CN111455175A - Method for removing calcium and magnesium from nickel-cobalt-manganese solution - Google Patents

Method for removing calcium and magnesium from nickel-cobalt-manganese solution Download PDF

Info

Publication number
CN111455175A
CN111455175A CN202010518668.0A CN202010518668A CN111455175A CN 111455175 A CN111455175 A CN 111455175A CN 202010518668 A CN202010518668 A CN 202010518668A CN 111455175 A CN111455175 A CN 111455175A
Authority
CN
China
Prior art keywords
nickel
cobalt
magnesium
calcium
solution
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
CN202010518668.0A
Other languages
Chinese (zh)
Inventor
郑朝振
刘三平
王海北
秦树辰
张学东
邓超群
周起帆
王玉芳
谢铿
苏立峰
李强
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.)
BGRIMM Technology Group Co Ltd
Original Assignee
BGRIMM Technology Group Co 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
Application filed by BGRIMM Technology Group Co Ltd filed Critical BGRIMM Technology Group Co Ltd
Priority to CN202010518668.0A priority Critical patent/CN111455175A/en
Publication of CN111455175A publication Critical patent/CN111455175A/en
Pending legal-status Critical Current

Links

Images

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
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method for removing calcium and magnesium from a nickel-cobalt-manganese solution, belonging to the field of nickel-cobalt hydrometallurgy, which comprises the following operation steps: (1) heating the nickel-cobalt-manganese solution to a certain temperature, adding a certain amount of precipitator, and keeping for a certain time; the precipitator is one or a mixture of more of nickel fluoride, cobalt fluoride and manganese fluoride; (2) carrying out liquid-solid separation on the ore pulp to obtain a solution and calcium and magnesium removing slag; (3) the solution is processed by subsequent processes to obtain nickel products and cobalt products. The invention overcomes the problems of calcium sulfate crystallization and difficult separation caused by P507 extraction and magnesium removal in the traditional P204 extraction and calcium removal method, and is an efficient and green method for removing calcium and magnesium from a nickel-cobalt solution.

Description

Method for removing calcium and magnesium from nickel-cobalt-manganese solution
Technical Field
The invention belongs to the technical field of nickel-cobalt hydrometallurgy, and relates to a method for removing calcium and magnesium from a nickel-cobalt-manganese solution.
Background
The mixed nickel cobalt hydroxide is a nickel cobalt intermediate product obtained by carrying out high-pressure acid leaching, impurity removal, neutralization and precipitation on the laterite nickel ore, and is an important production raw material for producing products such as battery-grade nickel sulfate, battery-grade cobalt sulfate and the like. The mixed nickel hydroxide and cobalt hydroxide are used to produce battery-grade nickel sulfate and battery-grade cobalt sulfate by a hydrometallurgical process, and the procedures generally comprise sulfuric acid leaching, neutralization and iron and aluminum removal, P204 extraction and impurity removal, P507 nickel, cobalt and magnesium separation and other process steps, such as the method adopted by the companies of Jiangxi river tungsten, Jinchuan and Huayouyi industries.
Conventionally, in the aspect of removing calcium and magnesium from a nickel-cobalt solution, a fluoride precipitation method, a solvent extraction method and the like are mainly used. Fluoride precipitation method using MgF2And CaF2And (3) adding NaF reagent to remove calcium and magnesium ions in the solution, wherein the solubility of the calcium and magnesium ions is very low. The disadvantage of this method is that a large amount of sodium ions is introduced into the solution. The solvent extraction method adopts P204 to extract and remove impurities such as Ca, Mn, Cu, Zn and the like, and P507 to separate nickel, cobalt and magnesium from P204 raffinate to produce battery-grade nickel sulfate and battery-grade cobalt sulfate products, which is also a commonly used method at present. The extraction method for removing calcium and magnesium has the following problems: the P204 is adopted for extraction and calcium removal, a large amount of calcium sulfate crystals block an extraction tank and a pipeline, and the calcium sulfate crystals need to be removed periodically; the P207 is adopted to separate magnesium, a long extraction stage number is needed, and the separation difficulty is also high.
Disclosure of Invention
The invention provides a method for removing calcium and magnesium from a nickel-cobalt-manganese solution, which utilizes a precipitator to remove calcium and magnesium, and the solution after calcium and magnesium removal is sent to the next step for extraction, impurity removal and separation. The new process adopts one or more of nickel fluoride, cobalt fluoride and manganese fluoride as calcium and magnesium precipitating agents, the dosage of the precipitating agents is added according to the theoretical quantity of calcium and magnesium, new impurity ions are not introduced, the influence of calcium sulfate crystallization on P204 extraction can be greatly reduced, the operation quantity of P507 extraction and magnesium separation is reduced, and the method is an efficient and green method for removing calcium and magnesium from a nickel-cobalt solution.
The invention solves the technical problem of providing a method for removing calcium and magnesium from a nickel-cobalt-manganese solution, which adopts one or more of nickel fluoride, cobalt fluoride and manganese fluoride as a calcium-magnesium precipitator, adds the amount of the precipitator according to the theoretical amount of calcium and magnesium, does not introduce new impurity ions, can greatly reduce the influence of calcium sulfate crystallization on P204 extraction, reduces the operation amount of P507 extraction and separation of magnesium, and is an efficient and green method for removing calcium and magnesium from the nickel-cobalt solution.
The technical scheme adopted by the invention is as follows:
a method for removing calcium and magnesium from a nickel-cobalt-manganese solution comprises the following steps:
(1) heating the nickel-cobalt-manganese solution to a certain temperature, adding a precipitator, and keeping for a certain time; the precipitator is one or more of nickel fluoride, cobalt fluoride and manganese fluoride;
(2) carrying out liquid-solid separation on the ore pulp to obtain a solution and calcium and magnesium removing slag;
(3) the solution is processed by subsequent processes to obtain nickel products and cobalt products.
Further, the adding amount of the precipitating agent in the step (1) is that the ratio of the amount of fluorine added into the precipitating agent to the amount of calcium and magnesium ion-containing substances in the nickel-cobalt solution is 2: 1.
Further, the nickel-cobalt-manganese solution in the step (1) is a sulfate or chloride system.
Further, the nickel-cobalt-manganese solution in the step (1) contains one or more ions of nickel, cobalt and manganese.
Further, the certain temperature in the step (1) is 25-95 ℃.
Further, the certain time in the step (1) is 0.5-10 hours.
The invention provides a method for removing calcium and magnesium from a nickel-cobalt-manganese solution, which relates to the following reaction principle:
the nickel fluoride, cobalt fluoride and manganese fluoride are easy to dissolve in water, and the added precipitator can decompose fluorine ions in a solution system. Calcium fluoride and magnesium fluoride are insoluble in water, and fluoride ions in the precipitator and calcium and magnesium ions in the nickel-cobalt-manganese solution are combined to generate precipitates to be removed. The process takes place as follows:
2F-+Ca2+＝CaF2↓
2F-+Mg2+＝MgF2↓
thereby realizing the removal of calcium and magnesium from the nickel-cobalt-manganese solution.
The invention has the following advantages: one or more of nickel fluoride, cobalt fluoride and manganese fluoride are used as a calcium-magnesium precipitator, the amount of the precipitator is added according to the theoretical amount of calcium and magnesium, no new impurity ions are introduced, the influence of calcium sulfate crystallization on P204 extraction can be greatly reduced, and the operation amount of P507 extraction separation of magnesium is reduced. The method has the advantages of simple process, strong operability and easy industrial implementation.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
Example 1
The iron-removed liquid of the nickel-cobalt-manganese solution in a certain plant comprises the following components:
element(s) Al Fe Ca Co Cr Cu Mg Mn Ni Zn
component/(g/L) 0.06 0.004 0.56 9.09 0.025 0.24 1.56 3.54 95.7 1.73
Heating the solution 500m L to 30 deg.C, adding 3.78g nickel fluoride according to theoretical amount of calcium and magnesium, removing calcium and magnesium for 6h, separating liquid from solid to obtain calcium and magnesium residue and calcium and magnesium-removed liquid, wherein the calcium and magnesium-removed liquid contains calcium 0.01 g/L and magnesium 0.02 g/L.
Example 2
The nickel-cobalt-manganese solution of a certain factory contains 0.54 g/L of calcium and 2.34 g/L of magnesium, the solution 500m L is heated to 70 ℃, 5.31g of nickel fluoride is added according to the theoretical calculation of calcium and magnesium, the time for removing calcium and magnesium is 5 hours, the liquid-solid separation is carried out to obtain calcium-magnesium slag and the liquid after removing calcium and magnesium, the liquid after removing calcium and magnesium contains 0.008 g/L of calcium and 0.016 g/L of magnesium.
Example 3
The nickel-cobalt-manganese solution of a certain factory contains 0.57 g/L of calcium and 2.03 g/L of magnesium, the solution 500m L is heated to 90 ℃, 4.74g of cobalt fluoride is added according to the theoretical amount of calcium and magnesium, the time for removing calcium and magnesium is 3 hours, liquid-solid separation is carried out to obtain calcium-magnesium slag and a liquid after removing calcium and magnesium, the liquid after removing calcium and magnesium contains 0.012 g/L of calcium and 0.018 g/L of magnesium.

Claims (6)

1. The method for removing calcium and magnesium from the nickel-cobalt-manganese solution is characterized by comprising the following operation steps:
(1) heating the nickel-cobalt-manganese solution to a certain temperature, adding a precipitator, and keeping for a certain time; the precipitator is one or more of nickel fluoride, cobalt fluoride and manganese fluoride;
(2) carrying out liquid-solid separation on the ore pulp to obtain a solution and calcium and magnesium removing slag;
(3) the solution is processed by subsequent processes to obtain nickel products and cobalt products.
2. The method of claim 1, wherein the amount of the precipitant added in step (1) is such that the ratio of the amount of fluorine added to the precipitant to the amount of calcium and magnesium ions contained in the nickel cobalt solution is 2: 1.
3. The method of claim 1, wherein the nickel cobalt manganese solution in step (1) is a sulfate or chloride system.
4. The method of claim 1, wherein the nickel-cobalt-manganese solution in step (1) contains one or more ions of nickel, cobalt, and manganese.
5. The method according to claim 1, wherein the certain temperature in step (1) is 25 to 95 ℃.
6. The method according to claim 1, wherein the certain time in the step (1) is 0.5 to 10 hours.
CN202010518668.0A 2020-06-09 2020-06-09 Method for removing calcium and magnesium from nickel-cobalt-manganese solution Pending CN111455175A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010518668.0A CN111455175A (en) 2020-06-09 2020-06-09 Method for removing calcium and magnesium from nickel-cobalt-manganese solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010518668.0A CN111455175A (en) 2020-06-09 2020-06-09 Method for removing calcium and magnesium from nickel-cobalt-manganese solution

Publications (1)

Publication Number Publication Date
CN111455175A true CN111455175A (en) 2020-07-28

Family

ID=71679715

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010518668.0A Pending CN111455175A (en) 2020-06-09 2020-06-09 Method for removing calcium and magnesium from nickel-cobalt-manganese solution

Country Status (1)

Country Link
CN (1) CN111455175A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112095013A (en) * 2020-09-27 2020-12-18 贵州中伟资源循环产业发展有限公司 Method for removing calcium and magnesium ions in nickel-cobalt-manganese solution and method for recycling nickel-cobalt-manganese ternary waste
CN113249593A (en) * 2021-07-06 2021-08-13 金驰能源材料有限公司 Two-stage process for removing calcium and magnesium from solutions containing nickel, cobalt, manganese and lithium

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102234721A (en) * 2011-06-15 2011-11-09 金川集团有限公司 Treatment method of nickel-cobalt material
CN102557153A (en) * 2010-12-28 2012-07-11 上海轻工业研究所有限公司 Method for removing calcium-magnesium impurities from nickel sulfate solution
CN103224259A (en) * 2013-05-15 2013-07-31 大冶有色金属有限责任公司 Method for refining crude nickel sulphate and recycling valuable metals
CN103773961A (en) * 2014-01-23 2014-05-07 广西有色金属集团汇元锰业有限公司 Method for extracting cobalt and nickel from manganese, cobalt and nickel waste residue
CN108517403A (en) * 2018-06-30 2018-09-11 贵州中伟资源循环产业发展有限公司 A kind of method of metallic cobalt battery grade cobalt sulfate
CN110157911A (en) * 2019-04-03 2019-08-23 张响 A kind of technique of comprehensive reutilization electrolytic manganese residues and manganese tailing

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557153A (en) * 2010-12-28 2012-07-11 上海轻工业研究所有限公司 Method for removing calcium-magnesium impurities from nickel sulfate solution
CN102234721A (en) * 2011-06-15 2011-11-09 金川集团有限公司 Treatment method of nickel-cobalt material
CN103224259A (en) * 2013-05-15 2013-07-31 大冶有色金属有限责任公司 Method for refining crude nickel sulphate and recycling valuable metals
CN103773961A (en) * 2014-01-23 2014-05-07 广西有色金属集团汇元锰业有限公司 Method for extracting cobalt and nickel from manganese, cobalt and nickel waste residue
CN108517403A (en) * 2018-06-30 2018-09-11 贵州中伟资源循环产业发展有限公司 A kind of method of metallic cobalt battery grade cobalt sulfate
CN110157911A (en) * 2019-04-03 2019-08-23 张响 A kind of technique of comprehensive reutilization electrolytic manganese residues and manganese tailing

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112095013A (en) * 2020-09-27 2020-12-18 贵州中伟资源循环产业发展有限公司 Method for removing calcium and magnesium ions in nickel-cobalt-manganese solution and method for recycling nickel-cobalt-manganese ternary waste
CN112095013B (en) * 2020-09-27 2022-04-19 贵州中伟资源循环产业发展有限公司 Method for removing calcium and magnesium ions in nickel-cobalt-manganese solution and method for recycling nickel-cobalt-manganese ternary waste
CN113249593A (en) * 2021-07-06 2021-08-13 金驰能源材料有限公司 Two-stage process for removing calcium and magnesium from solutions containing nickel, cobalt, manganese and lithium

Similar Documents

Publication Publication Date Title
CN111455174A (en) Method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel hydroxide cobalt
CN108002408B (en) Method for preparing nickel sulfate, manganese, lithium, cobalt and cobaltosic oxide from battery waste
US11459636B2 (en) Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore
CN109234526B (en) Treatment method of laterite-nickel ore
CN109518005B (en) Production method of battery-grade cobalt sulfate crystal
CN110835683B (en) Method for selectively extracting lithium from waste lithium ion battery material
CN106435213A (en) Method for comprehensively recovering zinc nickel cadmium from copper cadmium residues
CN111455175A (en) Method for removing calcium and magnesium from nickel-cobalt-manganese solution
CN111500862A (en) Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate
CN113474069A (en) Method for producing a solution containing nickel and cobalt from a nickel and cobalt-containing hydroxide
JP2022502564A (en) Methods for Preparing High Purity Hydrated Nickel Sulfate
CN105274352B (en) A kind of method that copper cobalt manganese is separated in the manganese cobalt calcium zinc mixture from copper carbonate
US10570482B2 (en) Method for recovering scandium
CN114959311A (en) Method for comprehensively recovering rare and noble metals from high-copper molybdenum concentrate
JP5867727B2 (en) Separation method of rare earth elements
CN113120941A (en) Method for extracting high-purity scandium oxide from scandium-containing nickel cobalt hydroxide in short process
CN112813287B (en) Method for recovering molybdenum from waste hydrogenation catalyst
CN108463567B (en) Scandium recovery method
CN101195869A (en) Solvent extraction method for materials after nickelous oxide mine chloridization oxidation treatment
CN115491518B (en) Method for producing nickel sulfate and cobalt sulfate by chlorination process
CN114645143B (en) Method for separating nickel, cobalt, copper and manganese from laterite-nickel ore
CN111961850B (en) Treatment method of copper-cobalt ore
CN112626337B (en) Cobalt-containing copper raffinate treatment process
CN113277547B (en) Method for producing zinc sulfate by using low-zinc material
CN115893530B (en) Cobalt nickel hydroxide raw material combined treatment method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200728