CN1195086C - Preparation method of metal lithium - Google Patents
Preparation method of metal lithium Download PDFInfo
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- CN1195086C CN1195086C CNB011073330A CN01107333A CN1195086C CN 1195086 C CN1195086 C CN 1195086C CN B011073330 A CNB011073330 A CN B011073330A CN 01107333 A CN01107333 A CN 01107333A CN 1195086 C CN1195086 C CN 1195086C
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Abstract
The present invention belongs to a method for preparing metal lithium. Li2CO3, Al2O3 and aluminum power are used as raw materials, and synthesis reaction is carried at 600 to 850 DEG C and 50 to 10 bar for 4 to 8 hours; reduction reaction is carried for 8 to 12 hours at 900 to 1175 DEG C and 10 to 2 bar so as to prepare the lithium metal, the gram molar ratio of the Li2CO3 to the Al2O3 is 1 to 5:1, and aluminum power amount is 40 to 70% over a theoretical amount. The present invention increases the productivity for preparing the lithium metal, reduces energy consumption, reduces and shortens technical process, reduces labor amount and has convenient operation and safe production. Compared with the lithium metal preparation method of chloride electrolysis, the present invention has the advantages of good product quality and no environmental pollution.
Description
Technical field: the invention belongs to field of metallurgy, especially relate to the metallic lithium preparation method.
Background technology: USSR (Union of Soviet Socialist Republics) inventors certificate No.1543844 (on May 13rd, 1988) provides a kind of vacuum-thermal reduction device that metallic lithium is used for preparing, this device is work like this: with synthetic list lithium aluminate and aluminium powder mixing in air in advance, briquetting, and put into the basket that hangs of vertical reducing jar, heating then, the lithium vapor condensation is in crystallizer, then under argon atmospher in the product vessel of the Sheng lithium of remelting in retort.The shortcoming of this method is very long, a higher consumes energy of reduction reaction cycle, also need be equipped with the vacuum monitoring device.
Patent of invention number is No.2149911, apply on July 29th, 1999, inventing the Russ P that is published in 25 days the 15th phases of May in 2000 also provides a kind of preparation method of metallic lithium, the shortcoming of this method is to calcine synthetic lithium aluminate by initial material in air respectively, and then be ready to furnace charge, send to another equipment behind the briquetting and carry out vacuum-thermal reduction and produce metallic lithium; Used during synthetic lithium aluminate can only be active aluminium hydroxide, contains one or more water molecules.The Al that in selecting this patent for use, mentions
2O
3Inadvisable on the synthetic lithium aluminate technology in air, because this wants to go to finish in tens hours building-up process, utilize the reductive slag to do raw material having lost in such cases, go value (the consisting of of slag: Al of synthetic lithium aluminate again
2O
3Li
2OAl
2O
3Li
2O5Al
2O
3, even more stable a phase Al appears in the slag
2O
3).
The shortcoming of this method can not obtain lithium aluminate in addition under 800～850 ℃ condition, because its synthesis temperature is higher than LiOH and Li
2CO
3Fusing point, their content in furnace charge increases in building-up process, and the lithium aluminate content that obtains is few, fused lithium salts oxide compound has severe corrosive, and be difficult to from wherein decompositing moisture and carbonic acid gas, therefore building-up reactions can not be carried through to the end fully, do not reach 92% the rate of recovery of mentioning in this patent.Particularly this method can not be used 5Li
2OAl
2O
3Be raw material, because 5Li
2OAl
2O
3The eutectic phase fusing point is arranged when being 965 ℃ near the reduction temperature that this patent is announced.Therefore when 1000～1100 ℃ of statement, furnace charge might melt, and makes the output capacity of lithium not reach 92%, and this patent is used Li
2OAl
2O, 0.5H
2O makes raw material and unlikely obtains very pure metallic lithium, because be to form with the lithium salts effect from dense NaOH solution, so carries very high sodium content in the product secretly.In addition, patent also has a shortcoming, is exactly the material boat that uses in the reduction process, and it is not high to utilize it to load furnace charge retort internal space utilization coefficient, and effusion and single jar of lithium output capacity that the result influences lithium steam are low.
The object of the present invention is to provide a kind of preparation method of metallic lithium, produce the product ability of metallic lithium with raising, cut down the consumption of energy, reduce and shortened process (process), reduce the labor force, the favourable operation of production equipment and the favourable safety in production of setting up, the quality of the metallic lithium that obtains surpasses product-metallic lithium that electrolysis of chloride method obtains, the chlorine contaminate environment of avoiding electrolytic process to produce.
The objective of the invention is to realize by following technical proposals:
Summary of the invention: with Li
2CO
3, γ phase Al
2O
3With aluminium powder be raw material, above-mentioned three kinds of mixing of materials are sent to after well are pressed into agglomerate, put into reduction reaction can, reduction reaction can is vacuumized, and reduction reaction can is heated stage by stage, at first at 600～850 ℃, vacuum tightness is carried out 4～8 hours building-up reactions, synthetic LiAlO under 50～10 crust
2Predetermined composition rises to temperature 900～1175 ℃ of reduction reactions of carrying out 8～12 hours then, and vacuum tightness remains below 10 crust, and this temperature remained to always finishes when vacuum tightness is reduced to 5～2 crust; Wherein, Li
2CO
3With γ Al mutually
2O
3Consumption be mole ratio Li
2CO
3: Al
2O
3=1～5: 1, the consumption of aluminium powder is in order to reduction LiAlO
2The aluminium powder theoretical amount excessive 40～70% that is consumed.
In the such scheme, reduction reaction can is made up of reaction cylinder (1), reaction cylinder cap (2), basketry (3), airway (4) with holes, cooling water jecket (5), impurity condensation cleaning district cooling water jecket (6) and the liquid metal lithium collector (7) of condensing zone, wherein, reduction reaction can is a Γ formula, vertical or horizontal, a bottom or an end are synthetic-reduction zone, and the top or the other end are condensation-purifying area; Reaction cylinder (1) is equipped with in synthetic-reduction zone, is the U-shaped round can, and round can is equipped with heating unit (10) outward; The basketry of U-shaped (3) place reaction cylinder (1) the bottom or-end, and can from the reaction cylinder cap (2) of reaction cylinder (1) top or the other end, pass in and out; Airway with holes (4) places the middle part of basketry (3) also coupled; Condensation one purifying area is a cylinder, and this cylinder one end links to each other with the top or the other end of reaction cylinder (1), and the cooling water jecket in cold doubtful district (5) is positioned at the top of cylinder or the top of the other end; Impurity condensation cleaning district cooling water jecket (6) is positioned at the top of the cylinder the other end: liquid metal lithium collector (7) places outside the cylinder, and itself and cylinder connecting place have heating unit (8).
In the such scheme, the slag of generation recycles substitute for Al
2O
3, reduce the aluminium powder consumption simultaneously.
In the such scheme, the slag of generation, what be used for the electrolytic aluminum process contains the lithium additive.
In the such scheme, with Li
2CO
3, γ phase Al
2O
3, or slag, aluminium powder be raw material, Li
2CO
3And Al
2O
3Consumption is Li
2CO
3: Al
2O
3=1～5: 1 (mole ratio), the consumption of aluminium powder are in order to reduction LiAlO
2The aluminium powder theoretical amount excessive 40～70% that is consumed, well later the sending to of above-mentioned three kinds of mixing of materials is pressed into agglomerate, put into U-shaped basketry (3), basketry (3) is inserted the bottom or an end of U-shaped reaction cylinder (1), build the reaction cylinder cap (2) that is positioned at reaction cylinder (1) top or the other end, reduction reaction can is vacuumized, and reduction reaction can heated stage by stage, the reaction of at first synthesizing lithium aluminate, 4～8 hours time, residual pressure (vacuum tightness) is controlled at 50～10 crust, and control was 630～750 ℃ when temperature began, and building-up reactions ending phase temperature is controlled at 800～850 ℃; Furnace temperature is risen to 900～950 ℃ then, rise to 1100～1175 ℃ again, vacuum degree control to 5～2 crust conditions, is carried out 8～12 hours thermite reduction reaction at last at 10～2 crust; The metallic lithium that generates becomes steam and enters in columnar condensation-purifying area by basketry (3) middle part airway (4) with holes, this moment the top by being positioned at the cylinder top or the other end the temperature of cooling water jecket (5) control condensation-purifying area of condensing zone at 250～650 ℃, the metallic lithium that is condensed is in a liquid state and is positioned at the liquid metal lithium collector (7) of cylindrical outer from the cylinder inner wall inflow; Be positioned at the vertical impurity condensation cleaning of cylinder district's cooling water jecket (6) vertical temperature is lower than below 95 ℃, make K, Na be condensed into solid-state and reach the purpose of removing K, Na impurity.
The present invention divides two stages to produce metallic lithium in a synthetic reduction process, at first Quilonum Retard (Li
2CO
3) and γ phase alumina (Al
2O
3) synthetic lithium aluminate, lithium aluminate carries out thermite reduction under vacuum condition then, but these two stages place a retort, in same technological process, finish.So, the present invention has improved the product ability of producing metallic lithium, reduced energy consumption, reduce and shortened technical process (process), reduce the labor force, the favourable operation of production equipment and the favourable safety in production of setting up, the quality of the metallic lithium that obtains has surpassed product-metallic lithium that electrolysis of chloride method obtains, the chlorine contaminate environment of having avoided electrolytic process to produce.
Further specify concrete scheme of the present invention below in conjunction with drawings and Examples of the present invention.
Description of drawings:
Fig. 1 is a Γ formula reduction reaction can synoptic diagram of the present invention.
Among Fig. 1,1. reaction cylinder, 2. reaction cylinder cap, 3. basketry, airway 4. with holes, the 5. cooling water jecket of condensing zone, 6. impurity condensation cleaning district cooling water jecket, 7. liquid metal lithium collector, 8. heating unit, 9. thermal insulation layer, 10. heating unit.
Wherein, the reduction reaction pot bottom is synthetic-reducing zone, and top is condensation-purifying area, in the angle of this district and 1 one-tenth 90 °～180 ° of reaction cylinders; Reaction cylinder 1 is equipped with in synthetic-reducing zone, is the U shape round can of vertically-arranged, and round can is equipped with heater 10 outward; The basketry 3 of U-shaped places the bottom of reaction cylinder 1, and can pass in and out from the reaction cylinder cap 2 on reaction cylinder 1 top; Wireway 4 with holes places the middle part of basketry 3 and is connected with it, its diameter is about 1/3 of reaction cylinder 1 internal diameter, condensation-purifying area is horizontal or acclivitous cylinder, one end links to each other with the top of reaction cylinder 1, the cooling water jecket 5 of condensing zone is positioned at the top of the other end of cylinder, and there is heat-insulation layer 9 its underpart; Condensation-purifying area cooling water jecket 6 is positioned at the top of the other end of cylinder; Liquid metal lithium collector 7 places outside the cylinder, and itself and cylinder connecting place are with heater 8.
This reduction reaction can more furnace charge of can packing into, and it is about 5～10% to improve its production capacity, is subordinated to the diameter of wireway.
Embodiment:
Embodiment one
In order to prepare furnace charge, select γ phase Al for use
2O
3And Li
2CO
3By 1: 1 gram molecular weight proportioning, the preparation lithium aluminate, the aluminium powder of one-size 0.15～0.4mm then is by the LiAlO that generates in synthetic reaction process in order to reduction
2Excessive 50% uniform mixing of the aluminium powder theoretical amount that is consumed is sent the group's salt block material for preparing into basketry and is built in the reaction cylinder.Undertaken by a synthetic reduction reaction process system, generated time 4 hours, residual pressure (vacuum tightness) is controlled at 50～10 crust, when beginning, temperature is controlled at 700 ℃, the end of synthesis temperature is controlled at 750～800 ℃, furnace temperature is risen to 1175 ℃ then, vacuum degree control is being lower than under the 10 crust conditions, carry out 8 hours reduction reaction, metallic lithium steam enters in condensation-purifying area around here, its temperature is controlled at 400～500 ℃, and the lithium that is condensed transforms the metal that is in a liquid state from gaseous state and flows in the product receptor from the condenser inwall, and to crystallize into the output capacity of solid-state this process be 87% to lithium then.
Embodiment two
Furnace charge is prepared, and gets γ phase Al
2O
3And Li
2CO
3Pressed mole ratio 1: 3, by the LiAlO that in synthetic reaction process, generates in order to reduction
2The aluminium powder theoretical amount that is consumed is excessive 40%, and all other operations are all with embodiment one, and the output capacity of metallic lithium is 92%.
Embodiment three
Furnace charge is prepared, and gets γ phase Al
2O
3And Li
2CO
3Pressed mole ratio 1: 5, by the LiAlO that in synthetic reaction process, generates in order to reduction
2The aluminium powder theoretical amount excessive 70% that is consumed, heat-processed is carried out stage by stage, the synthesis technique operation is with embodiment one, preceding 3 hours temperature of reduction reaction are got 900 ℃, improve reduction temperature to 1175 ℃ maintenance 5 hours then, fawn on Shu Hecheng-reduction reaction to vacuum tightness less than 5, the output capacity of metallic lithium is 95%.
Embodiment four
In order to prepare furnace charge, use the slag of synthetic-reduction process to make raw material, consist of through the levigated slag:
γ phase Al
2O
3(containing part α phase) 40%～50%
LiAl
5O
8 10～15％
LiAlO
2 6～10％
Al 10～15％
Add the Li that calculates institute's expense to furnace charge-slag
2CO
3, consider the compound that it interacts and generate with slag, be 1: 1 by calculating required mole ratio, by the LiAlO that in synthetic reaction process, generates in order to reduction
2The aluminium powder theoretical amount that is consumed is excessive 50%, when calculating the aluminium powder consumption, should be taken into account its content in slag.Remaining operation steps, it is outer identical with embodiment one to remove building-up process, owing to occur active lower α phase Al in the slag
2O
3So the time of building-up process, need are grown 2 hours than former process, its length is subordinated to α phase Al in slag
2O
3Content what and decide.
Owing to use the slag of synthetic-reduction reaction, therefore in the metallic lithium product of producing out, the content of some volatile impurity such as sodium, potassium, magnesium has significantly reduced their content, and reason is that these impurity have carried out initial purge in the raw material that uses first in synthetic-reduction process.In addition, owing to use slag to make raw material, the consumption of aluminium powder will reduce 20～30%.
Embodiment five
Furnace charge one slag adding to embodiment four is the Li of 1: 3 expense by mole ratio
2CO
3, by the LiAlO that in synthetic reaction process, generates in order to reduction
2The aluminium powder theoretical amount that is consumed is excessive 50%, remaining operation steps, and it is outer with embodiment one to remove building-up process, owing to occur active lower α phase Al in the slag
2O
3So the time of building-up process, need are grown 2 hours than former process, its length is subordinated to α phase Al in slag
2O
3Content what and decide.
Embodiment six
Furnace charge-slag adding to embodiment four is the Li of 1: 5 expense by mole ratio
2CO
3, by the LiAlO that in synthetic reaction process, generates in order to reduction
2The aluminium powder theoretical amount that is consumed is excessive 50%, remaining operation steps, and it is outer with embodiment three to remove building-up process, owing to occur active lower α phase Al in the slag
2O
3So the time of building-up process, need are grown 2 hours than former process, its length is subordinated to α phase Al in slag
2O
3Content what and decide.
Embodiment the results are shown in the table one.
According to the result of embodiment one～six as seen, the per unit area yield throughput of device and the output capacity of metallic lithium are that ratio along with lithium-containing compound mole ratio in the furnace charge raises and improves.
Utilize the slag of synthetic-reduction output to recycle, though extended the synthetic reaction process time, it has provided more purified metallic lithium product, has reduced the consumption of aluminium powder accordingly, has reduced product cost preferably.
The result of table one embodiment one～six
| Numbering | Example example one | Example example two | Example example three | Example example four | Example example five | Example example six |
| Charge composition | Al 2O 3+ Li 2CO 3+Al | Al 2O 3+ Li 2CO 3+Al | Al 2O 3+ Al 2CO 3+Al | Slag+Li 2CO 3+Al | Slag+Li 2CO 3+Al | Slag+Li 2CO 3+Al |
| Li 2CO 3/ Al 2O 3(mol) | 1∶1 | 3∶1 | 5∶1 | 1∶1 | 3∶1 | 5∶1 |
| Stage | 1，2 | 1，2 | 1，2，3 | 1，2 | 1，2 | 1，2，3 |
| Synthesis temperature (℃) | 700～800 | 700～800 | 700～800 | 700～800 | 700～800 | 700～800 |
| Reduction temperature (℃) | 1175 | 1175 | 900 (3 hours), 1175 | 1175 | 1175 | 900 (3 hours), 1175 |
| Synthetic vacuum tightness (crust) | 50-10 | 50-10 | 50-10 | 50-10 | 50-10 | 50-10 |
| Reduction vacuum tightness (crust) | ＜10 | ＜10 | ＜5 | ＜10 | ＜10 | ＜5 |
| Time (hr) | 4，8 | 4，8 | 4，3，5， | 6，8 | 6，8 | 6，3，5 |
| Output capacity (%) | 87 | 92 | 95 | 88 | 92 | 96 |
Claims (4)
1. the preparation method of metallic lithium is characterized in that with Li
2CO
3, γ phase Al
2O
3And aluminium powder is raw material, above-mentioned three kinds of mixing of materials sent to after well be pressed into agglomerate, put into reduction reaction can, reduction reaction can is vacuumized, and reduction reaction can is heated stage by stage, at first at 600～850 ℃, vacuum tightness is carried out 4～8 hours building-up reactions, synthetic LiAIO under 50～10 crust
2Predetermined composition rises to temperature 900～1175 ℃ of reduction reactions of carrying out 8～12 hours then, and vacuum tightness remains below 10 crust, and this temperature remained to always finishes when vacuum tightness is reduced to 5～2 crust; Wherein, Li
2CO
3With γ Al mutually
2O
3Consumption be mole ratio Li
2CO
3: Al
2O
3=1～5: 1, the consumption of aluminium powder is in order to reduction LiAIO
2The aluminium powder theoretical amount excessive 40～70% that is consumed.
2, the preparation method of metallic lithium according to claim 1, it is characterized in that reduction reaction can is made up of reaction cylinder (1), reaction cylinder cap (2), basketry (3), airway (4) with holes, cooling water jecket (5), impurity condensation cleaning district cooling water jecket (6) and the liquid metal lithium collector (7) of condensing zone, wherein, reduction reaction can is a Γ formula, vertical or horizontal, a bottom or an end are synthetic-reduction zone, and the top or the other end are condensation one purifying area; Reaction cylinder (1) is equipped with in a synthetic reduction zone, is the U-shaped round can, and round can is equipped with heating unit (10) outward: the basketry of U-shaped (3) places the bottom or an end of reaction cylinder (1), and can pass in and out from the reaction cylinder cap (2) of reaction cylinder (1) top or the other end; Airway with holes (4) places the middle part of basketry (3) also coupled; Condensation one purifying area is a cylinder, and an end of this cylinder links to each other with the top or the other end of reaction cylinder (1), and the cooling water jecket of condensing zone (5) is positioned at the top of cylinder or the top of the other end; Impurity condensation cleaning district cooling water jecket (6) is positioned at the top of the cylinder the other end; Liquid metal lithium collector (7) places outside the cylinder, and itself and cylinder connecting place have heating unit (8).
3. the preparation method of metallic lithium according to claim 1 and 2 is characterized in that the slag that produces recycles substitute for Al
2O
3, reduce the aluminium powder consumption simultaneously.
4. according to the preparation method of claim 1 or 3 described metallic lithiums, it is characterized in that with Li
2CO
3, γ phase Al
2O
3Or slag, aluminium powder are raw material, well later the sending to of above-mentioned three kinds of mixing of materials is pressed into agglomerate, put into U-shaped basketry (3), basketry (3) is inserted the bottom or an end of U-shaped reaction cylinder (1), build the reaction cylinder cap (2) that is positioned at reaction cylinder (1) top or the other end, reduction reaction can is vacuumized, and reduction reaction can heated stage by stage, the reaction of at first synthesizing lithium aluminate, 4～8 hours time, residual pressure (vacuum tightness) is controlled at 50～10 crust, is controlled at 630～750 ℃ when temperature begins, and building-up reactions ending phase temperature is controlled at 800～850 ℃; Furnace temperature is risen to 900～950 ℃ then, rise to 1100～1175 ℃ again, vacuum degree control to 5～2 crust conditions, is carried out 8～12 hours thermite reduction reaction at last at 10～2 crust; The metallic lithium that generates becomes steam and enters in columnar condensation-purifying area by basketry (3) middle part airway (4) with holes, this moment the top by being positioned at the cylinder top or the other end the temperature of cooling water jecket (5) control condensation-purifying area of condensing zone at 250～650 ℃, the metallic lithium that is condensed is in a liquid state and is positioned at the liquid metal lithium collector (7) of cylindrical outer from the cylinder inner wall inflow; Be positioned at the vertical impurity condensation cleaning of cylinder district's cooling water jecket (6) vertical temperature is lower than below 95 ℃, make K, Na be condensed into solid-state and reach the purpose of removing K, Na impurity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011073330A CN1195086C (en) | 2001-04-09 | 2001-04-09 | Preparation method of metal lithium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011073330A CN1195086C (en) | 2001-04-09 | 2001-04-09 | Preparation method of metal lithium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1380430A CN1380430A (en) | 2002-11-20 |
| CN1195086C true CN1195086C (en) | 2005-03-30 |
Family
ID=4656275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011073330A Expired - Fee Related CN1195086C (en) | 2001-04-09 | 2001-04-09 | Preparation method of metal lithium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1195086C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008011788A1 (en) * | 2006-07-17 | 2008-01-31 | Mg Century Mining Corporation | A reduction retort, a preparation method thereof and a vacuum metal refining reduction furnace using the reduction retort |
| CN102191419B (en) * | 2011-03-29 | 2012-12-05 | 奉新赣锋锂业有限公司 | Method for preparing high-sodium metal lithium from recovered lithium-sodium alloy, and high-sodium metal lithium prepared using same |
| CN109811145B (en) * | 2019-04-09 | 2021-04-16 | 北京欧菲金太科技有限责任公司 | Method for preparing metallic lithium from lithium-containing mineral |
| CN111057850B (en) * | 2020-01-03 | 2020-12-25 | 四川万邦胜辉新能源科技有限公司 | Method for preparing high-purity lithium metal by vacuum thermal reduction method |
| CN115490251B (en) * | 2022-10-28 | 2023-08-29 | 华能国际电力股份有限公司 | Lithium metaaluminate powder, preparation method and application thereof |
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2001
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