provided by the precipitant A to generate nickel-cobalt hydroxide;
  • the second overflow in step S4 obtained from the second stage nickel-cobalt precipitation reaction
  • the precipitant B strong base such as NaOH
  • the alkali conversion formed is mainly magnesium hydroxide, which is a process from a strong base to a weak base:
  • Part of the underflow obtained from the first stage nickel-cobalt precipitation reaction is used as a seed crystal and mixed with the reactants after the alkali transfer reaction to obtain the alkali transfer crystal slurry after manganese removal, and then returned to the first stage nickel-cobalt precipitation reaction: on the one hand, the alkali transfer crystal slurry itself has less manganese and will not bring insoluble and non-reactive manganese oxides due to the problem of over-alkali, thereby reducing the manganese content in the nickel-cobalt hydroxide product; on the other hand, magnesium hydroxide acts as a precipitant in the first stage nickel-cobalt precipitation. At the same time, magnesium hydroxide is a weak base, which effectively avoids the local over-alkali phenomenon that is easy to occur in the traditional direct use of strong alkali as a precipitant.
  • the overflow liquid after the second stage of nickel and cobalt precipitation is used for alkali conversion, that is, the liquid after manganese removal is used for alkali conversion, which can eliminate the insoluble manganese oxides caused by local over-alkali and further reduce the manganese content of nickel and cobalt hydroxide products;
  • Manganese open circuit increases some manganese products to offset or reduce the cost of open circuit processing
  • the actual nickel-cobalt precipitation agent is weak base magnesium hydroxide, and by controlling the amount of returned crystal seeds, the particle size distribution range of nickel-cobalt hydroxide particles can be effectively reduced, the filtering and washing performance of nickel-cobalt hydroxide can be increased, and the water content of nickel-cobalt hydroxide products can be reduced.
  • the method of the invention realizes the preparation of high-quality nickel-cobalt precipitates by optimizing precipitation conditions and controlling precipitation process.
  • iron and aluminum removal liquid all uses 3.5g/L nickel, 0.33g/L cobalt, 2.75g/L manganese, and 5.67g/L magnesium.
  • the present invention provides a method for improving the quality of nickel cobalt hydroxide, comprising the following steps:
  • the de-iron and de-aluminum liquid first undergoes a manganese removal process: SO2 produced by a sulfuric acid plant is mixed with air at a volume ratio of 1:30, and then the de-iron and de-aluminum liquid is introduced within a pH range of 4-5. The reaction time is controlled to oxidize and remove about 40% of the manganese in the de-iron and de-aluminum liquid to obtain a manganese oxide product and the first de-manganese liquid.
  • the first manganese-removed liquid is subjected to a nickel-cobalt precipitation reaction, sodium hydroxide is added during the first reaction, and the ratio of the total molar amount of nickel and cobalt in the first manganese-removed liquid to the molar amount of OH- is 1:1.8;
  • the reactants after the first nickel-cobalt precipitation reaction are densely separated to obtain an underflow and a first overflow, and the underflow is divided into a first underflow and a second underflow, and the separation ratio of the first underflow and the second underflow is 1:6, wherein the first underflow is washed and filtered to obtain a nickel-cobalt hydroxide product;
  • the second manganese-removed liquid is first mixed with sodium hydroxide to carry out a mixed alkali-transfer reaction, wherein the ratio of the amount of sodium hydroxide to the total molar amount of nickel and cobalt in the first manganese-removed liquid is 1.8:1, and the ratio of the molar amount of Mg2 + in the second manganese-removed liquid to the total molar amount of nickel and cobalt in the first manganese-removed liquid is controlled to be 0.8:1; and then added to the seed tank together with the second underflow to obtain an alkali-transfer slurry, and the alkali-transfer slurry is returned to a first nickel-cobalt precipitation reaction tank for a first nickel-cobalt precipitation reaction.
  • Example 1 The only difference from Example 1 is that the separation ratio of the first underflow and the second underflow is adjusted to 1:4, and the other steps and conditions are the same as those in Example 1.
  • the specific ratios and test results are shown in Table 1 below.
  • Example 1 The only difference from Example 1 is that the separation ratio of the first underflow and the second underflow is adjusted to 1:8, and the other steps and conditions are the same as those in Example 1.
  • the specific ratios and test results are shown in Table 1 below.
  • Example 1 The only difference from Example 1 is that the separation ratio of the first underflow and the second underflow is adjusted to 1:10, and the other steps and conditions are the same as those in Example 1.
  • the specific ratios and test results are shown in Table 1 below.
  • Example 1 The only difference from Example 1 is that the separation ratio of the first underflow and the second underflow is adjusted to 1:2, and the other steps and conditions are the same as those in Example 1.
  • the specific ratios and test results are shown in Table 1 below.
  • the separation ratio of the first underflow and the second underflow can regulate the particle size distribution range of the nickel cobalt hydroxide particles.
  • the preferred separation ratio of the first underflow and the second underflow in the present invention is 1: (2 to 10), and the most preferred ratio is 1: (6 to 8).
  • Example 2 The only difference from Example 1 is that the manganese removal rate of the first manganese removal is adjusted to 20%, and the other steps and conditions are the same as those of Example 1. The specific proportions and test results are shown in Table 2 below.
  • Example 2 The only difference from Example 1 is that the manganese removal rate of the first manganese removal is adjusted to 30%, and the other steps and conditions are the same as those of Example 1. The specific proportions and test results are shown in Table 2 below.
  • the Mn content in the nickel cobalt hydroxide product can be regulated by adjusting different manganese removal rates.
  • the preferred manganese removal rate of the present invention is 40%.
  • Example 1 The only difference from Example 1 is that the manganese removal process in step S1 is removed, and the other steps and conditions are the same as those in Example 1.
  • Example 1 The only difference from Example 1 is that the manganese removal rate in step S1 is controlled at 50%, and the other steps and conditions are the same as those in Example 1.
  • the manganese removal rate is preferably controlled at 30-40%.
  • the present invention directly uses sulfur dioxide and air to oxidize manganese after removing iron and aluminum, and directly converts it into manganese oxides such as manganese dioxide, thereby removing manganese first and saving the cost of continuously adding reducing agent; the alkali-converted crystal slurry after manganese removal has a low manganese content itself, and will not produce insoluble and non-reactive manganese oxides due to the problem of excessive alkali, thereby reducing the manganese content in the nickel cobalt hydroxide product and improving the quality of the nickel cobalt hydroxide product.

Landscapes

  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé d'amélioration de la qualité de l'hydroxyde de nickel-cobalt. Dans la présente invention, du fer et de l'aluminium sont éliminés, puis du dioxyde de soufre et de l'air sont directement utilisés pour oxyder le manganèse dans un liquide dont le fer et l'aluminium ont été éliminés, pour convertir directement le manganèse en oxydes de manganèse tels que du dioxyde de manganèse ; le manganèse est éliminé en premier, de sorte que les coûts d'addition continue d'un agent réducteur sont économisés ; et le liquide dont le manganèse a été éliminé est traité pour être une bouillie de cristaux de conversion alcali dont la teneur en manganèse est réduite, et les oxydes de manganèse non réactifs insolubles ne seraient pas produits en raison d'un excès d'alcali, de sorte que la teneur en manganèse dans les produits d'hydroxyde de nickel-cobalt est réduite, et la qualité des produits d'hydroxyde de nickel-cobalt est améliorée.
PCT/CN2023/105022 2023-06-30 2023-06-30 Procédé d'amélioration de la qualité de l'hydroxyde de nickel-cobalt Pending WO2025000491A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2023/105022 WO2025000491A1 (fr) 2023-06-30 2023-06-30 Procédé d'amélioration de la qualité de l'hydroxyde de nickel-cobalt
CN202380009962.0A CN117083248A (zh) 2023-06-30 2023-06-30 一种氢氧化镍钴质量提升方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2023/105022 WO2025000491A1 (fr) 2023-06-30 2023-06-30 Procédé d'amélioration de la qualité de l'hydroxyde de nickel-cobalt

Publications (1)

Publication Number Publication Date
WO2025000491A1 true WO2025000491A1 (fr) 2025-01-02

Family

ID=88719887

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/105022 Pending WO2025000491A1 (fr) 2023-06-30 2023-06-30 Procédé d'amélioration de la qualité de l'hydroxyde de nickel-cobalt

Country Status (2)

Country Link
CN (1) CN117083248A (fr)
WO (1) WO2025000491A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117858849A (zh) * 2023-11-29 2024-04-09 青美邦新能源材料有限公司 硫代硫酸钠作为沉镍钴辅助剂的应用
CN117836442A (zh) * 2023-11-30 2024-04-05 青美邦新能源材料有限公司 一种降低红土镍矿mhp产品含水率并提高其锰含量的方法
CN119487225A (zh) * 2024-09-29 2025-02-18 Esg新能源材料有限公司 一种沉mhp用沉淀剂的制备系统
CN119571082B (zh) * 2025-02-10 2025-04-29 中国恩菲工程技术有限公司 氢氧化镍钴中间产品中主成分的提升方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080203032A1 (en) * 2007-02-28 2008-08-28 Inco Limited Method for removing manganese from nickel laterite waste liquors
US20110135547A1 (en) * 2009-02-04 2011-06-09 Sumitomo Metal Mining Co., Ltd. Method for recovering nickel from sulfuric acid aqueous solution
CN110484727A (zh) * 2019-09-19 2019-11-22 中国恩菲工程技术有限公司 锰离子的去除方法及其在湿法冶金炼锌领域中的应用
CN113073207A (zh) * 2021-03-23 2021-07-06 中国恩菲工程技术有限公司 从高镁型红土镍矿中提取有价金属的方法
CN114854987A (zh) * 2022-07-11 2022-08-05 中国恩菲工程技术有限公司 红土镍矿酸浸除铁铝溶液的镍钴沉淀方法
CN116334417A (zh) * 2023-03-14 2023-06-27 西安建筑科技大学 一种高效净化处理镍钴锰共存的混合溶液中锰的工艺方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102061387A (zh) * 2011-01-06 2011-05-18 广西银亿科技矿冶有限公司 一种二段式沉镍方法
CN106086409B (zh) * 2016-08-03 2018-05-11 中国恩菲工程技术有限公司 处理沉镍钴后液的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080203032A1 (en) * 2007-02-28 2008-08-28 Inco Limited Method for removing manganese from nickel laterite waste liquors
US20110135547A1 (en) * 2009-02-04 2011-06-09 Sumitomo Metal Mining Co., Ltd. Method for recovering nickel from sulfuric acid aqueous solution
CN110484727A (zh) * 2019-09-19 2019-11-22 中国恩菲工程技术有限公司 锰离子的去除方法及其在湿法冶金炼锌领域中的应用
CN113073207A (zh) * 2021-03-23 2021-07-06 中国恩菲工程技术有限公司 从高镁型红土镍矿中提取有价金属的方法
CN114854987A (zh) * 2022-07-11 2022-08-05 中国恩菲工程技术有限公司 红土镍矿酸浸除铁铝溶液的镍钴沉淀方法
CN116334417A (zh) * 2023-03-14 2023-06-27 西安建筑科技大学 一种高效净化处理镍钴锰共存的混合溶液中锰的工艺方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG, WENSHENG ET AL.: "Oxidative Precipitation of Manganese with SO2/O2 and Separation from Cobalt and Nickel", HYDROMETALLURGY, vol. 63, no. 2, 31 December 2002 (2002-12-31), XP004336033, ISSN: 0304-386X, DOI: 10.1016/S0304-386X(01)00205-5 *

Also Published As

Publication number Publication date
CN117083248A (zh) 2023-11-17

Similar Documents

Publication Publication Date Title
WO2025000491A1 (fr) Procédé d'amélioration de la qualité de l'hydroxyde de nickel-cobalt
CN114854987B (zh) 红土镍矿酸浸除铁铝溶液的镍钴沉淀方法
EP4286325A1 (fr) Méthode de recyclage de ressources d'alliage nickel-fer et son utilisation
CN112779419B (zh) 一种镍钴锰铜溶液常压除铁铝硅的方法
CN114214517B (zh) 去除锂电池正极浸出液中氟的方法
CN106086409B (zh) 处理沉镍钴后液的方法
WO2025000492A1 (fr) Procédé de préparation en continu de précipité d'hydroxyde mixte au moyen d'hydrométallurgie de minerai latérite-nickel
CN116377243A (zh) 一种镍钴氢氧化物原料分离镍钴锰的方法
CN115109943A (zh) 从氯化铜锰锌钴溶液中分步提取回收铜、锌、钴、锰金属的方法
CN113355540B (zh) 一种从含钪氢氧化镍钴中回收钪的方法
CN116463508B (zh) 一种处理镍钴氢氧化物的方法
CN113430394A (zh) 镍铁合金分离镍和铁的方法和制备电池级硫酸镍的方法
WO2025000369A1 (fr) Procédé d'élimination de silicium et procédé de réutilisation de silicium dans un processus de lixiviation de précipité d'hydroxyde mixte
CN114959302B (zh) 采用红土镍矿制备硫酸镍/钴的方法
CN116411164A (zh) 一种红土镍矿与镍锍合金协同浸出的方法
WO2025152926A1 (fr) Procédé de traitement de minerais de nickel latéritiques
CN110668502A (zh) 一种提纯制备硫酸锰的方法
CN110092423B (zh) 一种氧化镍快速溶解、镍皂脱酸除杂生产硫酸镍溶液的方法
US12297125B2 (en) Method for preparing battery-grade nickel-cobalt-manganese sulfate crystals from low nickel matte
CN119176532B (zh) 一种利用镍铁合金制备电池级磷酸铁和电池级硫酸镍的方法
CN119118227A (zh) 从硫酸镍溶液制备过程中去除硅的方法
CN111302400A (zh) 一种提纯制备硫酸锰的方法
CN118019865A (zh) 红土镍矿高压浸出液制备电池级镍的两步萃取工艺
WO2025111905A1 (fr) Procédé de récupération de mn, mg, ni et co à partir de résidus de minerai de latérite-nickel
WO2025111906A1 (fr) Procédé de réduction de la teneur en eau d'un produit mhp de minerai de latérite-nickel et d'augmentation de sa teneur en manganèse

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23942989

Country of ref document: EP

Kind code of ref document: A1