CN106507705B - The method for removing calcium and magnesium impurity from the high lithium solution of calcium-magnesium-containing - Google Patents
The method for removing calcium and magnesium impurity from the high lithium solution of calcium-magnesium-containingInfo
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- CN106507705B CN106507705B CN200810078417.4A CN200810078417A CN106507705B CN 106507705 B CN106507705 B CN 106507705B CN 200810078417 A CN200810078417 A CN 200810078417A CN 106507705 B CN106507705 B CN 106507705B
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- magnesium
- calcium
- solution
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- carbonate
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Abstract
The present invention relates to a kind of method for removing calcium and magnesium in high lithium solution from calcium-magnesium-containing, the method is initially charged a certain amount of sodium carbonate liquor, add a certain amount of sodium hydroxide solution and adjust pH value, obtain the mixed slurry containing magnesium carbonate, calcium carbonate and magnesium hydroxide, calcium hydroxide, pour out supernatant, obtain compressing slurry, compression slurry is returned in lithium solution and repeats 6～8 times, qualified crystal seed is just obtained, crystal seed is added in lithium solution the good precipitation of sedimentation function is obtained, supernatant can go to precipitate and obtain qualified lithium carbonate.The inventive method substantially improves the strainability of slurry reaction liquid, with industrial practicality.The inventive method can remove calcium and magnesium impurity from the salt lake bittern of lithium high in salt, high, and reduce the loss of lithium during removing calcium and magnesium as far as possible, obtain the qualified material liquid for preparing lithium carbonate.
Description
Technical field
The present invention relates to the method that calcium and magnesium impurity is removed using chemical method, and in particular to a kind of from calcium-magnesium-containing
High lithium solution in remove calcium and magnesium impurity method.
Background technology
China is important lithium resource big country, and wherein bittern lithium accounts for the 79% of gross reserves, is distributed mainly on green grass or young crops
In the salt lake in sea and Tibet, therefore lithium carbonate is prepared with greatly reality meaning by raw material of salt lake bittern
Justice, can bring considerable economic benefit.Because salt lake bittern has higher Mg/Li ratio, using absorption method
The high lithium solution obtained from the technique of extracting lithium from salt lake brine still contains a small amount of magnesium, calcium, so by
Initial ion exchanges the necessary depth deliming of product liquid of Separation of Li and Mg, magnesium, could make as qualified products liquid
With so as to obtain satisfactory Li2CO3Product.Therefore, invent a kind of from simple possible and height
The deliming magnesium method of effect is very necessary.
Chemical method removing calcium and magnesium has equipment compared with the ion-exchange removing calcium and magnesium that chlorine industry is generally used
The advantages of small investment, simple technique, but under normal circumstances, magnesium hydroxide crystal particle is small, in cotton-shaped or
Colloidal, it is precipitated and strainability is poor, directly influences production efficiency, and in Ca2+With CaCO3
Form might have Li while be removed2CO3Generation causes the loss of lithium.
The content of the invention
It is an object of the invention to provide the side that calcium and magnesium impurity is removed in a kind of high lithium solution from calcium-magnesium-containing
Method, it can remove calcium and magnesium impurity from the salt lake bittern of high in salt, high lithium, and reduction is removed as far as possible
The loss of lithium during calcium and magnesium, obtains the qualified material liquid for being used to prepare lithium carbonate.
What the present invention was realized in：A kind of method that calcium and magnesium is removed in high lithium solution from calcium-magnesium-containing, institute
The high lithium solution for the calcium-magnesium-containing stated includes Li+15~20g/L, Na+50~70g/L, Mg2+0.1~
2.4g/L, Ca2+0.1~0.75g/L, this method is carried out as follows：
(1) sodium carbonate liquor is added into the high lithium solution of pending calcium-magnesium-containing, at 20 DEG C~40 DEG C
20~60min of stirring reaction；The sodium carbonate liquor concentration added is 30~70g/L, sodium carbonate amount
The 1~1.1 of theoretical amount for needed for institute's calcic, magnesium ion in pending solution are precipitated as carbonate completely
Times；
(2) sodium hydroxide solution is added into step (1) resulting solution, regulation reacting liquid pH value is arrived
11~12, continue to stir 40~60min, obtain containing magnesium carbonate, calcium carbonate and magnesium hydroxide, hydroxide
The mixed slurry of calcium, stands 15~20h by above-mentioned slurry, isolates supernatant liquor, obtains compressing slurry；
(3) the high lithium solution of the pending calcium-magnesium-containing of step (1) same amount is taken, above-mentioned steps are added
Gained compresses slurry, and repeat step (1) and step (2), obtains compressing slurry again；
(4) such as step (3) iterative cycles 6~8 times, the compression slurry as crystal seed finally obtained；
(5) add the high lithium solution of pending calcium-magnesium-containing into crystal seed obtained by step (4), crystal seed and
The volume ratio of the high lithium solution of pending calcium-magnesium-containing be 1: (1~3), then repeat step (1) and step
Suddenly (2), filter, finally obtain Mg in clear liquid and compression filter cake, clear liquid2+Concentration is 0.21~3.65mg/L,
Ca2+Concentration is 5.6~10.2mg/L, Li+Concentration is 10.9~14.5g/L, is used as the conjunction for preparing lithium carbonate
Reaction grid liquid.
The method that calcium and magnesium is removed in a kind of high lithium solution from calcium-magnesium-containing as described above, its step (5)
In be filtrated to get clear liquid and compression filter cake when, filtrate speed of production be 67.2~82.8L/m2H, liquid-solid ratio is
92~110, filtering rate is in 125~150L/min.
Effect of the invention is that：The present invention carries out separating calcium and magnesium for the first time by ion exchange, then locates repeatedly
Reason compression slurry formation crystal seed, last removing calcium and magnesium obtains the qualified reaction solution for being used to produce lithium carbonate.By
It is flocculent deposit in magnesium hydroxide, particle is excessively fine and closely woven, and sinking speed is very slow, and is difficult to filter, institute
Magnesium ion is first precipitated with sodium carbonate with the present invention, calcium carbonate and carbonic acid magnesium precipitate is produced, then again by adjusting
Section pH value obtains the precipitation mixture of magnesium carbonate and magnesium hydroxide.The carbonic acid magnesium precipitate being initially formed is to hydrogen-oxygen
The precipitation process for changing magnesium plays facilitation, while using the method for returning to magnesium hydroxide crystal seed, can make to sink
Shallow lake granularity is greatly increased, and improves its strainability, adds the feasibility of this technique, obtain calcic and
The low high lithium solution of magnesium.The inventive method substantially improves the strainability of slurry reaction liquid, with industry
On practicality.The inventive method can remove calcium and magnesium impurity from the salt lake bittern of high in salt, high lithium,
And the loss of lithium during removing calcium and magnesium is reduced as far as possible, obtain the qualified raw material for being used to prepare lithium carbonate
Liquid.
Specific embodiment
Embodiment 1
The lithium solution composition of calcium-magnesium-containing employed in the present embodiment is as follows：
The method that calcium and magnesium impurity is removed in high lithium solution of the present invention from calcium-magnesium-containing, it is by following step
It is rapid to carry out：
(1) sodium carbonate liquor is added into the lithium solution of calcium-magnesium-containing, in 30 DEG C of stirring reaction 20min；
The sodium carbonate liquor concentration of addition is 50g/L, and consumption is precipitated as carbon completely for institute's calcic, magnesium ion in liquid
Theoretical amount needed for hydrochlorate；
(2) and then sodium hydroxide solution regulation reacting liquid pH value is added, makes pH value to 11.5, continue
40min is stirred, the mixed slurry containing magnesium carbonate, calcium carbonate and magnesium hydroxide, calcium hydroxide is obtained, will
Above-mentioned slurry stands 15h, pours out supernatant, obtains compressing slurry；
(3) the lithium solution of the calcium-magnesium-containing of step (1) same amount is taken, adds and compressed obtained by step (2)
Slurry, and reacted by step (1) and (2) same method and consumption, supernatant is obtained again
With compression slurry；
(4) the method iterative cycles as described in step (3) 6 times, the compression slurry finally obtained is
Crystal seed；
(5) crystal seed 150ml obtained by step (4) is taken, the high lithium solution of pending calcium-magnesium-containing is added
300ml, then repeat step (1) and the same method of step (2) and consumption reacted, will be anti-
Liquid is answered to be filtrated to get clear liquid and compression filter cake, wherein slurries filtration speed is 125L/min, and liquid-solid ratio is
93, filtrate speed of production is 67.2L/m2Mg in h, clear liquid2+Concentration is 0.72mg/L, Ca2+Concentration is
10.2mg/L, Li+Concentration is 10.9g/L, can be used as the qualified reaction solution for preparing lithium carbonate.
Embodiment 2
The lithium solution composition of calcium-magnesium-containing employed in the present embodiment is as follows：
The method that calcium and magnesium impurity is removed in high lithium solution of the present invention from calcium-magnesium-containing, it is by following step
It is rapid to carry out：
(1) sodium carbonate liquor is added into the lithium solution of calcium-magnesium-containing, in 40 DEG C of stirring reaction 40min；
The sodium carbonate liquor concentration of addition is 30g/L, and consumption is precipitated as carbonic acid completely for contained calcium ions and magnesium ions in liquid
1.1 times of theoretical amount needed for salt；
(2) then add sodium hydroxide solution regulation reacting liquid pH value, make pH value to 11, continue to stir
50min is mixed, the mixed slurry containing magnesium carbonate, calcium carbonate and magnesium hydroxide, calcium hydroxide is obtained, will be upper
State slurry and stand 20h, pour out supernatant, obtain compressing slurry；
(3) the lithium solution of the calcium-magnesium-containing of step (1) same amount is taken, compression obtained by step (2) is starched
Material is added in above-mentioned high lithium solution, and is reacted by step (1) and (2) same method and consumption,
Obtain supernatant and slurry；
(4) the method iterative cycles as described in step (3) 8 times, regard gained compression slurry as crystal seed；
(5) crystal seed 100ml obtained by step (4) is taken, the pending high lithium solution 300 of calcic and magnesium is added
Ml, is then reacted by step (1) and (2) same method and consumption, reacting liquid filtering is obtained
To clear liquid and compression filter cake；Above-mentioned slurries filtration speed is 150L/min, and liquid-solid ratio is 92, filtrate life
Production speed is 82.8L/m2Mg in h, clear liquid2+Concentration is 0.4mg/L, Ca2+Concentration is 7.2mg/L, Li+
Concentration is 10.9g/L, can be used as the qualified reaction solution for preparing lithium carbonate.
Embodiment 3
The lithium solution composition of calcium-magnesium-containing employed in the present embodiment is as follows：
The method that calcium and magnesium impurity is removed in high lithium solution of the present invention from calcium-magnesium-containing, it is by following step
It is rapid to carry out：
(1) sodium carbonate liquor is added into the lithium solution of calcium-magnesium-containing, in 20 DEG C of stirring reaction 60min；
The sodium carbonate liquor concentration of addition is 70g/L, and consumption is precipitated as carbonic acid completely for contained calcium ions and magnesium ions in liquid
Theoretical amount needed for salt；
(2) then add sodium hydroxide solution regulation reacting liquid pH value, make pH value to 12, continue to stir
60min is mixed, the mixed slurry containing magnesium carbonate, calcium carbonate and magnesium hydroxide, calcium hydroxide is obtained, will be upper
State slurry and stand 18h, pour out supernatant, obtain compressing slurry；
(3) the lithium solution of the calcium-magnesium-containing of step (1) same amount is taken, compression obtained by step (2) is starched
Material is added in above-mentioned high lithium solution, and is reacted by step (1) and (2) same method and consumption,
Obtain supernatant and slurry；
(4) the method iterative cycles as described in step (3) 7 times, regard gained compression slurry as crystal seed；
(5) crystal seed 100ml obtained by step (4) is taken, the pending high lithium solution 100 of calcic and magnesium is added
Ml, is then reacted by step (1) and (2) same method and consumption, reacting liquid filtering is obtained
To clear liquid and compression filter cake；Above-mentioned slurries filtration speed is 135L/min, and liquid-solid ratio is 110, filtrate life
Production speed is 70.5L/m2Mg in h, clear liquid2+Concentration is 0.3mg/L, Ca2+Concentration is 5.7mg/L, Li+
Concentration is 13.9g/L, can be used as the qualified reaction solution for preparing lithium carbonate.
Claims (2)
1. the method for calcium and magnesium is removed in a kind of high lithium solution from calcium-magnesium-containing, described calcium-magnesium-containing
High lithium solution includes Li+15~20g/L, Na+50~70g/L, Mg2+0.1~2.4g/L, Ca2+
0.1~0.75g/L, this method is carried out as follows：
(1) add sodium carbonate liquor into the high lithium solution of pending calcium-magnesium-containing, 20 DEG C~
40 DEG C of 20~60min of stirring reaction；The sodium carbonate liquor concentration added is 30~70g/L, carbon
Sour sodium consumption is theoretical for needed for institute's calcic, magnesium ion in pending solution are precipitated as carbonate completely
1~1.1 times of consumption；
(2) sodium hydroxide solution, regulation reaction solution pH are added into step (1) resulting solution
It is worth 11~12, continues to stir 40~60min, obtains containing magnesium carbonate, calcium carbonate and hydroxide
The mixed slurry of magnesium, calcium hydroxide, stands 15~20h by above-mentioned slurry, isolates supernatant liquor,
Obtain compressing slurry；
(3) take in the high lithium solution of the pending calcium-magnesium-containing of step (1) same amount, addition
Compression slurry obtained by step, and repeat step (1) and step (2) are stated, is compressed again
Slurry；
(4) such as step (3) iterative cycles 6~8 times, the compression slurry finally obtained is crystalline substance
Kind；
(5) the high lithium solution of pending calcium-magnesium-containing is added into crystal seed obtained by step (4),
The volume ratio of the high lithium solution of crystal seed and pending calcium-magnesium-containing is 1: (1~3), then repeat to walk
Suddenly (1) and step (2), filtering, finally obtains Mg in clear liquid and compression filter cake, clear liquid2+
Concentration is 0.21~3.65mg/L, Ca2+Concentration is 5.6~10.2mg/L, Li+Concentration be 10.9~
14.5g/L, is used as the qualified reaction solution for preparing lithium carbonate.
2. calcium and magnesium is removed in a kind of high lithium solution from calcium-magnesium-containing according to claim 1
Method, it is characterised in that：When clear liquid and compression filter cake are filtrated to get in step (5), filtrate life
Production speed is 67.2~82.8L/m2H, liquid-solid ratio is 92~110, filtering rate 125~
150L/min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810078417.4A CN106507705B (en) | 2008-12-12 | 2008-12-12 | The method for removing calcium and magnesium impurity from the high lithium solution of calcium-magnesium-containing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810078417.4A CN106507705B (en) | 2008-12-12 | 2008-12-12 | The method for removing calcium and magnesium impurity from the high lithium solution of calcium-magnesium-containing |
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| CN106507705B true CN106507705B (en) | 2011-07-27 |
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ID=58264209
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354238A (en) * | 2018-10-12 | 2019-02-19 | 天津大学 | The method and its processing unit of hardness in multistep combined removal water |
| CN110078099A (en) * | 2019-04-26 | 2019-08-02 | 核工业北京化工冶金研究院 | A method of scavenging solution, which is leached, from lepidolite prepares lithium carbonate |
| CN116426758A (en) * | 2023-05-12 | 2023-07-14 | 中铝郑州有色金属研究院有限公司 | Purification method and system for lithium extraction solution of aluminum electrolysis waste |
| CN117125683A (en) * | 2020-11-21 | 2023-11-28 | 周思齐 | Method for producing battery-grade lithium phosphate from salt lake brine |
-
2008
- 2008-12-12 CN CN200810078417.4A patent/CN106507705B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354238A (en) * | 2018-10-12 | 2019-02-19 | 天津大学 | The method and its processing unit of hardness in multistep combined removal water |
| CN110078099A (en) * | 2019-04-26 | 2019-08-02 | 核工业北京化工冶金研究院 | A method of scavenging solution, which is leached, from lepidolite prepares lithium carbonate |
| CN117125683A (en) * | 2020-11-21 | 2023-11-28 | 周思齐 | Method for producing battery-grade lithium phosphate from salt lake brine |
| CN116426758A (en) * | 2023-05-12 | 2023-07-14 | 中铝郑州有色金属研究院有限公司 | Purification method and system for lithium extraction solution of aluminum electrolysis waste |
| CN116426758B (en) * | 2023-05-12 | 2023-12-05 | 中铝郑州有色金属研究院有限公司 | Purification method and system for lithium extraction solution of aluminum electrolysis waste |
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