CN110964927A - Neutralization treatment method for liquid after nickel and cobalt precipitation - Google Patents
Neutralization treatment method for liquid after nickel and cobalt precipitation Download PDFInfo
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- CN110964927A CN110964927A CN201911369071.8A CN201911369071A CN110964927A CN 110964927 A CN110964927 A CN 110964927A CN 201911369071 A CN201911369071 A CN 201911369071A CN 110964927 A CN110964927 A CN 110964927A
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- Prior art keywords
- nickel
- cobalt
- solution
- manganese
- precipitation
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Classifications
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a neutralization treatment method of post-nickel cobalt precipitation liquid, which comprises the following operation steps of preparing low-manganese leachate by using a nickel cobalt lithium manganate positive electrode material, heating the low-manganese leachate to 60-90 ℃, slowly adding oxalic acid solid with the addition amount of 1.4-1.7 times of the mass theoretically required by nickel cobalt precipitation, reacting for 1-2 hours, and filtering to obtain the nickel cobalt oxalate solid and the post-nickel cobalt precipitation liquid, wherein the nickel content in the post-nickel cobalt precipitation liquid is less than 0.2g/L, the cobalt content is less than 0.4g/L, and the manganese content is less than 0.01 g/L; neutralizing the solution after nickel and cobalt precipitation with calcium hydroxide, treating with active carbon to remove residual nickel, cobalt and manganese impurities, and finally adding sodium carbonate to precipitate lithium to obtain the industrial-grade lithium carbonate. The method is beneficial to separating nickel and cobalt elements in the waste batteries.
Description
Technical Field
The invention belongs to the technical field of treatment of nickel cobalt lithium manganate positive electrode materials, and particularly relates to a neutralization treatment method of a nickel cobalt precipitation solution.
Background
Along with the continuous increase of the consumption of electronic products by human beings, the generated scrapped batteries are more and more, and the waste lithium ion batteries contain high-value metals such as cobalt, nickel, iron, aluminum, copper and the like, so that the method has important significance for recycling the high-value metals in the waste lithium batteries.
Disclosure of Invention
The invention aims to provide a neutralization treatment method of a post-nickel-cobalt precipitation solution, which is used for separating nickel and cobalt from waste batteries and is different from the common neutralization method using sodium hydroxide, and the post-nickel-cobalt precipitation solution contains extremely high sodium sulfate, is easy to crystallize and causes the problem of high process difficulty.
In order to achieve the above purpose, the invention provides the following technical scheme:
a neutralization treatment method of a liquid after nickel and cobalt precipitation comprises the following operation steps,
s1, preparing a low-manganese leaching solution by using a nickel cobalt lithium manganate positive electrode material, heating the low-manganese leaching solution to 60-90 ℃, slowly adding oxalic acid solid, wherein the adding amount is 1.4-1.7 times of the mass required by a nickel cobalt precipitation theory, reacting for 1-2 hours, and filtering to obtain the nickel cobalt oxalate solid and a nickel cobalt precipitation solution, wherein the nickel content in the nickel cobalt precipitation solution is less than 0.2g/L, the cobalt content is less than 0.4g/L, and the manganese content is less than 0.01 g/L;
and S2, neutralizing the solution after nickel and cobalt precipitation with calcium hydroxide, treating with activated carbon to remove impurities of nickel, cobalt and manganese, and finally adding sodium carbonate to precipitate lithium to obtain the industrial-grade lithium carbonate.
Further, in S1, the low manganese leaching solution is prepared by calcining the nickel cobalt lithium manganate positive electrode material at 600 ℃ and 300 ℃ for 5-10 min; preparing 250g/L dilute sulfuric acid solution of 200-.
Further, adding calcium hydroxide solid into the solution after nickel and cobalt precipitation until the ph is 6-7, reacting for 1-2 hours, and filtering.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
the calcium hydroxide neutralizes the post-nickel-cobalt precipitation solution, so that the purpose of neutralization can be achieved, the content of sodium sulfate in the post-solution can be reduced, and trace nickel, cobalt and manganese in the post-solution can be removed.
Detailed Description
The invention will now be further illustrated, but not by way of technical limitation, with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
1) Calcining the nickel cobalt lithium manganate positive electrode material at the temperature of 300-600 ℃, wherein the calcination retention time is about 5-10 min; preparing 250g/L dilute sulfuric acid solution of 200-.
2) Heating the low-manganese leaching solution to 60 ℃, slowly adding oxalic acid solid with the addition amount being 1.4 times of the mass theoretically required by nickel and cobalt precipitation, reacting for 2 hours, and filtering to obtain the nickel and cobalt oxalate solid and a solution after nickel and cobalt precipitation, wherein the nickel content in the solution after nickel and cobalt precipitation is less than 0.2g/L, the cobalt content is less than 0.4g/L, and the manganese content is less than 0.01 g/L.
3) Neutralizing the solution after nickel and cobalt precipitation with calcium hydroxide solid until ph is 6-7, reacting for 2 hours, treating with active carbon to remove impurities such as nickel, cobalt, manganese and the like, and finally adding sodium carbonate to precipitate lithium to obtain the industrial grade lithium carbonate.
Example 2
1) Calcining the nickel cobalt lithium manganate positive electrode material at the temperature of 300-600 ℃, wherein the calcination retention time is about 5-10 min; preparing 250g/L dilute sulfuric acid solution of 200-.
2) Heating the low-manganese leaching solution to 70 ℃, slowly adding oxalic acid solid with the addition amount being 1.4 times of the mass theoretically required by nickel and cobalt precipitation, reacting for 1 hour, and filtering to obtain the nickel and cobalt oxalate solid and a solution after nickel and cobalt precipitation, wherein the nickel content in the solution after nickel and cobalt precipitation is less than 0.2g/L, the cobalt content is less than 0.4g/L, and the manganese content is less than 0.01 g/L.
3) Neutralizing the solution after nickel and cobalt precipitation with calcium hydroxide solid until ph is 6-7, reacting for 1.5 hours, treating with active carbon to remove impurities such as nickel, cobalt, manganese and the like, and finally adding sodium carbonate to precipitate lithium to obtain the industrial grade lithium carbonate.
Example 3
1) Calcining the nickel cobalt lithium manganate positive electrode material at the temperature of 300-600 ℃, wherein the calcination retention time is about 5-10 min; preparing 250g/L dilute sulfuric acid solution of 200-.
2) Heating the low-manganese leaching solution to 90 ℃, slowly adding oxalic acid solid with the addition amount being 1.4 times of the theoretical required mass of nickel and cobalt precipitation, reacting for 1 hour, and filtering to obtain the nickel and cobalt oxalate solid and a solution after nickel and cobalt precipitation, wherein the nickel content in the solution after nickel and cobalt precipitation is less than 0.2g/L, the cobalt content is less than 0.4g/L, and the manganese content is less than 0.01 g/L.
3) Neutralizing the solution after nickel and cobalt precipitation with calcium hydroxide solid until ph is 6-7, reacting for 1 hour, treating with active carbon to remove impurities such as nickel, cobalt, manganese and the like, and finally adding sodium carbonate to precipitate lithium to obtain industrial-grade lithium carbonate.
Example 4
1) Calcining the nickel cobalt lithium manganate positive electrode material at the temperature of 300-600 ℃, wherein the calcination retention time is about 5-10 min; preparing 250g/L dilute sulfuric acid solution of 200-.
2) Heating the low-manganese leaching solution to 60 ℃, slowly adding oxalic acid solid with the addition amount being 1.7 times of the mass theoretically required by nickel and cobalt precipitation, reacting for 2 hours, and filtering to obtain the nickel and cobalt oxalate solid and a solution after nickel and cobalt precipitation, wherein the nickel content in the solution after nickel and cobalt precipitation is less than 0.2g/L, the cobalt content is less than 0.4g/L, and the manganese content is less than 0.01 g/L.
3) Neutralizing the solution after nickel and cobalt precipitation with calcium hydroxide solid until ph is 6-7, reacting for 1 hour, treating with active carbon to remove impurities such as nickel, cobalt, manganese and the like, and finally adding sodium carbonate to precipitate lithium to obtain industrial-grade lithium carbonate.
Example 5
1) Calcining the nickel cobalt lithium manganate positive electrode material at the temperature of 300-600 ℃, wherein the calcination retention time is about 5-10 min; preparing 250g/L dilute sulfuric acid solution of 200-.
2) Heating the low-manganese leaching solution to 90 ℃, slowly adding oxalic acid solid with the addition amount being 1.7 times of the mass theoretically required by nickel and cobalt precipitation, reacting for 2 hours, and filtering to obtain the nickel and cobalt oxalate solid and a solution after nickel and cobalt precipitation, wherein the nickel content in the solution after nickel and cobalt precipitation is less than 0.2g/L, the cobalt content is less than 0.4g/L, and the manganese content is less than 0.01 g/L.
3) Neutralizing the solution after nickel and cobalt precipitation with 3 calcium hydroxide solid until ph is 6-7, reacting for 2 hours, treating with active carbon to remove impurities such as nickel, cobalt, manganese and the like, and finally adding sodium carbonate to precipitate lithium to obtain the industrial grade lithium carbonate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (3)
1. A neutralization treatment method of a liquid after nickel and cobalt precipitation, which is characterized in that,
s1, preparing a low-manganese leaching solution by using a nickel cobalt lithium manganate positive electrode material, heating the low-manganese leaching solution to 60-90 ℃, slowly adding oxalic acid solid, wherein the adding amount is 1.4-1.7 times of the mass required by a nickel cobalt precipitation theory, reacting for 1-2 hours, and filtering to obtain the nickel cobalt oxalate solid and a nickel cobalt precipitation solution, wherein the nickel content in the nickel cobalt precipitation solution is less than 0.2g/L, the cobalt content is less than 0.4g/L, and the manganese content is less than 0.01 g/L;
and S2, neutralizing the solution after nickel and cobalt precipitation with calcium hydroxide, treating with activated carbon to remove impurities of nickel, cobalt and manganese, and finally adding sodium carbonate to precipitate lithium to obtain the industrial-grade lithium carbonate.
2. The method as claimed in claim 1, wherein in S1, the low manganese leach solution is prepared by calcining the lithium nickel cobalt manganese oxide positive electrode material at 600 ℃ and 300 ℃ for a residence time of about 5-10 min; preparing 250g/L dilute sulfuric acid solution of 200-.
3. The method for neutralizing the post nickel cobalt precipitation solution as claimed in claim 1, wherein the post nickel cobalt precipitation solution is added with calcium hydroxide solid until ph is 6-7, reacted for 1-2 hours and then filtered.
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| CN201911369071.8A CN110964927A (en) | 2019-12-26 | 2019-12-26 | Neutralization treatment method for liquid after nickel and cobalt precipitation |
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| CN201911369071.8A CN110964927A (en) | 2019-12-26 | 2019-12-26 | Neutralization treatment method for liquid after nickel and cobalt precipitation |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH116020A (en) * | 1997-06-18 | 1999-01-12 | Nisso Kinzoku Kagaku Kk | Method for recovering high-purity cobalt compound from scrap lithium ion battery |
| JP2012229481A (en) * | 2011-04-27 | 2012-11-22 | Japan Metals & Chem Co Ltd | Method for separating and recovering valuable material from used lithium ion battery |
| CN104911359A (en) * | 2015-06-29 | 2015-09-16 | 北京科技大学 | Process method for extracting cobalt and nickel from manganese waste slag |
| CN105907977A (en) * | 2016-07-08 | 2016-08-31 | 长沙理工大学 | Method for recycling lithium cobalt oxides from waste lithium-ion batteries |
| CN108767354A (en) * | 2018-05-29 | 2018-11-06 | 中南大学 | A method of recycling valuable metal from waste lithium ion cell anode material |
| CN110396600A (en) * | 2019-07-29 | 2019-11-01 | 先进储能材料国家工程研究中心有限责任公司 | The lithium recovery process of waste and old lithium ion battery |
| CN110541075A (en) * | 2019-09-20 | 2019-12-06 | 甘肃睿思科新材料有限公司 | Method for recycling lithium cobaltate positive electrode material |
-
2019
- 2019-12-26 CN CN201911369071.8A patent/CN110964927A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH116020A (en) * | 1997-06-18 | 1999-01-12 | Nisso Kinzoku Kagaku Kk | Method for recovering high-purity cobalt compound from scrap lithium ion battery |
| JP2012229481A (en) * | 2011-04-27 | 2012-11-22 | Japan Metals & Chem Co Ltd | Method for separating and recovering valuable material from used lithium ion battery |
| CN104911359A (en) * | 2015-06-29 | 2015-09-16 | 北京科技大学 | Process method for extracting cobalt and nickel from manganese waste slag |
| CN105907977A (en) * | 2016-07-08 | 2016-08-31 | 长沙理工大学 | Method for recycling lithium cobalt oxides from waste lithium-ion batteries |
| CN108767354A (en) * | 2018-05-29 | 2018-11-06 | 中南大学 | A method of recycling valuable metal from waste lithium ion cell anode material |
| CN110396600A (en) * | 2019-07-29 | 2019-11-01 | 先进储能材料国家工程研究中心有限责任公司 | The lithium recovery process of waste and old lithium ion battery |
| CN110541075A (en) * | 2019-09-20 | 2019-12-06 | 甘肃睿思科新材料有限公司 | Method for recycling lithium cobaltate positive electrode material |
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Application publication date: 20200407 |