CN111500862A - Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate - Google Patents

Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate Download PDF

Info

Publication number
CN111500862A
CN111500862A CN202010526336.7A CN202010526336A CN111500862A CN 111500862 A CN111500862 A CN 111500862A CN 202010526336 A CN202010526336 A CN 202010526336A CN 111500862 A CN111500862 A CN 111500862A
Authority
CN
China
Prior art keywords
nickel
cobalt
iron
aluminum
hydroxide
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
CN202010526336.7A
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 CN202010526336.7A priority Critical patent/CN111500862A/en
Publication of CN111500862A publication Critical patent/CN111500862A/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
    • 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

Abstract

The invention discloses a method for removing iron and aluminum from a mixed nickel cobalt hydroxide leaching solution, belonging to the technical field of nickel cobalt hydrometallurgy. Aiming at the defects of the prior art, the invention avoids the introduction of a large amount of calcium ions due to the iron removal by using calcium oxide in the prior art, adopts a nickel-based/cobalt-based precipitator (comprising one or more of mixed nickel cobalt hydroxide, nickel hydroxide, cobalt hydroxide, nickel carbonate and cobalt carbonate) to remove iron and aluminum, acid dissolution is carried out on the iron-removed slag to recover nickel and cobalt, and the solution after iron removal is sent to the next step for impurity removal and separation. The new process adopts nickel salt/cobalt salt as a reagent for removing iron and aluminum, does not introduce new or existing impurity ions, can greatly reduce the influence of calcium sulfate crystallization on subsequent extraction, greatly reduces the use amount of calcium oxide and the loss of nickel and cobalt in the process of removing iron and aluminum, and is an efficient and green method for removing iron and aluminum from the mixed nickel and cobalt hydroxide leachate.

Description

Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate
Technical Field
The invention belongs to the field of nickel cobalt hydrometallurgy, and relates to a method for removing iron and aluminum from a mixed nickel cobalt hydroxide leachate.
Background
With the exhaustion of the mining of nickel sulfide ores and the increasing demand for nickel, the attention is paid to the extraction of nickel and cobalt from laterite-nickel ores with abundant reserves. At present, the whole wet treatment process of the laterite-nickel ore is mainly a high-pressure acid leaching method. In order to facilitate transportation and save cost, laterite-nickel ore is often processed into a mixed nickel-cobalt hydroxide (MHP) intermediate product, which is obtained by high-pressure acid leaching, impurity removal, neutralization and precipitation, and the mixed nickel-cobalt hydroxide 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 is used to produce battery-grade nickel sulfate and battery-grade cobalt sulfate mostly by a hydrometallurgical process, and the procedures generally comprise sulfuric acid leaching, neutralization and iron and aluminum removal, extraction and impurity removal, nickel and cobalt separation and other processes, for example, the method is adopted by companies such as Jiangxi river tungsten, Jinchuan and Hua Yong cobalt industries. Because the components of the mixed cobalt hydroxide are complex, the requirements of battery-grade nickel sulfate and cobalt sulfate on impurities are extremely strict, and the impurity removal and separation processes of the leachate are not complete. The mixed nickel cobalt hydroxide sulfuric acid leaching solution contains elements such as Fe, Al, Ca, Mg, Cr, Cu, Mn, Zn and the like besides Ni and Co. A large amount of common impurity ions can be removed by an oxidation neutralization method, a substitution method, a sulfide method, a fluoride method, or the like.
At present, the method for removing iron and aluminum from an acidic nickel-cobalt solution obtained by mixing nickel-cobalt hydroxide mainly adopts a calcium oxide slurry neutralization method. The process is widely adopted, but has the problems that calcium oxide neutralizes and removes iron and aluminum to obtain a large amount of iron and aluminum slag, the nickel content is 6-12%, the nickel cannot be recovered to cause a large amount of nickel loss, and the nickel loss rate is about 1.5%. On the other hand, Ca ions are introduced into the system by the added calcium oxide, the Ca ions in the nickel-cobalt solution are in a saturated state, and a large amount of calcium sulfate crystals are separated out from the Ca ions in the P204 extraction and back extraction to block pipelines and seriously hinder the extraction, so that the technical problem to be solved urgently in the process of producing battery-grade nickel sulfate and battery-grade cobalt sulfate by using mixed nickel-cobalt hydroxide is solved.
People urgently need a new method for removing iron and aluminum from a mixed nickel cobalt hydroxide leaching solution, so that pipeline blockage caused by a large amount of calcium sulfate crystals precipitated in P204 extraction and back extraction of Ca ions is avoided, and the yield of nickel and cobalt is improved.
Disclosure of Invention
The invention adopts a nickel-based/cobalt-based precipitator (comprising one or more of mixed nickel cobalt hydroxide, nickel hydroxide, cobalt hydroxide, nickel carbonate and cobalt carbonate) to remove iron and aluminum, acid dissolution is carried out on iron-removed slag to recover nickel and cobalt, and the solution after iron removal is sent to the next step for impurity removal and separation. The new process adopts nickel salt/cobalt salt as a reagent for removing the aluminum, does not introduce new or existing impurity ions, can greatly reduce the influence of calcium sulfate crystallization on subsequent extraction, and greatly reduces the use amount of calcium oxide and the loss of nickel and cobalt in the process of removing the aluminum.
The invention aims to provide a method for removing iron and aluminum from a mixed nickel cobalt hydroxide leachate, which adopts a nickel-based/cobalt-based neutralizer for neutralization and iron removal, does not introduce new or existing impurity ions, avoids the introduction of a large amount of calcium ions due to the existing use of calcium oxide for iron removal, greatly reduces the influence of calcium sulfate crystals on extraction, and is an efficient and green method for removing iron and aluminum from the mixed nickel cobalt hydroxide leachate.
The technical scheme adopted by the invention is as follows:
a method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate comprises the following steps:
(1) heating the mixed nickel cobalt hydroxide leachate to a certain temperature, adjusting the pH value of the solution to a set value by adopting a nickel-based/cobalt-based neutralizer, and keeping the solution for a certain time;
(2) carrying out liquid-solid separation on the ore pulp to obtain solution and iron slag;
(3) the solution is processed by subsequent processes to obtain nickel products and cobalt products, and the iron-removing slag is sent to acid dissolution to recover valuable metals.
Further, the nickel-based/cobalt-based neutralizer in the step (1) is one or more of mixed nickel cobalt hydroxide, nickel hydroxide, cobalt hydroxide, nickel carbonate, cobalt carbonate, basic nickel carbonate, basic cobalt carbonate, cobalt oxide and nickel oxide.
Further, in some embodiments, the nickel/cobalt-based neutralizing agent in step (1) is mixed nickel cobalt hydroxide.
Further, the temperature in the step (1) is 25-95 ℃.
Further, the pH value of the solution in the step (1) is 3.0-5.0.
Further, the certain time in the step (1) is 0.5-10 hours.
The invention provides a method for removing iron and aluminum from a mixed nickel cobalt hydroxide leaching solution, which relates to the following reaction principle:
added precipitant can decompose OH in solution system-Or CO3 2-And the reaction with the residual acid in the mixed nickel cobalt hydroxide leaching solution is as follows:
H++OH-＝H2O
2H++CO3 2-＝H2O+CO2
free H in Ni-Co solution+With OH in the precipitant-Or CO3 2-After the reaction has taken place, free H+Decrease in OH-Become rich in Fe3+And Al3+Will react with OH-A precipitate formed and the following reaction took place:
Fe3++3OH-＝Fe(OH)3↓
Al3++3OH-＝Al(OH)3↓
thereby realizing the removal of iron and aluminum from the nickel-cobalt solution.
The invention has the following advantages:
(1) the nickel-based/cobalt-based neutralizer is adopted for neutralization and deironing, so that the phenomenon that calcium ions are introduced due to the fact that calcium oxide is used for deironing in the prior art is avoided, the influence of calcium sulfate crystallization on extraction is greatly reduced, and the technical problem to be solved in the prior art is solved.
(2) Greatly reduces the use amount of calcium oxide and the corresponding loss of nickel and cobalt in the process of removing the aluminum.
(3) The method has the advantages of simple process, strong operability and easy industrial realization.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
Example 1
The mixed nickel cobalt hydroxide pickle liquor of a certain foreign factory comprises the following components:
element(s) Al Fe Ca Co Cr Cu Mg Mn Ni Zn
component/(g/L) 0.25 0.50 0.15 9.09 0.025 0.24 1.56 3.54 95.7 1.73
Heating the solution 500m L to 70 ℃, adding mixed nickel cobalt hydroxide to adjust the pH value of the solution to 3.50, removing aluminum for 3h, and carrying out liquid-solid separation to obtain aluminum-removed slag and a liquid after iron removal, wherein the liquid after iron removal contains 4.5 mg/L of iron and 63 mg/L of aluminum.
Example 2
The iron content of the mixed nickel cobalt hydroxide acidic leaching solution in a certain foreign factory is about 0.1 g/L, the aluminum content of the mixed nickel cobalt hydroxide acidic leaching solution is 0.32 g/L, 500m of L solution is heated to 30 ℃, the mixed nickel cobalt hydroxide is added to adjust the pH value of the solution to 4.0, the time for removing the iron and the aluminum is 5 hours, liquid-solid separation is carried out to obtain iron and aluminum removing slag and iron removing liquid, the iron and aluminum removing liquid contains 2.3 mg/L and the aluminum content of 35 mg/L.
Example 3
The iron content of the mixed nickel cobalt hydroxide acidic leaching solution in a certain foreign factory is about 0.2 g/L, the aluminum content is 0.44 g/L, 500m of L solution is heated to 90 ℃, mixed nickel cobalt hydroxide is added to adjust the pH value of the solution to 4.5, the time for removing the iron and the aluminum is 8 hours, the liquid-solid separation is carried out to obtain iron and aluminum removing slag and iron removing liquid, the iron content of the iron and aluminum removing liquid is less than 1 mg/L, and the aluminum content of the iron and aluminum removing liquid is 16 mg/L.
Example 4
The iron content of the mixed nickel cobalt hydroxide acidic leaching solution in a certain foreign factory is about 0.12 g/L, the aluminum content is 0.40 g/L, 500m of L solution is heated to 70 ℃, nickel hydroxide is added to adjust the pH value of the solution to 4.0, the time for removing the iron and the aluminum is 3 hours, the liquid-solid separation is carried out to obtain iron and aluminum removing slag and iron removing liquid, the iron content of the iron and aluminum removing liquid is less than 1 mg/L, and the aluminum content of the iron and aluminum removing liquid is 36 mg/L.
Example 5
The iron content of the mixed nickel cobalt hydroxide acidic leaching solution in a certain foreign factory is about 0.18 g/L, the aluminum content is 0.46 g/L, 500m of L solution is heated to 65 ℃, nickel carbonate is added to adjust the pH value of the solution to 4.2, the time for removing the iron and the aluminum is 3 hours, the liquid-solid separation is carried out to obtain iron and aluminum removing slag and iron removing liquid, the iron content of the iron removing liquid is less than 1 mg/L, and the aluminum content of the iron removing liquid is 30 mg/L.

Claims (6)

1. A method for removing iron and aluminum from a mixed nickel cobalt hydroxide leaching solution is characterized by comprising the following operation steps:
(1) heating the mixed nickel cobalt hydroxide leachate to a certain temperature, adjusting the pH value of the solution to a set value by adopting a nickel-based/cobalt-based neutralizer, and keeping the solution for a certain time;
(2) carrying out liquid-solid separation on the ore pulp to obtain solution and iron slag;
(3) the solution is processed by subsequent processes to obtain nickel products and cobalt products, and the iron-removing slag is sent to acid dissolution to recover valuable metals.
2. The method of claim 1, wherein the nickel-based/cobalt-based neutralizer in step (1) is one or more of mixed nickel cobalt hydroxide, nickel hydroxide, cobalt hydroxide, nickel carbonate, cobalt carbonate, nickel hydroxycarbonate, cobalt oxide, and nickel oxide.
3. The method of claim 2, wherein the nickel/cobalt-based neutralizing agent in step (1) is mixed nickel-cobalt hydroxide.
4. The method according to claim 1, wherein the temperature in step (1) is 25 to 95 ℃.
5. The method according to claim 1, wherein the pH of the solution in step (1) is 3.0 to 5.0.
6. The method according to claim 1, wherein the certain time in the step (1) is 0.5 to 10 hours.
CN202010526336.7A 2020-06-09 2020-06-09 Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate Pending CN111500862A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010526336.7A CN111500862A (en) 2020-06-09 2020-06-09 Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010526336.7A CN111500862A (en) 2020-06-09 2020-06-09 Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate

Publications (1)

Publication Number Publication Date
CN111500862A true CN111500862A (en) 2020-08-07

Family

ID=71873621

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010526336.7A Pending CN111500862A (en) 2020-06-09 2020-06-09 Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate

Country Status (1)

Country Link
CN (1) CN111500862A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112250120A (en) * 2020-12-21 2021-01-22 矿冶科技集团有限公司 Method for preparing ternary precursor and lithium carbonate by using waste lithium ion battery black powder and nickel cobalt sulfide ore in synergy mode and application
CN113897499A (en) * 2021-10-11 2022-01-07 金川集团股份有限公司 Method for removing iron by cobalt solution goethite method
CN115321972A (en) * 2022-08-09 2022-11-11 矿冶科技集团有限公司 Chromium removal method of bonded permanent magnetic ferrite and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468972A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Treatment method for comprehensive recycling of scandium and nickel cobalt from lateritic nickel ore
CN104911353A (en) * 2015-04-29 2015-09-16 中国恩菲工程技术有限公司 Cobalt nickel hydroxide filter cake after-acid-dissolution liquid dechlorination method
CN105274332A (en) * 2015-11-20 2016-01-27 金川集团股份有限公司 Isolation technology and process for extracting Ni and Co from nickel-containing high-cobalt hydroxide
CN109234526A (en) * 2018-11-26 2019-01-18 中国恩菲工程技术有限公司 The processing method of lateritic nickel ore
CN111041217A (en) * 2019-12-28 2020-04-21 湖南金源新材料股份有限公司 Method for preparing pre-extraction solution in comprehensive recovery of ternary battery waste
CN111092273A (en) * 2019-09-14 2020-05-01 湖南金源新材料股份有限公司 Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468972A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Treatment method for comprehensive recycling of scandium and nickel cobalt from lateritic nickel ore
CN104911353A (en) * 2015-04-29 2015-09-16 中国恩菲工程技术有限公司 Cobalt nickel hydroxide filter cake after-acid-dissolution liquid dechlorination method
CN105274332A (en) * 2015-11-20 2016-01-27 金川集团股份有限公司 Isolation technology and process for extracting Ni and Co from nickel-containing high-cobalt hydroxide
CN109234526A (en) * 2018-11-26 2019-01-18 中国恩菲工程技术有限公司 The processing method of lateritic nickel ore
CN111092273A (en) * 2019-09-14 2020-05-01 湖南金源新材料股份有限公司 Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste
CN111041217A (en) * 2019-12-28 2020-04-21 湖南金源新材料股份有限公司 Method for preparing pre-extraction solution in comprehensive recovery of ternary battery waste

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112250120A (en) * 2020-12-21 2021-01-22 矿冶科技集团有限公司 Method for preparing ternary precursor and lithium carbonate by using waste lithium ion battery black powder and nickel cobalt sulfide ore in synergy mode and application
CN113897499A (en) * 2021-10-11 2022-01-07 金川集团股份有限公司 Method for removing iron by cobalt solution goethite method
CN113897499B (en) * 2021-10-11 2023-03-14 金川集团股份有限公司 Method for removing iron by cobalt solution goethite method
CN115321972A (en) * 2022-08-09 2022-11-11 矿冶科技集团有限公司 Chromium removal method of bonded permanent magnetic ferrite and application thereof
CN115321972B (en) * 2022-08-09 2023-10-24 矿冶科技集团有限公司 Chromium removal method and application of bonded permanent magnetic ferrite

Similar Documents

Publication Publication Date Title
AU2020102537A4 (en) Method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel-cobalt hydroxide
CN109234526B (en) Treatment method of laterite-nickel ore
RU2741429C1 (en) Method and system for complete reprocessing of copper-nickel sulphide ore
CN111500862A (en) Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate
KR101412462B1 (en) Highly Purified Nickel Sulfate from Nickel and Cobalt Mixed hydroxide precipitation and the Manufacturing Method of the Same
EP2212253B1 (en) Producing nickel hydroxide suitable for pelletization with iron-containing ore and for stainless steel manufacture
AU2017218246B2 (en) Sulfuration treatment method, sulfide production method, and hydrometallurgical process for nickel oxide ore
EP2975142B1 (en) Hydrometallurgical plant for nickel oxide ore and method for operating said hydrometallurgical plant
JP2020509166A (en) How to recover iron from zinc sulfate solution
CN105274352B (en) A kind of method that copper cobalt manganese is separated in the manganese cobalt calcium zinc mixture from copper carbonate
CN113215399A (en) Oxygen pressure leaching method of nickel sulfide concentrate
AU2016374348B2 (en) Method for recovering scandium
CN100554453C (en) A kind of leaching method of materials after nickelous oxide mine chloridization oxidation treatment
WO2016194709A1 (en) Free acid-removing equipment, free acid-removing method, and method for manufacturing mixed nickel and cobalt sulfide
KR102041294B1 (en) Method for recovering covalt from solution comprising covalt, nickel and iron
CN111455175A (en) Method for removing calcium and magnesium from nickel-cobalt-manganese solution
JP2016113703A (en) Neutralization method by wet type refining of nickel oxide ore
CN108463567B (en) Scandium recovery method
CN117642519A (en) Production of high purity nickel and cobalt compounds
CN115029551A (en) High-magnesium low-nickel concentrate acid leaching magnesium reduction method
CN114058847A (en) Iron removal method for chlorine leachate of nickel concentrate
CN110438339B (en) Method for removing manganese in nickel hydroxide cobalt dissolving solution
CN112593080A (en) Method for treating laterite-nickel ore by combination of pyrogenic process and wet process
CN112626337B (en) Cobalt-containing copper raffinate treatment process
KR101654198B1 (en) Method for recovering cobalt and nickel from a waste liquor upon smelting low-grade nickel ore

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20200807

RJ01 Rejection of invention patent application after publication