CN109592699A - The preparation method of LITHIUM BATTERY lithium hydroxide - Google Patents
The preparation method of LITHIUM BATTERY lithium hydroxide Download PDFInfo
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- CN109592699A CN109592699A CN201811558098.7A CN201811558098A CN109592699A CN 109592699 A CN109592699 A CN 109592699A CN 201811558098 A CN201811558098 A CN 201811558098A CN 109592699 A CN109592699 A CN 109592699A
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- lithium
- chloride
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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
- C01D15/02—Oxides; Hydroxides
Abstract
The present invention provides a kind of preparation methods of LITHIUM BATTERY lithium hydroxide comprising following steps, and the brine of chloride containing lithium is carried out reacting sinker with lye, obtains lithium hydroxide crude product and sinker mother liquor by: S1；S2 successively carries out first time washing, evaporative crystallization, second of washing, drying to lithium hydroxide crude product, obtains LITHIUM BATTERY lithium hydroxide.The LITHIUM BATTERY lithium hydroxide that purity is met the requirements can be prepared using method provided by the invention, especially chloride ion content is very low.Meanwhile the present invention has many advantages, such as that the lithium rate of recovery is high, process is short, simple process, at low cost, safety and environmental protection, easy to industrialized production.
Description
Technical field
The present invention relates to field of inorganic materials, in particular to a kind of preparation method of LITHIUM BATTERY lithium hydroxide.
Background technique
Currently, using lithium chloride as raw material prepare the method for lithium hydroxide mainly there are several types of:
(1) lithium carbonate causticizing process
Sodium carbonate is added into lithium chloride solution, is settled out lithium carbonate；Milk of lime is mixed with lithium carbonate again, is adjusted certain
Causticization liquid concentration, be heated to boiling and strong stirring, causticizing reaction is as follows
Ca(OH)2+Li2CO3=CaCO3+2LiOH.H2O
The lithium hydroxide solution of concentration about 3.5% can be obtained in reaction, removes insoluble residue (mainly CaCO3), point
Mother liquor is concentrated under reduced pressure from after, is crystallized, is dried to obtain lithium hydroxide product.The technique is more mature at present, prepares hydrogen-oxygen at present
Change lithium to be substantially using this method.However, the technology is using sodium carbonate sinker, the technique of calcium hydroxide causticization, long flow path, energy
Consume that big, at high cost, conversion ratio is low；The residual quantity of lithium is larger in slag after causticization, and calcium content is high in obtained lithium hydroxide, cannot
Applied in anode material of lithium battery.
(2) lithium chloride electrolysis method
To refine brine (main component is LiCl) as anolyte, lithium hydroxide solution is electrolysed as catholyte, Li+
Lithium hydroxide monohydrate solution is obtained in cathode chamber by cationic membrane, through evaporation and concentration, crystallisation by cooling, washing drying, is obtained
To monohydrate lithium hydroxide product.The lithium hydroxide quality of this method preparation is high, can achieve LITHIUM BATTERY.However, the technology is entire
Treatment process is complex, long flow path, by-product is more, system entirety energy consumption is higher；Simultaneously as the corrosivity of lithium chloride, right
Electrode material it is more demanding；And it is immature with mantle, later maintenance cost is high, and by-product chlorine or hydrogen chloride are in salt lake
Area is difficult to digest.
(3) lithium chloride causticizing process
Patent CN106006675A discloses a kind of method for preparing monohydrate lithium hydroxide using lithium chloride solution for raw material,
It, which is mixed under certain temperature, pressure using certain density lithium chloride solution with certain density lye, is reacted, reaction
Liquid is concentrated to get monohydrate lithium hydroxide precipitating, and precipitating is filtered, is washed, is dried to obtain monohydrate lithium hydroxide product.However,
Product purity is low for monohydrate lithium hydroxide made from this method, may not apply in anode material of lithium battery, while sinker after causticization
The residual quantity of lithium is larger in mother liquor, and the loss of lithium is big, and one-way yield is low, at high cost.
(4) other methods
Patent CN107108245A discloses a kind of production method of lithium hydroxide, severe using sodium hydroxide and lithium chloride
Change reaction and lithium hydroxide is prepared, heating and melting lithium hydroxide generates anhydrous lithium hydroxide, filtering under 500 DEG C of high temperature by it
After be quenched with water, be dried to obtain monohydrate lithium hydroxide product.However, the consumption of this method energy consumption is big, it is not easy industrialized production.
To sum up, being prepared made from the method for lithium hydroxide at present, lithium hydroxide purity is low, chlorinty is high or preparation
Problem at high cost.
Summary of the invention
The main purpose of the present invention is to provide a kind of preparation methods of LITHIUM BATTERY lithium hydroxide, to solve in the prior art
The problem that lithium hydroxide purity is low, chlorinty is high or preparation cost is high when preparation LITHIUM BATTERY lithium hydroxide.In addition to this, this hair
Bright process flow is short, operating procedure is simple, production cost is low, the three wastes are few, safety and environmental protection, easy to industrialized production.Especially
After technique advanced optimizes, lithium resource of the invention is lost less, the lithium rate of recovery is high.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of preparation of LITHIUM BATTERY lithium hydroxide
Method comprising following steps: S1 carries out the brine of chloride containing lithium with lye to react sinker, obtain lithium hydroxide crude product and
Sinker mother liquor；S2 successively carries out first time washing, evaporative crystallization, second of washing, drying to lithium hydroxide crude product, obtains electricity
Pond grade lithium hydroxide.
Further, further comprising the steps of: S3, the compound of carbanion can be introduced into water as precipitating
Precipitating reagent is passed through in sinker mother liquor and carries out precipitation reaction by agent, obtains lithium carbonate crude product and filtrated stock；S4, to filtrated stock
It is successively evaporated concentration and drying, obtains chloride.
Further, in above-mentioned steps S1, the mass concentration of lithium chloride is 27~35% in the brine of chloride containing lithium, and alkali
The mass concentration of hydroxide ion is 10~15% in liquid.
Further, in step S1, react sinker during reaction temperature be 0~95 DEG C, the reaction time be 10~
120min。
Further, lye is sodium hydrate aqueous solution, potassium hydroxide aqueous solution or ammonium hydroxide；When lye is sodium hydroxide water
When solution, precipitating reagent is sodium carbonate and/or carbon dioxide, and chloride is sodium chloride；When lye is potassium hydroxide aqueous solution, sink
Shallow lake agent is potassium carbonate and/or carbon dioxide, and chloride is potassium chloride；When lye is ammonium hydroxide, precipitating reagent is ammonium carbonate and/or two
Carbonoxide, chloride are ammonium chloride.
Further, in step S2, the detergent used in washing for the first time and second of washing is that lithium hydroxide is full
And solution.
Further, in step S2, the temperature of evaporative crystallization is 50~95 DEG C, and pressure is 0~0.1MPa.
Further, in step S2, evaporation and crystal process include: by by first time wash after lithium hydroxide crude product with
Water is mixed and is completely dissolved, and obtains lysate；It dissolves by heating liquid and with evaporation section water and crystallization is precipitated, obtain residual solution；It will be residual
Extraction raffinate is cooled down, and evaporation and crystal process is completed.
Further, in evaporation and crystal process, residual solution after cooling is filtered, filtrate is back to first time washing process
In；The cleaning solution generated in second of washing process is back in first time washing process together；By first time washing process
The further evaporative crystallization of the cleaning solution of middle generation, is then filtered, and obtained filtrate is back in step S1 as part lye
Reaction sinker process is participated in, and obtained filter residue is merged with lithium hydroxide crude product and carries out first time washing process.
Further, after obtaining lithium carbonate crude product, step S3 further include: lithium carbonate crude product is successively washed and done
It is dry, obtain battery-level lithium carbonate.
Further, the cleaning solution generated during lithium carbonate crude product will be washed and be back in sinker mother liquor that participate in precipitating anti-
It answers；Preferably, after the step of being evaporated concentration to filtrated stock, step S4 further include: by the mistake by being concentrated by evaporation
It filters mother liquor and carries out secondary filter, obtain chloride crude product；Chloride crude product is washed, then dries, obtains the chloride of technical grade；
Preferably, the filtrate generated in secondary filter step is back in step S3, for configuring precipitating reagent；Preferably, it will wash
The cleaning solution generated during chloride crude product is back to evaporation-concentration step.
The present invention provides a kind of preparation methods of LITHIUM BATTERY lithium hydroxide comprising following steps: S1, by chloride containing lithium
Brine carry out reacting sinker with lye, obtain lithium hydroxide crude product and sinker mother liquor；S2 successively carries out lithium hydroxide crude product
Washing for the first time, evaporative crystallization, second of washing, drying, obtain LITHIUM BATTERY lithium hydroxide.Utilize method energy provided by the invention
The LITHIUM BATTERY lithium hydroxide that purity is met the requirements enough is prepared, especially chlorinty is very low.Meanwhile the present invention also has the lithium rate of recovery
It is high, process flow is short, operating procedure is simple, production cost is low, safety and environmental protection, easy to industrialized production.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the flow chart of LITHIUM BATTERY lithium hydroxide preparation method in a kind of typical embodiment according to the present invention.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
As described in background technology part, it is pure that there are lithium hydroxides when preparing LITHIUM BATTERY lithium hydroxide in the prior art
Spend the problem that the loss of low or lithium is serious or preparation cost is high.
To solve the above-mentioned problems, the present invention provides a kind of preparation methods of LITHIUM BATTERY lithium hydroxide, as shown in Figure 1,
It carries out the brine of chloride containing lithium with lye to react sinker the following steps are included: S1, obtains lithium hydroxide crude product and sinker is female
Liquid；S2 successively carries out first time washing, evaporative crystallization, second of washing, drying to lithium hydroxide crude product, obtains LITHIUM BATTERY hydrogen
Lithia.
In above-mentioned steps S1, lithium hydroxide and chloride (such as sodium chloride or potassium chloride) can be obtained by brine causticization
Mixed solution.In the step, since the solubility of lithium hydroxide and these chloride impurities is very close to and solubility is all with temperature
Variation difference very little, so will should also have a large amount of chlorine in the process if monohydrate lithium hydroxide directly is precipitated by evaporative crystallization
Compound is precipitated together therewith, and many chloride impurities can should be covered by lithium hydroxide lattice structure in the process, at that time
It calculates and uses a large amount of washing procedures in the later period, it is also difficult to the two be kept completely separate, cause the lithium hydroxide purity of preparation lower, especially
Chlorinty is very high, this prepares the difficult point of the higher LITHIUM BATTERY lithium hydroxide of purity also with the brine causticization of chloride containing lithium.And
In preparation method provided by the invention, before the step of being evaporated crystallization in step s 2, first with first time washing by hydrogen
Then chloride impurity removal in lithia crude product recycles evaporative crystallization and second of washing that LITHIUM BATTERY hydrogen-oxygen is prepared
Change lithium, chlorinty is very low, may be directly applied in anode material of lithium battery.In addition, the lithium rate of recovery of the invention is high, process flow
It is short, operating procedure is simple, production cost is low, safety and environmental protection, easy to industrialized production.
In a preferred embodiment, above-mentioned preparation method is further comprising the steps of: S3, can introduce into water
Precipitating reagent is passed through in sinker mother liquor as precipitating reagent and carries out precipitation reaction, it is thick to obtain lithium carbonate by the compound of carbanion
Product and filtrated stock；S4 is successively evaporated concentration and drying to filtrated stock, obtains chloride.
After reaction sinker, a large amount of chloride (such as sodium chloride or chlorine are also remained in obtained sinker mother liquor
Change potassium) impurity, also there is the unprecipitated lithium ion in part.The present invention is sunk the part lithium ion using the precipitation reaction in step S3
Shallow lake comes out, to reduce the lithium loss in preparation process.Then, it after being evaporated concentration and drying to filtrated stock, obtains
Chloride by-product.In this way, can be in the LITHIUM BATTERY lithium hydroxide that preparation purity is met the requirements using method provided by the invention
While, also by the precipitation process to filtrated stock, elemental lithium therein has effectively been recycled, has reduced lithium loss.
In order to more fully wash away the chloride impurity in lithium hydroxide crude product, in a preferred embodiment, on
It states in step S2, the detergent used in washing for the first time and second of washing is lithium hydroxide saturated aqueous solution.More preferably
Ground, in step S2, the temperature of evaporative crystallization is 50~95 DEG C, and pressure is 0~0.1MPa.The hydroxide obtained under the process conditions
Lithium purity is higher.
In above-mentioned steps S1, the brine of the chloride containing lithium of use can come from preparation method commonly used in the art, such as
Lithium chloride concentrate after salt lake absorption, film process is further concentrated, and forms reaction raw materials.In a kind of preferred embodiment party
In formula, in above-mentioned steps S1, the mass concentration of lithium chloride is 27~35% in the brine of chloride containing lithium, hydroxide ion in lye
Mass concentration be 10%~15%.Under above-mentioned reaction condition, the formation efficiency of lithium hydroxide is more preferable.On it is further preferred that
It states in step S1, the reaction temperature during reaction sinker is 0~95 DEG C, and the reaction time is 10~120min.
Preferably, lye is sodium hydrate aqueous solution, potassium hydroxide aqueous solution or ammonium hydroxide.When lye is that sodium hydroxide is water-soluble
When liquid, precipitating reagent is sodium carbonate and/or carbon dioxide, and chloride is sodium chloride；When lye is potassium hydroxide aqueous solution, precipitating
Agent is potassium carbonate and/or carbon dioxide, and chloride is potassium chloride；When lye is ammonium hydroxide, precipitating reagent is ammonium carbonate and/or dioxy
Change carbon, chloride is ammonium chloride.When using sodium hydrate aqueous solution, corresponding chloride is sodium chloride, using potassium hydroxide water
When solution, corresponding chloride is potassium chloride, and when using ammonium hydroxide, corresponding chloride is ammonium chloride.
In a preferred embodiment, in above-mentioned steps S2, evaporation and crystal process includes: will be by washing for the first time
Lithium hydroxide crude product afterwards is mixed and is completely dissolved with water, obtains lysate；It dissolves by heating liquid and with evaporation section water and knot is precipitated
Crystalline substance obtains residual solution；Residual solution is cooled down, evaporation and crystal process is completed.Because eliminating big portion in first time washing process
Divide impurity, the lithium hydroxide purity that precipitation is crystallized in evaporation and crystal process is higher.During dissolving by heating liquid, lithium hydroxide knot
Partial crystallization goes out, and then cools down residual solution, and evaporative crystallization steps can be completed.
In a preferred embodiment, in evaporation and crystal process, residual solution after cooling is filtered, filtrate is back to
In first time washing process.Be conducive to recycling for resource in this way, while lithium loss can also be further reduced.More preferably exist
First this part solution is further concentrated by evaporation before returning, after removing a part of water and filter, then is about to filtrate return.It is excellent
The cleaning solution generated in second of washing process is back in first time washing process by selection of land together.
In first time washing process, inevitably there is part lithium hydroxide is washed to be dissolved in cleaning solution, it is preferable that by first
The further evaporative crystallization of the cleaning solution generated in secondary washing process, is then filtered, and obtained filtrate is back in step S1 and is made
The reaction sinker process is participated in for part lye, and obtained filter residue is merged into progress with lithium hydroxide crude product and is washed for the first time
It washs.Be conducive to be further reduced lithium loss in this way.
After second is washed, preferably by the lithium hydroxide filter cake after secondary washing under the conditions of 50~80 DEG C of temperature
It is dried, by the free water removal in filter cake, finally obtains the monohydrate lithium hydroxide product of LITHIUM BATTERY.
In order to further purify lithium carbonate, in a preferred embodiment, as shown in Figure 1, thick obtaining lithium carbonate
After product, step S3 further include: lithium carbonate crude product is successively washed and dried, battery-level lithium carbonate is obtained.It is anti-by precipitating
Also remain some chloride impurities in the lithium carbonate crude product that should be generated, by washing and drying, it is higher purity can be obtained
Battery-level lithium carbonate.Preferably, during washing to lithium carbonate crude product, the detergent used is water.
In order to promote maximally utilizing for resource, in a preferred embodiment, as shown in Figure 1, carbonic acid will be washed
The cleaning solution generated during lithium crude product, which is back in sinker mother liquor, participates in precipitation reaction.
In a preferred embodiment, after the step of being evaporated concentration to filtrated stock, step S4 is also wrapped
It includes: secondary filter will be carried out by the filtrated stock being concentrated by evaporation, obtain chloride crude product；Chloride crude product is washed, is then done
It is dry, obtain the chloride of technical grade.Chloride can be further purified in this way, obtain technical grade chloride.It preferably, will be secondary
The filtrate generated in filtration step is back in step S3, for configuring precipitating reagent；Preferably, chloride crude product process will be washed
The cleaning solution of middle generation is back to evaporation-concentration step.In this way, generated all cleaning solutions and mother liquor are equal in the preparation method
The use of primitive reaction liquid can be applied or be configured, reduces the discharge of waste water, improves the rate of recovery of lithium.
Beneficial effects of the present invention are further illustrated by the following examples:
Embodiment 1
Process is as shown in Figure 1:
Take 1m3Amount containing lithium is that 20g/L refines brine, and the amount containing lithium that is concentrated into is that (mass concentration of conversion LiCl is about by 44.5g/L
For 27%), sodium hydroxide solution that 443kg mass concentration is about 25.8% is wherein added, (hydroxide ion mass concentration is
10.9%) 60min, is reacted at room temperature, the solid-liquid mixture precipitated containing lithium hydroxide is formed, slurries is filtered, using saturation
Lithium hydroxide solution washing removes a large amount of sodium chloride as impurity carried secretly in filter cake, obtains lithium hydroxide filter cake；In a heated condition,
After being completely dissolved lithium hydroxide filter cake with 300kg deionized water, heating boils off 2/3 water, carries out crystallisation by cooling, control crystallization temperature
For degree at 60 DEG C, the lithium hydroxide filter cake that chlorinty is 150ppm is obtained by filtration in 0.01MPa in pressure；Filter cake is washed again
It washs, removes remaining a small amount of sodium chloride as impurity；Lithium hydroxide filter cake is dried in vacuo 5h under the conditions of 50 DEG C, is removed in filter cake
Free water finally obtains the monohydrate lithium hydroxide product of 30kg LITHIUM BATTERY, product purity 98.6%, chlorinty 7ppm.
Lithium recycles in mother liquor: sodium carbonate is added in sinker mother liquor and is reacted, filtered filter cake is washed, dry,
Obtain 70kg battery-level lithium carbonate, purity 99.8%.Filtrate is concentrated by evaporation, is filtered, washed, being dried to obtain industrial grade sodium chloride
Product.
Cleaning solution processing: will be after cooling in the cleaning solution and evaporation and crystal process after second of the washing of lithium hydroxide crude product
The filtrate that residual solution is obtained by filtration merges, and is then back in first time washing process jointly；It is obtained in first time washing process
Cleaning solution carries out evaporative crystallization next time, cooling, and obtained filtrate is back to and is used to configure lye, as part alkali by filtering
Liquid participates in reaction sinker process, and obtained filter residue is merged with lithium hydroxide crude product and carries out first time washing process；Lithium carbonate
Cleaning solution, which returns to sinker mother liquor, to be continued to prepare lithium carbonate；NaCl liquid returns to evaporation-concentration step；Sodium chloride filtered fluid returns
Return configuration sodium carbonate liquor.
Embodiment 2
Process is as shown in Figure 1:
Take 1m3Amount containing lithium is that 20g/L refines brine, and the amount containing lithium that is concentrated into is that (mass concentration of conversion LiCl is about by 44.5g/L
For 27%), sodium hydroxide solution that 443kg mass concentration is about 25.8% is wherein added, (hydroxide ion mass concentration is
10.9%) 120min, is reacted under the conditions of 80 DEG C, forms the solid-liquid mixture precipitated containing lithium hydroxide, slurries are filtered, are made
The a large amount of sodium chloride as impurity for removing and carrying secretly in filter cake are washed with saturation lithium hydroxide solution, obtain lithium hydroxide filter cake；It is heating
Under the conditions of, after being completely dissolved lithium hydroxide filter cake with 300kg deionized water, heating boils off 2/3 water, carries out crystallisation by cooling, control
For crystallization temperature processed at 80 DEG C, the lithium hydroxide filter cake that chlorinty is 180ppm is obtained by filtration in 0.02MPa in pressure；Again by filter cake
It is secondary to be washed, remove remaining a small amount of sodium chloride as impurity；Lithium hydroxide filter cake is dried in vacuo 5h under the conditions of 50 DEG C, is removed
Free water in filter cake, finally obtains the monohydrate lithium hydroxide product of 30kg LITHIUM BATTERY, product purity 98.5%, and chlorinty is
10ppm。
Lithium recycles in mother liquor: sodium carbonate is added in sinker mother liquor and is reacted, filtered filter cake is washed, dry,
Obtain 70kg battery-level lithium carbonate, purity 99.8%.Filtrate is concentrated by evaporation, is filtered, washed, being dried to obtain industrial grade sodium chloride
Product.
Cleaning solution processing: will be after cooling in the cleaning solution and evaporation and crystal process after second of the washing of lithium hydroxide crude product
The filtrate that residual solution is obtained by filtration merges, and is then back in first time washing process jointly；It is obtained in first time washing process
Cleaning solution carries out evaporative crystallization next time, cooling, and obtained filtrate is back to and is used to configure lye, as part alkali by filtering
Liquid participates in reaction sinker process, and obtained filter residue is merged with lithium hydroxide crude product and carries out first time washing process；Lithium carbonate
Cleaning solution, which returns to sinker mother liquor, to be continued to prepare lithium carbonate；NaCl liquid returns to evaporation-concentration step；Sodium chloride filtered fluid returns
Return configuration sodium carbonate liquor.
Embodiment 3
Process is as shown in Figure 1:
Take 1m3Amount containing lithium be 20g/L refine brine, be concentrated into amount containing lithium be 52g/L (conversion LiCl mass concentration be about
32%), the sodium hydroxide solution that 370kg mass concentration is about 30.8% is wherein added, (hydroxide ion mass concentration is
13.1%) 60min, is reacted under the conditions of 80 DEG C, forms the solid-liquid mixture precipitated containing lithium hydroxide, slurries are filtered, are made
The a large amount of sodium chloride as impurity for removing and carrying secretly in filter cake are washed with saturation lithium hydroxide solution, obtain lithium hydroxide filter cake；It is heating
Under the conditions of, after being completely dissolved lithium hydroxide filter cake with 300kg deionized water, heating boils off 2/3 water, carries out crystallisation by cooling, control
For crystallization temperature processed at 60 DEG C, the lithium hydroxide filter cake that chlorinty is 200ppm is obtained by filtration in 0.01MPa in pressure；Again by filter cake
It is secondary to be washed, remove remaining a small amount of sodium chloride as impurity；Lithium hydroxide filter cake is dried in vacuo 5h under the conditions of 50 DEG C, is removed
Free water in filter cake, finally obtains the monohydrate lithium hydroxide product of 60kg LITHIUM BATTERY, product purity 98.4%, and chlorinty is
10ppm。
Lithium recycles in mother liquor: sodium carbonate is added in sinker mother liquor or is passed through carbon dioxide and is reacted, filtered filter
Cake is washed, dry, obtains 45kg battery-level lithium carbonate, purity 99.5%.Filtrate is concentrated by evaporation, is filtered, washed, dries
To industrial grade sodium chloride product.
Cleaning solution processing: will be after cooling in the cleaning solution and evaporation and crystal process after second of the washing of lithium hydroxide crude product
The filtrate that residual solution is obtained by filtration merges, and is then back in first time washing process jointly；It is obtained in first time washing process
Cleaning solution carries out evaporative crystallization next time, cooling, and obtained filtrate is back to and is used to configure lye, as part alkali by filtering
Liquid participates in reaction sinker process, and obtained filter residue is merged with lithium hydroxide crude product and carries out first time washing process；Lithium carbonate
Cleaning solution, which returns to sinker mother liquor, to be continued to prepare lithium carbonate；NaCl liquid returns to evaporation-concentration step；Sodium chloride filtered fluid returns
Return configuration sodium carbonate liquor.
Embodiment 4
Process is as shown in Figure 1:
Take 1m3Amount containing lithium be 20g/L, purification brine be concentrated into amount containing lithium be 52g/L (conversion LiCl mass concentration be about
32%), the sodium hydroxide solution that 370kg mass concentration is about 30.8% is wherein added, (hydroxide ion mass concentration is
13.1%) 60min, is reacted at room temperature, the solid-liquid mixture precipitated containing lithium hydroxide is formed, slurries is filtered, using saturation
Lithium hydroxide solution washing removes a large amount of sodium chloride as impurity carried secretly in filter cake, obtains lithium hydroxide filter cake；In a heated condition,
After being completely dissolved lithium hydroxide filter cake with 300kg deionized water, heating boils off 2/3 water, carries out crystallisation by cooling, control crystallization temperature
For degree at 60 DEG C, the lithium hydroxide filter cake that chlorinty is 160ppm is obtained by filtration in 0.01MPa in pressure；Filter cake is washed again
It washs, removes remaining a small amount of sodium chloride as impurity；Lithium hydroxide filter cake is dried in vacuo 5h under the conditions of 50 DEG C, is removed in filter cake
Free water finally obtains the monohydrate lithium hydroxide product of 70kg LITHIUM BATTERY, product purity 98.6%, chlorinty 7ppm.
Lithium recycles in mother liquor: sodium carbonate is added in sinker mother liquor or is passed through carbon dioxide and is reacted, filtered filter
Cake is washed, dry, obtains 38kg battery-level lithium carbonate, purity 99.6%.Filtrate is concentrated by evaporation, is filtered, washed, washs
To industrial grade sodium chloride product.
Cleaning solution processing: will be after cooling in the cleaning solution and evaporation and crystal process after second of the washing of lithium hydroxide crude product
The filtrate that residual solution is obtained by filtration merges, and is then back in first time washing process jointly；It is obtained in first time washing process
Cleaning solution carries out evaporative crystallization next time, cooling, and obtained filtrate is back to and is used to configure lye, as part alkali by filtering
Liquid participates in reaction sinker process, and obtained filter residue is merged with lithium hydroxide crude product and carries out first time washing process；Lithium carbonate
Cleaning solution, which returns to sinker mother liquor, to be continued to prepare lithium carbonate；NaCl liquid returns to evaporation-concentration step；Sodium chloride filtered fluid returns
Return configuration sodium carbonate liquor.
Embodiment 5
Take 1m3Amount containing lithium is that 20g/L refines brine, and the amount containing lithium that is concentrated into is that (mass concentration of conversion LiCl is about by 57.6g/L
For lithium chloride solution 35%), be wherein added sodium hydroxide solution that 340kg mass concentration is about 33.6% (hydroxyl from
Protonatomic mass concentration is 14.3%), to react at room temperature 60min, forms the solid-liquid mixture precipitated containing lithium hydroxide, slurries were carried out
Filter removes a large amount of sodium chloride as impurity carried secretly in filter cake using saturation lithium hydroxide solution washing, obtains lithium hydroxide filter cake；?
Under heating condition, after being completely dissolved lithium hydroxide filter cake with 300kg deionized water, heating boils off 2/3 water, carries out cooling knot
Crystalline substance, for control crystallization temperature at 80 DEG C, the lithium hydroxide filter cake that chlorinty is 250ppm is obtained by filtration in 0.02MPa in pressure；It will filter
Cake is washed again, removes remaining a small amount of sodium chloride as impurity；Lithium hydroxide filter cake is dried in vacuo 5h under the conditions of 50 DEG C,
The free water in filter cake is removed, the monohydrate lithium hydroxide product of 72kg LITHIUM BATTERY is finally obtained, product purity 98.3% contains chlorine
Amount is 18ppm.
Lithium recycles in mother liquor: sodium carbonate is added in sinker mother liquor or is passed through carbon dioxide and is reacted, filtered filter
Cake is washed, dry, obtains 36kg battery-level lithium carbonate, purity 99.5%.Filtrate is concentrated by evaporation, is filtered, washed, dries
To industrial grade sodium chloride product.
Cleaning solution processing: will be after cooling in the cleaning solution and evaporation and crystal process after second of the washing of lithium hydroxide crude product
The filtrate that residual solution is obtained by filtration merges, and is then back in first time washing process jointly；It is obtained in first time washing process
Cleaning solution carries out evaporative crystallization next time, cooling, and obtained filtrate is back to and is used to configure lye, as part alkali by filtering
Liquid participates in reaction sinker process, and obtained filter residue is merged with lithium hydroxide crude product and carries out first time washing process；Lithium carbonate
Cleaning solution, which returns to sinker mother liquor, to be continued to prepare lithium carbonate；NaCl liquid returns to evaporation-concentration step；Sodium chloride filtered fluid returns
Return configuration sodium carbonate liquor.
Embodiment 6
Take 1m3Amount containing lithium is that 20g/L refines brine, and the amount containing lithium that is concentrated into is that (mass concentration of conversion LiCl is about by 57.6g/L
For lithium chloride solution 35%), be wherein added sodium hydroxide solution that 350kg mass concentration is about 37.5% (hydroxyl from
Protonatomic mass concentration is 15%), 10min to be reacted at 95 DEG C, forms the solid-liquid mixture precipitated containing lithium hydroxide, slurries were carried out
Filter removes a large amount of sodium chloride as impurity carried secretly in filter cake using saturation lithium hydroxide solution washing, obtains lithium hydroxide filter cake；?
Under heating condition, after being completely dissolved lithium hydroxide filter cake with 300kg deionized water, heating boils off 2/3 water, carries out cooling knot
Crystalline substance, for control crystallization temperature at 95 DEG C, the lithium hydroxide filter cake that chlorinty is 230ppm is obtained by filtration in 0.05MPa in pressure；It will filter
Cake is washed again, removes remaining a small amount of sodium chloride as impurity；Lithium hydroxide filter cake is dried in vacuo 5h under the conditions of 80 DEG C,
The free water in filter cake is removed, the monohydrate lithium hydroxide product of 58kg LITHIUM BATTERY is finally obtained, product purity 98.3% contains chlorine
Amount is 16ppm.
Lithium recycles in mother liquor: sodium carbonate is added in sinker mother liquor or is passed through carbon dioxide and is reacted, filtered filter
Cake is washed, dry, obtains 47kg battery-level lithium carbonate, purity 99.5%.Filtrate is concentrated by evaporation, is filtered, washed, dries
To industrial grade sodium chloride product.
Cleaning solution processing: will be after cooling in the cleaning solution and evaporation and crystal process after second of the washing of lithium hydroxide crude product
The filtrate that residual solution is obtained by filtration merges, and is then back in first time washing process jointly；It is obtained in first time washing process
Cleaning solution carries out evaporative crystallization next time, cooling, and obtained filtrate is back to and is used to configure lye, as part alkali by filtering
Liquid participates in reaction sinker process, and obtained filter residue is merged with lithium hydroxide crude product and carries out first time washing process；Lithium carbonate
Cleaning solution, which returns to sinker mother liquor, to be continued to prepare lithium carbonate；NaCl liquid returns to evaporation-concentration step；Sodium chloride filtered fluid returns
Return configuration sodium carbonate liquor.
Embodiment 7
Take 1m3Amount containing lithium is that 20g/L refines brine, and the amount containing lithium that is concentrated into is that (mass concentration of conversion LiCl is about by 57.6g/L
For lithium chloride solution 35%), be wherein added sodium hydroxide solution that 350kg mass concentration is about 37.5% (hydroxyl from
Protonatomic mass concentration is 15%), 120min to be reacted at 0 DEG C, forms the solid-liquid mixture precipitated containing lithium hydroxide, slurries were carried out
Filter removes a large amount of sodium chloride as impurity carried secretly in filter cake using saturation lithium hydroxide solution washing, obtains lithium hydroxide filter cake；?
Under heating condition, after being completely dissolved lithium hydroxide filter cake with 300kg deionized water, heating boils off 2/3 water, carries out cooling knot
Crystalline substance, for control crystallization temperature at 50 DEG C, the lithium hydroxide filter cake that chlorinty is 260ppm is obtained by filtration in 0.009MPa in pressure；It will
Filter cake is washed again, removes remaining a small amount of sodium chloride as impurity；Lithium hydroxide filter cake is dried in vacuo under the conditions of 80 DEG C
5h removes the free water in filter cake, finally obtains the monohydrate lithium hydroxide product of 60kg LITHIUM BATTERY, product purity 98.3%,
Chlorinty is 20ppm.
Lithium recycles in mother liquor: sodium carbonate is added in sinker mother liquor or is passed through carbon dioxide and is reacted, filtered filter
Cake is washed, dry, obtains 45kg battery-level lithium carbonate, purity 99.5%.Filtrate is concentrated by evaporation, is filtered, washed, dries
To industrial grade sodium chloride product.
Cleaning solution processing: will be after cooling in the cleaning solution and evaporation and crystal process after second of the washing of lithium hydroxide crude product
The filtrate that residual solution is obtained by filtration merges, and is then back in first time washing process jointly；It is obtained in first time washing process
Cleaning solution carries out evaporative crystallization next time, cooling, and obtained filtrate is back to and is used to configure lye, as part alkali by filtering
Liquid participates in reaction sinker process, and obtained filter residue is merged with lithium hydroxide crude product and carries out first time washing process；Lithium carbonate
Cleaning solution, which returns to sinker mother liquor, to be continued to prepare lithium carbonate；NaCl liquid returns to evaporation-concentration step；Sodium chloride filtered fluid returns
Return configuration sodium carbonate liquor.
It should be noted that can also be taken after the lye in above-described embodiment is replaced with potassium hydroxide aqueous solution or ammonium hydroxide
Similar effect is obtained, details are not described herein.
In short, the preparation method provided through the invention, reaction obtains battery-stage monohydrate lithium hydroxide, one-way yield 25
~61%, total lithium recovery per pass of monohydrate lithium hydroxide and lithium carbonate is 91.2~94.3%.Shown here is one-way yield,
Refer to the single treatment yield after not recycled each cleaning solution etc., in the actual operation process, due to by each cleaning solution into
It has gone recycled, the yield of lithium can have been further increased, this is that those skilled in the art should be understood that.
LITHIUM BATTERY lithium hydroxide product compositions content/% is as follows in the embodiment of the present invention 1:
| Chemical component | LiOH.H2O | Na | Cl- | Fe | Ca | Mg | SO4 2- | CO3 2- |
| Mass fraction/% | > 98 | 0.0027 | 0.0007 | 0.0001 | 0.0002 | 0.0036 | 0.005 | 0.7 |
| Chemical component | Li2CO3 | Na | Cl- | Fe | Ca | Mg | SO42- |
| Mass fraction/% | > 99.5 | 0.0025 | 0.0007 | 0.0001 | 0.001 | 0.007 | 0.02 |
Comparative example 1
Lithium hydroxide is prepared using purification-washing process in patent CN106006675A, is lacked compared to present invention process
First time washing before evaporative crystallization, detailed process are as follows:
Take 1m3It is the 44.5g/L (mass concentration of conversion LiCl that purification brine (amount containing lithium is 20g/L), which is concentrated into amount containing lithium,
About 27%), sodium hydroxide solution (the hydroxide ion mass concentration that 243kg mass concentration is about 47.1% is wherein being added
For 20%), solution pH value is about 13,30min is reacted at room temperature, forms the solid-liquid mixture precipitated containing lithium hydroxide.Heating will be molten
Water in liquid is concentrated and crystallizes, and obtains being filtered slurries containing the slurries of certain solid phase, with saturation lithium hydroxide solution pair
Lithium hydroxide filter cake is washed three times respectively, is washed for four times.Lithium hydroxide filter cake is dried in vacuo 5h under the conditions of 50 DEG C, is removed
The free water in filter cake is removed, finally obtains 30kg monohydrate lithium hydroxide product, product purity 97.8%, in lithium hydroxide product
Chloride ion-containing amount is respectively 443ppm, 357ppm, and chlorinty is very high, and reacted sinker mother liquor is not reprocessed.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of LITHIUM BATTERY lithium hydroxide, which comprises the following steps:
The brine of chloride containing lithium and alkaline reaction sinker are obtained lithium hydroxide crude product and sinker mother liquor by S1；
S2 successively carries out first time washing, evaporative crystallization, second of washing, drying to the lithium hydroxide crude product, obtains described
LITHIUM BATTERY lithium hydroxide.
2. preparation method according to claim 1, which is characterized in that further comprising the steps of:
The precipitating reagent is passed through the sinker as precipitating reagent by S3, the compound can introduce carbanion into water
Precipitation reaction is carried out in mother liquor, obtains lithium carbonate crude product and filtrated stock；
S4 is successively evaporated concentration, filtering and drying to the filtrated stock, obtains chloride.
3. preparation method according to claim 1, which is characterized in that in the step S1, the brine of the chloride containing lithium
The mass concentration of middle lithium chloride is 27~35%, and the mass concentration of hydroxide ion is 10~15% in the lye.
4. preparation method according to claim 3, which is characterized in that in the step S1, during the reaction sinker
Reaction temperature be 0~95 DEG C, the reaction time be 10~120min.
5. preparation method according to any one of claim 1 to 3, which is characterized in that the lye is sodium hydroxide water
Solution, potassium hydroxide aqueous solution or ammonium hydroxide；When the lye be sodium hydrate aqueous solution when, the precipitating reagent be sodium carbonate and/
Or carbon dioxide, the chloride are sodium chloride；When the lye is potassium hydroxide aqueous solution, the precipitating reagent is potassium carbonate
And/or carbon dioxide, the chloride are potassium chloride；When the lye is ammonium hydroxide, the precipitating reagent is ammonium carbonate and/or two
Carbonoxide, the chloride are ammonium chloride.
6. preparation method according to claim 1, which is characterized in that in the step S2, the first time washing and institute
Stating the detergent used in second of washing is lithium hydroxide saturated solution.
7. preparation method according to claim 1, which is characterized in that in the step S2, the temperature of the evaporative crystallization
It is 50~95 DEG C, pressure is 0~0.1MPa.
8. according to claim 1, preparation method described in 3,6 or 7, which is characterized in that in the step S2, the evaporative crystallization
Process includes:
The lithium hydroxide crude product after first time washing is mixed and is completely dissolved with water, lysate is obtained；
The lysate is heated with evaporation section water and crystallization is precipitated, obtains residual solution；
The residual solution is cooled down, the evaporation and crystal process is completed.
9. preparation method according to claim 8, which is characterized in that in the evaporation and crystal process, by institute after cooling
Residual solution filtering is stated, filtrate is back in the first time washing process；
The cleaning solution generated in second of washing process is back to together in the first time washing process；
The further evaporative crystallization of cleaning solution that will be generated in the first time washing process, then filters, obtained filtrate is returned
It is back in the step S1 and participates in the reaction sinker process as the part lye, and by obtained filter residue and the hydrogen-oxygen
Change lithium crude product and merges the progress first time washing process.
10. preparation method according to claim 2, which is characterized in that after obtaining the lithium carbonate crude product, the step
S3 further include: the lithium carbonate crude product is successively washed and dried, battery-level lithium carbonate is obtained；
Preferably, the cleaning solution generated during the lithium carbonate crude product will be washed to be back in the sinker mother liquor described in participation
Precipitation reaction；It is highly preferred that the step S4 is also wrapped after the step of carrying out the evaporation and concentration to the filtrated stock
It includes:
The filtrated stock Jing Guo the evaporation and concentration is subjected to secondary filter, obtains chloride crude product；
The chloride crude product is washed, is then dried, the chloride of technical grade is obtained；
Preferably, the filtrate generated in the secondary filter step is back in the step S3, for configuring the precipitating
Agent；
Preferably, the cleaning solution generated during the chloride crude product will be washed and is back to the evaporation-concentration step.
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