CN107200338A - The technique that a kind of acidization extracts lithium hydroxide from amblygonite - Google Patents
The technique that a kind of acidization extracts lithium hydroxide from amblygonite Download PDFInfo
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- CN107200338A CN107200338A CN201710577799.4A CN201710577799A CN107200338A CN 107200338 A CN107200338 A CN 107200338A CN 201710577799 A CN201710577799 A CN 201710577799A CN 107200338 A CN107200338 A CN 107200338A
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- amblygonite
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
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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
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Abstract
The invention belongs to the lithium battery material extractive technique field in inorganic chemical industry.Its process route is：Amblygonite is by levigate and dispensing → roasting → clinker is levigate and leach → purification and impurity removal → evaporation and concentration → causticization → freezing analysis sodium → evaporative crystallization → recrystallization → drying and packaging together with the concentrated sulfuric acid.Using the technology of the present invention, lithium can be extracted from amblygonite, become standard compliant monohydrate lithium hydroxide product, the yield of lithium can reach more than 86%.Amblygonite is used to carry lithium by the present invention, has widened the scope for carrying lithium raw material.
Description
Technical field：
Research and development technology field is extracted the present invention relates to the lithium of amblygonite, more particularly to a kind of acidization is from amblygonite
The middle technique for extracting lithium hydroxide.
Background technology：The industrial mineral of lithium mainly has following several on the earth：
The industrial mineral of the lithium of table 1
Wherein the most famous with spodumene, because spodumene is big into ore deposit scale, composition is simple, carries lithium technical maturity, is mesh
It is preceding to use most lithium minerals.And although lepidolite is also into ore deposit scale than larger, but due to its complicated component, put forward lithium technique
Also it is complicated thus less for carrying lithium, it is mainly used in glass ceramics industry.Zinnwaldite, amblygonite and petalite then by
It is rare in distribution, into ore deposit small scale, there is not the report of commercial Application so far, and on carrying lithium technique side to this three kinds of mineral
The more not disclosed report of rule.
Our amblygonites to be studied are a kind of highest lithium minerals of amount containing lithium, and its minal oxide containing lithium amount is
10.1%, but it is not common in nature, and it is also very little scale to be occasionally found, not as the value of commercial mining.But it is existing
Then there is certain scale in this amblygonite ore deposit found in Africa, the value for possessing commercial mining.
Amblygonite is often the shaft-like such as irregular block and near, and color is grey, yellowish-white, green white etc., a certain amount of due to having
Other paragenous minerals, it is actual to contain Li2O8~9.5%, is the industrial mineral of highest containing lithium, originates in granite peamatite, sometimes
Also see in greisen and high quartz arteries and veins.Amblygonite is a kind of fluorophosphate containing lithium, aluminium, originates in granite peamatite, with
Spodumene, tourmaline, lepidolite and apatite symbiosis, are mainly used as extracting the resource of lithium.
The composition of amblygonite is as follows：%
Table 2
The content of the invention：
An object of the present invention is to provide the technique that a kind of acidization extracts lithium hydroxide from amblygonite, especially
It is the technique that a kind of initiative acidization extracts lithium hydroxide from amblygonite.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：A kind of acidization extracts hydrogen-oxygen from amblygonite
The technique for changing lithium, it is characterised in that：Comprise the following steps：
(1) raw material is levigate：Amblygonite raw material is carried out levigate；
(2) dispensing：By amblygonite of the step (1) after levigate and the concentrated sulfuric acid using weight ratio as 1:0.25~0.37 enters
Row mixing；
(3) it is calcined：Step (2) mixed material is calcined, clinker is obtained；
(4) size mixing leaching：Step (3) clinker is placed in reactor and adds water progress heating stirring, obtain the leaching containing lithium
Go out liquid；
(5) purification and impurity removal：To removing the impurity such as aluminium or calcium in the solution of leaching in step (4)；
(6) it is concentrated by evaporation：Solution after the completion of being reacted in step (5) is evaporated concentration, obtains lithium sulfate solution；
(7) causticization：Together, addition is completely converted into wherein lithium for lithium sulfate and crude product mother solution after step (6) is concentrated
Amount of calculation needed for lithium hydroxide is higher by the sodium hydroxide solution of 20~40% additions, then filter, and obtains containing lithium, sodium
Sulfate and hydroxide mixed solution；
(8) freezing analysis sodium：After the completion of obtain freezed containing lithium, the sulfate of sodium and hydroxide mixed solution；
(9) evaporative crystallization：The low sodium mixed solution obtained after the completion of step (8) is evaporated together with fine work mother liquor
Crystallization；
(10) recrystallize：The monohydrate lithium hydroxide solid obtained after the completion of step (9) is dissolved in water, heating stirring makes
Whole dissolving, then filter, filtrate is evaporated crystallization again；
(11) dry：The fine work monohydrate lithium hydroxide obtained after the completion of 9th step is dried.
It is levigate to the raw material in amblygonite to 100~200 mesh in step (1) as preferred.
As preferred, temperature control is calcined at 500 DEG C~800 DEG C in step (3), and roasting time is 20~
60 minutes.
It is after material cooling that clinker is levigate to 100~200 mesh after step (4) medium roasting as preferred.
As preferred, in step (4)) middle leaching liquid-solid ratio 3~5：1, extraction temperature is 20 DEG C~150 DEG C, constant temperature leaching
Go out the time 0.5~2 hour.
As preferred, in step (8), mixed solution is put into refrigerator and freezed, and treats that temperature is reduced to -10 DEG C of left sides
When right, substantial amounts of sodium sulphate is separated out in the form of sal glauberi is crystallized,
The solution and sal glauberi crystal of low sodium are obtained after separation.
As preferred, in step (10), 60-90 DEG C is heated to, stirring is filtered after being allowed to all dissolvings, and filtrate is again
It is secondary to be evaporated crystallization, after occurring a certain amount of crystallization in solution, stop heating, continue to stir, and naturally cool to 50 DEG C
Suction filtration separation, obtains fine work monohydrate lithium hydroxide product and fine work mother liquor after below.
As preferred, monohydrate lithium hydroxide solid in step (10) is dissolved in water, liquid-solid ratio is 3:1.
As preferred, in step (5), the leachate that step (4) is obtained with solid sodium hydroxide adjust PH to 7~
8, heated solution to 80~90 DEG C and isothermal reaction 10~15 minutes；To neutralize the acid in solution and remove aluminium in solution etc.
Impurity, will be filtered after the completion of reactive aluminum；Then repeated hydrogenation sodium oxide molybdena adjusts PH to 14；Add the carbonic acid of amount of calculation excessive 10%
Sinker mother liquor in sodium saturated solution or production, heated solution is to 80~90 DEG C and 10~15 points of isothermal reactions in course of reaction
Filtered after the completion of clock, question response, the clear liquid after filtering adjusts PH to 6.5~7.5 with sulfuric acid again, it is miscellaneous to remove calcium therein with depth
Matter.
The advantage of the invention is that：
1 there is provided the technique that a kind of initiative amblygonite extracts lithium hydroxide；It is by amblygonite through overground
The thin and dispensing → roasting → clinker is levigate and leaches → purification and impurity removal → evaporation and concentration → causticization → freezing analysis together with the concentrated sulfuric acid
The steps such as sodium → evaporative crystallization → recrystallization → drying extract monohydrate lithium hydroxide product；
2, proportioning of the material provided in the present invention, time etc. of reaction can with its raw material of the extraction and application of economy, with
Meet the commercial value of the exploitation to the raw material, further to improve its competitiveness of product in market；
3, the scheme of experiment is reliable, and impurity is few, and process route is simple, and can be further to the mother liquor in process
Utilization；
4, lithium can be extracted from amblygonite, become standard compliant monohydrate lithium hydroxide product, the receipts of lithium
Rate can reach more than 86%, and amblygonite is used to carry lithium, the scope for carrying lithium raw material has been widened.
Brief description of the drawings：
Accompanying drawing 1 extracts the process chart of monohydrate lithium hydroxide for the acidization of embodiment from amblygonite；
Accompanying drawing 2 is the sodium sulphate solubility with temperature change curve of embodiment.
Embodiment：
Embodiment 1：The technique that a kind of acidization extracts lithium hydroxide from amblygonite, it is characterised in that：Including following
Step：
(1) raw material is levigate：Amblygonite raw material is carried out levigate；
(2) dispensing：By amblygonite of the step (1) after levigate and the concentrated sulfuric acid using weight ratio as 1:0.25~0.37 enters
Row mixing；
(3) it is calcined：Step (2) mixed material is calcined, clinker is obtained；
(4) size mixing leaching：Step (3) clinker is placed in reactor and adds water progress heating stirring, obtain the leaching containing lithium
Go out liquid；
(5) purification and impurity removal：To removing the impurity such as aluminium or calcium in the solution of leaching in step (4)；
(6) it is concentrated by evaporation：Solution after the completion of being reacted in step (5) is evaporated concentration, obtains lithium sulfate solution；
(7) causticization：Together, addition is completely converted into wherein lithium for lithium sulfate and crude product mother solution after step (6) is concentrated
Amount of calculation needed for lithium hydroxide is higher by the sodium hydroxide solution of 20~40% additions, then filter, and obtains containing lithium, sodium
Sulfate and hydroxide mixed solution.
(8) freezing analysis sodium：After the completion of obtain freezed containing lithium, the sulfate of sodium and hydroxide mixed solution；
(9) evaporative crystallization：The low sodium mixed solution obtained after the completion of step (8) is evaporated together with fine work mother liquor
Crystallization；
(10) recrystallize：The monohydrate lithium hydroxide solid obtained after the completion of step (9) is dissolved in water, heating stirring makes
Whole dissolving, then filter, filtrate is evaporated crystallization again；
(11) dry：The fine work monohydrate lithium hydroxide obtained after the completion of 9th step is dried.
It is levigate to amblygonite raw material to 100~200 mesh in step (1) as preferred.
As preferred, temperature control is calcined at 500 DEG C~800 DEG C in step (3), and roasting time is 20~
60 minutes.
It is after material cooling that clinker is levigate to 100~200 mesh after step (4) medium roasting as preferred.
As preferred, in step (4)) middle leaching liquid-solid ratio 3~5：1, extraction temperature room temperature (about 20 DEG C)~150 DEG C,
Constant temperature extraction time 0.5~2 hour.
As preferred, in step (8), mixed solution is put into refrigerator and freezed, and treats that temperature is reduced to -10 DEG C of left sides
When right, substantial amounts of sodium sulphate is separated out in the form of sal glauberi is crystallized, and the solution and ten water sulfuric acid of low sodium are obtained after separation
Sodium crystal.
As preferred, in step (10), 60-90 DEG C is heated to, stirring is filtered after being allowed to all dissolvings, and filtrate is again
It is secondary to be evaporated crystallization, after occurring a certain amount of crystallization in solution, stop heating, continue to stir, and naturally cool to 50 DEG C
Suction filtration separation, obtains fine work monohydrate lithium hydroxide product and fine work mother liquor after below.
As preferred, monohydrate lithium hydroxide solid in step (10) is dissolved in water, liquid-solid ratio is 3:1.
As preferred, in step (5), the leachate that step (4) is obtained with solid sodium hydroxide adjust PH to 7~
8, heated solution to 80~90 DEG C and isothermal reaction 10~15 minutes；To neutralize the acid in solution and remove aluminium in solution etc.
Impurity, will be filtered after the completion of reactive aluminum；Then repeated hydrogenation sodium oxide molybdena adjusts PH to 14；Add the carbonic acid of amount of calculation excessive 10%
Sinker mother liquor in sodium saturated solution or production, heated solution is to 80~90 DEG C and 10~15 points of isothermal reactions in course of reaction
Filtered after the completion of clock, question response, the clear liquid after filtering adjusts PH to 6.5~7.5 with sulfuric acid again, it is miscellaneous to remove calcium therein with depth
Matter.
Details are as follows for the dominating process route and technical characteristic of the present invention：
1st, raw material is levigate and dispensing
Raw material is levigate and mixed in dispensing and be conducive to being smoothed out for solid phase reaction, and dispensing is in order to which add can be with
Amblygonite ore deposit is reacted and lithium is at utmost converted into water-soluble lithium compound, so as to be conducive to subsequent handling to extract
Lithium.
1.1st, then weigh amblygonite ore deposit is levigate, be put into a porcelain crucible to 180 mesh.Then it is proportionally added into dense
Sulfuric acid, then manual mixing is carried out, untill well mixed.
The proportioning of amblygonite and sulfuric acid is：Amblygonite：Sulfuric acid=1：0.25~~0.37
Formula be have passed through after pre-selection, and several groups of main formulas are listed.
Specific test recipe such as table 3 below：
| Numbering | 1 | 2 | 3 | 4 |
| Formula | 1:0.25 | 1:0.30 | 1:0.35 | 1:0.37 |
2nd, it is calcined
By roasting, water insoluble lithium is converted into water-soluble lithium compound in material.
The material prepared is put into Muffle furnace the roasting that heats up, sintering temperature control is in 500~700 DEG C of (each sample settings
Different sintering temperatures), constant temperature calcining time control is 30 minutes.
Sintering temperature is determined by testing, and the constant temperature calcining time is then with calcining kiln high temperature general in industrial production
About half an hour section passage time is foundation.By taking 4 formulas in table as an example, the lithium conversion ratio under its different sintering temperature is as follows
Table：
Table 4
Sintering temperature is determined by testing, and the constant temperature calcining time is then with calcining kiln high temperature general in industrial production
About half an hour section passage time is foundation.By taking 4 formulas in table as an example, the lithium conversion ratio under its different sintering temperature is as follows
Table：
Table 4-1 is (with amblygonite：Sulfuric acid=1:Exemplified by the roasting of 0.37 proportioning)
Table 4-2 is (with amblygonite：Sulfuric acid=1:Exemplified by 0.37 proportioning and 30 minutes constant temperature calcinings)
| Levigate fineness (mesh) | 500℃ | 600℃ | 650℃ | 700℃ | 800℃ |
| 100 | 32.49% | 35.26% | 45.25% | 56.28% | 63.63% |
| 180 | 79.65% | 86.96% | 95.11% | 97.48% | 97.69% |
| 200 | 81.52% | 87.32% | 95.45% | 97.62% | 97.96% |
3rd, size mixing leaching
Roasting clinker is levigate to 180 mesh, then weigh a certain amount (general 2.5~~10 grams) and add reaction
In kettle, then measure 100ml distilled water add reactor, reactor is installed, open heating and stir, set reaction temperature as
95~150 DEG C, the reaction time 1~~2 hours, reaction closes heating after terminating, and continues to stir and cool, then filters,
Filtrate sampling analysis, leached mud adds 50ml water heating stirring to wash, and filtering, slag adds 50ml water wash twice, put after filtering again
Enter and weighed after drying in oven, cooling and sampling analysis slag oxide containing lithium amount.Slag washing water is returned for leaching (during due to experiment
Metering and analysis reason do not return to leaching).
In order to obtain higher concentration and large volume of lithium solution, 200~400 grams of roasting clinkers are weighed every time solid with liquid
Than 3~5:1 ratio is leached in stainless steel reaction pot, and electric furnace is then used in heating, and uses electric stirring.Same reaction temperature
Spend for 95~150 DEG C, the reaction time 1~~2 hours.Natural cooling after the completion of reaction, is then filtered, using buchner funnel and filter
Bottle and vavuum pump are filtered by vacuum, and leached mud is taken out after being filtered dry with liquid-solid ratio 3：1 adds water and heating stirring washing, heating
10~20 minutes time, 80 DEG C or so of heating-up temperature, then suction filtration again, adds water elution twice, each leacheate after draining
Gu than being 0.5：1, take out to be put into after drying in oven, cooling after suction filtration is dry and weigh and sampling analysis slag oxide containing lithium amount, washery slag
Water can be returned for leaching and (being measured during due to experiment and analysis reason does not return to leaching).Leachate analysis result (1#,
The corresponding formulas of 2# are 1 respectively:0.35 and 1:0.37)
Table 5 (mg/l)
Note：1#2# is to use result of the reactor in high liquid-solid ratio, and 3# is to use result of the reaction pot in low liquid-solid ratio.
The influence of different extraction temperatures and different extraction times to leaching rate is as follows
Table 6
Leached mud analysis result is as follows：
Table 7 (%)
4th, purification and impurity removal
The leachate that 3rd step is obtained adjusts PH to 7~8, heated solution to 80~90 DEG C and constant temperature with solid sodium hydroxide
Reaction 10~15 minutes, to neutralize the acid in solution and remove the impurity such as the aluminium in solution, is filtered after the completion of reaction.Then again
Reinforcing body sodium hydroxide adjusts PH to 14, to remove magnesium in solution and the impurity such as partial calcium.In order to which depth removal is therein
Calcium, also to add the saturated solution of sodium carbonate of amount of calculation excessive 10% (can be replaced, using wherein in production with sinker mother liquor
Carbonate).Heated solution is answered in course of reaction to 80~90 DEG C and isothermal reaction 10~15 minutes, mistake after the completion of question response
Filter.
Clear liquid after filtering adjusts PH to 6.5~7.5 with sulfuric acid again.
The main chemical reactions of purification and impurity removal are as follows：
Al3++OH-→Al(OH)3↓
Mg2++OH-→Mg(OH)2↓
Ca2++OH-→Ca(OH)2↓
Ca2++CO3 2-→CaCO3↓
5th, it is concentrated by evaporation
The solution obtained after the completion of 4th step is added in beaker or stainless steel reaction pot, heating on electric furnace is placed in and is steamed
Hair concentration, when aoxidizing lithium concentration when being concentrated in solution for 45g/l or so, stops heating, suction filtration is removed in evaporation process and analysed
Some impurity (impurity such as calcium and magnesium that mainly supersaturation is separated out) gone out, obtain limpid lithium sulfate concentrate, solution composition
It is as follows：(g/l)
Table 8
6th, causticization
By the lithium sulfate concentrated solution (sample number into spectrum 2#) obtained after the completion of the 5th step together with crude product mother solution, amount of calculation is added
Sodium hydroxide solution (concentration of sodium hydroxide solution 30%) within excessive 40%, makes lithium therein be completely converted into hydroxide
Lithium, is then filtered, and is obtained containing lithium, the sulfate of sodium and hydroxide mixed solution.Li in solution after causticization2O concentration 45
~50g/l, OH-75~80g/l of concentration.
7th, freezing analysis sodium
What is obtained after 6th step is not completed is freezed containing lithium, the sulfate of sodium and hydroxide mixed solution.
In solution after causticization, containing substantial amounts of sodium sulphate, this solution is directly such as evaporated, then can separate out monohydrate lithium hydroxide
Sodium sulphate can be also separated out simultaneously, so most of sodium sulphate must be removed first.Using the reduction of sodium sulphate solubility with temperature
The property drastically declined, is put into refrigerator by above-mentioned mixed solution and is freezed, substantial amounts of when temperature is reduced to -10 DEG C or so
Sodium sulphate is separated out in the form of sal glauberi is crystallized, and the solution and sal glauberi crystal of low sodium are obtained after separation.Separation
The sulfate radical content in solution afterwards is reduced to 30g/l or so.In the industrial production, the sal glauberi separated can be with
As byproduct direct marketing, anhydrous sodium sulfate can also be made and sells again.Sodium sulphate solubility with temperature change curve is shown in attached
Fig. 2.
8th, evaporative crystallization
The low sodium mixed solution obtained after the completion of 7th step is evaporated together with fine work mother liquor, with the concentration of lithium
Improve constantly, lithium hydroxide progressively supersaturation and separate out monohydrate lithium hydroxide crystallization, amount to be crystallized reach it is a certain amount of after, stop
Only heating evaporation, is progressively cooled down in the case where mixing slowly, and is allowed to separate out more monohydrate lithium hydroxide crystal.It is to be cooled to arrive close
Room temperature, is separated, and obtains monohydrate lithium hydroxide solid and crystalline mother solution.Resulting monohydrate lithium hydroxide solid is referred to as slightly
Product, impurity content is higher, it is necessary to carry out recrystallization purification.The crude product mother solution isolated returns to causticization process, dense with lithium sulfate
Solution carries out causticization again together.
9th, recrystallize
By the monohydrate lithium hydroxide solid plus distilled water or dissolved in purified water that are obtained after the completion of the 8th step, liquid-solid ratio is 3:1,
80 DEG C or so are heated to, stirring is allowed to whole dissolvings, then filters.Filtrate is evaporated crystallization again, treats occur one in solution
After quantitative crystallization, stop heating, continue to stir, and naturally cool to less than 50 DEG C, then suction filtration is separated, and obtains fine work list
Water lithium hydroxide product and fine work mother liquor, fine work monohydrate lithium hydroxide go to next step, and fine work mother liquor returns to the 8th step crude product.
10th, dry
The fine work monohydrate lithium hydroxide obtained after the completion of 9th step is fitted into a small porcelain dish, lid is covered, leaves a bit
Gap goes out water vapour, opens heating, and it is 95 DEG C to set heating-up temperature, is dried one hour at a temperature of 95 DEG C, and taking-up is positioned over drying
In device, it is cooled to after room temperature and weighs, sampling analysis.
Table 9
Embodiment 2:
(1) raw material is levigate and dispensing:
It is first that amblygonite ore deposit is levigate to 180 mesh.A porcelain crucible is taken, drying is cleaned, weighs, then by levigate lithium phosphorus
Aluminium stone flour is added weighs in porcelain crucible, weighs weight for 400 grams, then weighs 140 grams of concentrated sulfuric acids with a plastic beaker, will weigh up
The concentrated sulfuric acid add porcelain crucible in mixed with amblygonite, manual mixing is uniform.Formula and proportioning now be：Lithium phosphorus aluminium
Stone：Sulfuric acid=1：0.35.
(2) it is calcined:
The material that 1st step is prepared is installed with two porcelain crucibles, is put into Muffle furnace, opens heating, and setting maximum temperature is
700℃.After Muffle in-furnace temperature is raised to 700 DEG C, constant temperature calcining 30 minutes, to the time after closing switch stop heating.Then
Take out and put in drier after furnace temperature lowers, be cooled to room temperature, weigh.Then it is its is levigate to 180 mesh sieves excessively.
(3-1) is leached：
The 2nd step is weighed into 400 grams through the levigate clinker to after 180 mesh to add in stainless steel reaction pot, according to liquid-solid ratio 5:
1 ratio measures 2000ml distilled water with graduated cylinder and added in stainless steel reaction pot, and reaction pot is placed on electric furnace, loaded onto electronic
Stirring, covered lid, opens heating and stirs, in 95 DEG C or so isothermal reactions 1 hour, during the course of the reaction multiple moisturizing with
Ensure that liquid-solid ratio is basically unchanged.
After the completion of reaction, hot solution is filtered.Suction filtration is carried out using bottle,suction herein, filtrate 1827ml, sampling point is obtained
Analysis, analysis result is as follows：(g/l)
Leached mud is with liquid-solid ratio about 3:1 ratio add water heating stirring washing, then elute again.Wet slag weighs 427 grams, use
Graduated cylinder measures 1000ml distilled water and added in stainless steel reaction pot, and reaction pot is placed on electric furnace, loads onto electric stirring, Ran Houkai
Open heating and stir, stir and wash 15 minutes at a temperature of 70~80 DEG C, be then filtered by vacuum with bottle,suction, and the elution two that adds water
Secondary, added water 100ml every time, is filtered dry, and washed wet slag is installed with enamel tray to be put into baking oven, is dried at a temperature of 105 DEG C, cold
But weigh afterwards, and sampling analysis, analysis result is as follows：(%)
(3-2) is leached：
Clinker of 2nd step after levigate is levigate to 100 mesh, weigh 400 grams and add in stainless steel reaction pot, according to liquid
Admittedly than 4:1 ratio measures 1600ml distilled water with graduated cylinder and added in stainless steel reaction pot, and reaction pot is placed on electric furnace, fills
Upper electric stirring, covered lid, opens heating and stirs, in 95 DEG C or so isothermal reactions 1 hour.After the completion of reaction, by heat
Solution is filtered.Suction filtration is carried out using bottle,suction herein, filtrate 1455ml is obtained, sampling analysis, analysis result is as follows：(g/l)
Leached mud is with liquid-solid ratio about 3:1 ratio add water heating stirring washing, then elute again.Wet slag weighs 410 grams, use
Graduated cylinder measures 1000ml distilled water and added in stainless steel reaction pot, and reaction pot is placed on electric furnace, loads onto electric stirring, Ran Houkai
Open heating and stir, stir and wash 15 minutes at a temperature of 70~80 DEG C, be then filtered by vacuum with bottle,suction, and the elution two that adds water
Secondary, added water 100ml every time, is filtered dry, and washed wet slag is installed with enamel tray to be put into baking oven, is dried at a temperature of 105 DEG C, cold
But weigh afterwards, and sampling analysis, analysis result is as follows：(%)
(3-3) is leached：
Clinker of 2nd step after levigate is levigate to 200 mesh, weigh 400 grams and add in stainless steel reaction pot, according to liquid
Admittedly than 3:1 ratio measures 1200ml distilled water with graduated cylinder and added in stainless steel reaction pot, and reaction pot is placed on electric furnace, fills
Upper electric stirring, covered lid, opens heating and stirs, in 95 DEG C or so isothermal reactions 1 hour.After the completion of reaction, by heat
Solution is filtered.Suction filtration is carried out using bottle,suction herein, filtrate 1056ml is obtained, sampling analysis, analysis result is as follows：(g/l)
Leached mud is with liquid-solid ratio about 3:1 ratio add water heating stirring washing, then elute again.Wet slag weighs 413 grams, use
Graduated cylinder measures 1000ml distilled water and added in stainless steel reaction pot, and reaction pot is placed on electric furnace, loads onto electric stirring, Ran Houkai
Open heating and stir, stir and wash 15 minutes at a temperature of 70~80 DEG C, be then filtered by vacuum with bottle,suction, and the elution two that adds water
Secondary, added water 100ml every time, is filtered dry, and washed wet slag is installed with enamel tray to be put into baking oven, is dried at a temperature of 105 DEG C, cold
But weigh afterwards, and sampling analysis, analysis result is as follows：(%)
(4) purification and impurity removal
3-1 is walked to obtained leachate and adjusts PH to 7~8 with solid sodium hydroxide, heated solution is to 80~90 DEG C and permanent
Temperature reaction 10~15 minutes, to neutralize the acid in solution and remove the impurity such as the aluminium in solution, is filtered after the completion of reaction.Then
Reinforcing body sodium hydroxide adjusts PH to 14 again, to remove magnesium in solution and the impurity such as partial calcium.In order to which depth is removed wherein
Calcium, also to add the saturated solution of sodium carbonate of amount of calculation excessive 10% (can be replaced with sinker mother liquor in production, utilize it
In carbonate).Heated solution is answered in course of reaction to 80~90 DEG C and isothermal reaction 10~15 minutes, after the completion of question response
Filtering.Clear liquid after filtering adjusts PH to 6.5~7.5 with sulfuric acid again.
(5) it is concentrated by evaporation：
The solution 1794ml obtained after the completion of 4th step is added in beaker, heating on electric furnace is placed in and is evaporated concentration,
Until being concentrated to solution about 550ml, stop heating, stand cooling, some then separated out in suction filtration removal evaporation process are miscellaneous
Matter (impurity such as calcium and magnesium that mainly supersaturation is separated out), obtains limpid lithium sulfate concentrate 541ml, solution composition is as follows：
(g/l)
| Solution composition | Li2O | Na | K | Ca | Mg | Fe | SO4 |
| Testing result | 46.74 | 9.63 | 0.54 | 0.055 | 0.003 | 0.003 | 169.26 |
(6-1) causticization
By the lithium sulfate concentrated solution obtained after the completion of the 5th step together with crude product mother solution, addition is totally converted lithium therein
The sodium hydroxide solution (concentration of sodium hydroxide solution 30%) of amount of calculation excessive 30%, then filters, obtains for needed for lithium hydroxide
To containing lithium, the sulfate of sodium and hydroxide mixed solution.Li in solution after causticization2O concentration 45~50g/l, OH-Concentration 65
~70g/l.
(6-2) causticization
By the lithium sulfate concentrated solution obtained after the completion of the 5th step together with crude product mother solution, addition is totally converted lithium therein
The sodium hydroxide solution (concentration of sodium hydroxide solution 30%) of amount of calculation excessive 20%, then filters, obtains for needed for lithium hydroxide
To containing lithium, the sulfate of sodium and hydroxide mixed solution.Li in solution after causticization2O concentration 48~52g/l, OH-Concentration 60
~65g/l.
(7) freezing analysis sodium
What is obtained after the completion of 6-1 is walked is freezed containing lithium, the sulfate of sodium and hydroxide mixed solution.
In solution after causticization, containing substantial amounts of sodium sulphate, this solution is directly such as evaporated, then can separate out monohydrate lithium hydroxide
Sodium sulphate can be also separated out simultaneously, so most of sodium sulphate must first be removed, using the reduction of sodium sulphate solubility with temperature
The property drastically declined, is put into refrigerator by above-mentioned mixed solution and is freezed, what substantial amounts of sodium sulphate was crystallized with sal glauberi
Form is separated out, and the solution and sal glauberi crystal of low sodium are obtained after separation.
(8) evaporative crystallization
The low sodium mixed solution obtained after the completion of 7th step is evaporated together with fine work mother liquor, with the concentration of lithium
Improve constantly, lithium hydroxide progressively supersaturation and separate out monohydrate lithium hydroxide crystallization, amount to be crystallized reach it is a certain amount of after, stop
Only heating evaporation, is progressively cooled down in the case where mixing slowly, and is allowed to separate out more monohydrate lithium hydroxide crystal.It is to be cooled to arrive close
Room temperature, is separated, and obtains monohydrate lithium hydroxide solid and crystalline mother solution.Resulting monohydrate lithium hydroxide solid is referred to as slightly
Product, impurity content is higher, it is necessary to carry out recrystallization purification.The mother liquor isolated returns to causticization process, with lithium sulfate concentrated solution
Carry out causticization again together.
(9) recrystallize
By the monohydrate lithium hydroxide solid plus distilled water or dissolved in purified water that are obtained after the completion of the 8th step, liquid-solid ratio is 3:1,
80 DEG C or so are heated to, stirring is allowed to whole dissolvings, then filters.Filtrate is evaporated crystallization again, treats occur one in solution
After quantitative crystallization, stop heating, continue to stir, and naturally cool to less than 50 DEG C, then suction filtration is separated, and obtains fine work list
Water lithium hydroxide product and fine work mother liquor, fine work monohydrate lithium hydroxide go to next step, and fine work mother liquor returns to the 8th step crude product.
(10) dry
The fine work monohydrate lithium hydroxide obtained after the completion of 9th step is fitted into a small porcelain dish, lid is covered, leaves a bit
Gap goes out water vapour, opens heating, and it is 95 DEG C to set heating-up temperature, is dried one hour at a temperature of 95 DEG C, and taking-up is positioned over drying
In device, it is cooled to after room temperature and weighs, sampling analysis.
The monohydrate lithium hydroxide product obtained by above process meets professional standard, and the rate of recovery of lithium is more than 86%.
Certainly, better embodiment of the present invention is these are only, the use scope of the present invention is not limited with this, therefore, it is every
Equivalent change is made in the principle of the invention to should be included within the scope of the present invention.
Claims (10)
1. the technique that a kind of acidization extracts lithium hydroxide from amblygonite, it is characterised in that：Comprise the following steps：
(1) raw material is levigate：Amblygonite raw material is carried out levigate；
(2) dispensing：By amblygonite of the step (1) after levigate and the concentrated sulfuric acid using weight ratio as 1:0.25~0.37 is mixed
Close；
(3) it is calcined：Step (2) mixed material is calcined, clinker is obtained；
(4) size mixing leaching：Step (3) clinker is placed in reactor and adds water progress heating stirring, obtain the leachate containing lithium；
(5) purification and impurity removal：To removing the impurity such as aluminium or calcium in the solution of leaching in step (4)；
(6) it is concentrated by evaporation：Solution after the completion of being reacted in step (5) is evaporated concentration, obtains lithium sulfate solution；
(7) causticization：Together, addition makes wherein lithium be completely converted into hydrogen-oxygen for lithium sulfate and crude product mother solution after step (6) is concentrated
Amount of calculation needed for changing lithium is higher by the sodium hydroxide solution of 20~40% additions, then filters, obtains the sulfate containing lithium, sodium
With hydroxide mixed solution；
(8) freezing analysis sodium：After the completion of obtain freezed containing lithium, the sulfate of sodium and hydroxide mixed solution, then
Isolate sal glauberi crystallization；
(9) evaporative crystallization：The low sodium mixed solution obtained after the completion of step (8) is evaporated crystallization together with fine work mother liquor；
(10) recrystallize：The monohydrate lithium hydroxide solid obtained after the completion of step (9) is dissolved in water, heating stirring is allowed to all
Dissolving, is then filtered, filtrate is evaporated crystallization again；
(11) dry：The fine work monohydrate lithium hydroxide obtained after the completion of 9th step is dried.
2. the technique that a kind of acidization according to claim 1 extracts lithium hydroxide from amblygonite, it is characterised in that：
It is levigate to amblygonite raw material to 100~200 mesh in step (1).
3. the technique that a kind of acidization according to claim 1 extracts lithium hydroxide from amblygonite, it is characterised in that：
Temperature control is calcined at 500 DEG C~800 DEG C in step (3), and roasting time is 20~60 minutes.
4. the technique that a kind of acidization according to claim 1 extracts lithium hydroxide from amblygonite, it is characterised in that：
It is after material cooling that clinker is levigate to 100~200 mesh after step (4) medium roasting.
5. the technique that a kind of acidization according to claim 1 extracts lithium hydroxide from amblygonite, it is characterised in that：
In step (4)) middle leaching liquid-solid ratio 3~5：1.
6. the technique that a kind of acidization according to claim 1 extracts lithium hydroxide from amblygonite, it is characterised in that：
In step (4)) in extraction temperature be 20~150 DEG C, constant temperature extraction time 0.5~2 hour.
7. a kind of acidization according to claim any one of 1-6 extracts the technique of lithium hydroxide from amblygonite, its
It is characterised by：In step (8), mixed solution is put into refrigerator and freezed, substantial amounts of when temperature is reduced to -10 DEG C or so
Sodium sulphate is separated out in the form of sal glauberi is crystallized, and the solution and sal glauberi crystal of low sodium are obtained after separation.
8. a kind of acidization according to claim any one of 1-6 extracts the technique of lithium hydroxide from amblygonite, its
It is characterised by：In step (10), 60-90 DEG C is heated to, stirring is filtered after being allowed to all dissolvings, and filtrate is evaporated knot again
Crystalline substance, after occurring a certain amount of crystallization in solution, stops heating, continues to stir, and naturally cools to suction filtration point after less than 50 DEG C
From obtaining fine work monohydrate lithium hydroxide product and fine work mother liquor.
9. a kind of acidization according to claim any one of 1-6 extracts the technique of lithium hydroxide from amblygonite, its
It is characterised by：Monohydrate lithium hydroxide solid in step (10) is dissolved in water, liquid-solid ratio is 3:1.
10. a kind of acidization according to claim any one of 1-6 extracts the technique of lithium hydroxide from amblygonite, its
It is characterised by：In step (5), the leachate that step (4) is obtained adjusts PH to 7~8 with solid sodium hydroxide, and heated solution is extremely
80~90 DEG C and isothermal reaction 10~15 minutes；To neutralize the acid in solution and remove the impurity such as the aluminium in solution, by reactive aluminum
After the completion of filter；Then repeated hydrogenation sodium oxide molybdena adjusts PH to 14；Add saturated solution of sodium carbonate or the life of amount of calculation excessive 10%
Heated solution is to 80~90 DEG C and isothermal reaction 10~15 minutes in sinker mother liquor in production, course of reaction, after the completion of question response
Filtering, the clear liquid after filtering adjusts PH to 6.5~7.5 with sulfuric acid again, and calcium impurities therein are removed with depth.
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| CN201710577799.4A CN107200338A (en) | 2017-07-15 | 2017-07-15 | The technique that a kind of acidization extracts lithium hydroxide from amblygonite |
| PCT/CN2017/098777 WO2019015013A1 (en) | 2017-07-15 | 2017-08-24 | Process for extracting lithium hydroxide from amblygonite using acidification method |
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| CN108862227A (en) * | 2018-09-21 | 2018-11-23 | 深圳市德方纳米科技股份有限公司 | One kind extracting lithium from amblygonite and prepares iron-containing phosphatic method |
| CN109761251A (en) * | 2019-04-11 | 2019-05-17 | 天齐锂业资源循环技术研发(江苏)有限公司 | A method of lithium hydroxide is prepared using waste and old lithium ion battery |
| CN110817829A (en) * | 2019-12-13 | 2020-02-21 | 九江天赐高新材料有限公司 | Method for preparing high-purity anhydrous aluminum orthophosphate from solid raw material containing aluminum and phosphorus |
| CN112624158A (en) * | 2020-12-23 | 2021-04-09 | 中南大学 | Novel environment-friendly process for producing lithium hydroxide monohydrate |
| US20220017991A1 (en) * | 2018-12-06 | 2022-01-20 | Ecopro Innovation Co., Ltd. | Method of producing lithium hydroxide from lithium concentrate through sodium sulfate addition and roasting |
| CN114369715A (en) * | 2021-12-30 | 2022-04-19 | 江西永兴特钢新能源科技有限公司 | Method for grinding and leaching lepidolite roasting clinker |
| CN115432721A (en) * | 2022-07-08 | 2022-12-06 | 江苏容汇通用锂业股份有限公司 | Process for preparing lithium hydroxide |
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| CN108862227A (en) * | 2018-09-21 | 2018-11-23 | 深圳市德方纳米科技股份有限公司 | One kind extracting lithium from amblygonite and prepares iron-containing phosphatic method |
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| US20220017991A1 (en) * | 2018-12-06 | 2022-01-20 | Ecopro Innovation Co., Ltd. | Method of producing lithium hydroxide from lithium concentrate through sodium sulfate addition and roasting |
| EP3892587A4 (en) * | 2018-12-06 | 2022-02-16 | Ecopro Innovation Co., Ltd. | Method for producing lithium hydroxide from lithium concentrate by mixing and roasting lithium concentrate with sodium sulfate |
| CN109761251A (en) * | 2019-04-11 | 2019-05-17 | 天齐锂业资源循环技术研发(江苏)有限公司 | A method of lithium hydroxide is prepared using waste and old lithium ion battery |
| CN110817829A (en) * | 2019-12-13 | 2020-02-21 | 九江天赐高新材料有限公司 | Method for preparing high-purity anhydrous aluminum orthophosphate from solid raw material containing aluminum and phosphorus |
| CN112624158A (en) * | 2020-12-23 | 2021-04-09 | 中南大学 | Novel environment-friendly process for producing lithium hydroxide monohydrate |
| CN114369715A (en) * | 2021-12-30 | 2022-04-19 | 江西永兴特钢新能源科技有限公司 | Method for grinding and leaching lepidolite roasting clinker |
| CN115432721A (en) * | 2022-07-08 | 2022-12-06 | 江苏容汇通用锂业股份有限公司 | Process for preparing lithium hydroxide |
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