CN105525101B - A kind of CeO2The method that direct calciothermic reduction produces metal Ce - Google Patents
A kind of CeO2The method that direct calciothermic reduction produces metal Ce Download PDFInfo
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- CN105525101B CN105525101B CN201410514367.5A CN201410514367A CN105525101B CN 105525101 B CN105525101 B CN 105525101B CN 201410514367 A CN201410514367 A CN 201410514367A CN 105525101 B CN105525101 B CN 105525101B
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000006184 cosolvent Substances 0.000 claims description 55
- 229910014810 CaCl2—CaF2 Inorganic materials 0.000 claims description 44
- 230000006698 induction Effects 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 29
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 230000001360 synchronised effect Effects 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 238000009849 vacuum degassing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000000462 isostatic pressing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 239000007787 solid Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 3
- 229910020187 CeF3 Inorganic materials 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to Ce Metal Production technical fields, and in particular to a kind of CeO2The method that direct calciothermic reduction produces metal Ce, it is therefore an objective to solve conventional process flow complexity, high energy consumption, yield is low, the problem of easily cause environmental pollution.Characterized in that, the step of the step of it includes determining the step of produce scheme, determines inventory, pretreatment of material, the step of feed in the reactor and metal Ce preparation the step of.The present invention utilizes CeO2The Ce metal product regular shapes of direct calciothermic reduction technique productions, clean surface, density is up to 6.3g/cm3, close to its solid density, (Ce solid density is 6.6g/cm3), reduction yield reaches more than 98%.
Description
Technical field
The present invention relates to Ce Metal Production technical fields, and in particular to a kind of CeO2Direct calciothermic reduction produces metal Ce's
Method.
Background technology
Ce is one of important rare earth element, with unique physics and chemical property, in steel, non-ferrous metal and its conjunction
It is widely used in the industrial circles such as gold, pyrophoric alloy, permanent-magnet material, hydrogen storage material.
The production of Ce metals uses fused salt electrolysis process, including the fused salt electrolysis process of cerium chloride and melting for cerium oxide always
Salt electrolysis.Wherein the fused salt electrolysis process of cerium chloride is with CeCl3For raw material, KCl is auxiliary material, by dispensing, fusing, electrolysis, casting
Ingot, washing except electrolyte, the technological process acquisition Ce metal products such as dry, pack.Use the Ce ingots purity of the technique productions for
99%~99.5%, yield is 85%~90%, the accessory substance Cl produced in production process2Absorbed with NaOH solution.Cerium oxide
Fused salt electrolysis process with CeO2For raw material, CeF3, LiF and BaF2For auxiliary material, (ratio is CeF3∶LiF∶BaF2=73: 17: 10),
CeO2Need to be continuously added in electrolytic process, the fused salt electrolysis process of technological process and cerium chloride is essentially identical.Given birth to using the technique
The Ce ingots purity of production is 99%~99.5%, and yield is 95%, and CO and CO is produced in production process2Gas.Two kinds of production technologies
The Ce metal product surfaces of acquisition are clean, and new section is in silver gray, without obvious field trash.
Although chloride/oxide effectively can be reduced into metal by process above, work in whole production process
Skill flow is complicated, and time-consuming longer, energy consumption is higher, and yield is relatively low, can produce Cl in electrolytic process in addition2, the gas such as CO, it is easily right
Environment is polluted, and adds the difficulty of subsequent treatment work, the development of Ce Metal Productions is also constrained to a certain extent.
The content of the invention
Present invention aim to address conventional process flow complexity, high energy consumption, yield is low, easily cause asking for environmental pollution
Inscribe there is provided a kind of technological process of simplified Ce Metal Productions, reduction production cost, raising production efficiency and reduction yield, subtract
The CeO of the light pollution to environment2The method that direct calciothermic reduction produces metal Ce.
What the present invention was realized in：
A kind of CeO2The method that direct calciothermic reduction produces metal Ce, specifically includes following steps：
The first step：It is determined that producing scheme；
Second step：Determine inventory；
3rd step：The pretreatment of material；
4th step：Feed in the reactor；
5th step：Metal Ce preparation.
The first step as described above, with CeO2For raw material, metal Ca makees reducing agent, CaCl2-CaF2Make fluxing agent, chemistry is anti-
The equation is answered to be：CeO2+2Ca+nCaCl2-CaF2=Ce+2CaOnCaCl2-CaF2。
Second step as described above, according to the stoichiometric proportion in the chemical equation determined in the first step, reduction
There is excessive value in agent Ca, excessive value scope is 25%~40% (mol ratio)；Cosolvent CaCl2-CaF2Proportioning be 80%
CaCl2- 20%CaF2(mol ratio), cosolvent CaCl2-CaF2With raw material CeO2Mol ratio be 15:1.
3rd step as described above, specifically includes following steps：
Step 3.1：Raw material CeO2Pretreatment；
To raw material CeO in 225~250 DEG C of temperature, relative pressure -0.085~-0.075MPa vacuum drying chamber2It is dry
Dry 15~20 hours；
Step 3.2：Reducing agent Ca pretreatment；
Under argon gas protective condition, from Ca ingots get on the bus specification processed be 0.8 × 0.8 × 5mm~1 × 1 × 10mm Ca consider to be worth doing；Also
Former agent Ca weighing, encapsulation, transport process are both needed to carry out in the case where argon gas is protected；
Step 3.3：Cosolvent CaCl2-CaF2Pretreatment；
By analytically pure CaCl2And CaF2It is well mixed by the proportioning determined in second step, in 225~250 DEG C of temperature, phase
After being dried 10~15 hours in pressure -0.085~-0.075MPa vacuum drying chamber, it is 10 that thickness is pressed on press
~15mm round pie agglomerate, then goes back in drying box and continues dry 5~10 hours under same process；
Step 3.4：The pretreatment of reactor；
Reactor is using preceding 950~1000 DEG C of vacuum degassing in induction furnace 3~5 hours；
Step 3.5：The pretreatment of agitating paddle；
Agitating paddle is stored in vacuum drying chamber and preserved, it is synchronous with step 3.1 to carry out.
In step 3.4 as described above, reactor is by containing 3mol%Y2O3High-purity 97mol%MgO using isostatic pressed into
Type high temperature sintering is made.
In step 3.5 as described above, agitating paddle material selection metal tantalum, type is double-deck reversely hinging type.
4th step as described above, charging method is to disperse isolated charging, and reducing agent Ca is placed in into reactor top, will
Raw material CeO2Reactor bottom is placed in, by cosolvent CaCl2-CaF2Divide three layers of arrangement, bottom cosolvent CaCl2-CaF2Layer is with
Between cosolvent CaCl2-CaF2It is raw material CeO between layer2Layer, intermediate co-solvent CaCl2-CaF2Layer and top cosolvent CaCl2-
CaF2It is Ca layers of reducing agent between layer；Charging process is carried out in the glove box of inert atmosphere protection.
4th step as described above, specifically includes following steps：
Step 4.1：Fill bottom cosolvent CaCl2-CaF2Layer；
It will should be arranged in the cosolvent CaCl of reactor bottom2-CaF2Reactor is added, compacting forms bottom cosolvent
CaCl2-CaF2Layer；
Step 4.2：Filling material CeO2Layer；
By whole raw material CeO2Reactor is added, bottom cosolvent CaCl is placed in2-CaF2Layer top, compacting forms raw material
CeO2Layer；
Step 4.3：Fill intermediate co-solvent CaCl2-CaF2Layer；
Raw material CeO should be arranged in2Cosolvent CaCl between Ca layers of layer and reducing agent2-CaF2Reactor is added, is compacted,
Form intermediate co-solvent CaCl2-CaF2Layer；
Step 4.4：Fill Ca layers of reducing agent；
Restore All agent Ca is added into reactor, intermediate co-solvent CaCl is placed in2-CaF2Layer top, compacting forms reduction
Ca layers of agent；
Step 4.5：Filling top cosolvent CaCl2-CaF2Layer；
By remaining cosolvent CaCl2-CaF2Reactor is added, Ca layers of top of reducing agent are placed in, compacting forms top and helped
Solvent C aCl2-CaF2Layer.
5th step as described above, specifically includes following steps：
Step 5.1：Shove charge；
Reactor after being fed through the 4th step is put into graphite heater, is put into the lump in induction furnace, agitating paddle is consolidated
On the agitating shaft for being scheduled on induction furnace bell, induction furnace is covered；
Step 5.2：Evacuate and heat；
Slow open vacuumizes control valve, to being vacuumized in induction furnace, while to induction furnace power transmission, induction furnace passes through stone
Black heater is heated to reactor, and rate of temperature rise is 7~15 DEG C/min, and temperature of reactor rises to 400~500 DEG C, end
Vacuumize；Induction furnace continues to be powered, and the temperature of charge in reactor is persistently increased；
Step 5.3：It is filled with argon gas；
After end is vacuumized, the argon gas that purity is more than 99.99% is filled with into induction furnace, inertia is formed in induction furnace
Atmosphere protection；When sensing furnace pressure more than ambient atmosphere pressure, stopping is filled with argon gas；
Step 5.4：Start chemical reaction；
After material melting is finished, control agitating paddle is descending, stretches into and is stirred inside the material in reactor, according to first
The chemical equation determined in step starts chemical reaction；In whipping process, by temperature of reactor control at 800~840 DEG C；
The lower end of agitating paddle close to reactor bottom, rotating speed of agitator scope between 200~800rpm, mixing time 25~
Between 35min, wherein, the time of more than rotating speed 600rpm high-speed stirred more than 20min, was turned to as the overlook direction inverse time
Pin, makes lower floor's blade play castering action, and upper strata blade removes pressure effect；
Step 5.5：Insulation；
After stirring terminates, control agitating paddle is up, disengages it from material, chemical reaction terminates；Reactor is heated to 950
~1000 DEG C, rate of temperature rise is 7~15 DEG C/min, is incubated 20~30min；
Step 5.6：Cooling is come out of the stove；
Insulation has a power failure induction furnace after terminating, and induction furnace is begun to cool down, when sensing furnace temperature is reduced to room temperature, from sensing
Reactor is taken out in stove, is crushed, the Ce metal products restored are taken out from reactor bottom.
The beneficial effects of the invention are as follows：
The present invention utilizes the Ce metal product regular shapes of the direct calciothermic reduction technique productions of CeO2, clean surface, density
Up to 6.3g/cm3, close to its solid density (Ce solid density is 6.6g/cm3), reduction yield reaches more than 98%.
Brief description of the drawings
Fig. 1 is a kind of CeO of the present invention2Direct calciothermic reduction produces the charging schematic diagram of metal Ce method.
Embodiment
The present invention is described further with reference to the accompanying drawings and examples.
A kind of CeO2The method that direct calciothermic reduction produces metal Ce, specifically includes following steps：
The first step：It is determined that producing scheme.
With CeO2For raw material, metal Ca makees reducing agent, CaCl2-CaF2Make fluxing agent, chemical equation is：CeO2+
2Ca+nCaCl2-CaF2=Ce+2CaOnCaCl2-CaF2
Second step：Determine inventory.
According to the stoichiometric proportion in the chemical equation determined in the first step, there is excessive value, mistake in reducing agent Ca
Value scope is 25%~40% (mol ratio).Cosolvent CaCl2-CaF2Proportioning be 80%CaCl2- 20%CaF2(mole
Than), cosolvent CaCl2-CaF2With raw material CeO2Mol ratio be 15:1.
3rd step：The pretreatment of material.
Step 3.1：Raw material CeO2Pretreatment.
To raw material CeO in 225~250 DEG C of temperature, relative pressure -0.085~-0.075MPa vacuum drying chamber2It is dry
Dry 15~20 hours.
Step 3.2：Reducing agent Ca pretreatment.
Under argon gas protective condition, from Ca ingots get on the bus specification processed be 0.8 × 0.8 × 5mm~1 × 1 × 10mm Ca consider to be worth doing.Also
Former agent Ca weighing, encapsulation, transport process are both needed to carry out in the case where argon gas is protected.
Step 3.3：Cosolvent CaCl2-CaF2Pretreatment.
By analytically pure CaCl2And CaF2It is well mixed by the proportioning determined in second step, in 225~250 DEG C of temperature, phase
After being dried 10~15 hours in pressure -0.085~-0.075MPa vacuum drying chamber, it is 10 that thickness is pressed on press
~15mm round pie agglomerate, then goes back in drying box and continues dry 5~10 hours under same process.
Step 3.4：The pretreatment of reactor.
Reactor is using preceding 950~1000 DEG C of vacuum degassing in induction furnace 3~5 hours.Reactor be by containing
3mol%Y2O3High-purity 97mol%MgO be made using isostatic pressing high temperature sintering.
Step 3.5：The pretreatment of agitating paddle.
Agitating paddle is stored in vacuum drying chamber and preserved, it is synchronous with step 3.1 to carry out.Agitating paddle material selection metal
Tantalum, type is double-deck reversely hinging type, and blade dimensions and inclination angle are determined according to reactor inside dimension and agitating paddle design principle.
4th step：Feed in the reactor.Charging method is to disperse isolated charging, and reducing agent Ca is placed on reactor
Portion, by raw material CeO2Reactor bottom is placed in, by cosolvent CaCl2-CaF2Divide three layers of arrangement, bottom cosolvent CaCl2-CaF2Layer
With intermediate co-solvent CaCl2-CaF2It is raw material CeO between layer2Layer, intermediate co-solvent CaCl2-CaF2Layer and top cosolvent
CaCl2-CaF2It is Ca layers of reducing agent between layer.Charging process is carried out in the glove box of inert atmosphere protection.
Step 4.1：Fill bottom cosolvent CaCl2-CaF2Layer.
It will should be arranged in the cosolvent CaCl of reactor bottom2-CaF2Reactor is added, compacting forms bottom cosolvent
CaCl2-CaF2Layer.
Step 4.2：Filling material CeO2Layer.
By whole raw material CeO2Reactor is added, bottom cosolvent CaCl is placed in2-CaF2Layer top, compacting forms raw material
CeO2Layer.
Step 4.3：Fill intermediate co-solvent CaCl2-CaF2Layer.
Raw material CeO should be arranged in2Cosolvent CaCl between Ca layers of layer and reducing agent2-CaF2Reactor is added, is compacted,
Form intermediate co-solvent CaCl2-CaF2Layer.
Step 4.4：Fill Ca layers of reducing agent.
Restore All agent Ca is added into reactor, intermediate co-solvent CaCl is placed in2-CaF2Layer top, compacting forms reduction
Ca layers of agent.
Step 4.5：Filling top cosolvent CaCl2-CaF2Layer.
By remaining cosolvent CaCl2-CaF2Reactor is added, Ca layers of top of reducing agent are placed in, compacting forms top and helped
Solvent C aCl2-CaF2Layer.
5th step：Metal Ce preparation.
Step 5.1：Shove charge.
Reactor after being fed through the 4th step is put into graphite heater, is put into the lump in induction furnace, agitating paddle is consolidated
On the agitating shaft for being scheduled on induction furnace bell, induction furnace is covered.
Step 5.2：Evacuate and heat.
Slow open vacuumizes control valve, to being vacuumized in induction furnace, while to induction furnace power transmission, induction furnace passes through stone
Black heater is heated to reactor, and rate of temperature rise is 7~15 DEG C/min, and temperature of reactor rises to 400~500 DEG C.Terminate
Vacuumize.Induction furnace continues to be powered, and the temperature of charge in reactor is persistently increased.
Step 5.3：It is filled with argon gas.
After end is vacuumized, the argon gas that purity is more than 99.99% is filled with into induction furnace, inertia is formed in induction furnace
Atmosphere protection.When sensing furnace pressure more than ambient atmosphere pressure, stopping is filled with argon gas.
Step 5.4：Start chemical reaction.
After material melting is finished, control agitating paddle is descending, stretches into and is stirred inside the material in reactor, according to first
The chemical equation determined in step starts chemical reaction.In whipping process, by temperature of reactor control at 800~840 DEG C.
The lower end of agitating paddle close to reactor bottom, rotating speed of agitator scope between 200~800rpm, mixing time 25~
Between 35min, wherein, the time of more than rotating speed 600rpm high-speed stirred more than 20min, was turned to as the overlook direction inverse time
Pin, makes lower floor's blade play castering action, and upper strata blade removes pressure effect.
Step 5.5：Insulation.
After stirring terminates, control agitating paddle is up, disengages it from material, chemical reaction terminates.Reactor is heated to 950
~1000 DEG C, rate of temperature rise is 7~15 DEG C/min, is incubated 20~30min.
Step 5.6：Cooling is come out of the stove.
Insulation has a power failure induction furnace after terminating, and induction furnace is begun to cool down, when sensing furnace temperature is reduced to room temperature, from sensing
Reactor is taken out in stove, is crushed, the Ce metal products restored are taken out from reactor bottom.
The present invention utilizes CeO2The Ce metal product regular shapes of direct calciothermic reduction technique productions, clean surface, density
Up to 6.3g/cm3, close to its solid density (Ce solid density is 6.6g/cm3), reduction yield reaches more than 98%.Production
During do not produce poisonous gas, environment will not be polluted.Single batch hectogram magnitude production scale is time-consuming 3~4 hours, raw
Production scale depend on reactor volume, and expand the scale of production be conducive to reduce yield further raising.
Claims (6)
1. a kind of CeO2The method that direct calciothermic reduction produces metal Ce, specifically includes following steps：
The first step：It is determined that producing scheme；
Second step：Determine inventory；
3rd step：The pretreatment of material；
4th step：Feed in the reactor；
5th step：Metal Ce preparation；
The described first step, with CeO2For raw material, metal Ca makees reducing agent, CaCl2-CaF2Make fluxing agent, chemical equation
For：CeO2+2Ca+nCaCl2-CaF2=Ce+2CaOnCaCl2-CaF2；
Described second step, according to the stoichiometric proportion in the chemical equation determined in the first step, reducing agent Ca is present
Excessive value, excessive value scope mol ratio is 25%~40%；Cosolvent CaCl2-CaF2Proportioning be 80%CaCl2- 20%CaF2
Mol ratio, cosolvent CaCl2-CaF2With raw material CeO2Mol ratio be 15:1；
The 3rd described step, specifically includes following steps：
Step 3.1：Raw material CeO2Pretreatment；
To raw material CeO in 225~250 DEG C of temperature, relative pressure -0.085~-0.075MPa vacuum drying chamber2Dry 15~
20 hours；
Step 3.2：Reducing agent Ca pretreatment；
Under argon gas protective condition, from Ca ingots get on the bus specification processed be 0.8 × 0.8 × 5mm~1 × 1 × 10mm Ca consider to be worth doing；Reducing agent
Ca weighing, encapsulation, transport process are both needed to carry out in the case where argon gas is protected；
Step 3.3：Cosolvent CaCl2-CaF2Pretreatment；
By analytically pure CaCl2And CaF2It is well mixed by the proportioning determined in second step, in 225~250 DEG C of temperature, relative pressure
After being dried 10~15 hours in power -0.085~-0.075MPa vacuum drying chamber, be pressed on press thickness for 10~
15mm round pie agglomerate, then goes back in drying box and continues dry 5~10 hours under same process；
Step 3.4：The pretreatment of reactor；
Reactor is using preceding 950~1000 DEG C of vacuum degassing in induction furnace 3~5 hours；
Step 3.5：The pretreatment of agitating paddle；
Agitating paddle is stored in vacuum drying chamber and preserved, it is synchronous with step 3.1 to carry out.
2. CeO according to claim 12The method that direct calciothermic reduction produces metal Ce, it is characterised in that：Described step
In rapid 3.4, reactor is by containing 3mol%Y2O3High-purity 97mol%MgO be made using isostatic pressing high temperature sintering.
3. CeO according to claim 12The method that direct calciothermic reduction produces metal Ce, it is characterised in that：Described step
In rapid 3.5, agitating paddle material selection metal tantalum, type is double-deck reversely hinging type.
4. CeO according to claim 12The method that direct calciothermic reduction produces metal Ce, it is characterised in that：Described
Four steps, charging method is to disperse isolated charging, reducing agent Ca is placed in into reactor top, by raw material CeO2It is placed in reactor bottom
Portion, by cosolvent CaCl2-CaF2Divide three layers of arrangement, bottom cosolvent CaCl2-CaF2Layer and intermediate co-solvent CaCl2-CaF2Layer
Between be raw material CeO2Layer, intermediate co-solvent CaCl2-CaF2Layer and top cosolvent CaCl2-CaF2It is reducing agent Ca between layer
Layer；Charging process is carried out in the glove box of inert atmosphere protection.
5. CeO according to claim 12The method that direct calciothermic reduction produces metal Ce, it is characterised in that：Described
Four steps, specifically include following steps：
Step 4.1：Fill bottom cosolvent CaCl2-CaF2Layer；
It will should be arranged in the cosolvent CaCl of reactor bottom2-CaF2Reactor is added, compacting forms bottom cosolvent CaCl2-
CaF2Layer；
Step 4.2：Filling material CeO2Layer；
By whole raw material CeO2Reactor is added, bottom cosolvent CaCl is placed in2-CaF2Layer top, compacting forms raw material CeO2
Layer；
Step 4.3：Fill intermediate co-solvent CaCl2-CaF2Layer；
Raw material CeO should be arranged in2Cosolvent CaCl between Ca layers of layer and reducing agent2-CaF2Reactor is added, is compacted, is formed
Intermediate co-solvent CaCl2-CaF2Layer；
Step 4.4：Fill Ca layers of reducing agent；
Restore All agent Ca is added into reactor, intermediate co-solvent CaCl is placed in2-CaF2Layer top, compacting forms reducing agent Ca
Layer；
Step 4.5：Filling top cosolvent CaCl2-CaF2Layer；
By remaining cosolvent CaCl2-CaF2Reactor is added, Ca layers of top of reducing agent are placed in, compacting forms top cosolvent
CaCl2-CaF2Layer.
6. CeO according to claim 12The method that direct calciothermic reduction produces metal Ce, it is characterised in that：Described
Five steps, specifically include following steps：
Step 5.1：Shove charge；
Reactor after being fed through the 4th step is put into graphite heater, is put into the lump in induction furnace, agitating paddle is fixed on
On the agitating shaft of induction furnace bell, induction furnace is covered；
Step 5.2：Evacuate and heat；
Unlatching vacuumizes control valve, to being vacuumized in induction furnace, while to induction furnace power transmission, induction furnace passes through graphite heater
Reactor is heated, rate of temperature rise is 7~15 DEG C/min, temperature of reactor rises to 400~500 DEG C；End is vacuumized；Sense
Answer stove to continue to be powered, the temperature of charge in reactor is persistently increased；
Step 5.3：It is filled with argon gas；
After end is vacuumized, the argon gas that purity is more than 99.99% is filled with into induction furnace, inert atmosphere is formed in induction furnace
Protection；When sensing furnace pressure more than ambient atmosphere pressure, stopping is filled with argon gas；
Step 5.4：Start chemical reaction；
After material melting is finished, control agitating paddle is descending, stretches into and is stirred inside the material in reactor, according in the first step
The chemical equation of determination starts chemical reaction；In whipping process, by temperature of reactor control at 800~840 DEG C；Stirring
The lower end of oar close to reactor bottom, rotating speed of agitator scope between 200~800rpm, mixing time 25~35min it
Between, turn to as overlook direction counterclockwise, lower floor's blade is played castering action, upper strata blade removes pressure effect；
Step 5.5：Insulation；
After stirring terminates, control agitating paddle is up so that it departs from material, and chemical reaction terminates；Reactor is heated to 950~
1000 DEG C, rate of temperature rise is 7~15 DEG C/min, is incubated 20~30min；
Step 5.6：Cooling is come out of the stove；
Insulation has a power failure induction furnace after terminating, and induction furnace is begun to cool down, when sensing furnace temperature is reduced to room temperature, out of induction furnace
Reactor is taken out, is crushed, the Ce metal products restored are taken out from reactor bottom.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100813A (en) * | 1984-10-05 | 1986-10-01 | 通用汽车公司 | The metallothermic reduction of rare earth oxide |
| WO2014071510A1 (en) * | 2012-11-08 | 2014-05-15 | Electrochem Technologies & Materials Inc. | Process for recovering rare earth oxides from phosphors, fluorescent lamps and light bulbs, cathode ray tubes and other industrial wastes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100813A (en) * | 1984-10-05 | 1986-10-01 | 通用汽车公司 | The metallothermic reduction of rare earth oxide |
| WO2014071510A1 (en) * | 2012-11-08 | 2014-05-15 | Electrochem Technologies & Materials Inc. | Process for recovering rare earth oxides from phosphors, fluorescent lamps and light bulbs, cathode ray tubes and other industrial wastes |
Non-Patent Citations (1)
| Title |
|---|
| 金属铈的生产及应用;林河成;《中国有色冶金》;20050630(第03期);31-34、50 * |
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