CN108428893A - Preparation method of brine battery-grade lithium carbonate - Google Patents
Preparation method of brine battery-grade lithium carbonate Download PDFInfo
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Abstract
The invention discloses a preparation method of brine battery-grade lithium carbonate, which comprises the steps of carrying out lithium-rich magnesium reduction treatment on old brine in a salt lake to obtain a lithium chloride salt lithium-rich solution with L i content of 6.0-30 g/L, Mg content of 8.0-1740 Mg/L and Ca content of 1.2-50 Mg/L, and then adding Na under stirring2CO3Solution, Na added after completion of the addition2CO3The solution is continuously stirred for reaction, and finally L i is prepared by synthesis, filtration, washing and drying2CO3The lithium carbonate product for the brine battery grade comprises 93.9-99.4% of Mg, and 0.04-1.3% of Mg. The method does not need deep magnesium removal, and realizes high value of impurity magnesium; the brine battery-grade lithium carbonate is taken as a lithium source, so that the uniform doping of lithium ion battery anode material lithium iron phosphate and ternary material magnesium (or magnesium and rare earth) is easy to realize, and the electrical property of the lithium ion anode material is favorably improved; meanwhile, the battery-grade lithium carbonate has the advantages of low production cost, short process flow, high cost performance, easy industrial production and obvious economic benefit.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, and in particular to a kind of to be prepared by raw material of the richness lithium solution of salt lake bittern
The method of brine battery-level lithium carbonate.The brine battery-level lithium carbonate can be used as a kind of for producing lithium ion cell positive material
The lithium source of material --- LiFePO4, ternary material.
Background technology
Battery-level lithium carbonate（Li2CO3）It is a kind of important inorganic chemical product.With electronics, the height of electric vehicle industry
Speed development, the usage amount of battery-level lithium carbonate increase rapidly.Battery-level lithium carbonate its purity, price and added value are compared with technical grade
Lithium carbonate is high.Currently, battery-level lithium carbonate is mainly for the preparation of anode material for lithium-ion batteries（Cobalt acid lithium, ternary material, phosphoric acid
Iron lithium etc.）.
The production of lithium carbonate withLithiumOre（Spodumene, lepidolite）And brine is raw material.The whole world is produced by raw material of brine
Lithium carbonate account for about the 85% of lithium carbonate yield.Since global most salt lake resources are all the low lithium types of high magnesium（Mg/Li is usual
For 10-1837）, therefore extraction prepares lithium carbonate and there is a problem of that technological difficulty is big from the low lithium of high magnesium old halogen.LITHIUM BATTERY
Lithium carbonate is stringent to the quality requirement of lithium carbonate product.The battery-level lithium carbonate that China is produced using ore as raw material, it is desirable that its
Li2CO3Content >=99.5%, impurity Pb contents<0.0003%, Ca<0.005%、Mg<0.008%.It is tentatively verified in Qinghai Salt Lake
Lithium chloride reserves up to 22,480,000 tons, it is the first to occupy China.To make full use of Qinghai Salt Lake resource, at present usually in the conventional way
From salt lake bittern（Mg/Li is than 10~1630）After middle separation and Extraction sodium, potassium, boron and most of magnesium, then respectively in the following manner
Produce battery-level lithium carbonate：First, electrodialysis ion-selective membrane isolation technics is used, such as Qinghai Li Ye companies；Second is that utilizing ion
Switching technology（Absorption method）, such as Qinghai Saltlake Fozhao Lake Lithium Co., Ltd.；Third, carrying out magnesium lithium point using calcination method
From such as Investment Co., Ltd of CITIC Guoan.Above-mentioned three kinds of technology paths are used in actual production.From energy consumption, ring
Protect etc. considers that ion-selective membrane isolation technics and absorption method separating magnesium and lithium technology are by the old halogen of Qinghai-Tibet salt lake high Mg/Li ratio
Prepare the convenient technology of lithium carbonate.
Brine battery-level lithium carbonate provincial standard（DB63/T1113-2012）It is required that the content of magnesium of lithium carbonate product be less than etc.
In 0.015%.Since Qinghai Salt Lake lithium resource is present in high Mg/Li ratio（Mg/Li is than 40~1837）In brine, separating magnesium and lithium technology
Difficulty is big, is difficult that the magnesium in brine is dropped to very low range in production process, content of magnesium is general in the lithium carbonate product of output
Between 0.02%~0.03%.Therefore, lithium carbonate is produced by raw material of the old halogen of high Mg/Li ratio, it usually needs add depth demagging work
Sequence thereby increases the production cost of lithium carbonate product so that the content of magnesium of product is controlled less than or equal to 0.015%.Such as disclosure
Number CN102976367A, denomination of invention " a method of producing battery-level lithium carbonate using salt lake bittern "；And publication number
CN105540619A, denomination of invention " a method of directly producing out battery-level lithium carbonate from salt lake brine with high magnesium-lithium ratio ",
Depth or multiple demagging process are all referred to.China withLithiumOre（Spodumene, lepidolite）Battery-level lithium carbonate is prepared for raw material
It is required that its Mg content<0.008%, prepare battery-level lithium carbonate requirement its Mg content by raw material of brine<0.015%.As it can be seen that traditional
The battery-level lithium carbonate of concept has stringent limitation using magnesium as a kind of impurity, to its content.
Although battery-level lithium carbonate professional standard (YS/T582-2013) has relevant regulatory requirements to the quality of lithium carbonate（In detail
It is shown in Table 1）：
The requirement of 1 battery-level lithium carbonate major impurity of table/<%
| Li2CO3 | Mg | Na | Fe | Pb | Ca | Al | Si | Cl | SO4 2- |
| 99.5 | 0.008 | 0.025 | 0.001 | 0.0003 | 0.005 | 0.001 | 0.003 | 0.003 | 0.08 |
But the present invention is according to will usually add the Hubeiwans such as magnesium when preparing LiFePO4, ternary material（With beneficial element
Organic salt, the addition of inorganic salts form, or it is compound in advance in ferric phosphate, ferrous oxalate, nickel cobalt manganese hydroxide）To carry
The actual conditions of its high electrical property, when preparing battery-level lithium carbonate as raw material using the richness lithium solution of salt lake bittern, only appropriateness is removed
Remove the magnesium in raw material（Save depth demagging process）, you can it is prepared containing appropriate magnesium（Content of magnesium is significantly higher than industry mark
It is accurate）, or the battery-level lithium carbonate containing appropriate magnesium and rare earth Hubeiwan, and using this battery-level lithium carbonate as raw material, realize lithium
Ion battery positive electrode（LiFePO4, ternary material）The Uniform Doped of magnesium and/or rare earth Hubeiwan, it is electrical to obtain
The advantageous anode material for lithium-ion batteries of energy.This can both reduce the old stew in soy sauce in salt lake for the production cost of battery-level lithium carbonate, also
Impurity magnesium can be turned harm into good, realize high-qualityization of magnesium.Above-mentioned technical method at home and abroad so far there are no relevant report.
Invention content
In order to solve in the prior art, battery-level lithium carbonate is prepared as raw material using the old halogen of the low lithium of high magnesium and is needed to obtained richness
Lithium solution deep or multiple demagging, production cost are higher.Battery-level lithium carbonate obtained is as production LiFePO4, ternary material
Lithium source when, be difficult to be uniformly mixed, influence the electrical property of material when adulterating with the magnesium salts of addition or Hubeiwan (magnesium, rare earth),
There is also the abrasive material time it is longer the problems such as, the present invention provides a kind of preparation methods of brine battery-level lithium carbonate.By this method
Brine battery-level lithium carbonate obtained, content of magnesium are 0.045%~1.3%, realize the high-valued and lithium ion of impurity magnesium
The Uniform Doped of cell positive material --- LiFePO4, ternary material magnesium or magnesium and rare earth is conducive to improve lithium ion anode
Electrical property of material, including discharge performance, high rate performance and cycle performance etc..Meanwhile the life of battery-level lithium carbonate of the present invention
Production cost is relatively low, and technological process is more brief, cost-effective, is easy to industrialized production, can generate more significant economic benefit.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of brine battery-level lithium carbonate, it is characterised in that：By Li contents be 300~6000mg/L old halogen into
Row richness lithium drop magnesium processing, acquisition Li contents are 6.0~38g/L, Mg contents are 8~1740mg/L, Ca contents are 1.2~50mg/L
Chlorination lithium salts richness lithium solution after, chlorination lithium salts richness lithium solution is warming up to 70~95 DEG C, Na is added under agitation2CO3It is molten
Liquid finishes Na2CO3Solution continues to be stirred to react 60~130min, finally through synthesizing, being filtered, washed, dry obtained Li2CO3Contain
Amount is the brine battery-level lithium carbonate product that 93.9~99.4%, Mg contents are 0.04~1.3%.
When the synthesis temperature of lithium carbonate is higher, i.e., the temperature of the described chlorination lithium salts richness lithium solution is up to 85~95 DEG C, in order to
The granularity of lithium carbonate product is efficiently controlled, usually before synthetic reaction also into sodium carbonate liquor or chlorination lithium salts richness lithium solution
Polyethylene glycol is added, the addition of the polyethylene glycol is the 0.2~0.4% of lithium carbonate product weight.
The Na2CO3Solution, wherein Na2CO3Content be 200~310g/L, the content of Mg is 20~30mg/L, often
Rise Na in chlorination lithium salts richness lithium solution2CO3The addition of solution is 1.07~1.17 times of stoichiometry.
In order to make lithium carbonate product that there is more preferably performance, can also Na be added2CO3To lithium chloride while solution
The earth solution of the rare earth containing Hubeiwan is slowly added dropwise in salt richness lithium solution；The earth solution is rare earth element ce, La, Nd
In one or more inorganic compound solutions, also or be that one or more in rare earth element ce, La, Nd organise
Polymer solution；The content of the earth solution middle rare earth is 5.0~80g/L, and rare earth is in brine battery-level lithium carbonate product
Content is：0.05~3.2%.
As the Li/Ca mass ratio ＜ 4300 of the chlorination lithium salts richness lithium solution, the Ca being first selectively removed in solution is miscellaneous
After matter, Na is added2CO3Solution, specific method are：The hydrogen of a concentration of 75~120g/L is added in chlorination lithium salts richness lithium solution
It is 6.5~7.0 that sodium hydroxide solution, which adjusts pH value, is warming up to 30~60 DEG C, then 1.7~2.2 times of additions stoichiometrically
Na2CO3, 40~60min is reacted, removes in rich lithium solution 70~94% Ca impurity using filter.
The mode that magnesium salts is added into rich lithium solution also can be used in Mg contents in the brine battery-level lithium carbonate product
It is adjusted, controls；The magnesium salts is magnesium chloride, magnesium sulfate, magnesium nitrate or magnesium acetate.
The synthesis is filtered, washed, dries and refers to：Na2CO3Solution is chemically reacted with chlorination lithium salts richness lithium solution
Afterwards, by material filtering, then with temperature it is 70~90 DEG C of pure water, by the weight ratio washing filter cake of wash water/product=3.7~5.6,
Then filter cake is subjected to drying and processing at a temperature of 130~350 DEG C.
The Li contents are the old halogen of 300~6000mg/L, are that salt lake bittern passes through precipitation NaCl, analysis according to a conventional method
Go out KCl, be settled out sulfate（Including potassium sulfate, potassium magnesium sulfate, calcium sulfate）, be precipitated magnesium salts, be precipitated boron compound after obtain.
The described rich lithium drop magnesium is and to combine chemical precipitation using ion-selective membrane isolation technics or ion exchange technique
Method, concentration method, to the rich lithium solution that is obtained through ion-selective membrane partition method or ion-exchange carry out further concentration lithium and
Demagging, Calcium treatment.
It illustrates：Percentage involved by heretofore described " content " is weight percentage.
Compared with prior art, the present invention has the following advantages and beneficial effect：
When 1, preparing battery-level lithium carbonate as raw material using the salt lake bittern of the low lithium of high magnesium due to the prior art, typically contained using magnesium
Measure the rich lithium solution of as low as possible (the about 0.5mg/L containing Mg) and the Na of purified demagging2CO3Solution (10mg/L of ＜ containing Mg), therefore
It must be to lithium salt solution and sodium carbonate liquor depth demagging, to ensure that battery-level lithium carbonate product reaches Li2CO3Content >=
99.5%, the quality requirement of Mg content≤0.015%, production process is more, flow is longer, cost is higher；
And the present invention when preparing LiFePO4, ternary material according to will usually add the Hubeiwans such as magnesium to improve its electrical property
Actual conditions, when preparing battery-level lithium carbonate as raw material using the richness lithium solution of salt lake bittern, only by ion select
The lithium solution of membrane separation technique or absorption method richness lithium drop magnesium is eliminated depth demagging process, is permitted with chemical precipitation method appropriateness demagging
Perhaps there is product higher Mg, Mg contents may be up to 0.04~1.3%；Sodium carbonate is only removed by filtration after being dissolved in pure water simultaneously
Insoluble matter eliminates Na2CO3Solution individually purifies demagging process.Thus its technological process is more brief, and production cost is relatively
It is low, it is easy to industrialized production, economic benefit is more significant.
Although the 2, Li of brine battery-level lithium carbonate product prepared by the present invention2CO3Content is only 93.9~99.4%（Significantly
Less than the 99.5% of professional standard）, but impurity magnesium and/or rare earth due to being distributed in lithium carbonate, preparing lithium ion battery
Anode material for lithium-ion batteries is easily achieved when positive electrode（LiFePO4, ternary material）The Uniform Doped of magnesium and/or rare earth,
Therefore, with excellent performance, performance when brine battery-level lithium carbonate of the present invention is used as the lithium source of the positive material material of lithium electricity
Price is relatively high.
Specific implementation mode
For the technology contents that the present invention will be described in detail and the technique effect realized, following examples are provided, but implement
Example is not construed as limiting the invention itself.
Embodiment 1（Including embodiment 1-1,1-2,1-3）
The old halogen that Li contents are 1500mg/L uses ion-selective membrane isolation technics（Old halogen membrane separation process）Rich lithium drops magnesium, with carbonic acid
Sodium solution appropriateness demagging, concentration, it is 13.2mg/L, Ca that its Li content of the lithium chloride richness lithium solution of acquisition, which is 12.5g/L, Mg content,
Content is 2.8mg/L；The Li/Ca mass ratioes ≈ 4464 of solution, Mg/Li mass ratioes ≈ 0.00106.
Embodiment 1-1
Rich lithium solution 3L is taken, is added in reaction kettle, is warming up to 70 DEG C, Na is added under agitation2CO3Solution（Wherein,
Na2CO3Content is that 282g/L, Mg content are 29mg/L；Na2CO3Dosage is 1.16 times of stoichiometry）1.18L finishes Na2CO3
Solution continues to be stirred to react 100min, filtering, then fully washs filter cake with the pure water 600mL that temperature is 80 DEG C, then will obtain
Lithium carbonate filter cake（Containing attached water 29.5%）In 130 DEG C of drying to get brine battery-level lithium carbonate product 159.7g；Lithium is primary
Yield 79.50%.
Its Li of the product2CO3Content be 99.4%, Mg contents be 0.045%, Ca contents are 0.005%, D50（Average grain diameter）
3.6μm。
Synthesis finishes, filter gained synthesis mother liquid and washing lotion in contain about 9g/L Li2CO3, returned according to a conventional method
Receipts.
Embodiment 1-2
Rich lithium solution 3L is taken, is added in reactor, is warming up to 90 DEG C, MgCl is added2·6H2O 17.5g, stirring and dissolving；Exist again
Na is added under stirring condition2CO3Solution (wherein, Na2CO3Content is that 282g/L, Mg content are 29mg/L；Dissolved with polyethylene glycol
0.51g；Na2CO3Dosage is 1.16 times of stoichiometry) 1.18L, finish Na2CO3Solution continues to be stirred to react 60min, mistake
Filter, then filter cake is fully washed with the pure water 670mL that temperature is 85 DEG C, then by the lithium carbonate filter cake of acquisition in 230 DEG C of drying, i.e.,
Obtain brine battery-level lithium carbonate product 170.7g；Yield 81.02% of lithium.
Its Li of the product2CO3Content is that 94.7%, Mg contents are 1.28%, Pb contents<0.0001%, Fe content 0.0005%,
D50 4.2μm。
Synthesis finishes, and filters and contains Li in the synthesis mother liquid of gained2CO3 About 8g/L, the about 56g/L containing NaCl, according to a conventional method
It is recycled.
Embodiment 1-3
Rich lithium solution 3L is taken, is added in reactor, is warming up to 80 DEG C, magnesium chloride is added（Mg 0.96g are added）, stirring and dissolving；Again
Na is added under agitation2CO3Solution (wherein, Na2CO3Content is that 296g/L, Mg content are 30mg/L；Na2CO3Dosage is
1.17 times of stoichiometry) 1.15L, while solution of cerium chloride by oxidation 16mL is slowly added dropwise（Contain Ce 0.082g）, finish Na2CO3It is molten
Liquid continues to be stirred to react 80min, filtering, then fully washs filter cake with the pure water 700mL that temperature is 70 DEG C, then by acquisition
Lithium carbonate filter cake（Containing attached water 30%）In 160 DEG C of drying to get brine battery-level lithium carbonate product 163.9g.
Its Li of the product2CO3Content be 97.0%, Mg contents be 0.63%, Ce contents are 0.050%, Pb contents<0.0003%.
Embodiment 2（Including embodiment 2-1,2-2,2-3）
Using old halogen membrane separation process richness lithium drop magnesium, sodium carbonate liquor appropriateness demagging, concentration, it is that 16.2g/L, Mg contain to obtain Li contents
Amount is the rich lithium solution that 50mg/L, Ca content are 3.7mg/L；The Li/Ca mass ratioes ≈ 4378 of solution, Mg/Li mass ratioes ≈
0.0031。
Embodiment 2-1
Rich lithium solution 3L is taken, is added in reaction kettle, is warming up to 80 DEG C, Na is added under agitation2CO3Solution（Wherein,
Na2CO3Content is that 269g/L, Mg content are 27mg/L；Na2CO3Dosage is 1.09 times of stoichiometry), while chlorine is slowly added dropwise
Change lanthanum solution 92mL（79.7g/L containing La）, finish Na2CO3Solution continues to be stirred to react 90min, filtering, then with temperature for 85
DEG C pure water 920mL fully wash filter cake, then by the lithium carbonate filter cake of acquisition（Containing attached water 30.1%）In 150 DEG C of drying, i.e.,
Obtain brine battery-level lithium carbonate product 229.5g.
Its Li of the product2CO3Content be 93.9%, Mg contents be 0.083%, La contents are 3.2%, Ca contents are 0.005%,
D50 4.4μm。
Synthesis finishes, filter gained synthesis mother liquid and washing lotion in contain about 8.4g/L Li2CO3, carry out according to a conventional method
Recycling.
Embodiment 2-2
Rich lithium solution 3L is taken, is added in reactor, is warming up to 80 DEG C, the epsom salt of 12.53g is added（Containing Mg1.23g）, stir
Dissolving is mixed, Na is added under stirring condition2CO3Solution (wherein, Na2CO3Content is that 270g/L, Mg content are 27mg/L；
Na2CO3Dosage is 1.12 times of stoichiometry) 1.54L, while the solution of cerium chloride by oxidation of 15mL is slowly added dropwise (containing Ce
0.45g), Na is finished2CO3Solution continues to be stirred to react 100min, filtering, then is fully washed with the pure water 900mL that temperature is 70 DEG C
Filter cake is washed, then by the lithium carbonate filter cake of acquisition（Containing attached water 31%）It is produced to get brine battery-level lithium carbonate in 160 DEG C of drying
Product 221.3g.
Its Li of the product2CO3Content be 96.6%, Mg contents be 0.64%, Ce contents are 0.20%, Pb contents<0.0003%,
D50 4.5μm。
Embodiment 2-3
Rich lithium solution 3L is taken, is added in reactor, is warming up to 90 DEG C, magnesium chloride is added（2.30g containing Mg）, stirring and dissolving；Then at
Na is added under stirring condition2CO3Solution (wherein, Na2CO3Content is that 210g/L, Mg content are 21mg/L；Dissolved with polyethylene glycol
0.67g；Na2CO3Dosage is 1.12 times of stoichiometry) 1.98L, while the neodymium nitrate solution that 23mL is slowly added dropwise (contains Nd
0.23g), Na is finished2CO3Solution continues to be stirred to react 60min, filtering, then is fully washed with the pure water 870mL that temperature is 80 DEG C
Then filter cake dries the lithium carbonate filter cake of acquisition to get brine battery-level lithium carbonate product 220.9g in 140 DEG C.
Its Li of the product2CO3Content be 97.0%, Mg contents be 0.61%, Nd contents are 0.10%, Pb contents<0.0003%,
D50 4.6μm。
Embodiment 3（Including embodiment 3-1,3-2）
The old halogen that Li contents are 5800mg/L drops magnesium, then appropriate demagging, concentration using ion-selective membrane isolation technics richness lithium, obtains
Lithium chloride richness lithium solution its Li content be 24.9g/L, Mg content be 1500mg/L, Ca content be 5.7mg/L；The Li/ of solution
Ca mass ratioes ≈ 4368, Mg/Li mass ratioes ≈ 0.0602.
Embodiment 3-1
Rich lithium solution 3L is taken, is added in reactor, is warming up to 80 DEG C, Na is added under stirring condition2CO3Solution is (wherein,
Na2CO3Content is that 270g/L, Mg content are 27mg/L；Na2CO3Dosage is 1.07 times of stoichiometry) 2.35L, it finishes
Na2CO3Solution continues to be stirred to react 100min, filtering, then fully washs filter cake with the pure water 1400mL that temperature is 70 DEG C, then
By the lithium carbonate filter cake of acquisition in 200 DEG C of drying to get brine battery-level lithium carbonate product 360.5g.
Its Li of the product2CO3Content is that 94.5%, Mg contents are 1.25%, Pb contents<0.0003%, Ca contents are 0.005%,
D50 4.5μm。
Embodiment 3-2
Rich lithium solution 3L is taken, is added in reactor, is warming up to 90 DEG C；Na is added under stirring condition2CO3Solution is (wherein,
Na2CO3Content is that 280g/L, Mg content are 27mg/L, dissolved with polyethylene glycol 1.0g；Na2CO3Dosage is the 1.11 of stoichiometry
Times) 2.35L, while solution of cerium chloride by oxidation 32.7mL (containing Ce 1.63g) is slowly added dropwise, finish Na2CO3It is anti-to continue stirring for solution
80min is answered, is filtered, then filter cake is fully washed with the pure water 1500mL that temperature is 80 DEG C, then by the lithium carbonate filter cake of acquisition（Contain
Attached water 29.2%）In 300 DEG C of drying to get brine battery-level lithium carbonate product 363.1g.
Its Li of the product2CO3Content be 94.0%, Mg contents be 1.25%, Ce contents are 0.45%, Pb contents<0.0003%、
Ca contents are 0.005%, D50 4.3μm。
Embodiment 4
Using old halogen membrane separation process richness lithium drop magnesium, sodium carbonate liquor appropriateness demagging, the Li contents of acquisition are that 6.2g/L, Mg content are
The rich lithium solution that 147mg/L, Ca content are 1.2mg/L is raw material；The Li/Ca mass ratioes ≈ 5167 of solution, Mg/Li mass ratioes ≈
0.024。
Rich lithium solution 3L is taken, is added in reactor, is warming up to 90 DEG C, Na is added under stirring condition2CO3Solution is (wherein,
Na2CO3Content is that 290g/L, Mg content are 28mg/L, dissolved with polyethylene glycol 0.24g；Na2CO3Dosage is the 1.11 of stoichiometry
Times) 550mL, finish Na2CO3Solution continues to be stirred to react 90min, filtering, then abundant with the pure water 360mL that temperature is 80 DEG C
Filter cake is washed, then dries the lithium carbonate filter cake of acquisition to get brine battery-level lithium carbonate product 71.6g in 180 DEG C.
Its Li of the product2CO3Content is that 97.1%, Mg contents are 0.63%, Pb contents<0.0003%, Ca contents are 0.005%,
D50 4.7μm。
Embodiment 5
The old halogen that Li contents are 500mg/L drops the magnesium, demagging of sodium carbonate liquor appropriateness, dense using ion-selective membrane isolation technics richness lithium
Contracting, it is the rich lithium solution that 310mg/L, Ca content are 1.4mg/L that the Li contents of acquisition, which are 6.7g/L, Mg content,；The Li/Ca of solution
Mass ratio ≈ 4786, Mg/Li mass ratioes ≈ 0.046.
Rich lithium solution 3L is taken, is added in reactor, is warming up to 90 DEG C, Na is added under stirring condition2CO3Solution (its
In, Na2CO3Content is that 310g/L, Mg content are 28mg/L, is dissolved with polyethylene glycol 0.27g；Na2CO3Dosage is stoichiometry
1.08 times) 550mL, finish Na2CO3Solution continues to be stirred to react 100min, filtering, then the pure water for being 93 DEG C with temperature
320mL fully washs filter cake, then dries the lithium carbonate filter cake of acquisition to get brine battery-level lithium carbonate product in 350 DEG C
82.3g。
Its Li of the product2CO3Content is that 95.5%, Mg contents are 1.14%, Pb contents<0.0003%, D50 4.6μm。
Embodiment 6（Including embodiment 6-1,6-2,6-3,6-4）
The old halogen that Li contents are 300mg/L is used into absorption method（Ion-exchange）Magnesium drops in rich lithium, and concentration, obtaining Li contents is
13.6g/L, Mg content are the lithium chloride richness lithium solution that 70mg/L, Ca content are 50mg/L, Li/Ca mass ratioes=272, Mg/Li
Mass ratio ≈ 0.005；Then be added in chlorination lithium salts richness lithium solution a concentration of 70g/L sodium hydroxide solution adjust pH value be
6.5,30 DEG C are warming up to, 2.2 times of addition Na stoichiometrically2CO3, 40min is reacted, obtaining Li contents using filter is
13.5g/L, Mg content are that 52mg/L, Ca content are 3mg/L（94% Ca is removed）Lithium chloride richness lithium solution.
Embodiment 6-1
Rich lithium solution 3L is taken, is added in reactor, is warming up to 95 DEG C；Na is added under stirring condition2CO3Solution is (wherein,
Na2CO3Content is that 305g/L, Mg content are 30mg/L, dissolved with the polyethylene glycol of 0.71g；Na2CO3Dosage is stoichiometry
1.16 times) 1.18L, finish Na2CO3Solution continues to be stirred to react 60min, filtering, then with pure water 1000mL at a temperature of 90 °C
Then fully washing filter cake dries the lithium carbonate filter cake of acquisition to get brine battery-level lithium carbonate product in 250 DEG C
179.1g。
Its Li of the product2CO3Content be 99.1%, Mg contents be 0.11%, Ca contents are 0.005%, Pb contents<0.0003%,
D50 4.8um。
Embodiment 6-2
Rich lithium solution 3L is taken, is added in reactor, is warming up to 80 DEG C, the magnesium chloride of 17.7g is added（Containing 2.10 g of Mg）, stirring
Dissolving；Na is added under stirring condition2CO3Solution (wherein, Na2CO3Content is that 290g/L, Mg content are 29mg/L；Na2CO3
Dosage is 1.11 times of stoichiometry) 1.22L, finish Na2CO3Solution continues to be stirred to react 120min, filtering, then with temperature
Filter cake is washed for 85 DEG C of pure water 900mL, then by the lithium carbonate filter cake of acquisition（Containing attached water 30.2%）In 150 DEG C of drying, i.e.,
Obtain brine battery-level lithium carbonate product 185.2g.
Its Li of the product2CO3Content be 94.7%, Mg contents be 1.22%, Ca contents are 0.007%, Pb contents<0.0003%.
Embodiment 6-3
Rich lithium solution 3L is taken, is added in reactor, is warming up to 75 DEG C, 8.10g magnesium chlorides are added（0.96g containing Mg）, stir molten
Solution；Na is added under stirring condition2CO3Solution (wherein, Na2CO3Content is that 280g/L, Mg content are 28mg/L；Na2CO3With
Amount is 1.14 times of stoichiometry) 1.28L, finish Na2CO3Solution continues to be stirred to react 110min, filtering, then is with temperature
80 DEG C of pure water 900mL washs filter cake, then dries the lithium carbonate filter cake of acquisition to get brine LITHIUM BATTERY carbonic acid in 170 DEG C
Lithium product 180.8g.
Its Li of the product2CO3Content is that 96.9%, Mg contents are 0.64%, Pb contents<0.0001%.
Embodiment 6-4
Rich lithium solution 3L is taken, is added in reactor, is warming up to 93 DEG C, magnesium chloride is added（0.81g containing Mg）6.83g, polyethylene glycol
0.74g, stirring and dissolving；Na is added under stirring condition2CO3Solution 1.22L (wherein, Na2CO3Content is that 290g/L, Mg contain
Amount is 29mg/L；Na2CO3Dosage is 1.22 times of stoichiometry), while the solution of cerium chloride by oxidation of 44mL is slowly added dropwise (containing Ce
0.66 g), finishes Na2CO3Solution continues to be stirred to react 60min, filtering, then is washed and filtered with pure water 1000mL at a temperature of 90 °C
Cake, then by the lithium carbonate filter cake of acquisition（Containing attached water 30%）In 200 DEG C of drying to get brine battery-level lithium carbonate product
183.8g。
Its Li of the product2CO3Content be 96.90%, Mg contents be 0.54%, Ce contents are 0.36%, Pb contents<0.0001%.
Embodiment 7（Including embodiment 7-1,7-2）
Using absorption method（Ion-exchange）Magnesium drops in rich lithium, concentrated, and it is 1.74g/ that acquisition Li contents, which are 29.9g/L, Mg content,
L, Ca contents are the lithium chloride richness lithium solution of 17mg/L, Li/Ca mass ratioes ≈ 1759, Mg/Li mass ratioes ≈ 0.0589；
The sodium hydroxide solution adjusting pH value that a concentration of 120g/L is added into chlorination lithium salts richness lithium solution is 7.0, is warming up to 60
DEG C, the Na of 1.7 times of stoichiometry is added under stirring condition2CO3Solution reacts 60min, and obtaining Li contents using filter is
29.7g/L, Mg content are that 1.73g/L, Ca content are 5mg/L（70.5% Ca is removed）Lithium chloride richness lithium solution.
Embodiment 7-1
Rich lithium solution 3L is taken, is added in reactor, is warming up to 90 DEG C, Na is added under stirring condition2CO3Solution is (wherein,
Na2CO3Content is that 290g/L, Mg content are 29mg/L, dissolved with polyethylene glycol 1.79g；Na2CO3Dosage is the 1.11 of stoichiometry
Times) 2.70L, it is stirred to react 120min, is filtered, then filter cake is washed with water 1700mL at a temperature of 90 °C, then by the carbon of acquisition
Sour lithium filter cake is in 200 DEG C of drying to get brine battery-level lithium carbonate product 444.9g.
Its Li of the product2CO3Content 94.9%, Mg contents 1.18%, Ca contents 0.003%, Pb contents<0.0001%.
Embodiment 7-2
Rich lithium solution 3L is taken, is added in reactor, is warming up to 80 DEG C, Na is added under stirring condition2CO3Solution is (wherein,
Na2CO3Content is that 290g/L, Mg content are 29mg/L, Na2CO3Dosage is 1.11 times of stoichiometry) 2.70L, while slowly
Mixed chlorinated rare earth solution 55mL is added dropwise（The partition of wherein La, Ce, Rd are respectively 33%, 52%, 15%, and rare earth is added altogether
0.52g), Na is finished2CO3Solution continues to be stirred to react 130min, filtering, then the water 1700mL washing filters for being 80 DEG C with temperature
Then cake dries the lithium carbonate filter cake of acquisition to get brine battery-level lithium carbonate product 439.8g in 300 DEG C.
Its Li of the product2CO3Content be 94.5%, Mg contents be 0.56%, content of rare earth 0.12%, Pb contents<
0.0001%。
Embodiment 8
It using old halogen membrane separation process richness lithium drop magnesium, the demagging of sodium carbonate liquor appropriateness, is concentrated by evaporation, the Li contents of acquisition are 37.2g/
L, it is raw material that Mg contents, which are the rich lithium solution that 882mg/L, Ca content are 7.1mg/L,；The Li/Ca mass ratioes ≈ 5239, Mg/ of solution
Li mass ratioes ≈ 0.024.
Rich lithium solution 3L is taken, is added in reactor, is warming up to 90 DEG C, Na is added under stirring condition2CO3Solution is (wherein,
Na2CO3Content is that 290g/L, Mg content are 28mg/L, dissolved with polyethylene glycol 1.63g；Na2CO3Dosage is the 1.11 of stoichiometry
Times) 3300mL, finish Na2CO3Solution continues to be stirred to react 80min, filtering, then is filled with pure water 2600mL at a temperature of 90 °C
Divide washing filter cake, then dries the lithium carbonate filter cake of acquisition to get brine battery-level lithium carbonate product 543.3g in 180 DEG C.
Its Li of the product2CO3Content is that 97.6%, Mg contents are 0.50%, Pb contents<0.0001%, Ca contents are 0.004%,
D50 4.5μm。
Contrast experiment
Under identical experiment condition, the lithium carbonate produced using the embodiment of the present invention and A factories makees lithium source synthesizing iron lithium phosphate
The part electrical performance data of positive electrode, obtained LiFePO4 is as shown in the table：
The electric performance test data of the LiFePO4 prepared using the lithium carbonate of different content of magnesium as lithium source shown in upper table can
See, it is higher with content of magnesium prepared by the present invention（Mg contents 0.045~1.25%）Lithium carbonate be raw material, preparing LiFePO4
When be advantageously implemented magnesium（Or magnesium and rare earth）Uniform Doped, the lithium iron phosphate positive material prepared its 0.1C discharge performance,
The more conventional brine battery-level lithium carbonate of 1C discharge performances is the more excellent of lithium source.With mixed with magnesium or mixed with magnesium and the LITHIUM BATTERY carbon of rare earth
Sour lithium is lithium source synthesizing iron lithium phosphate, is conducive to obtain the more excellent lithium iron phosphate positive material of discharge performance.
Claims (10)
1. a kind of preparation method of brine battery-level lithium carbonate, it is characterised in that：By the old halogen that Li contents are 300~6000mg/L
Carry out rich lithium drop magnesium processing, obtain Li contents be 6.0~38g/L, Mg contents are 8.0~1740mg/L, Ca contents be 1.2~
After the chlorination lithium salts richness lithium solution of 50mg/L, chlorination lithium salts richness lithium solution is warming up to 70~95 DEG C, is added under agitation
Na2CO3Solution finishes Na2CO3Solution continues to be stirred to react 60~130 min, finally through synthesizing, being filtered, washed, dry system
Obtain Li2CO3Content is the brine battery-level lithium carbonate product that 93.9~99.4%, Mg contents are 0.04~1.3%.
2. a kind of preparation method of brine battery-level lithium carbonate according to claim 1, it is characterised in that：The lithium chloride
When the temperature of salt richness lithium solution is up to 85~95 DEG C, it is added into sodium carbonate liquor or chlorination lithium salts richness lithium solution before synthetic reaction
Polyethylene glycol；The addition of the polyethylene glycol is the 0.2~0.4% of lithium carbonate product weight.
3. a kind of preparation method of brine battery-level lithium carbonate according to claim 1, it is characterised in that：Described
Na2CO3Solution, wherein Na2CO3Content be 200~310g/L, the content of Mg is 20~30mg/L, every liter of chlorination lithium salts richness lithium
Na in solution2CO3The addition of solution is 1.07~1.17 times of stoichiometry.
4. a kind of preparation method of brine battery-level lithium carbonate according to claim 1, it is characterised in that：The Na2CO3
Solution is slowly added dropwise the earth solution of the rare earth containing Hubeiwan while being added, the earth solution be rare earth element ce,
One or more inorganic compound solutions of La, Nd；Either rare earth element ce, the one or more of La, Nd organise
Polymer solution.
5. a kind of preparation method of brine battery-level lithium carbonate according to claim 4, it is characterised in that：The rare earth is molten
The content of liquid middle rare earth is 5.0~80g/L, and content of the rare earth in brine battery-level lithium carbonate product is：0.05~3.2%.
6. a kind of preparation method of brine battery-level lithium carbonate according to claim 1, it is characterised in that：The lithium chloride
When the Li/Ca mass ratio ＜ 4300 of salt richness lithium solution, after first removing the Ca impurity in solution, Na is added2CO3Solution, specific side
Method is：Be added in chlorination lithium salts richness lithium solution a concentration of 70~120g/L sodium hydroxide solution adjust pH value be 6.5~
7.0,30~60 DEG C are warming up to, then 1.7~2.2 times of addition Na stoichiometrically2CO3, 40~60min is reacted, using filter
In rich lithium solution 70~94% Ca impurity is removed.
7. a kind of preparation method of brine battery-level lithium carbonate according to claim 1, it is characterised in that：The brine electricity
Mg contents in the level lithium carbonate product of pond are adjusted by the way of adding magnesium salts into rich lithium solution, are controlled；The magnesium
Salt is magnesium chloride, magnesium sulfate, magnesium nitrate or magnesium acetate.
8. a kind of preparation method of brine battery-level lithium carbonate according to claim 1, it is characterised in that：The conjunction
At, be filtered, washed, dry and refer to：Na2CO3After solution is chemically reacted with chlorination lithium salts richness lithium solution, by material filtering, then
Be 70~90 DEG C of pure water with temperature, by the weight ratio washing filter cake of wash water/product=3.7~5.6, then by filter cake in 130~
Drying and processing is carried out at a temperature of 350 DEG C.
9. a kind of preparation method of brine battery-level lithium carbonate according to claim 1, it is characterised in that：The Li contains
Amount is the old halogen of 300~6000mg/L, is salt lake bittern by NaCl is precipitated, and KCl is precipitated, be settled out potassium sulfate, potassium magnesium sulfate,
Magnesium salts is precipitated in calcium sulfate, is obtained after boron compound is precipitated.
10. a kind of preparation method of brine battery-level lithium carbonate according to claim 1, it is characterised in that：The richness
It is using ion-selective membrane isolation technics or ion exchange technique, and combination chemical precipitation method, concentration method, to through ion that magnesium drops in lithium
The rich lithium solution that selection membrane separation process or ion-exchange obtain carries out further concentration lithium and demagging, Calcium treatment.
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| CN109987618A (en) * | 2019-04-12 | 2019-07-09 | 中国科学院青海盐湖研究所 | The preparation method of battery-level lithium carbonate |
| CN117125683A (en) * | 2020-11-21 | 2023-11-28 | 周思齐 | Method for producing battery-grade lithium phosphate from salt lake brine |
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