CN1226429C - Process of recoverying lithium and manganese from their oxide - Google Patents

Process of recoverying lithium and manganese from their oxide Download PDF

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Publication number
CN1226429C
CN1226429C CNB2004100128054A CN200410012805A CN1226429C CN 1226429 C CN1226429 C CN 1226429C CN B2004100128054 A CNB2004100128054 A CN B2004100128054A CN 200410012805 A CN200410012805 A CN 200410012805A CN 1226429 C CN1226429 C CN 1226429C
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lithium
manganese oxide
lithium manganese
added
manganese
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CN1560288A (en
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雷家珩
郭丽萍
陈永熙
童辉
杜小弟
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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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
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Abstract

The present invention relates to a method for separating and recovering lithium and manganese from lithium manganese oxide. After lithium manganese oxide is pulverized, carbon powder is added to be mixed, and concentrated sulfuric acid is added during stirring to react. The weight ratio of lithium manganese oxide to carbon powder to concentrated sulfuric acid is 1.0:0.05 to 0.8:1.2 to 2.0. The mixture is heated for complete reaction, is further heated for evaporation to dryness and then is roasted to be gray at 400 to 600 DEG C in a stove, and the mixture is taken out to be leached by hot water and is filtered after cooling to obtain filtered solution containing MnSO4 and Li2SO4. The filtered solution is concentrated and crystallized to obtain crystals of manganese sulfate. NaHCO3 is added into mother solution, and after being boiled, the solution is cooled and filtered to obtain MnCO3. After NaOH is added to regulate the pH of the filtered solution to be larger than 12, saturated NaCO3 solution is added to precipitate Li2CO3, and solid Li2CO3 is obtained through filtration and drying. The method of the present invention has the advantages of simple technology, low production cost, resource saving, effective separation and recovery of lithium and manganese in lithium manganese oxide, high recovery rate and high purity of recovered reagents.

Description

The method of Separation and Recovery lithium and manganese from lithium manganese oxide
Technical field
The present invention relates to the method for a kind of Separation and Recovery lithium and manganese, particularly a kind of method that from lithium manganese oxide, adopts precipitator method Separation and Recovery lithium and manganese.
Background technology
Metallic lithium and compound thereof are widely used in the every field of national economy, and people are described as metallic lithium " VITAMIN of metallic substance ", " new forms of energy of 21 century ".The positive electrode material of lithium-ion secondary cell mainly is LiCoO at present 2Because the cobalt resource poorness, cost an arm and a leg and harmful, so people are actively seeking LiCoO environment 2Substitute material.Spinel structure Li xMn 2-xO 4Lithium ion is had good memory performance, and manganese element wide material sources, with low cost, price is 1/40 of a cobalt only, and does not have the environment public hazards, so the Li of normal spinel structure xMn 2-xO 4Be considered to replace LiCoO 2Become the preferred material of lithium ion secondary battery positive electrode.While Li xMn 2-xO 4Also may become the new technology material that extracts lithium resource in salt lake brine and the seawater.Along with Li xMn 2-xO 4Cell positive material and salt lake brine are proposed the further investigation of lithium new technology and are progressively used, the depleted lithium manganese oxide will produce in a large number, how reclaiming and utilize lithium useful in this compound and manganese fully, reduce the waste of resource, is the technical problem that people must consider.
Summary of the invention
The objective of the invention is at the problems referred to above provide a kind of from lithium manganese oxide the method for Separation and Recovery lithium and manganese.A kind of novel method that combines Separation and Recovery lithium, manganese from lithium manganese oxide by condensing crystal and carbonate deposition has been proposed.
Main processes of the present invention is: under acidic conditions, lithium manganese oxide, method Separation and Recovery lithium and the manganese from lithium manganese oxide that combines with carbonate deposition by condensing crystal are again decomposed in reduction with carbon.
The method steps of Separation and Recovery lithium and manganese is from lithium manganese oxide:
(1) lithium manganese oxide was pulverized 40 orders with top sieve, adding distilled water and carbon dust also mixes, and distilled water is 25～29mL/100 gram with the ratio of carbon dust, under agitation adds the vitriol oil, thermal degradation;
(2) resolvent soaks with 60～80 ℃ of hot water, filters after cooling, obtains containing MnSO 4And Li 2SO 4Filtrate, filtrate heating condensing crystal obtains the manganous sulfate crystal;
(3) add NaHCO in the residue mother liquor behind step (2) fractional crystallization 3, boil postcooling, filter and make solid MnCO 3
(4) filtrate that obtains of step (3) is regulated pH to greater than after 12 with NaOH, adds saturated NaCO 3Solution makes lithium be precipitated as Li 2CO 3, after filtration, dry Li 2CO 3Solid.
The weight proportion of described thermal degradation reactant is a lithium manganese oxide: carbon dust: the vitriol oil=1.0: 0.05～0.8: 1.2～2.0.
Described thermal degradation condition is; After it fully being reacted lithium manganese oxide and carbon dust and vitriol oil mixture heating up, further heating evaporation is to doing, place then High Temperature Furnaces Heating Apparatus 400 ℃～600 ℃ following roastings to being canescence.
It is simple that the present invention has technology, and production cost is low, economizes on resources, and can make lithium, manganese in the lithium manganese oxide obtain effective Separation and Recovery, and rate of recovery height, reclaims the high characteristics of reagent purity.
Description of drawings
Fig. 1 is the Separation and Recovery schema of lithium manganese in the lithium manganese oxide
Lithium manganese oxide sample and carbon dust and the vitriol oil be under the condition of mixing among the figure, thermal degradation, make the manganous sulfate solid with hot water leaching, filtration, filtrate heating condensing crystal then after, in its mother liquor, add NaHCO 3Precipitation reagent carries out primary sedimentation, filters to make solid MnCO 3In its filtrate, add NaOH reagent then and regulate pH, add saturated NaCO again 3Solution, carry out secondary sedimentation, precipitation after filtration, drying makes solid Li 2CO 3Reagent.
Embodiment
Embodiment 1
500 gram lithium manganese oxides were crushed to 60 mesh standard sieves, add 50mL distilled water and 200 gram carbon dusts and make mixing of materials even, under agitation add the 350mL vitriol oil, being heated to boiling reacts fully and carries out, further heating evaporation is to doing, place then the high-temperature roasting stove 500 ℃ of following roastings to being canescence, the hot water that takes out with 60 ℃ leached 40 minutes, filter after cooling, obtain containing MnSO 4And Li 2SO 4Filtrate.Filtrate is heated to carries out condensing crystal more than 70 ℃, and suction filtration obtains the manganous sulfate crystal while hot.The NaHCO that in the residue mother liquor, adds 0.2mol/L 3Reagent further precipitates manganese, boils the postcooling filtration and makes solid MnCO 3The NaOH that adds 10mol/L in filtrate regulates pH to greater than after 12, adds saturated NaCO again 3Solution makes lithium be precipitated as Li 2CO 3, obtain solid Li after filtration after the drying 2CO 3Present embodiment is 92% to the rate of recovery of manganese, MnSO 4And MnCO 3Purity be respectively 92% and 94%; The rate of recovery to lithium is 87%, and the purity of lithium is 95%.
Embodiment 2
300 gram lithium manganese oxides were crushed to 100 mesh standard sieves, add 20mL distilled water and 70 gram carbon dusts and make mixing of materials even, under agitation add the 250mL vitriol oil, being heated to boiling reacts fully and carries out, further heating evaporation is to doing, place then the high-temperature roasting stove 450 ℃ of following roastings to being canescence, the hot water that takes out with 80 ℃ leached 60 minutes, filter after cooling, obtain containing MnSO 4And Li 2SO 4Filtrate.Filtrate is heated to carries out condensing crystal more than 80 ℃, and suction filtration obtains the manganous sulfate crystal while hot.The NaHCO that in the residue mother liquor, adds 0.1mol/L 3Reagent further precipitates manganese, boils the postcooling filtration and makes solid MnCO 3The NaOH that adds 12mol/L in filtrate regulates pH to greater than after 12, adds saturated NaCO again 3Solution makes lithium be precipitated as Li 2CO 3, obtain solid Li after filtration after the drying 2CO 3Present embodiment is 95% to the rate of recovery of manganese, MnSO 4And MnCO 3Purity be respectively 95% and 96%; The rate of recovery to lithium is 90%, and the purity of lithium is 96%.

Claims (3)

1, a kind of from lithium manganese oxide the method for Separation and Recovery manganese and lithium, it is characterized in that being undertaken by following step:
(1) lithium manganese oxide was pulverized 40 above mesh sieves, adding distilled water and carbon dust also mixes, and distilled water is 25～29mL/100 gram with the ratio of carbon dust, under agitation adds the vitriol oil, thermal degradation;
(2) resolvent soaks with 60～80 ℃ of hot water, filters after cooling, obtains containing MnSO 4And Li 2SO 4Filtrate, filtrate heating condensing crystal obtains the manganous sulfate crystal;
(3) add NaHCO in the residue mother liquor behind step (2) fractional crystallization 3, boil postcooling, filter and make MnCO 3Solid;
(4) filtrate that obtains of step (3) is regulated pH to greater than after 12 with NaOH, adds saturated Na 2CO 3Solution make lithium precipitation, after filtration, dry Li 2CO 3Solid.
2, the method for claim 1, the weight proportion that it is characterized in that described thermal degradation reactant is a lithium manganese oxide: carbon dust: the vitriol oil=1.0: 0.05～0.8: 1.2～2.0.
3, the method for claim 1 is characterized in that described thermal degradation method is; After it fully being reacted lithium manganese oxide and carbon dust and vitriol oil mixture heating up, further heating evaporation is to doing, place then High Temperature Furnaces Heating Apparatus 400 ℃～600 ℃ following roastings to being canescence.
CNB2004100128054A 2004-03-03 2004-03-03 Process of recoverying lithium and manganese from their oxide Expired - Fee Related CN1226429C (en)

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Publication number Priority date Publication date Assignee Title
IT1402160B1 (en) 2010-10-18 2013-08-28 Eco Recycling S R L PLANT AND PROCESS FOR FILE TREATMENT AND EXHAUSTED ACCUMULATORS
CN103937999B (en) * 2014-04-23 2015-09-23 北京科技大学 A kind of vacuum distilling ferromanganese extracts method and the device of manganese metal
CN105838895B (en) * 2016-05-16 2017-11-17 长沙矿冶研究院有限责任公司 A kind of method that lithium and manganese are extracted from Mn-rich slag containing lithium
CN105925812B (en) * 2016-05-16 2018-03-09 长沙矿冶研究院有限责任公司 A kind of method that manganese is extracted from Mn-rich slag
CN108559846B (en) * 2018-02-24 2020-04-14 北京矿冶科技集团有限公司 Method for comprehensively recovering anode material of waste lithium ion battery
CN109706318A (en) * 2018-12-28 2019-05-03 池州西恩新材料科技有限公司 A kind of resource recycle method of the useless positive electrode of nickel and cobalt containing manganese lithium
CN109734107A (en) * 2018-12-28 2019-05-10 池州西恩新材料科技有限公司 A kind of resource recycle method of the useless positive electrode of lithium battery
CN111206154B (en) * 2020-02-25 2021-11-02 中国科学院过程工程研究所 Method for separating and recovering valuable metal ions in waste ternary battery material

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