CN101845559B - Device and method for preparing lithium metal by using vacuum metal heat reduction - Google Patents
Device and method for preparing lithium metal by using vacuum metal heat reduction Download PDFInfo
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- CN101845559B CN101845559B CN2010101440655A CN201010144065A CN101845559B CN 101845559 B CN101845559 B CN 101845559B CN 2010101440655 A CN2010101440655 A CN 2010101440655A CN 201010144065 A CN201010144065 A CN 201010144065A CN 101845559 B CN101845559 B CN 101845559B
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Abstract
The invention discloses a device and a method for preparing lithium metal by using vacuum metal heat reduction. The device comprises a reaction chamber and a collection chamber, wherein the reaction chamber consists of a reaction chamber furnace shell and a lining arranged inside the reaction chamber furnace shell; a resistance heater is arranged inside the reaction chamber; the lateral surface of the reaction chamber is provided with a reaction chamber furnace door, the lower part of the reaction chamber is provided with a hole, and the collection chamber is arranged at the position corresponding to the hole below the reaction chamber; and the collection chamber is provided with a collection chamber shell arranged on the lower part of the reaction chamber, a condenser is arranged on the inner upper part of the collection chamber shell and below the reaction chamber, a collection container is arranged in the collection chamber corresponding to the underside of the condenser, the lateral surface of the collection chamber shell is provided with a collection chamber furnace door, and the lower part of the collection chamber is provided with a vacuum pumping pipe orifice. The method comprises the following steps of: mixing, pressing and calcining CaO generated by calcining CaCO3 and Li2CO3, grinding the generated Li2O and CaO, mixing and pressing the ground powder and a metal reducer, putting the mixture into the reaction chamber, and heating the mixture under a vacuum condition to perform reduction reaction so as to obtain the lithium metal.
Description
Technical field:
The present invention relates to the smelting technology and the production unit of metallic lithium, be specifically related to a kind of devices and methods therefor of preparing lithium metal by using vacuum metal heat reduction.
Background technology:
At present, fused salt electrolysis process is mostly adopted in the production of metallic lithium both at home and abroad, and this method adopts electrolysis of chloride plastome, with direct current electrolysis LiCl-KCl molten salt electrolyte, adopts refractory materials to make lining, and anode material is a graphite, and cathode material is iron negative electrode.In the electrolytic process, anode generates chlorine (Cl
2) generate metallic lithium on the negative electrode, float on the surface of electrolyte melt, take out with special instrument.Fused salt electrolysis process is produced the metallic lithium, (Cl of not only energy consumption height, and electrolyte melt and generation
2) all equipment there is very big corrosive nature, also environment is had a significant impact.The LiCl that is consumed in the electrolytic process is that the neutralization reaction with Quilonum Retard and hydrochloric acid generates, and produces LiCl and need consume very a large amount of hydrochloric acid, and the LiCl of generation need dewater and deacidify and carry out drying.This chemical process that relates to acid also exerts an influence to environment, and consumes more energy, increases the production cost of metallic lithium.
It is a kind of production method that metallic lithium also has in addition, is exactly the vacuum metal hot reducing method, the ultimate principle of this method: under vacuum condition, use metal as reductive agent, and the reduction-oxidation lithium, used reductive agent has silicon and aluminium.This method is with respect to electrolytic process, its biggest advantage is that whole technological process does not relate to muriate, product does not have corrodibility and toxic substance yet, be the green production process of a comparatively eco-friendly metallic lithium therefore, but this method is not widely used.What reason was that this method implements is the external resistance heating.The external resistance heating is the inside that reaction mass is in reactor, and thermal source is in the outside of reactor, and heat at first needs by reactor wall, and then passes to inner reaction mass, and simultaneously, outside heat radiation is more, and thermo-efficiency is very low.And reactor is owing to be subjected to the restriction of mass transfer and heat transfer process; the size and the size of reactor are restricted; its industrial scale and single stove production capacity also all are restricted; the technology and the technology of collecting metallic lithium in addition are also not really ripe; cause the production cost of lithium also very high; power consumption is very big, is difficult to row established practice modelling and produces.
Summary of the invention:
At the deficiencies in the prior art, the invention provides a kind of devices and methods therefor of preparing lithium metal by using vacuum metal heat reduction, use this device to adopt preparing lithium metal by using vacuum metal heat reduction to shorten reaction time greatly, improve single furnace output, cut down the consumption of energy the productivity height.
A kind of device of preparing lithium metal by using vacuum metal heat reduction, comprise reaction chamber and collecting chamber, reaction chamber is made up of reaction chamber furnace shell and the liner that is arranged on reaction chamber furnace shell inside, inside at reaction chamber is equipped with resistance heater, be provided with the reaction chamber fire door in the side of reaction chamber, the bottom of reaction chamber has the hole, the position of corresponding aperture is equipped with collecting chamber below reaction chamber, collecting chamber has a collecting chamber shell that is installed in the reaction chamber bottom, at collecting chamber shell internal upper part, condenser is installed below the reaction chamber, in collecting chamber, be provided with collection container below the corresponding condenser, have the collecting chamber fire door in the side of collecting chamber shell, be provided with in the bottom of collecting chamber and vacuumize the mouth of pipe.
The outer upper of described collecting chamber shell is equipped with watercooling jacket.
Be provided with the vacuum packing ring between described reaction chamber fire door and the reaction chamber furnace shell.
Be provided with the vacuum packing ring between described collecting chamber fire door and the collecting chamber shell.
Described resistance heater is to be made by high temperature metallic material nickelic, Gao Ge, and is placed in the inside of reaction chamber, and the reduction reaction material places between the resistance heater.
Pillar is installed below the described reaction chamber.
Described liner adopts light-weight insulating brick or calcium silicate board or schamotte brick.
A kind of method of preparing lithium metal by using vacuum metal heat reduction will be calcined CaCO
3The CaO and the Li that generate
2CO
3Be pressed into spherical agglomerate after 1～2 mixing in molar ratio and place calcining furnace, under 1000～1200 ℃ temperature, calcine, make its generation contain Li
2The material of O and CaO compound composition, and then this material worn into powder, granularity needs below 0.15mm, and mix with excessive 3～10% metallic reducing agent and to be pressed into spherical agglomerate, become the reaction mass of metallothermic reduction vacuum refining lithium, again reaction mass is placed in the reaction chamber of device of preparing lithium metal by using vacuum metal heat reduction, heat by the resistance heater in the reaction chamber, make temperature reach 1000-1300 ℃, simultaneously to vacuumizing in the reaction chamber, keep the vacuum tightness in the reaction chamber to reach below the 20Pa, carry out the vacuum metal thermal reduction reaction, reaction formula is xLi
2O+yCaO+xM → xMOyCaO+2xLi, metallic lithium is gaseous state and overflows from the reduction reaction material in reaction chamber, become liquid state after entering the collecting chamber of lithium, and in the collection container of inflow collecting chamber below, after reaction finishes, stop heating, continue to keep vacuum tightness below 20Pa, the question response room temp is reduced to below 200 ℃, to charging into argon gas in the reaction chamber, but after temperature drops to manual operation by the time, open the collecting chamber fire door, take out the collection container that has contained the frozen metal lithium, obtain metallic lithium.
Described M is a metallic reducing agent, and metallic reducing agent is silicon or aluminium or aluminum silicon alloy.
Beneficial effect of the present invention:
Preparing lithium metal by using vacuum metal heat reduction device of the present invention adopts the internal resistance heating, and heat is directly passed to reaction mass, and heat radiation is few, and thermo-efficiency is high, and energy consumption is low, can shorten the cycle of reaction greatly, and single furnace output is big, the productivity height.
Description of drawings:
Fig. 1 is apparatus of the present invention structural representation;
Among the figure: 1-reaction chamber, 2-reaction chamber furnace shell, 3-resistance heater, 4-liner, 5-condenser, the 6-collecting chamber, 7-collecting chamber shell, the 8-collection container, 9-vacuumizes the mouth of pipe, 10-collecting chamber fire door, 11-vacuum packing ring, 12-watercooling jacket, 13-reaction chamber fire door, 14-pillar
Embodiment:
Embodiment 1:
A kind of device of preparing lithium metal by using vacuum metal heat reduction, comprise reaction chamber 1 and collecting chamber 6, reaction chamber 1 is made up of reaction chamber furnace shell 2 and the liner 4 that is arranged on reaction chamber furnace shell 2 inside, the material of liner 4 adopts light-weight insulating brick, the main heat-insulation and heat-preservation that plays a part, reducing heat scatters and disappears, in the inside of reaction chamber 1 resistance heater 3 is installed, resistance heater 3 is by nickelic, the high temperature metallic material of Gao Ge is made, and be placed in the inside of reaction chamber 1, the reduction reaction material places between the resistance heater 3, in the reduction reaction process, reaction mass is heated, have reaction chamber fire door 13 in the side of reaction chamber 1, between reaction chamber fire door 13 and the reaction chamber furnace shell 2 vacuum packing ring 11 is installed, guarantee sealing, there is gas to enter when avoiding in to reaction chamber 1, vacuumizing, the bottom of reaction chamber 1 has the hole, lithium after the heating is gaseous state, enter in the collecting chamber 6 below the reaction chamber 1 by the hole, passive pillar 14 is installed below the reaction chamber 1, the position of corresponding aperture is equipped with collecting chamber 6 below reaction chamber 1, collecting chamber 6 has a collecting chamber shell 7, the top of collecting chamber shell 7 is fixed on the lower wall surface of reaction chamber 1, one week of outer upper of collecting chamber shell 7 is equipped with watercooling jacket 12, condenser 5 is carried out forced refrigeration, improve refrigeration, accelerate the condensation of gaseous state lithium, at collecting chamber shell 7 internal upper parts, condenser 5 is installed below the reaction chamber 1, condenser 5 is fixed on the lower wall surface of reaction chamber 1, underneath over against condenser 5 in collecting chamber 6 is equipped with collection container 8, the gasiform lithium is after condenser 5 internal cooling become liquid state, flow in the collection container 8 below the condenser 5 and store, have collecting chamber fire door 10 in the side of collecting chamber shell 7, between collecting chamber fire door 10 and the collecting chamber furnace shell vacuum packing ring 11 is installed, guarantee sealing, there is gas to enter when avoiding in to collecting chamber 6, vacuumizing, be provided with in the bottom of collecting chamber 6 and vacuumize the mouth of pipe 9, vacuumize by vacuumizing in 9 pairs of reaction chambers 1 of the mouth of pipe and the collecting chamber 6.
Adopt the method for aforesaid device preparing lithium metal by using vacuum metal heat reduction, will calcine CaCO
3The CaO and the Li that generate
2CO
3Be to be pressed into spherical agglomerate after 1 mixing to place calcining furnace in molar ratio, under 1000 ℃ temperature, calcine, make its generation contain Li
2The material of O and CaO compound composition, wherein the rate of decomposition of Quilonum Retard reaches more than 99%, and then this material worn into powder, granularity needs below 0.15mm, and mix with excessive 3% metallic reducing agent silicon and to be pressed into spherical agglomerate, become the reaction mass of metallothermic reduction vacuum refining lithium, again reaction mass is placed in the reaction chamber of device of preparing lithium metal by using vacuum metal heat reduction, heat by the resistance heater in the reaction chamber, make temperature reach 1000 ℃,, keep the vacuum tightness in the reaction chamber to reach below the 20Pa simultaneously to vacuumizing in the reaction chamber, carry out the vacuum metal thermal reduction reaction, reaction formula is xLi
2O+yCaO+xM → xMOyCaO+2xLi, M is a metallic reducing agent, metallic lithium is gaseous state and overflows from the reduction reaction material in reaction chamber, become liquid state after entering the collecting chamber of lithium, and in the collection container of inflow collecting chamber below, after reaction finishes, stop heating, continue to keep vacuum tightness below 20Pa, the question response room temp is reduced to below 200 ℃, to charging into argon gas in the reaction chamber, after but temperature drops to manual operation by the time, open the collecting chamber fire door, take out the collection container that has contained the frozen metal lithium, obtain metallic lithium.
Embodiment 2:
The device of the preparing lithium metal by using vacuum metal heat reduction of present embodiment has on the identical architecture basics with embodiment 1, and difference is that liner 4 materials of reaction chamber adopt calcium silicate board.
Adopt the method for aforesaid device preparing lithium metal by using vacuum metal heat reduction, will calcine CaCO
3The CaO and the Li that generate
2CO
3Be to be pressed into spherical agglomerate after 2 mixing to place calcining furnace in molar ratio, under 1100 ℃ temperature, calcine, make its generation contain Li
2The material of O and CaO compound composition, wherein the rate of decomposition of Quilonum Retard reaches more than 99%, and then this material worn into powder, granularity needs below 0.15mm, and mix with excessive 6% metallic reducing agent aluminium and to be pressed into spherical agglomerate, become the reaction mass of metallothermic reduction vacuum refining lithium, again reaction mass is placed in the reaction chamber of device of preparing lithium metal by using vacuum metal heat reduction, heat by the resistance heater in the reaction chamber, make temperature reach 1200 ℃,, keep the vacuum tightness in the reaction chamber to reach below the 20Pa simultaneously to vacuumizing in the reaction chamber, carry out the vacuum metal thermal reduction reaction, reaction formula is xLi
2O+yCaO+xM → xMOyCaO+2xLi, M is a metallic reducing agent, metallic lithium is gaseous state and overflows from the reduction reaction material in reaction chamber, become liquid state after entering the collecting chamber of lithium, and in the collection container of inflow collecting chamber below, after reaction finishes, stop heating, continue to keep vacuum tightness below 20Pa, the question response room temp is reduced to below 200 ℃, to charging into argon gas in the reaction chamber, after but temperature drops to manual operation by the time, open the collecting chamber fire door, take out the collection container that has contained the frozen metal lithium, obtain metallic lithium.
Embodiment 3:
The device of the preparing lithium metal by using vacuum metal heat reduction of present embodiment has on the identical architecture basics with embodiment 1, and difference is that liner 4 materials of reaction chamber adopt schamotte brick.
Adopt the method for aforesaid device preparing lithium metal by using vacuum metal heat reduction, will calcine CaCO
3The CaO and the Li that generate
2CO
3Be to be pressed into spherical agglomerate after 2 mixing to place calcining furnace in molar ratio, under 1200 ℃ temperature, calcine, make its generation contain Li
2The material of O and CaO compound composition, wherein the rate of decomposition of Quilonum Retard reaches more than 99%, and then this material worn into powder, granularity needs below 0.15mm, and mix with excessive 10% metallic reducing agent silumin and to be pressed into spherical agglomerate, become the reaction mass of metallothermic reduction vacuum refining lithium, again reaction mass is placed in the reaction chamber of device of preparing lithium metal by using vacuum metal heat reduction, heat by the resistance heater in the reaction chamber, make temperature reach 1300 ℃,, keep the vacuum tightness in the reaction chamber to reach below the 20Pa simultaneously to vacuumizing in the reaction chamber, carry out the vacuum metal thermal reduction reaction, reaction formula is xLi
2O+yCaO+xM → xMOyCaO+2xLi, M is a metallic reducing agent, metallic lithium is gaseous state and overflows from the reduction reaction material in reaction chamber, become liquid state after entering the collecting chamber of lithium, and in the collection container of inflow collecting chamber below, after reaction finishes, stop heating, continue to keep vacuum tightness below 20Pa, the question response room temp is reduced to below 200 ℃, to charging into argon gas in the reaction chamber, after but temperature drops to manual operation by the time, open the collecting chamber fire door, take out the collection container that has contained the frozen metal lithium, obtain metallic lithium.
Claims (9)
1. the device of a preparing lithium metal by using vacuum metal heat reduction, comprise reaction chamber and collecting chamber, it is characterized in that reaction chamber is made up of reaction chamber furnace shell and the liner that is arranged on reaction chamber furnace shell inside, inside at reaction chamber is equipped with resistance heater, be provided with the reaction chamber fire door in the side of reaction chamber, the bottom of reaction chamber has the hole, the position of corresponding aperture is equipped with collecting chamber below reaction chamber, collecting chamber has a collecting chamber shell that is installed in the reaction chamber bottom, at collecting chamber shell internal upper part, condenser is installed below the reaction chamber, in collecting chamber, be provided with collection container below the corresponding condenser, have the collecting chamber fire door in the side of collecting chamber shell, be provided with in the bottom of collecting chamber and vacuumize the mouth of pipe.
2. the device of a kind of preparing lithium metal by using vacuum metal heat reduction according to claim 1 is characterized in that the outer upper of described collecting chamber shell is equipped with watercooling jacket.
3. the device of a kind of preparing lithium metal by using vacuum metal heat reduction according to claim 1 is characterized in that being provided with the vacuum packing ring between described reaction chamber fire door and the reaction chamber furnace shell.
4. the device of a kind of preparing lithium metal by using vacuum metal heat reduction according to claim 1 is characterized in that being provided with the vacuum packing ring between described collecting chamber fire door and the collecting chamber shell.
5. the device of a kind of preparing lithium metal by using vacuum metal heat reduction according to claim 1, it is characterized in that described resistance heater is to be made by high temperature metallic material nickelic, Gao Ge, and be placed in the inside of reaction chamber, the reduction reaction material places between the resistance heater.
6. the device of a kind of preparing lithium metal by using vacuum metal heat reduction according to claim 1, it is characterized in that described reaction chamber below pillar is installed.
7. the device of a kind of preparing lithium metal by using vacuum metal heat reduction according to claim 1 is characterized in that described liner adopts light-weight insulating brick or calcium silicate board or schamotte brick.
8. adopt the described device of claim 1 to produce the method for metallic lithium, it is characterized in that calcining CaCO
3The CaO and the Li that generate
2CO
3Be pressed into spherical agglomerate after 1～2 mixing in molar ratio and place calcining furnace, under 1000～1200 ℃ temperature, calcine, make its generation contain Li
2The material of O and CaO compound composition, and then this material worn into powder, granularity needs below 0.15mm, and mix with excessive 3～10% metallic reducing agent and to be pressed into spherical agglomerate, become the reaction mass of metallothermic reduction vacuum refining lithium, again reaction mass is placed in the reaction chamber of device of preparing lithium metal by using vacuum metal heat reduction, heat by the resistance heater in the reaction chamber, make temperature reach 1000-1300 ℃, simultaneously to vacuumizing in the reaction chamber, keep the vacuum tightness in the reaction chamber to reach below the 20Pa, carry out the vacuum metal thermal reduction reaction, metallic lithium is gaseous state and overflows from the reduction reaction material in reaction chamber, become liquid state after entering the collecting chamber of lithium, and in the collection container of inflow collecting chamber below, after reaction finishes, stop heating, continue to keep vacuum tightness below 20Pa, the question response room temp is reduced to below 200 ℃, to charging into argon gas in the reaction chamber, but after temperature drops to manual operation by the time, open the collecting chamber fire door, take out the collection container that has contained the frozen metal lithium, obtain metallic lithium.
9. the method for a kind of preparing lithium metal by using vacuum metal heat reduction according to claim 8 is characterized in that described metallic reducing agent is silicon or aluminium or aluminum silicon alloy.
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| CN2010101440655A CN101845559B (en) | 2010-04-12 | 2010-04-12 | Device and method for preparing lithium metal by using vacuum metal heat reduction |
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| CN2010101440655A CN101845559B (en) | 2010-04-12 | 2010-04-12 | Device and method for preparing lithium metal by using vacuum metal heat reduction |
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| CN104178645B (en) * | 2014-08-19 | 2017-03-01 | 北京神雾环境能源科技集团股份有限公司 | The method preparing lithium metal |
| CN104388688B (en) * | 2014-11-17 | 2016-07-06 | 东北大学 | A kind of device and method of vacuum metal thermal reduction refining lithium |
| CN108165768A (en) * | 2018-01-15 | 2018-06-15 | 东北大学 | The apparatus and method of lithium are produced in a kind of vacuum metal thermal reduction |
| CN110289391B (en) * | 2019-06-25 | 2020-12-04 | 中南大学 | Metal lithium alloy and preparation method and application thereof |
| 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 |
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| CN100342045C (en) * | 2006-03-24 | 2007-10-10 | 东北大学 | Inner resistance heating metallothermic reduction furnace for melting magnesium |
| CN101672573B (en) * | 2007-11-09 | 2012-07-25 | 江西赣锋锂业股份有限公司 | Metallic lithium vacuum distillation purification device |
| CN101445874B (en) * | 2008-12-24 | 2010-11-10 | 大连天熙创展科技有限公司 | Production method for high-purity lithium metal and special equipment thereof |
| CN201660686U (en) * | 2010-04-12 | 2010-12-01 | 东北大学 | Device of preparing metallic lithium by vacuum metallothermic reduction |
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