CN105525101A - Method for preparing metal Ce through direct calciothermy of CeO2 - Google Patents
Method for preparing metal Ce through direct calciothermy of CeO2 Download PDFInfo
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- CN105525101A CN105525101A CN201410514367.5A CN201410514367A CN105525101A CN 105525101 A CN105525101 A CN 105525101A CN 201410514367 A CN201410514367 A CN 201410514367A CN 105525101 A CN105525101 A CN 105525101A
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- caf
- cacl
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- layer
- ceo
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 72
- 230000006698 induction Effects 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 230000002829 reductive effect Effects 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000002203 pretreatment Methods 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000006184 cosolvent Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 238000000462 isostatic pressing Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005245 sintering Methods 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
- 238000005303 weighing Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 229910016036 BaF 2 Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 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 invention relates to the technical field of Ce metal production, in particular to a method for preparing metal Ce through direct calciothermy of CeO2, and the method aims at solving the problems that in a traditional technology, processes are complex, energy consumption is high, the yield is low, and environmental pollution is liable to be caused. The method is characterized by comprising the step of determining a preparing scheme, the step of determining the feeding amount, the step of pre-treating materials, the step of loading a reactor and the step of preparing metal Ce. According to the method for preparing metal Ce through direct calciothermy of CeO2, a Ce metal product produced through a CeO2 direct calciothermy process is regular in shape and clean in surface, the density can reach 6.3 g/cm<3> and is close to the theoretical density (the theoretical density of Ce is 6.6 g/cm <3>) of the Ce, and the reduction yield reaches more than 98%.
Description
Technical field
The present invention relates to Ce Metal Production technical field, be specifically related to a kind of CeO
2direct calciothermic reduction produces the method for metal Ce.
Background technology
Ce is one of important rare earth element, has unique physics and chemistry character, is widely used in the industrial circles such as iron and steel, non ferrous metal and their alloy, sparking alloy, permanent magnet material, hydrogen storage material.
What the production of Ce metal adopted always is fused salt electrolysis process, comprises the fused salt electrolysis process of Cerium II Chloride and the fused salt electrolysis process of cerium oxide.Wherein the fused salt electrolysis process of Cerium II Chloride is with CeCl
3for raw material, KCl is auxiliary material, through batching, fusing, electrolysis, ingot casting, washing except ionogen, dry, the technical process such as packaging obtains Ce metal product.The Ce ingot purity adopting this explained hereafter is 99% ~ 99.5%, and yield is 85% ~ 90%, the by product Cl produced in production process
2absorb by NaOH solution.The fused salt electrolysis process of cerium oxide is with CeO
2for raw material, CeF
3, LiF and BaF
2for auxiliary material, (ratio is CeF
3: LiF: BaF
2=73: 17: 10), CeO
2need to add continuously in electrolytic process, technical process is substantially identical with the fused salt electrolysis process of Cerium II Chloride.The Ce ingot purity adopting this explained hereafter is 99% ~ 99.5%, and yield is 95%, produces CO and CO in production process
2gas.The Ce metal product surface cleaning that two kinds of production technique obtain, new cross section is silver gray, without obvious inclusion.
Although muriate/Reduction of Oxide effectively can be become metal by above technique, in whole production process, technical process is complicated, and consuming time longer, energy consumption is higher, and yield is lower, can produce Cl in electrolytic process in addition
2, the gas such as CO, easily to environment, add the difficulty of subsequent disposal work, also constrain the development of Ce Metal Production to a certain extent.
Summary of the invention
The object of the invention is to solve that conventional process flow is complicated, energy consumption is high, yield is low, easily cause the problem of environmental pollution, provide a kind of technical process of the Ce of simplification Metal Production, reduce production cost, enhance productivity and reduce yield, alleviate the CeO of the pollution to environment
2direct calciothermic reduction produces the method for metal Ce.
The present invention is achieved in that
A kind of CeO
2direct calciothermic reduction produces the method for metal Ce, specifically comprises the steps:
The first step: determine to produce scheme;
Second step: determine charging capacity;
3rd step: the pre-treatment of material;
4th step: feed in the reactor;
5th step: the preparation of metal Ce.
The first step as above, with CeO
2for raw material, metal Ca makes reductive agent, CaCl
2-CaF
2make fusing assistant, chemical equation is: CeO
2+ 2Ca+nCaCl
2-CaF
2=Ce+2CaOnCaCl
2-CaF
2.
Second step as above, according to the stoichiometric ratio in the chemical equation determined in the first step, there is excessive value in reductive agent Ca, and excessive value scope is 25% ~ 40% (mol ratio); Solubility promoter CaCl
2-CaF
2proportioning be 80%CaCl
2-20%CaF
2(mol ratio), solubility promoter CaCl
2-CaF
2with raw material CeO
2mol ratio be 15:1.
3rd step as above, specifically comprises the steps:
Step 3.1: raw material CeO
2pre-treatment;
Temperature 225 ~ 250 DEG C, to raw material CeO in the vacuum drying oven of relative pressure-0.085 ~-0.075MPa
2dry 15 ~ 20 hours;
Step 3.2: the pre-treatment of reductive agent Ca;
Under argon shield condition, from Ca ingot get on the bus specification processed be 0.8 × 0.8 × 5mm ~ 1 × 1 × 10mm Ca bits; The weighing of reductive agent Ca, encapsulation, transport process all need carry out under argon shield;
Step 3.3: solubility promoter CaCl
2-CaF
2pre-treatment;
By analytically pure CaCl
2and CaF
2mix by the proportioning determined in second step, temperature 225 ~ 250 DEG C, in the vacuum drying oven of relative pressure-0.085 ~-0.075MPa after dry 10 ~ 15 hours, press is pressed into the round pie agglomerate that thickness is 10 ~ 15mm, goes back to subsequently in loft drier and continue dry 5 ~ 10 hours under same process;
Step 3.4: the pre-treatment of reactor;
Reactor 950 ~ 1000 DEG C of vacuum stripping 3 ~ 5 hours in induction furnace before use;
Step 3.5: the pre-treatment of stirring rake;
Stirring rake is left in vacuum drying oven and preserves, synchronously carry out with step 3.1.
In step 3.4 as above, reactor is by containing 3mol%Y
2o
3high-purity 97mol%MgO utilize isostatic pressing high temperature sintering to make.
In step 3.5 as above, stirring rake material selection metal tantalum, type is double-deck oppositely hinging type.
4th step as above, charging method is the isolated charging of dispersion, reductive agent Ca is placed in reactor top, by raw material CeO
2be placed in reactor bottom, by solubility promoter CaCl
2-CaF
2divide three layers of layout, bottom solubility promoter CaCl
2-CaF
2layer and intermediate co-solvent CaCl
2-CaF
2be raw material CeO between layer
2layer, intermediate co-solvent CaCl
2-CaF
2layer and top solubility promoter CaCl
2-CaF
2be reductive agent Ca layer between layer; Charging process carries out in the glove box of inert atmosphere protection.
4th step as above, specifically comprises the steps:
Step 4.1: fill bottom solubility promoter CaCl
2-CaF
2layer;
The solubility promoter CaCl of reactor bottom should be arranged in
2-CaF
2add reactor, compacting, form bottom solubility promoter CaCl
2-CaF
2layer;
Step 4.2: fill raw material CeO
2layer;
By whole raw material CeO
2add reactor, be placed in bottom solubility promoter CaCl
2-CaF
2layer top, compacting, forms raw material CeO
2layer;
Step 4.3: fill intermediate co-solvent CaCl
2-CaF
2layer;
Raw material CeO should be arranged in
2solubility promoter CaCl between layer and reductive agent Ca layer
2-CaF
2add reactor, compacting, form intermediate co-solvent CaCl
2-CaF
2layer;
Step 4.4: fill reductive agent Ca layer;
Restore All agent Ca is added reactor, is placed in intermediate co-solvent CaCl
2-CaF
2layer top, compacting, forms reductive agent Ca layer;
Step 4.5: fill top solubility promoter CaCl
2-CaF
2layer;
By remaining solubility promoter CaCl
2-CaF
2add reactor, be placed in above reductive agent Ca layer, compacting, form top solubility promoter CaCl
2-CaF
2layer.
5th step as above, specifically comprises the steps:
Step 5.1: shove charge;
Reactor after the 4th step charging is put into graphite heater, puts into induction furnace in the lump, stirring rake is fixed on the stir shaft of induction furnace bell, induction furnace is covered;
Step 5.2: find time and heat;
Slow unlatching vacuumizes by-pass valve control, vacuumizes in induction furnace, and give induction furnace power transmission, induction furnace is heated reactor by graphite heater, and rate of temperature rise is 7 ~ 15 DEG C/min, and temperature of reactor rises to 400 ~ 500 DEG C, terminates to vacuumize simultaneously; Induction furnace continues energising, makes the temperature of charge in reactor continue to rise;
Step 5.3: be filled with argon gas;
After end vacuumizes, in induction furnace, be filled with the argon gas that purity is more than 99.99%, in induction furnace, form inert atmosphere protection; When induction furnace internal pressure is greater than ambient atmosphere pressure, stop being filled with argon gas;
Step 5.4: start chemical reaction;
After material melting, control stirring rake descending, the internal batch stretched in reactor stirs, and starts chemical reaction according to the chemical equation determined in the first step; In whipping process, temperature of reactor is controlled at 800 ~ 840 DEG C; The lower end of stirring rake is close to reactor bottom, rotating speed of agitator scope is between 200 ~ 800rpm, churning time is between 25 ~ 35min, wherein, the time of the high-speed stirring of more than rotating speed 600rpm is being greater than 20min, turn to as overlooking direction counterclockwise, make lower floor's blade play castering action, upper strata blade removes pressure effect;
Step 5.5: insulation;
After stirring terminates, control stirring rake up, make it depart from material, chemical reaction terminates; Reactor is heated to 950 ~ 1000 DEG C, rate of temperature rise is 7 ~ 15 DEG C/min, insulation 20 ~ 30min;
Step 5.6: cooling is come out of the stove;
Had a power failure by induction furnace after insulation terminates, induction furnace begins to cool down, and when induction furnace temperature is reduced to room temperature, in induction furnace, takes out reactor, broken, takes out the Ce metal product restored from reactor bottom.
The invention has the beneficial effects as follows:
The present invention utilizes the Ce metal product regular shape of the direct calciothermic reduction explained hereafter of CeO2, clean surface, and density can reach 6.3g/cm3, and close to its theoretical density (theoretical density of Ce is 6.6g/cm3), reduction yield reaches more than 98%.
Accompanying drawing explanation
Fig. 1 is a kind of CeO of the present invention
2direct calciothermic reduction produces the charging schematic diagram of the method for metal Ce.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described further.
A kind of CeO
2direct calciothermic reduction produces the method for metal Ce, specifically comprises the steps:
The first step: determine to produce scheme.
With CeO
2for raw material, metal Ca makes reductive agent, CaCl
2-CaF
2make fusing assistant, chemical equation is: CeO
2+ 2Ca+nCaCl
2-CaF
2=Ce+2CaOnCaCl
2-CaF
2
Second step: determine charging capacity.
According to the stoichiometric ratio in the chemical equation determined in the first step, there is excessive value in reductive agent Ca, and excessive value scope is 25% ~ 40% (mol ratio).Solubility promoter CaCl
2-CaF
2proportioning be 80%CaCl
2-20%CaF
2(mol ratio), solubility promoter CaCl
2-CaF
2with raw material CeO
2mol ratio be 15:1.
3rd step: the pre-treatment of material.
Step 3.1: raw material CeO
2pre-treatment.
Temperature 225 ~ 250 DEG C, to raw material CeO in the vacuum drying oven of relative pressure-0.085 ~-0.075MPa
2dry 15 ~ 20 hours.
Step 3.2: the pre-treatment of reductive agent Ca.
Under argon shield condition, from Ca ingot get on the bus specification processed be 0.8 × 0.8 × 5mm ~ 1 × 1 × 10mm Ca bits.The weighing of reductive agent Ca, encapsulation, transport process all need carry out under argon shield.
Step 3.3: solubility promoter CaCl
2-CaF
2pre-treatment.
By analytically pure CaCl
2and CaF
2mix by the proportioning determined in second step, temperature 225 ~ 250 DEG C, in the vacuum drying oven of relative pressure-0.085 ~-0.075MPa after dry 10 ~ 15 hours, press is pressed into the round pie agglomerate that thickness is 10 ~ 15mm, goes back to subsequently in loft drier and continue dry 5 ~ 10 hours under same process.
Step 3.4: the pre-treatment of reactor.
Reactor 950 ~ 1000 DEG C of vacuum stripping 3 ~ 5 hours in induction furnace before use.Reactor is by containing 3mol%Y
2o
3high-purity 97mol%MgO utilize isostatic pressing high temperature sintering to make.
Step 3.5: the pre-treatment of stirring rake.
Stirring rake is left in vacuum drying oven and preserves, synchronously carry out with step 3.1.Stirring rake material selection metal tantalum, type is double-deck oppositely hinging type, and blade dimensions and inclination angle are determined according to reactor inside dimension and stirring rake principle of design.
4th step: feed in the reactor.Charging method is the isolated charging of dispersion, reductive agent Ca is placed in reactor top, by raw material CeO
2be placed in reactor bottom, by solubility promoter CaCl
2-CaF
2divide three layers of layout, bottom solubility promoter CaCl
2-CaF
2layer and intermediate co-solvent CaCl
2-CaF
2be raw material CeO between layer
2layer, intermediate co-solvent CaCl
2-CaF
2layer and top solubility promoter CaCl
2-CaF
2be reductive agent Ca layer between layer.Charging process carries out in the glove box of inert atmosphere protection.
Step 4.1: fill bottom solubility promoter CaCl
2-CaF
2layer.
The solubility promoter CaCl of reactor bottom should be arranged in
2-CaF
2add reactor, compacting, form bottom solubility promoter CaCl
2-CaF
2layer.
Step 4.2: fill raw material CeO
2layer.
By whole raw material CeO
2add reactor, be placed in bottom solubility promoter CaCl
2-CaF
2layer top, compacting, forms raw material CeO
2layer.
Step 4.3: fill intermediate co-solvent CaCl
2-CaF
2layer.
Raw material CeO should be arranged in
2solubility promoter CaCl between layer and reductive agent Ca layer
2-CaF
2add reactor, compacting, form intermediate co-solvent CaCl
2-CaF
2layer.
Step 4.4: fill reductive agent Ca layer.
Restore All agent Ca is added reactor, is placed in intermediate co-solvent CaCl
2-CaF
2layer top, compacting, forms reductive agent Ca layer.
Step 4.5: fill top solubility promoter CaCl
2-CaF
2layer.
By remaining solubility promoter CaCl
2-CaF
2add reactor, be placed in above reductive agent Ca layer, compacting, form top solubility promoter CaCl
2-CaF
2layer.
5th step: the preparation of metal Ce.
Step 5.1: shove charge.
Reactor after the 4th step charging is put into graphite heater, puts into induction furnace in the lump, stirring rake is fixed on the stir shaft of induction furnace bell, induction furnace is covered.
Step 5.2: find time and heat.
Slow unlatching vacuumizes by-pass valve control, vacuumizes in induction furnace, and give induction furnace power transmission, induction furnace is heated reactor by graphite heater, and rate of temperature rise is 7 ~ 15 DEG C/min, and temperature of reactor rises to 400 ~ 500 DEG C simultaneously.End vacuumizes.Induction furnace continues energising, makes the temperature of charge in reactor continue to rise.
Step 5.3: be filled with argon gas.
After end vacuumizes, in induction furnace, be filled with the argon gas that purity is more than 99.99%, in induction furnace, form inert atmosphere protection.When induction furnace internal pressure is greater than ambient atmosphere pressure, stop being filled with argon gas.
Step 5.4: start chemical reaction.
After material melting, control stirring rake descending, the internal batch stretched in reactor stirs, and starts chemical reaction according to the chemical equation determined in the first step.In whipping process, temperature of reactor is controlled at 800 ~ 840 DEG C.The lower end of stirring rake is close to reactor bottom, rotating speed of agitator scope is between 200 ~ 800rpm, churning time is between 25 ~ 35min, wherein, the time of the high-speed stirring of more than rotating speed 600rpm is being greater than 20min, turn to as overlooking direction counterclockwise, make lower floor's blade play castering action, upper strata blade removes pressure effect.
Step 5.5: insulation.
After stirring terminates, control stirring rake up, make it depart from material, chemical reaction terminates.Reactor is heated to 950 ~ 1000 DEG C, rate of temperature rise is 7 ~ 15 DEG C/min, insulation 20 ~ 30min.
Step 5.6: cooling is come out of the stove.
Had a power failure by induction furnace after insulation terminates, induction furnace begins to cool down, and when induction furnace temperature is reduced to room temperature, in induction furnace, takes out reactor, broken, takes out the Ce metal product restored from reactor bottom.
The present invention utilizes CeO
2the Ce metal product regular shape of direct calciothermic reduction explained hereafter, clean surface, density can reach 6.3g/cm3, and close to its theoretical density (theoretical density of Ce is 6.6g/cm3), reduction yield reaches more than 98%.Poisonous gas is not produced in production process, can not to environment.3 ~ 4 hours consuming time of single batch of hectogram magnitude industrial scale, industrial scale depends on reactor volume, and expands the scale of production and be conducive to reducing the further raising of yield.
Claims (9)
1. a CeO
2direct calciothermic reduction produces the method for metal Ce, specifically comprises the steps:
The first step: determine to produce scheme;
Second step: determine charging capacity;
3rd step: the pre-treatment of material;
4th step: feed in the reactor;
5th step: the preparation of metal Ce.
2. CeO according to claim 1
2direct calciothermic reduction produces the method for metal Ce, it is characterized in that: the described the first step, with CeO
2for raw material, metal Ca makes reductive agent, CaCl
2-CaF
2make fusing assistant, chemical equation is: CeO
2+ 2Ca+nCaCl
2-CaF
2=Ce+2CaOnCaCl
2-CaF
2.
3. CeO according to claim 1
2direct calciothermic reduction produces the method for metal Ce, it is characterized in that: described second step, according to the stoichiometric ratio in the chemical equation determined in the first step, there is excessive value in reductive agent Ca, and excessive value scope is 25% ~ 40% (mol ratio); Solubility promoter CaCl
2-CaF
2proportioning be 80%CaCl
2-20%CaF
2(mol ratio), solubility promoter CaCl
2-CaF
2with raw material CeO
2mol ratio be 15:1.
4. CeO according to claim 1
2direct calciothermic reduction produces the method for metal Ce, it is characterized in that: the 3rd described step, specifically comprises the steps:
Step 3.1: raw material CeO
2pre-treatment;
Temperature 225 ~ 250 DEG C, to raw material CeO in the vacuum drying oven of relative pressure-0.085 ~-0.075MPa
2dry 15 ~ 20 hours;
Step 3.2: the pre-treatment of reductive agent Ca;
Under argon shield condition, from Ca ingot get on the bus specification processed be 0.8 × 0.8 × 5mm ~ 1 × 1 × 10mm Ca bits; The weighing of reductive agent Ca, encapsulation, transport process all need carry out under argon shield;
Step 3.3: solubility promoter CaCl
2-CaF
2pre-treatment;
By analytically pure CaCl
2and CaF
2mix by the proportioning determined in second step, temperature 225 ~ 250 DEG C, in the vacuum drying oven of relative pressure-0.085 ~-0.075MPa after dry 10 ~ 15 hours, press is pressed into the round pie agglomerate that thickness is 10 ~ 15mm, goes back to subsequently in loft drier and continue dry 5 ~ 10 hours under same process;
Step 3.4: the pre-treatment of reactor;
Reactor 950 ~ 1000 DEG C of vacuum stripping 3 ~ 5 hours in induction furnace before use;
Step 3.5: the pre-treatment of stirring rake;
Stirring rake is left in vacuum drying oven and preserves, synchronously carry out with step 3.1.
5. CeO according to claim 4
2direct calciothermic reduction produces the method for metal Ce, it is characterized in that: in described step 3.4, and reactor is by containing 3mol%Y
2o
3high-purity 97mol%MgO utilize isostatic pressing high temperature sintering to make.
6. CeO according to claim 4
2direct calciothermic reduction produces the method for metal Ce, it is characterized in that: in described step 3.5, stirring rake material selection metal tantalum, and type is double-deck oppositely hinging type.
7. CeO according to claim 1
2direct calciothermic reduction produces the method for metal Ce, it is characterized in that: the 4th described step, and charging method is the isolated charging of dispersion, reductive agent Ca is placed in reactor top, by raw material CeO
2be placed in reactor bottom, by solubility promoter CaCl
2-CaF
2divide three layers of layout, bottom solubility promoter CaCl
2-CaF
2layer and intermediate co-solvent CaCl
2-CaF
2be raw material CeO between layer
2layer, intermediate co-solvent CaCl
2-CaF
2layer and top solubility promoter CaCl
2-CaF
2be reductive agent Ca layer between layer; Charging process carries out in the glove box of inert atmosphere protection.
8. CeO according to claim 1
2direct calciothermic reduction produces the method for metal Ce, it is characterized in that: the 4th described step, specifically comprises the steps:
Step 4.1: fill bottom solubility promoter CaCl
2-CaF
2layer;
The solubility promoter CaCl of reactor bottom should be arranged in
2-CaF
2add reactor, compacting, form bottom solubility promoter CaCl
2-CaF
2layer;
Step 4.2: fill raw material CeO
2layer;
By whole raw material CeO
2add reactor, be placed in bottom solubility promoter CaCl
2-CaF
2layer top, compacting, forms raw material CeO
2layer;
Step 4.3: fill intermediate co-solvent CaCl
2-CaF
2layer;
Raw material CeO should be arranged in
2solubility promoter CaCl between layer and reductive agent Ca layer
2-CaF
2add reactor, compacting, form intermediate co-solvent CaCl
2-CaF
2layer;
Step 4.4: fill reductive agent Ca layer;
Restore All agent Ca is added reactor, is placed in intermediate co-solvent CaCl
2-CaF
2layer top, compacting, forms reductive agent Ca layer;
Step 4.5: fill top solubility promoter CaCl
2-CaF
2layer;
By remaining solubility promoter CaCl
2-CaF
2add reactor, be placed in above reductive agent Ca layer, compacting, form top solubility promoter CaCl
2-CaF
2layer.
9. CeO according to claim 1
2direct calciothermic reduction produces the method for metal Ce, it is characterized in that: the 5th described step, specifically comprises the steps:
Step 5.1: shove charge;
Reactor after the 4th step charging is put into graphite heater, puts into induction furnace in the lump, stirring rake is fixed on the stir shaft of induction furnace bell, induction furnace is covered;
Step 5.2: find time and heat;
Unlatching vacuumizes by-pass valve control, vacuumizes in induction furnace, and give induction furnace power transmission, induction furnace is heated reactor by graphite heater, and rate of temperature rise is 7 ~ 15 DEG C/min, and temperature of reactor rises to 400 ~ 500 DEG C simultaneously; End vacuumizes; Induction furnace continues energising, makes the temperature of charge in reactor continue to rise;
Step 5.3: be filled with argon gas;
After end vacuumizes, in induction furnace, be filled with the argon gas that purity is more than 99.99%, in induction furnace, form inert atmosphere protection; When induction furnace internal pressure is greater than ambient atmosphere pressure, stop being filled with argon gas;
Step 5.4: start chemical reaction;
After material melting, control stirring rake descending, the internal batch stretched in reactor stirs, and starts chemical reaction according to the chemical equation determined in the first step; In whipping process, temperature of reactor is controlled at 800 ~ 840 DEG C; The lower end of stirring rake is close to reactor bottom, rotating speed of agitator scope is between 200 ~ 800rpm, churning time is between 25 ~ 35min, wherein, the time of the high-speed stirring of more than rotating speed 600rpm is being greater than 20min, turn to as overlooking direction counterclockwise, make lower floor's blade play castering action, upper strata blade removes pressure effect;
Step 5.5: insulation;
After stirring terminates, control stirring rake up, make it depart from material, chemical reaction terminates; Reactor is heated to 950 ~ 1000 DEG C, rate of temperature rise is 7 ~ 15 DEG C/min, insulation 20 ~ 30min;
Step 5.6: cooling is come out of the stove;
Had a power failure by induction furnace after insulation terminates, induction furnace begins to cool down, and when induction furnace temperature is reduced to room temperature, in induction furnace, takes out reactor, broken, takes out the Ce metal product restored from reactor bottom.
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| 林河成: "金属铈的生产及应用", 《中国有色冶金》 * |
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