CN110002467A - The purification process of sodium hydroxide solution and its application in battery-level lithium carbonate production - Google Patents
The purification process of sodium hydroxide solution and its application in battery-level lithium carbonate production Download PDFInfo
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- CN110002467A CN110002467A CN201910293106.8A CN201910293106A CN110002467A CN 110002467 A CN110002467 A CN 110002467A CN 201910293106 A CN201910293106 A CN 201910293106A CN 110002467 A CN110002467 A CN 110002467A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/28—Purification; Separation
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses the purification process of sodium hydroxide solution in a kind of production of battery-level lithium carbonate, comprising steps of S1, industrial sodium hydroxide is configured to wherein Mg2+Content be 50ppm~200ppm, Ca2+Content be 50ppm~150ppm the thick solution of sodium hydroxide；S2, ion exchange resin is pre-processed, obtains ion exchange column；S3, the temperature by the thick solution of sodium hydroxide in 20 DEG C~60 DEG C and 1BVh‑1~15BVh‑1Flow velocity under by ion exchange column, obtain wherein Mg2+、Ca2+Content be no more than the sodium hydroxide purification solution of 1ppm.The present invention uses ion exchange resin, can be by the thick solution purification of sodium hydroxide made of industrial sodium hydroxide to wherein Mg by control cleansing temp and liquid phase flow rate2+、Ca2+Content be no more than 1ppm so that sodium hydroxide purification solution obtained meets the requirement of depth demagging in battery-level lithium carbonate preparation, simple process, cost is relatively low, and resin is can be recycled, there is larger superiority, has preferable industrialization prospect.
Description
Technical field
The invention belongs to battery-level lithium carbonate preparation technical fields, it relates in particular to which a kind of battery-level lithium carbonate produces
The purification process of middle sodium hydroxide solution and the sodium hydroxide purification solution obtained through the purification process are in battery-level lithium carbonate
Application in production.
Background technique
During using salt lake bittern and ore to prepare lithium carbonate for raw material, critical process first is that being removed using NaOH depth
Remove the Mg of the rich lithium solution of the enriched acquisition of front process2+.As the NaOH of one of production lithium carbonate raw material, examined from economy
Consider, mostly uses technical grade NaOH, but limited by its operational characteristic, the Ca in technical grade NaOH product2+、Mg2+Content is higher,
Fluctuate larger, Ca in technical grade NaOH2+、Mg2+Content is one of the important sources for influencing lithium carbonate quality, can be in demagging richness
In the final sinker technical process of lithium solution, by CaCO3、MgCO3Impurity is introduced into lithium carbonate product, makes Ca in lithium carbonate product2+、
Mg2+Impurity content is more difficult to control, and product quality undulation, product is unable to reach the standard of battery-level lithium carbonate.So need pair
The NaOH solution of battery-level lithium carbonate production process depth technology for removal of magnesium from phosphorous is purified, and wherein Ca is removed2+、Mg2+Foreign ion pair
It is significant in the battery-level lithium carbonate of preparation quality qualification.
Summary of the invention
To solve the above-mentioned problems of the prior art, the present invention provides hydroxides in a kind of production of battery-level lithium carbonate
The purification process of sodium, the sodium hydroxide purification solution obtained through the purification process are applied in battery-level lithium carbonate preparation process
When, it is more advantageous to the product quality for guaranteeing battery-level lithium carbonate.
In order to achieve the above object of the invention, present invention employs the following technical solutions:
The purification process of sodium hydroxide solution in a kind of production of battery-level lithium carbonate, comprising steps of
S1, industrial sodium hydroxide is configured to the thick solution of sodium hydroxide；Wherein, in the thick solution of the sodium hydroxide,
Mg2+Content be 50ppm~200ppm, Ca2+Content be 50ppm~150ppm；
S2, ion exchange resin is pre-processed, obtains ion exchange column；
S3, the temperature by the thick solution of the sodium hydroxide in 20 DEG C~60 DEG C and 1BVh-1~15BVh-1Flow velocity under
By the ion exchange column, sodium hydroxide purification solution is obtained；Wherein, in the sodium hydroxide purification solution, Mg2+Contain
Amount is no more than 1ppm, Ca2+Content be no more than 1ppm.
Further, in the step S1, the concentration of the thick solution of the sodium hydroxide is 15%~35%.
Further, in the step S1, the concentration of the thick solution of the sodium hydroxide is 25%~30%.
Further, in the step S3, the temperature and 5BV by the thick solution of the sodium hydroxide in 25 DEG C~40 DEG C
h-1~10BVh-1Flow velocity under pass through the ion exchange column.
Further, in the step S2, the ion exchange resin is chelating resin or sodium form resin cation.
Further, in the step S2, the ion exchange resin be LSC-100 amido carboxylic acid type chelating resin,
LSC-500 amido carboxylic acid type chelating resin, LSD-500 resin or SCD-120 resin.
Further, the specific method of the step S2 includes: that the ion exchange resin is fitted into resin column, is obtained
Loaded resin column；Successively with the first lye, water, the first acid solution, to which the loaded resin column can be handled, obtain the ion exchange
Column.
Further, in the step S3, the thick solution of the sodium hydroxide is by after the ion exchange column, it is described from
Sub- exchange column becomes loaded resin column；The successively loaded resin column described in the second lye, water, the second acid solution, water process obtains again
Green resin column.
Another object of the present invention is to provide a kind of preparation methods of battery-level lithium carbonate, comprising steps of
Q1, salt lake bittern is diluted to acquisition dilution brine, at the beginning of the dilution brine is carried out magnesium lithium in film separation system
Step separation obtains rich lithium solution；
Q2, the rich lithium solution is subjected in counter-infiltration system primary concentration, obtains primary concentration liquid；
Q3, the primary concentration liquid is carried out in electrodialysis system to secondary concentration, obtains secondary concentration liquid；
The hydrogen-oxygen obtained using any purification process of claim 1-8 is added in Q4, Xiang Suoshu secondary concentration liquid
Change sodium purification solution reaches 11~14 up to the pH of system, and 40min~60min is reacted at 50 DEG C~70 DEG C, obtains magnesium sinking
Mixed liquor, carries out secondary filtration to the magnesium sinking mixed liquor, carries out depth demagging to secondary concentration liquid, obtains demagging richness lithium
Solution；
Na is added in Q5, Xiang Suoshu demagging richness lithium solution2CO3Solution is until the pH of system reaches 8~14, in 80 DEG C~110
40min~90min is reacted at DEG C, obtains the battery-level lithium carbonate.
The present invention uses ion exchange resin, can be by industrial sodium hydroxide by control cleansing temp and liquid phase flow rate
The manufactured thick solution purification of sodium hydroxide is to wherein Mg2+、Ca2+Content be no more than 1ppm so that sodium hydroxide obtained
Purification solution meets the requirement of depth demagging in battery-level lithium carbonate preparation, and simple process, industrial chemicals is few, and the rate of recovery is high, choosing
Selecting property is good, and pollution is small, and cost is relatively low, and resin is can be recycled, there is larger superiority, has preferable industrialization prospect.
Specific embodiment
Hereinafter, detailed description of the present invention embodiment in future.However, it is possible to implement this hair in many different forms
It is bright, and the present invention should not be construed as limited to the specific embodiment illustrated here.On the contrary, provide these embodiments be for
Explanation the principle of the present invention and its practical application, to make others skilled in the art it will be appreciated that of the invention is various
Embodiment and the various modifications for being suitable for specific intended application.
Term " first ", " second " etc. herein can be used to describe various substances although will be appreciated that, these
Substance should not be limited by these terms.These terms are only used to distinguish a substance with another substance.
For battery-level lithium carbonate in the prior art use during the preparation process sodium hydroxide solution carry out depth demagging this
Ca present in industrial sodium hydroxide in one step2+、Mg2+The higher problem of content, and propose a kind of purifying sodium hydroxide
The method of solution, to be applied in the production process of battery-level lithium carbonate.
Specifically, which includes the following steps:
In step sl, industrial sodium hydroxide is configured to the thick solution of sodium hydroxide.
Specifically, the thick solution of sodium hydroxide that a mass concentration is 15%~35%, preferably 25%~30% is prepared
, to meet its concrete application in battery-level lithium carbonate preparation.
Further, in the thick solution of the sodium hydroxide, Mg2+Content be 50ppm~200ppm, Ca2+Content be
50ppm~150ppm.
In step s 2, ion exchange resin is pre-processed, obtains ion exchange column.
The ion exchange resin is specially chelating resin or sodium form resin cation, such as LSC-100 amido carboxylic acid type chela
Resin, LSC-500 amido carboxylic acid type chelating resin, LSD-500 resin or SCD-120 resin etc..
Specifically, pretreated specific steps are carried out to ion exchange resin are as follows: (1) ion exchange resin is packed into and is set
In rouge column, loaded resin column is obtained；(2) successively with the first lye, water, the first acid solution, to which loaded resin column can be handled, that is, obtain
Ion exchange column.
Further, following methods progress can be used in above-mentioned steps (2): being handled and is filled with certain density sodium hydroxide solution
After filling out resin column, it is washed to the loaded resin column and is in neutrality；The filling through washing is handled with certain density hydrochloric acid solution again
Resin column, then be washed to and be in neutrality.Wherein concentration of sodium hydroxide solution is 1%~6%, preferably 3%~5%；Hydrochloric acid
Solution concentration is 4%~12%, preferably 5%~8%.
In step s3, the temperature and 1BVh by the thick solution of sodium hydroxide in 20 DEG C~60 DEG C-1~15BVh-1Stream
Speed is lower by ion exchange column, obtains sodium hydroxide purification solution.
Further, above-mentioned temperature is preferably 25 DEG C~40 DEG C, and flow velocity is preferably 5BVh-1~10BVh-1。
In this way, in sodium hydroxide purification solution obtained, Mg2+And Ca2+Content i.e. controllable be no more than
1ppm。
Further, i.e. be changed into load has Mg to the ion exchange column after above-mentioned steps S3 purification process2+And Ca2+Deng
The loaded resin column of foreign ion.When the loaded resin column is for Mg2+And Ca2+Exchange capacity reach saturation after, can pass through
Regenerative operation is carried out to the loaded resin column and realizes material and recycles；Specifically, successively with the second lye, water,
Two acid solutions, water process the loaded resin column, can be obtained regenerating resin column.
Further, following methods progress can be used in above-mentioned regeneration duties resin column: with certain density sodium hydroxide
After solution handles loaded resin column, it is washed to the loaded resin column and is in neutrality；The warp is handled with certain density hydrochloric acid solution again
The loaded resin column of washing, then be washed to and be in neutrality.Wherein concentration of sodium hydroxide solution is 1%~6%, preferably 3%
~5%；Concentration of hydrochloric acid solution is 4%~12%, preferably 5%~8%.
In this way, the sodium hydroxide purification solution obtained through above-mentioned purification process can be applied to the preparation of battery-level lithium carbonate
In the process, to guarantee the product quality of pre-prepared battery-level lithium carbonate.
Specifically, battery-level lithium carbonate is prepared referring to following methods:
In step Q1, salt lake bittern is diluted and obtains dilution brine, dilution brine is subjected to magnesium in film separation system
Lithium initial gross separation obtains rich lithium solution.
The basic composition of the salt lake bittern is as follows: Li+Content be 1g/L~10g/L, Mg/Li ratio be 5:1~100:1,
Preferably 8:1~50:1；It can be seen that the salt lake bittern is a kind of salt lake bittern of high Mg/Li ratio.
It is worth noting that in the present invention, " Mg/Li ratio " refers to the mass ratio of magnesium ion and lithium ion.
Specifically, salt lake bittern is diluted and obtains dilution brine, then by dilution brine obtained in film separation system
Middle carry out separating magnesium and lithium obtains rich lithium solution.
More specifically, the basic composition of the dilution brine is as follows: Li+Content be 0.1g/L~0.8g/L, also,
In the rich lithium solution of acquisition, Li+Content be 0.3g/L~3g/L, preferably 0.6g/L~2g/L, Mg/Li ratio 0.01:1
~1:1, preferably 0.05:1~0.4:1.
In this step, nanofiltration separation system such as can be used as film separation system, carry out the initial gross separation of magnesium lithium.
In step Q2, rich lithium solution is subjected to primary concentration in counter-infiltration system, obtains primary concentration liquid.
The basic composition of primary concentration liquid obtained is as follows: Li+Content be 1.5g/L~8g/L, preferably 2.0g/L
~7.5g/L, Mg/Li ratio are 0.01:1~1:1, preferably 0.05:1~0.4:1.In step Q3, by primary concentration liquid in electricity
Secondary concentration is carried out in electrodialysis system, obtains secondary concentration liquid.
The basic composition of secondary concentration liquid obtained is as follows: Li+Content be 13.0g/L~22.0g/L, preferably
15.0g/L~20.0g/L, Mg/Li ratio are 0.03:1~1.5:1, preferably 0.05:1~1:1.
In step q 4, depth demagging is carried out to secondary concentration liquid.
Specifically, firstly, the sodium hydroxide purifying that addition is obtained by above-mentioned purification process into secondary concentration liquid is molten
Liquid is until the pH of system reaches 11~14, preferably 13~14, and reacts at 50 DEG C~70 DEG C, preferably 50 DEG C~60 DEG C
40min~60min obtains magnesium sinking mixed liquor；Then, secondary filtration is carried out to the magnesium sinking mixed liquor of the acquisition, is removed
Magnesium richness lithium solution.
Further, the reaction time of above-mentioned 40min~60min specifically include 20min~30min feed time and
The digestion time of 20min~30min.
Preferably, the concentration general control of the NaOH solution of used demagging is 20%~35% (wt%), excellent
It is selected as 25%~30%.
Above-mentioned secondary filtration specifically includes primary filter and secondary filter；More specifically, firstly, by magnesium sinking mixed liquor
It is sent into filter press and carries out primary filter, by bulky grain Mg (OH)2Precipitation and separation obtains filters pressing filtrate and filters pressing filter cake；Then,
Filters pressing filtrate is sent into filter accurate filter and carries out secondary filter, removes remaining little particle Mg (OH) in filters pressing filtrate2。
Wherein, filter cloth used in primary filter be 1300~2500 mesh, preferably 1500~2000；The filtering of accurate filter
Precision is 1 μm~5 μm, preferably 1 μm~2 μm.
The basic composition of demagging richness lithium solution obtained is as follows: Li+Content be 13.0g/L~22.0g/L, preferably
15.0g/L~20.0g/L, Mg2+Content be no more than 100ppm.
In step Q5, the preparation of battery-level lithium carbonate.
Specifically, Na is added into demagging richness lithium solution2CO3Solution until the pH of system reach 8~14, preferably 9~
13,40min~90min is reacted at 80 DEG C~110 DEG C, preferably 90 DEG C~100 DEG C；Control Na in the reaction system of the mixing+Content be Na+Content be 31g/L~77g/L, preferably 36g/L~48g/L, Cl-Content be 115g/L~195g/L,
Preferably 133g/L~177g/L controls mixing speed 100rpm~150rpm, is filtered, washed after reaction, dries and obtain
Battery-level lithium carbonate.
Further, the reaction time of above-mentioned 40min~90min specifically include 20min~50min feed time and
The digestion time of 20min~40min.
Preferably, used Na2CO3The concentration general control of solution is excessive 10%~30% (wt%), preferably
It is excessive 15%~25%；It is worth noting that the meaning of " excess " herein are as follows: will be according to Na2CO3With Li+Reaction generates
Li2CO3Required Na2CO3Na in solution2CO3Amount as 100%, and on this basis, excessive above range, with as far as possible
Ground is by Li in demagging richness lithium solution+Precipitating generates Li2CO3, sodium carbonate mass concentration be 10%~30%, preferably 18%~
25%, mixing speed is 50rpm~200rpm, preferably 100rpm~150rpm.
In this way, the test parameter for the battery-level lithium carbonate that this step obtains is as follows: Li2CO3Main content is not less than 99.5%,
Cl-Content is no more than 40ppm, Na+Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
It will illustrate the purifying of sodium hydroxide solution in above-mentioned battery-level lithium carbonate production by specific embodiment below
Method and its concrete application in battery-level lithium carbonate production；But the selection of parameter is only specifically to show in following embodiments
Example is not used in limitation all.
Embodiment 1
The old halogen that is generated after mentioning potassium from Qinghai salt lake of salt lake bittern that the present embodiment uses, Li in the salt lake bittern+Content is 1g/L, Mg/Li ratio 100.
The first step, into separating magnesium and lithium is carried out in film separation system, obtains rich lithium after salt lake bittern fresh water dilution
Solution.
Wherein, Li in the dilution brine obtained after dilution+Content is 0.2g/L；And the Li in the rich lithium solution obtained+Content
For 0.6g/L, Mg/Li ratio 0.01.
Rich lithium solution is entered counter-infiltration system and carries out primary concentration, obtains primary concentration liquid by second step.
Wherein, Li in primary concentration liquid+Content is 1.5g/L, Mg/Li ratio 0.01.
Primary concentration liquid is entered electrodialysis system and carries out secondary concentration, obtains secondary concentration liquid by third step.
Wherein, Li in secondary concentration liquid+Content is 22g/L, Mg/Li ratio 0.03.
The ED fresh water obtained through secondary concentration is blended with the rich lithium solution that the first step obtains, by anti-in second step
Osmosis system carries out primary concentration, to realize the remaining recycling of lithium and the reuse of fresh water.
4th step carries out depth demagging to secondary concentration liquid.
Specifically, the NaOH solution that concentration is 30% (wt%), control system terminal pH are added into secondary concentration liquid
It is 14, reaction temperature is 60 DEG C, reaction time 40min, forms magnesium sinking mixed liquor；Second level is carried out to the magnesium sinking mixed liquor
It filters, filter cloth mesh number used in by-pass filtration is 1300, and accurate filter filtering accuracy is 2 μm, obtains demagging richness lithium solution.
Li in demagging richness lithium solution after depth demagging+Content is 15g/L, Mg2+Content is no more than 10ppm.
Demagging richness lithium solution after depth demagging is heated to 90 DEG C by the 5th step, wherein lithium is 22g/ in rich lithium solution
L, and be added excessive 25% thereto (on the basis of quality of the reaction equation ratio after equivalent) mass fraction be 25% carbonic acid
Sodium solution, and control Na in the mixed solution of the acquisition+Content be 31g/L, Cl-Content be 177g/L, pH value in reaction is
13, mixing speed is that 150rpm carries out precipitation reaction 90min, and wherein feed time 50min, digestion time 40min are passed through after reaction
It is filtered, washed, dries, obtain battery-level lithium carbonate.
Li in prepared battery-level lithium carbonate2CO3Main content is not less than 99.5%, Cl-Content is no more than 40ppm, Na+
Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
Specifically, which is obtained using following methods:
S1, by technical grade sodium hydrate solid in sodium hydroxide solution make-up tank stirring and dissolving, being configured to mass fraction is
The thick solution of 30% sodium hydroxide.
Wherein, Ca2+Ion concentration is 50ppm, Mg2+Content is 100ppm.
S2, ion exchange resin is pre-processed, obtains ion exchange column.
LSC-100 amido carboxylic acid type chelating resin such as is specially taken to be filled into resin column, at 1% sodium hydroxide solution
After reason, it is washed to neutrality, then handled with 5% hydrochloric acid solution, is washed to neutrality, obtains ion exchange column.
S3, temperature and 10BVh by the thick solution of sodium hydroxide in 20 DEG C-1Flow velocity under by ion exchange column, obtain
Sodium hydroxide purification solution；Wherein, in sodium hydroxide purification solution, Mg2+Concentration be no more than 1ppm, Ca2+Concentration do not surpass
Cross 1ppm.
When the chelating resin in ion exchange column adsorbs Ca2+And Mg2+It is molten with 4% (wt%) sodium hydroxide after reaching saturation
After liquid processing, it is washed to neutrality, then handled with 5% (wt%) hydrochloric acid solution, is washed to neutrality, i.e., will be obtained in above-mentioned third step
Loaded resin column regeneration be regenerating resin column, can recycle.
Embodiment 2
The old halogen that is generated after mentioning potassium from Qinghai salt lake of salt lake bittern that the present embodiment uses, Li in the salt lake bittern+Content is 10g/L, Mg/Li ratio 5.
The first step, into separating magnesium and lithium is carried out in film separation system, obtains rich lithium after salt lake bittern fresh water dilution
Solution.
Wherein, Li in the dilution brine obtained after dilution+Content is 0.8g/L；And the Li in the rich lithium solution obtained+Content
For 2g/L, Mg/Li ratio 0.4.
Rich lithium solution is entered counter-infiltration system and carries out primary concentration, obtains primary concentration liquid by second step.
Wherein, Li in primary concentration liquid+Content is 7.5g/L, Mg/Li ratio 0.4.
Primary concentration liquid is entered electrodialysis system and carries out secondary concentration, obtains secondary concentration liquid by third step.
Wherein, Li in secondary concentration liquid+Content is 15g/L, Mg/Li ratio 1.
The ED fresh water obtained through secondary concentration is blended with the rich lithium solution that the first step obtains, by anti-in second step
Osmosis system carries out primary concentration, to realize the remaining recycling of lithium and the reuse of fresh water.
4th step carries out depth demagging to secondary concentration liquid.
Specifically, the NaOH solution that concentration is 35% (wt%), control system terminal pH are added into secondary concentration liquid
It is 13, reaction temperature is 70 DEG C, reaction time 60min, forms magnesium sinking mixed liquor；Second level is carried out to the magnesium sinking mixed liquor
It filters, filter cloth mesh number used in by-pass filtration is 2000, and accurate filter filtering accuracy is 5 μm, obtains demagging richness lithium solution.
Li in demagging richness lithium solution after depth demagging+Content is 15g/L, Mg2+Content is no more than 10ppm.
Demagging richness lithium solution after depth demagging is heated to 110 DEG C by the 5th step, wherein lithium is 15g/ in rich lithium solution
L, and be added excessive 10% thereto (on the basis of quality of the reaction equation ratio after equivalent) mass fraction be 30% carbonic acid
Sodium solution, and control Na in the mixed solution of the acquisition+Content be 48g/L, Cl-Content be 115g/L, pH value in reaction is
8, mixing speed is that 50rpm carries out precipitation reaction 40min, wherein feed time 20min, digestion time 20min, after reaction by
Filter, washing, dry, acquisition battery-level lithium carbonate.
Li in prepared battery-level lithium carbonate2CO3Main content is not less than 99.5%, Cl-Content is no more than 40ppm, Na+
Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
Specifically, which is obtained using following methods:
S1, by technical grade sodium hydrate solid in sodium hydroxide solution make-up tank stirring and dissolving, being configured to mass fraction is
The thick solution of 25% sodium hydroxide.
Wherein, Ca2+Ion concentration is 150ppm, Mg2+Content is 1500ppm.
S2, ion exchange resin is pre-processed, obtains ion exchange column.
LSC-500 amido carboxylic acid type chelating resin such as is specially taken to be filled into resin column, at 5% sodium hydroxide solution
After reason, it is washed to neutrality, then handled with 4% hydrochloric acid solution, is washed to neutrality.
S3, temperature and 1BVh by the thick solution of sodium hydroxide in 40 DEG C-1Flow velocity under by ion exchange column, obtain hydrogen
Sodium oxide molybdena purification solution；Wherein, in sodium hydroxide purification solution, Mg2+Concentration be no more than 1ppm, Ca2+Concentration be no more than
1ppm。
When the chelating resin in ion exchange column adsorbs Ca2+And Mg2+It is molten with 4% (wt%) sodium hydroxide after reaching saturation
After liquid processing, it is washed to neutrality, then handled with 5% (wt%) hydrochloric acid solution, is washed to neutrality, i.e., will be obtained in above-mentioned third step
Loaded resin column regeneration be regenerating resin column, can recycle.
Embodiment 3
The old halogen that is generated after mentioning potassium from Qinghai salt lake of salt lake bittern that the present embodiment uses, Li in the salt lake bittern+Content is 7g/L, Mg/Li ratio 8.
The first step, into separating magnesium and lithium is carried out in film separation system, obtains rich lithium after salt lake bittern fresh water dilution
Solution.
Wherein, Li in the dilution brine obtained after dilution+Content is 0.7g/L；And the Li in the rich lithium solution obtained+Content
For 3g/L, Mg/Li ratio 1.
Rich lithium solution is entered counter-infiltration system and carries out primary concentration, obtains primary concentration liquid by second step.
Wherein, Li in primary concentration liquid+Content is 8g/L, Mg/Li ratio 1.
Primary concentration liquid is entered electrodialysis system and carries out secondary concentration, obtains secondary concentration liquid by third step.
Wherein, Li in secondary concentration liquid+Content is 20g/L, Mg/Li ratio 1.5.
The ED fresh water obtained through secondary concentration is blended with the rich lithium solution that the first step obtains, by anti-in second step
Osmosis system carries out primary concentration, to realize the remaining recycling of lithium and the reuse of fresh water.
4th step carries out depth demagging to secondary concentration liquid.
Specifically, the NaOH solution that concentration is 25% (wt%), control system terminal pH are added into secondary concentration liquid
It is 14, reaction temperature is 50 DEG C, reaction time 50min, forms magnesium sinking mixed liquor；Second level is carried out to the magnesium sinking mixed liquor
It filters, filter cloth mesh number used in by-pass filtration is 2500, and accurate filter filtering accuracy is 1 μm, obtains demagging richness lithium solution.
Li in demagging richness lithium solution after depth demagging+Content is 20g/L, Mg2+Content is no more than 10ppm.
Demagging richness lithium solution after depth demagging is heated to 100 DEG C by the 5th step, wherein lithium is 20g/ in rich lithium solution
L, and be added excessive 15% thereto (on the basis of quality of the reaction equation ratio after equivalent) mass fraction be 18% carbonic acid
Sodium solution, and control Na in the mixed solution of the acquisition+Content be 77g/L, Cl-Content be 133g/L, pH value in reaction is
9, mixing speed is that 100rpm carries out precipitation reaction 70min, and wherein feed time 30min, digestion time 40min are passed through after reaction
It is filtered, washed, dries, obtain battery-level lithium carbonate.
Li in prepared battery-level lithium carbonate2CO3Main content is not less than 99.5%, Cl-Content is no more than 40ppm, Na+
Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
Specifically, which is obtained using following methods:
S1, by technical grade sodium hydrate solid in sodium hydroxide solution make-up tank stirring and dissolving, being configured to mass fraction is
The thick solution of 35% sodium hydroxide.
Wherein, Ca2+Ion concentration is 100ppm, Mg2+Content is 250ppm.
S2, ion exchange resin is pre-processed, obtains ion exchange column.
It specially takes LCD-500 resin to be such as filled into resin column, after being handled with 6% sodium hydroxide solution, is washed to
Property, then handled with 8% hydrochloric acid solution, it is washed to neutrality.
S3, temperature and 15BVh by the thick solution of sodium hydroxide in 25 DEG C-1Flow velocity under by ion exchange column, obtain
Sodium hydroxide purification solution；Wherein, in sodium hydroxide purification solution, Mg2+Concentration be no more than 1ppm, Ca2+Concentration do not surpass
Cross 1ppm.
When the chelating resin in ion exchange column adsorbs Ca2+And Mg2+It is molten with 4% (wt%) sodium hydroxide after reaching saturation
After liquid processing, it is washed to neutrality, then handled with 5% (wt%) hydrochloric acid solution, is washed to neutrality, i.e., will be obtained in above-mentioned third step
Loaded resin column regeneration be regenerating resin column, can recycle.
Embodiment 4
The old halogen that is generated after mentioning potassium from Qinghai salt lake of salt lake bittern that the present embodiment uses, Li in the salt lake bittern+Content is 2.5g/L, Mg/Li ratio 50.
The first step, into separating magnesium and lithium is carried out in film separation system, obtains rich lithium after salt lake bittern fresh water dilution
Solution.
Wherein, Li in the dilution brine obtained after dilution+Content is 0.1g/L；And the Li in the rich lithium solution obtained+Content
For 0.2g/L, Mg/Li ratio 0.05.
Rich lithium solution is entered counter-infiltration system and carries out primary concentration, obtains primary concentration liquid by second step.
Wherein, Li in primary concentration liquid+Content is 2g/L, Mg/Li ratio 0.05.
Primary concentration liquid is entered electrodialysis system and carries out secondary concentration, obtains secondary concentration liquid by third step.
Wherein, Li in secondary concentration liquid+Content is 13g/L, Mg/Li ratio 0.05.
The ED fresh water obtained through secondary concentration is blended with the rich lithium solution that the first step obtains, by anti-in second step
Osmosis system carries out primary concentration, to realize the remaining recycling of lithium and the reuse of fresh water.
4th step carries out depth demagging to secondary concentration liquid.
Specifically, the NaOH solution that concentration is 20% (wt%), control system terminal pH are added into secondary concentration liquid
It is 11, reaction temperature is 50 DEG C, reaction time 60min, forms magnesium sinking mixed liquor；Second level is carried out to the magnesium sinking mixed liquor
It filters, filter cloth mesh number used in by-pass filtration is 1500, and accurate filter filtering accuracy is 1 μm, obtains demagging richness lithium solution.
Li in demagging richness lithium solution after depth demagging+Content is 13g/L, Mg2+Content is no more than 10ppm.
Demagging richness lithium solution after depth demagging is heated to 80 DEG C by the 5th step, wherein lithium is 13g/ in rich lithium solution
L, and be added excessive 30% thereto (on the basis of quality of the reaction equation ratio after equivalent) mass fraction be 10% carbonic acid
Sodium solution, and control Na in the mixed solution of the acquisition+Content be 36g/L, Cl-Content be 195g/L, pH value in reaction is
14, mixing speed is that 200rpm carries out precipitation reaction 60min, and wherein feed time 30min, digestion time 30min are passed through after reaction
It is filtered, washed, dries, obtain battery-level lithium carbonate.
Li in prepared battery-level lithium carbonate2CO3Main content is not less than 99.5%, Cl-Content is no more than 40ppm, Na+
Content is no more than 150ppm, Mg2+Content is no more than 90ppm, Ca2+Content is no more than 50ppm.
Specifically, which is obtained using following methods:
S1, by technical grade sodium hydrate solid in sodium hydroxide solution make-up tank stirring and dissolving, being configured to mass fraction is
The thick solution of 15% sodium hydroxide.
Wherein, Ca2+Ion concentration is 80ppm, Mg2+Content is 350ppm.
S2, ion exchange resin is pre-processed, obtains ion exchange column.
It specially takes SCD-120 resin to be such as filled into resin column, after being handled with 3% sodium hydroxide solution, is washed to
Property, then handled with 12% hydrochloric acid solution, it is washed to neutrality.
S3, temperature and 5BVh by the thick solution of sodium hydroxide in 60 DEG C-1Flow velocity under by ion exchange column, obtain hydrogen
Sodium oxide molybdena purification solution；Wherein, in sodium hydroxide purification solution, Mg2+Concentration be no more than 1ppm, Ca2+Concentration be no more than
1ppm。
When the chelating resin in ion exchange column adsorbs Ca2+And Mg2+It is molten with 4% (wt%) sodium hydroxide after reaching saturation
After liquid processing, it is washed to neutrality, then handled with 5% (wt%) hydrochloric acid solution, is washed to neutrality, i.e., will be obtained in above-mentioned third step
Loaded resin column regeneration be regenerating resin column, can recycle.
Although the present invention has shown and described referring to specific embodiment, it should be appreciated by those skilled in the art that:
In the case where not departing from the spirit and scope of the present invention being defined by the claims and their equivalents, can carry out herein form and
Various change in details.
Claims (9)
1. the purification process of sodium hydroxide solution in a kind of battery-level lithium carbonate production, which is characterized in that comprising steps of
S1, industrial sodium hydroxide is configured to the thick solution of sodium hydroxide；Wherein, in the thick solution of the sodium hydroxide, Mg2+'s
Content is 50ppm~200ppm, Ca2+Content be 50ppm~150ppm；
S2, ion exchange resin is pre-processed, obtains ion exchange column；
S3, the temperature by the thick solution of the sodium hydroxide in 20 DEG C~60 DEG C and 1BVh-1~15BVh-1Flow velocity under pass through
The ion exchange column obtains sodium hydroxide purification solution；Wherein, in the sodium hydroxide purification solution, Mg2+Content not
More than 1ppm, Ca2+Content be no more than 1ppm.
2. purification process according to claim 1, which is characterized in that in the step S1, the sodium hydroxide is slightly molten
The concentration of liquid is 15%~35%.
3. purification process according to claim 2, which is characterized in that in the step S1, the sodium hydroxide is slightly molten
The concentration of liquid is 25%~30%.
4. purification process according to claim 1, which is characterized in that in the step S3, the sodium hydroxide is thick
Temperature and 5BVh of the solution in 25 DEG C~40 DEG C-1~10BVh-1Flow velocity under pass through the ion exchange column.
5. purification process according to claim 1, which is characterized in that in the step S2, the ion exchange resin
For chelating resin or sodium form resin cation.
6. purification process according to claim 5, which is characterized in that in the step S2, the ion exchange resin
For LSC-100 amido carboxylic acid type chelating resin, LSC-500 amido carboxylic acid type chelating resin, LSD-500 resin or SCD-120 tree
Rouge.
7. purification process according to claim 1, which is characterized in that the specific method of the step S2 includes:
The ion exchange resin is fitted into resin column, loaded resin column is obtained；
Successively with the first lye, water, the first acid solution, to which the loaded resin column can be handled, obtain the ion exchange column.
8. -7 any purification process according to claim 1, which is characterized in that in the step S3, the hydroxide
After the thick solution of sodium passes through the ion exchange column, the ion exchange column becomes loaded resin column；Successively with the second lye, water,
Loaded resin column described in second acid solution, water process obtains regenerating resin column.
9. a kind of preparation method of battery-level lithium carbonate, which is characterized in that comprising steps of
Q1, salt lake bittern is diluted to acquisition dilution brine, the dilution brine is subjected to magnesium lithium in film separation system and is tentatively divided
From the rich lithium solution of acquisition；
Q2, the rich lithium solution is subjected in counter-infiltration system primary concentration, obtains primary concentration liquid；
Q3, the primary concentration liquid is carried out in electrodialysis system to secondary concentration, obtains secondary concentration liquid；
The sodium hydroxide obtained using any purification process of claim 1-8 is added in Q4, Xiang Suoshu secondary concentration liquid
Until the pH of system reaches 11~14, and reacts 40min~60min at 50 DEG C~70 DEG C, acquisition magnesium sinking mixes purification solution
Feed liquid, carries out secondary filtration to the magnesium sinking mixed liquor, carries out depth demagging to secondary concentration liquid, it is molten to obtain demagging richness lithium
Liquid；
Na is added in Q5, Xiang Suoshu demagging richness lithium solution2CO3Solution is until the pH of system reaches 8~14, at 80 DEG C~110 DEG C
40min~90min is reacted, the battery-level lithium carbonate is obtained.
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| US4478722A (en) * | 1983-10-04 | 1984-10-23 | The Dow Chemical Company | Process for separating salts in aqueous streams |
| WO1997036823A1 (en) * | 1996-04-01 | 1997-10-09 | Aluminium Pechiney | Method for recovering sodium from alkaline industrial waste |
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