CN109553119A - A kind of method of lithium carbonate purifying and nanosizing - Google Patents
A kind of method of lithium carbonate purifying and nanosizing Download PDFInfo
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- CN109553119A CN109553119A CN201811570688.1A CN201811570688A CN109553119A CN 109553119 A CN109553119 A CN 109553119A CN 201811570688 A CN201811570688 A CN 201811570688A CN 109553119 A CN109553119 A CN 109553119A
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- lithium carbonate
- lithium
- raw material
- carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of methods of lithium carbonate purifying and nanosizing.Specific steps include, and lithium carbonate is discharged water middle mashing, is allowed to be converted into lithium bicarbonate by carbon dioxide and solubilising, insoluble impurities is left in solid phase.Supernatant is taken out, quickly flowing is carried out in microreactor with ethyl alcohol or ethanol water and mixes, lithium bicarbonate is precipitated due to solvent environment mutation with nano shape.Solid is filtered out and dries and thermally decomposes, obtains the nano lithium carbonate product that purity is higher than oxide spinel lithium.Nano lithium carbonate is prepared using the method, not only stable product quality, operating condition is mild, and can reduce the requirement to material purity, and solvent internal circulating load is smaller, has preferable economy.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, are related to the method for a kind of lithium carbonate purifying and nanosizing.
Background technique
Lithium carbonate be lithium resource there is one of widest form in nature and brine mention lithium process it is main in
Between product.The maximum purposes of lithium carbonate is as the lithium source for preparing lithium-containing materials, is the basic material of lithium ion battery industry.Carbon
Other important uses of sour lithium further include inhibiting mania, improve the schizoid disturbance of emotion；Addition as concrete
Agent improves workability, etc..In above-mentioned application, the purity and granularity of lithium carbonate are all very important index.High-purity
Side effect on the one hand will not be brought with the lithium carbonate of nanosizing, it is on the one hand again more controllable and efficient with the effect of other components,
Undoubtedly a kind of ideal carbonic acid lithium material.Preparation for nano-scale lithium carbonate particle is using bubble tower in early days, stirs
The traditional reactors such as kettle are mixed, precipitation reaction are carried out using carbon dioxide or carbonate and lithium hydroxide in aqueous solution, by adding
The auxiliary agents such as surfactant, dispersing agent, intercalating agent are added to inhibit the reunion and growth of particle.The problem of such methods, is: hydrogen-oxygen
Change lithium itself to need to be electrolysed manufacture by raw material of lithium carbonate, cost is relatively high, and purity is again low compared with lithium carbonate；Auxiliary agent addition leads to body
System is complicated, not only increases cost, but also influence purity.In recent years, this research team has developed the excellent biography using microreactor
Matter performance makes the method for the dilution crystallization product nano of lithium hydroxide carbonization precipitated product and lithium carbonate, system and method letter
It is single, avoid the introducing of impurity.But since the solubility of lithium carbonate in water is very low, lithium hydroxide is in precipitation reaction environment
In solubility it is also very low, both of which is faced with that low one-pass yield, solvent usage of unit product and internal circulating load be big, solvent
The problems such as regeneration cost is high, engineer application are restricted.In addition, there is no removal of impurities effects for both methods, to material purity
It is required that it is relatively high, there is further influence to economy.For this purpose, development requires carbonic acid low, that one-pass yield is high to material purity
Lithium purifying and method for making Nano, being still one has challenge and the work of significance.
Summary of the invention
In view of the deficiencies of the prior art, the invention proposes a kind of methods of lithium carbonate purifying and nanosizing.Specifically, originally
Lithium carbonate is converted to regard to lithium bicarbonate by carburizing reagent, insoluble impurity is on the one hand stayed in solid phase by invention, on the one hand
Solubility of the lithium in material solution is improved, the elemental lithium yield of conversion per pass is significantly improved；In turn, existed using lithium bicarbonate
The greatest differences of solubility, quickly change solvent environment by microring array in water and ethyl alcohol and ethanol water, by lithium bicarbonate
It quickly, is fully precipitated in the form of nano particle；Benefit
It is easily decomposed with lithium bicarbonate but feature not easy to reunite, is converted nano-calcium carbonate hydrogen lithium to by mild drying and received
Rice lithium carbonate simultaneously realizes solvent removal.
The method of the present invention the following steps are included:
(1) lithium carbonate and water are mixed in a certain proportion mashing；
(2) gaseous mixture of carbon dioxide or carbon dioxide and inert gas is passed through into lithium carbonate and water slurry, until two
Carbonoxide and lithium carbonate stop ventilating after sufficiently acting on, and stand, and take out supernatant；
(3) make supernatant carry out quickly flowing in microreactor with ethyl alcohol or ethanol water to mix, obtain mixing molten
Liquid makes lithium bicarbonate that solid be precipitated with nano shape due to solvent environment mutation；
(4) it is separated by filtration solid, is dried at a certain temperature, nano lithium carbonate product is obtained.
The weight ratio of the lithium carbonate and water is 1:(4~30).
The mixture of the carbon dioxide and inert gas, inert gas can be nitrogen or air, shared by inert gas
Volume ratio is 0%-80%.
The percentage by volume of ethyl alcohol is 80%-100% in the ethanol water.
The percentage by volume of ethyl alcohol is 50%-90% in the mixed solution.
The drying temperature is 60 DEG C to 130 DEG C.
Compared with prior art, the innovative protrusion effect that the present invention can obtain includes: that conversion process has separation pure
Change effect, the requirement to lithium carbonate material purity is low, is conducive to control cost of material；Generate the solvent that 1t nano lithium carbonate needs
Using, regeneration and internal circulating load can be reduced to 20t hereinafter, processing cost is greatly lowered；The repeatability and stabilization of products obtained therefrom
Property is good, and purity and granularity are guaranteed, and particle size is in 100nm or less and narrowly distributing.
Detailed description of the invention
Fig. 1 is the process flow diagram of the method for lithium carbonate of the present invention purifying and nanosizing.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples.It should be understood that these embodiments are only
It is only for illustratively illustrating, is not limitation of the present invention.Without departing from the scope of the subject in the invention to the present invention into
Capable any modification is each fallen in the scope of protection of present invention.
Embodiment 1
Use the microporous barrier that aperture is 5 microns as the micro-structured reactor of decentralized medium.1L water is taken, is added thereto
100g lithium carbonate is simultaneously beaten.It is passed through carbon dioxide into lithium carbonate and water slurry, until carbon dioxide is sufficiently acted on lithium carbonate
Stop ventilation afterwards, stand, supernatant is taken out, as raw material A.Raw material B is dehydrated alcohol.By raw material A from storage container with
The flow of 25mL/min is added micro-structured reactor, and micro-structured reactor is added with the flow of 25mL/min in raw material B, raw material A and
Raw material B is mixed in micro-structured reactor, and reactor outlet material, to gained solid phase through 80 DEG C of dryings, is obtained through being separated by solid-liquid separation
Final lithium carbonate particle, average grain diameter 80nm.Above-mentioned all operations are completed at 40 DEG C.
Embodiment 2
Use the Microtraps orifice plate that aperture is 1000 microns as the micro-structured reactor of decentralized medium.Take 100L water, Xiang Qi
Middle addition 20kg lithium carbonate is simultaneously beaten.Carbon dioxide-nitrogen that carbonated 20% is passed through into lithium carbonate and water slurry is mixed
Gas is closed, until carbon dioxide and lithium carbonate stop ventilating after sufficiently acting on, stands, supernatant is taken out, as raw material A.By raw material A
Micro-structured reactor is added with the flow of 500mL/min from storage container, micro- knot is added with the flow of 4500L/min in raw material B
Structure reactor, raw material A and raw material B are mixed in micro-structured reactor, and reactor outlet material is through being separated by solid-liquid separation, to gained solid phase
Through 130 DEG C of dryings, grinding obtains final lithium carbonate particle, average grain diameter 68nm.Above-mentioned all operations are complete at 20 DEG C
At.
Embodiment 3
Use the Microtraps orifice plate that aperture is 200 microns as the micro-structured reactor of decentralized medium.By 4kg lithium carbonate and
120L water is mixed with beating, and carbon dioxide-air Mixture of carbonated 70% is passed through into lithium carbonate and water slurry, until
Carbon dioxide and lithium carbonate stop ventilating after sufficiently acting on, and stand, and supernatant are taken out, as raw material A.Raw material B is ethyl alcohol quality
The ethanol water of score 0.9.Micro-structured reactor, raw material is added from storage container with the flow of 500mL/min in raw material A
Micro-structured reactor is added with the flow of 1500mL/min in B, and raw material A and raw material B are mixed in micro-structured reactor, and reactor goes out
Mouth material, to gained solid phase through 60 DEG C of dryings, obtains final lithium carbonate particle, average grain diameter 55nm through being separated by solid-liquid separation.On
All operations are stated to complete at 60 DEG C.
Embodiment 4
Use the microporous barrier that aperture is 20 microns as the micro-structured reactor of decentralized medium.Fetch water 100L, thereto
It is beaten after 25kg lithium carbonate, carbon dioxide-nitrogen mixture of carbonated 50% is passed through into lithium carbonate and water slurry, directly
Stop ventilating after sufficiently acting on to carbon dioxide and lithium carbonate, stand, supernatant is taken out, as raw material A.Raw material B is ethyl alcohol matter
Measure the ethanol water of score 0.8.Micro-structured reactor is added from storage container with the flow of 500mL/min in raw material A, it is former
Expect that micro-structured reactor is added with the flow of 2500L/min in B, raw material A and raw material B are mixed in micro-structured reactor, reactor
Outlet material is through being separated by solid-liquid separation, and to gained solid phase through 100 DEG C of dryings, grinding obtains final lithium carbonate particle, average grain diameter is
60nm.Above-mentioned all operations are completed at 30 DEG C.
Embodiment 5
Use the microporous barrier that aperture is 0.2 micron as the micro-structured reactor of decentralized medium.Fetch water 100L, thereto plus
It is beaten after entering 9kg lithium carbonate, is passed through carbonated into lithium carbonate and water slurry, until carbon dioxide is sufficiently made with lithium carbonate
It is ventilated, is stood with rear stopping, supernatant is taken out, as raw material A.Raw material B is dehydrated alcohol.By raw material A from storage container with
Micro-structured reactor is added in the flow of 500mL/min, and micro-structured reactor, raw material A is added with the flow of 2000mL/min in raw material B
It is mixed in micro-structured reactor with raw material B, reactor outlet material, to gained solid phase through 120 DEG C of dryings, is ground through being separated by solid-liquid separation
Mill, obtains final lithium carbonate particle, average grain diameter 45nm.Above-mentioned all operations are completed at 25 DEG C.
Claims (6)
1. a kind of method of lithium carbonate purifying and nanosizing, which comprises the following steps:
1) lithium carbonate and water are mixed with beating；
2) it is passed through the gaseous mixture of carbon dioxide or carbon dioxide and inert gas into slurry obtained by step 1), stands, in taking-up
Clear liquid；
3) supernatant obtained by step 2) is mixed in microreactor with ethyl alcohol or ethanol water, obtains mixed solution and is precipitated
Solid；
4) step 3) obtained solid is dry, obtain nano lithium carbonate product.
2. the method according to claim 1, wherein the weight ratio of lithium carbonate described in step 1) and water is 1:(4
~30).
3. lazy the method according to claim 1, wherein inert gas described in step 2) is nitrogen or air
Volume ratio shared by property gas is 0%-80%.
4. the method according to claim 1, wherein in the step 3) ethanol water ethyl alcohol volume basis
Number is 80%-100%.
5. the method according to claim 1, wherein in the step 3) mixed solution ethyl alcohol percentage by volume
For 50%-90%.
6. the method according to claim 1, wherein drying temperature described in step 4) is 60 DEG C to 130 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110510642A (en) * | 2019-09-27 | 2019-11-29 | 福州大学 | A kind of method that low-grade α spodumene economy mentions lithium |
| CN113526531A (en) * | 2020-04-17 | 2021-10-22 | 中国石油化工股份有限公司 | Method for recovering high-purity submicron lithium carbonate from lithium battery ternary material washing liquid |
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| CN101177288A (en) * | 2007-10-30 | 2008-05-14 | 中国科学院青海盐湖研究所 | Process for preparing high-purity lithium carbonate by using saline lithium resource |
| WO2010131664A1 (en) * | 2009-05-15 | 2010-11-18 | 日本化学工業株式会社 | High purity lithium carbonate and method for producing same |
| CN102180488A (en) * | 2010-04-09 | 2011-09-14 | 清华大学 | Method for preparing nano lithium carbonate |
| CN102267708A (en) * | 2011-07-01 | 2011-12-07 | 清华大学 | Method for preparing lithium carbonate nano-particle by crystallization method |
| CN102267707A (en) * | 2011-07-01 | 2011-12-07 | 清华大学 | Process for preparing nanometer lithium carbonate particle by precipitation |
| CN105399115A (en) * | 2015-12-31 | 2016-03-16 | 中国科学院青海盐湖研究所 | Preparation method for high-purity submicron lithium carbonate |
| CN107188206A (en) * | 2017-06-27 | 2017-09-22 | 瓮福（集团）有限责任公司 | A kind of lithium salts process for refining |
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2018
- 2018-12-21 CN CN201811570688.1A patent/CN109553119A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101177288A (en) * | 2007-10-30 | 2008-05-14 | 中国科学院青海盐湖研究所 | Process for preparing high-purity lithium carbonate by using saline lithium resource |
| WO2010131664A1 (en) * | 2009-05-15 | 2010-11-18 | 日本化学工業株式会社 | High purity lithium carbonate and method for producing same |
| CN102180488A (en) * | 2010-04-09 | 2011-09-14 | 清华大学 | Method for preparing nano lithium carbonate |
| CN102267708A (en) * | 2011-07-01 | 2011-12-07 | 清华大学 | Method for preparing lithium carbonate nano-particle by crystallization method |
| CN102267707A (en) * | 2011-07-01 | 2011-12-07 | 清华大学 | Process for preparing nanometer lithium carbonate particle by precipitation |
| CN105399115A (en) * | 2015-12-31 | 2016-03-16 | 中国科学院青海盐湖研究所 | Preparation method for high-purity submicron lithium carbonate |
| CN107188206A (en) * | 2017-06-27 | 2017-09-22 | 瓮福（集团）有限责任公司 | A kind of lithium salts process for refining |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110510642A (en) * | 2019-09-27 | 2019-11-29 | 福州大学 | A kind of method that low-grade α spodumene economy mentions lithium |
| CN113526531A (en) * | 2020-04-17 | 2021-10-22 | 中国石油化工股份有限公司 | Method for recovering high-purity submicron lithium carbonate from lithium battery ternary material washing liquid |
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