CN104120288B - A kind of method of direct thermal reduction continuous production samarium metal - Google Patents

A kind of method of direct thermal reduction continuous production samarium metal Download PDF

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CN104120288B
CN104120288B CN201410345625.1A CN201410345625A CN104120288B CN 104120288 B CN104120288 B CN 104120288B CN 201410345625 A CN201410345625 A CN 201410345625A CN 104120288 B CN104120288 B CN 104120288B
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samarium
high temperature
pelletizing
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metal
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张廷安
豆志河
张子木
刘燕
吕国志
赵秋月
牛丽萍
傅大学
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Northeastern University China
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Abstract

A method for direct thermal reduction continuous production samarium metal, belongs to non-ferrous metallurgy technology field.Preparation method of the present invention specifically comprises: by Sm 2o 3, Al, CaO or MgO batch mixing, wherein reductive agent is that Al can replace with the Si-Fe alloy of Ca or Si mass content 75%, through batching pelletizing, then pelletizing is carried out high temperature reduction reaction in the rare gas element or nitrogen atmosphere of flowing, the high temperature samarium vapor condensation finally will being carried out by the inert carrier gas flowed in high temperature reduction furnace or nitrogen, obtains samarium metal.Means that the inventive method have employed " relative vacuum ", eliminate vacuum system and vacuum reducing tank, achieve the continuous seepage of samarium metal, shorten reduction cycle, improve production efficiency, and the rate of recovery of samarium metal can reach more than 97%; Energy consumption significantly reduces, and is the energy-saving novel environment-friendly process that a kind of low cost prepares samarium metal; And simple to operate, equipment more simply requires low, reduces facility investment and running cost.

Description

A kind of method of direct thermal reduction continuous production samarium metal
Technical field
The invention belongs to non-ferrous metallurgy technology field, particularly a kind of method of direct thermal reduction continuous production samarium metal.
Background technology
Samarium metal (Sm) is one of staple product of light rare earth metal, has special physico-chemical property.Its fusing point 1074 DEG C, boiling point 1794 DEG C, hardness 45 ~ 65HB, density 7.536g/ml, ductility is good and be easy to processing and become a useful person.Samarium has very strong metallochemistry, under certain ambient conditions effect, easily interacts to oxygen, hydrogen, nitrogen, sulphur, carbon etc. and generates corresponding compound (Sm 2o 3, SmH 3, SmN etc.), alloy (as SmCo etc.) can be generated with some metal, different metal salt (SmCl can be generated with acid-base function 3, Sm 2(SO 4) 3, SmNO 3deng).As above samarium metal compound, alloy and salt etc. all have good practical technique and economic worth.
In recent years, samarium metal obtains applying more and more widely in the fields such as the alterant of rare earth permanent-magnetic material, alloy, the scavenging agent of iron and steel and nuclear power.Such as, because the orbital moment in Sm atom and spin moment all have desirable influence to magnetic moment, can be made into SmCo 5, Sm 2co 17and Sm 2fe 17n xdeng rare earth samarium permanent magnet material, industrial and commercial bank of the army of being widely used in ripple device and circulator.Because SmCo type energy density is large, can be made into the sealed valve of magnet valve for Nuclear power plants, reduce and reveal.Samarium permanent magnet material is also widely used in the biologic medical fields such as channels magnetotherpay device, instruments and medical magnetic sheet.The sparking alloy containing samarium is also had to be used for industrial gas lamp, welding gun lighter for ignition and torch portfire etc.; Samarium can deoxidation sulphur removal in steel-making and iron manufacturing process, thus raising steel and ferrum property; Samarium also can be made into rod heats neutron amount material for reactor internal control, absorbs the split speed of thermal neutron with regard to adjustable atom; Sm 2o 3also can be used for the component of the ceramic protective layer on nucleon reaction heap, or for controlling the nuclear reaction in atomic boiler, effect is fine.From the 80-90 age in last century, China produces Sm, and oneself reaches industrialized level, and oneself forms large-scale production, can meet the demand of domestic and international market.Since 2000, the production technology and equipments of China Sm is more perfect, and oneself becomes the big producing country of Sm, and output occupies first of the world.
At present, China's samarium metal main preparation methods is rare earth metal reduction distillation method, namely with Rare Earth Lanthanum (or cerium, praseodymium, neodymium) or lanthanum cerium alloy for reductive agent, Sm 2o 3for raw material 1200 ~ 1250 DEG C of high temperature reduction 90min under lower than the vacuum condition of 1Pa, then condensation, fractionation by distillation obtain samarium metal.The Processes and apparatus of the method is more ripe, own industrial applications.But the method also exists production capacity is little, samarium product unit output is low, when causing demand to increase soon, a lot of platform reduction furnace equipment must be used just to satisfy the demands, cause that facility investment is large, operation is numerous and diverse, productive expense is high and the problem such as management inconvenience.The method is reductive agent with rare earth metal simultaneously, there is the shortcomings such as production cost is high.For above problem, for improving samarium metal output, reduce its production cost, must fast Development samarium metal novel preparation method.Develop Sm in recent years 2o 3high temperature fused salt electrolysis method, calciothermy prepare samarium metal or samarium alloy, but above method all also exists the problems such as quality product is low, production efficiency is low, production cost is high, and cannot industrial applications.
Summary of the invention
The shortcoming and defect that samarium metal is produced and institute exists is prepared for existing rare earth vacuum reduction-distillation method, the present invention proposes a kind of method of direct thermal reduction continuous production samarium metal, namely in dynamic rare gas element or nitrogen, high temperature reduction is carried out, the high temperature samarium steam generated is carried away by the rare gas element that flows or nitrogen, and condensation obtains samarium metal.The invention provides a kind of under " relative vacuum " condition, metallothermics is adopted to refine the method for samarium continuously, achieve the low cost continuous seepage of samarium, solve traditional rare earth vacuum reduction-distillation method and prepare that energy consumption existing for samarium metal is high, the reductive jar life-span is short and the problem such as production cost is high; The inventive method speed of response is fast, and reduction efficiency is high, achieves the continuous seepage of samarium simultaneously.
A kind of method of direct thermal reduction continuous production samarium metal comprises the steps such as pelletizing in pelletizing group, relative vacuum atmosphere reduces continuously, the condensation of high temperature samarium steam.Wherein, pelletizing group refers to Sm 2o 3, reductive agent, interpolation reaction promoter CaO or MgO be mixed in proportion, wherein reductive agent is that Al can replace with Ca or 75Si-Fe alloy, adopts roller machine to be pressed into block or spherical pelletizing; Pelletizing in " relative vacuum " atmosphere continuously reduction refer to pelletizing carried out high temperature reduction reaction in the inert atmosphere or nitrogen atmosphere of flowing, the high temperature samarium steam that reaction generates is carried away by the inert carrier gas that flows or nitrogen immediately.For each reaction interface, reaction interface is have left because the high temperature samarium steam generated is carried by inert carrier gas or nitrogen immediately, so for the high temperature samarium steam in reaction interface, its dividing potential drop is in the negative pressure state lower than 1atm always, i.e. so-called " relative vacuum " state.Therefore, for the atmosphere generated on the reduction reaction interface of samarium steam, just look like that to have taken out vacuum the same for an airtight container, be referred to as " relative vacuum " or " negative relative ", this provides thermodynamic and kinetic conditions more fully for reaction; The condensation of samarium steam refers to and cools being carried the high temperature samarium steam come by rare gas element in high temperature reduction furnace or nitrogen the process obtaining samarium metal ingot fast.
The method of direct thermal reduction continuous production samarium metal of the present invention, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: adopt the one in following batching mode (1) ~ (4):
(1) by Sm 2o 3: Al: CaO in molar ratio 1: (2 ~ 2.4): (0 ~ 3) prepares burden;
(2) by Sm 2o 3: Al: MgO in molar ratio 1: (2 ~ 2.4): 1 batching;
(3) by Al and CaO in (1) or Al and MgO in (2), replace with Ca, wherein, the consumption Al of Ca determines, the Al of 1 mass unit can replace with the calcium of 2.2 times of mass units;
(4) by the Al in (1) or (2), replace with 75Si-Fe alloy, wherein, the Al of 1 mass unit replaces with the Si-Fe alloy that the Si content of 1 mass unit is 75%;
Pelletizing: batch mixing of preparing burden is even, at 100 ~ 250kg/cm 2pressure makes pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the rare gas element or nitrogen atmosphere of flowing, gas flow is 3.0 ~ 6.0m 3/ h, adds high temperature reduction furnace continuously by pelletizing, and reduction temperature is 900 ~ 1600 DEG C, recovery time is 20 ~ 60min, obtains high temperature samarium steam, and mixes with rare gas element or nitrogen, form high-temperature gas mixture, reducing slag is discharged high temperature reduction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
By high temperature samarium steam by flowing rare gas element or nitrogen carry out high temperature reduction furnace, be transported to condenser system by sealing pipeline and carry out condensation, obtain solid metal samarium.
Wherein, with roll squeezer, batching is pressed into block or spherical pelletizing during pelletizing in step 1; Rare gas element in step 2 is the high-purity argon gas that purity is more than or equal to 99.95%; Condensation method in step 3 is direct condensation or atomization condensation, and wherein directly condensation method adopts recirculated water cooling condensation; High temperature reduction furnace in step 2 or step 3 is medium-frequency induction furnace or high temperature resistance furnace.
Described 75Si-Fe alloy is the Si-Fe alloy of Si mass content 75%.
In above-mentioned step, work as Sm 2o 3: Al: CaO prepares burden 1: 2 in molar ratio: during (0 ~ 3) batching pelletizing, according to reaction formula (1) reaction, stoichiometric ratio is mol ratio;
Sm 2O 3(s)+2Al(l)+xCaO＝2Sm(g)+Al 2O 3·xCaO(s)(1)
The one that reaction formula (1) can exist in following several reaction formation is reacted:
Sm 2O 3(s)+2Al(l)＝2Sm(g)+Al 2O 3(s)(1-1)
Sm 2 O 3 ( s ) + 2 Al ( l ) + 1 2 CaO ( s ) = 2 Sm ( g ) + 1 2 2 A l 2 O 3 · CaO ( s ) - - - ( 1 - 2 )
Sm 2O 3(s)+2Al(l)+CaO(s)＝2Sm(g)+Al 2O 3·CaO(s)(1-3)
Sm 2 O 3 ( s ) + 2 Al ( l ) + 12 7 CaO ( s ) = 2 Sm ( g ) + 1 7 7 A l 2 O 3 · 12 CaO ( s ) - - - ( 1 - 4 )
Sm 2O 3(s)+2Al(l)+3CaO(s)＝2Sm(g)+Al 2O 3·3CaO(s)(1-5)
Work as Sm 2o 3: Al: MgO prepare burden in molar ratio 1: 2: 1 batching time, according to reaction formula (2) reaction, stoichiometric ratio is mol ratio;
Sm 2O 3(s)+2Al(l)+MgO(s)＝2Sm(g)+MgO·Al 2O 3(s)(2)
In order to ensure Sm 2o 3reduction effect, the actual dosage of reductive agent Al more excessive than theoretical amount 10% ~ 20% in batching.
Due to high temperature reduction reaction be flowing inert atmosphere in or carry out in nitrogen atmosphere, therefore the high temperature samarium steam generated in pelletizing reaction interface is carried away by the rare gas element that flows or nitrogen immediately, therefore in reaction interface to high temperature samarium steam, all the time the negative pressure state of a dividing potential drop far below 1atm is in, i.e. so-called " relative vacuum " or " negative relative ".Because the high temperature samarium steam generated is carried by inert carrier gas or nitrogen at any time, the reaction formula (1) or reaction formula (2) that greatly promote high temperature reduction generation samarium steam are carried out to the right, drastically increases Sm 2o 3reducing degree and reduction rate.The rate of recovery of samarium metal is greater than 97%.Reducing slag is directly discharged, and achieves the continuous seepage of samarium metal.
The method tool of the present invention's direct thermal reduction continuous production samarium metal has the following advantages:
(1) compared with refining samarium technology with traditional rare earth thermal reduction-distillation method, means that the inventive method have employed " relative vacuum " (also can cry " negative relative "), eliminate vacuum system and vacuum reducing tank, achieve the continuous seepage of samarium metal;
(2) because restoring operation carries out under " relative vacuum " condition, the energy consumption of technical solution of the present invention significantly reduces, because the hot metal samarium steam generated is carried away by the inert carrier gas that flows or nitrogen immediately, greatly will promote reaction (1) and move to positive dirction, significantly enhancing Sm 2o 3reduction generates the dynamic conditions of samarium metal, achieves continuous seepage, shortens reduction cycle; speed of response is fast, and the reduction reaction time, lower than 1h, improves production efficiency; the rate of recovery of samarium metal can reach more than 97%, inertia protection carrier gas simultaneously or nitrogen reusable edible.Therefore, the technology of the present invention is the energy-saving novel environment-friendly process that a kind of low cost prepares samarium metal.
(3) the technology of the present invention reduce with traditional vacuum-distillation method compared with, the present invention adopt use Al, Ca or Si-Fe alloy as reductive agent simultaneously, selectivity add CaO regulate Sm 2o 3the thermodynamic and kinetic conditions of reduction, then pelletizing, significantly improves the controllability that samarium metal generates.Use Al, Ca or Si-Fe alloy as reductive agent simultaneously, replace rare earth reductive agent, significantly reduce the raw materials cost of the production of samarium metal.
(4) simple to operate, equipment more simply requires low, reduces facility investment and running cost.
Embodiment
The Sm that following examples adopt 2o 3purity (massfraction) is greater than 99.0%, CaO and MgO purity (massfraction) is greater than 99.0%, and reductive agent Al and Ca purity are greater than 99.0%, and argon gas is the high-purity argon gas of 99.95%.Medium-frequency induction furnace ruhmkorff coil diameter used is 220mm.
Embodiment 1
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al is 1: 2.2 batching according to mol ratio;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 100kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas atmosphere of flowing, argon flow amount is 6.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1400 DEG C, and the recovery time is 60mins, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 97% of samarium metal.
Embodiment 2
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al is 1: 2.0 batching according to mol ratio;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 150kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 4.5m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1500 DEG C, and the recovery time is 40min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 97.2% of samarium metal.
Embodiment 3
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al is 1: 2.2 batching according to mol ratio;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 250kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 4.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1600 DEG C, and the recovery time is 30min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal ingot casting, the rate of recovery 97.3% of samarium metal.
Embodiment 4
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.2: 0.5 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 250kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the high pure nitrogen gas stream atmosphere of flowing, high pure nitrogen flow is 6.0m 3/ h, adds vertical medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 900 DEG C, and the recovery time is 60min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out vertical medium-frequency induction furnace by flowing High Purity Nitrogen air-flow, is delivered directly to jet atomization device by sealed can road, carries out atomization condensation and obtain samarium metal, the rate of recovery 97.1% of samarium metal.
Embodiment 5
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.2: 0.5 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 100kg/cm 2pressure make block pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 4.5m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1400 DEG C, and the recovery time is 40min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 98.5% of samarium metal.
Embodiment 6
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 0.5 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 200kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 5.5m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1600 DEG C, and the recovery time is 30min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.2% of samarium metal.
Embodiment 7
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 1 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 250kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 6.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 900 DEG C, and the recovery time is 60min, obtains high temperature samarium steam;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.0% of samarium metal.
Embodiment 8
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 1 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 150kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 5.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1200 DEG C, and the recovery time is 40min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.1% of samarium metal.
Embodiment 9
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 1 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 200kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 4.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1600 DEG C, and the recovery time is 20min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.3% of samarium metal.
Embodiment 10
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 12/7 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 200kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 6.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 900 DEG C, and the recovery time is 60min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 98.9% of samarium metal.
Embodiment 11
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 12/7 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 250kg/cm 2pressure make block pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas atmosphere of flowing, argon flow amount is 4.5m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1200 DEG C, and the recovery time is 40min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.3% of samarium metal.
Embodiment 12
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 12/7 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 150kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas atmosphere of flowing, argon flow amount is 3.5m 3/ h, adds high temperature resistance furnace continuously by pelletizing, and reduction temperature is 1600 DEG C, and the recovery time is 30min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged high temperature resistance furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out high temperature resistance furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.0% of samarium metal.
Embodiment 13
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 3 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 150kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 5.5m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 950 DEG C, and the recovery time is 60min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to jet atomization device by sealed can road, carries out atomization condensation and obtain samarium metal, the rate of recovery 99.3% of samarium metal.
Embodiment 14
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 3 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 250kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 4.5m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1250 DEG C, and the recovery time is 30min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.5% of samarium metal.
Embodiment 15
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: CaO according to mol ratio be 1: 2.4: 3 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 200kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 5.5m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1600 DEG C, and the recovery time is 25min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.6% of samarium metal.
Embodiment 16
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: MgO according to mol ratio be 1: 2.2: 1 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 250kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 6.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1000 DEG C, and the recovery time is 50min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.2% of samarium metal.
Embodiment 17
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: MgO according to mol ratio be 1: 2.4: 1 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 200kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 4.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1400 DEG C, and the recovery time is 40min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the rate of recovery 99.5% of samarium metal.
Embodiment 18
The method of direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Al: MgO according to mol ratio be 1: 2.4: 1 batching;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 150kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 5.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1600 DEG C, and the recovery time is 20min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal ingot casting, the rate of recovery 99.5% of samarium metal.
Embodiment 19
Adopt the method for direct thermal reduction continuous production samarium metal, specifically comprise the following steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Ca is 1: 3.3 batching according to mol ratio;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 250kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 5.0m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1450 DEG C, and the recovery time is 40min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the samarium metal rate of recovery 99.7%.
Embodiment 20
Adopt the method for direct thermal reduction continuous production samarium metal, specifically comprise the following steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: Ca is 1: 3.6 batching according to mol ratio;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 200kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 2.5m 3/ h, adds medium-frequency induction furnace continuously by pelletizing, and reduction temperature is 1600 DEG C, and the recovery time is 35min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged medium-frequency induction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out medium-frequency induction furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the samarium metal rate of recovery 99.8%.
Embodiment 21
Adopt the method for direct thermal reduction continuous production samarium metal, specifically comprise the following steps:
Step 1, batching pelletizing:
Batching: by Sm 2o 3: 75Si-Fe alloy: CaO is 1: 2.4: 1 batching according to mol ratio;
Pelletizing: batch mixing of preparing burden is even, adopts roll squeezer at 150kg/cm 2pressure make spherical pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the argon gas gas atmosphere of flowing, argon flow amount is 4.5m 3/ h, adds high temperature resistance furnace continuously by pelletizing, and reduction temperature is 1550 DEG C, and the recovery time is 50min, obtains high temperature samarium steam, and mixes with argon gas, forms high-temperature gas mixture, reducing slag is discharged high temperature resistance furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
High temperature samarium steam is carried out high temperature resistance furnace by flowing argon gas, is delivered directly to samarium drainer by sealed can road, carries out recirculated water cooling condensation and obtain samarium metal, the samarium metal rate of recovery 99.2%.

Claims (4)

1. a method for direct thermal reduction continuous production samarium metal, specifically comprises the steps:
Step 1, batching pelletizing:
Batching: adopt the one in following batching mode (1) ~ (4):
(1) by Sm 2o 3: Al: CaO in molar ratio 1: (2 ~ 2.4): (0 ~ 3) prepares burden;
(2) by Sm 2o 3: Al: MgO in molar ratio 1: (2 ~ 2.4): 1 batching;
(3) by Al and CaO in (1) or Al and MgO in (2), replace with Ca, wherein, the consumption Al of Ca determines, the Al of 1 mass unit can replace with the calcium of 2.2 times of mass units;
(4) by the Al in (1) or (2), replace with 75Si-Fe alloy, wherein, the Al of 1 mass unit replaces with the Si-Fe alloy that the Si content of 1 mass unit is 75%;
Pelletizing: batch mixing of preparing burden is even, at 100 ~ 250kg/cm 2pressure makes pelletizing;
Step 2, pelletizing high temperature reduces continuously:
In the rare gas element or nitrogen atmosphere of flowing, gas flow is 3.0 ~ 6.0m 3/ h, adds high temperature reduction furnace continuously by pelletizing, and reduction temperature is 900 ~ 1600 DEG C, recovery time is 20 ~ 60min, obtains high temperature samarium steam, and mixes with rare gas element or nitrogen, form high-temperature gas mixture, reducing slag is discharged high temperature reduction furnace continuously simultaneously;
Step 3, the condensation of high temperature samarium steam:
By high temperature samarium steam by flowing rare gas element or nitrogen carry out high temperature reduction furnace, be transported to condenser system by sealing pipeline and carry out condensation, obtain solid metal samarium, condensation method be direct condensation or atomization condensation.
2. the method for directly thermal reduction continuous production samarium metal as claimed in claim 1, is characterized in that, with roll squeezer, batching is pressed into block or spherical pelletizing in described step 1 during pelletizing.
3. the method for directly thermal reduction continuous production samarium metal as claimed in claim 1, it is characterized in that, the rare gas element in described step 2 is the high-purity argon gas that purity is more than or equal to 99.95%.
4. the method for directly thermal reduction continuous production samarium metal as claimed in claim 1, is characterized in that, the high temperature reduction furnace in described step 2 or step 3 is medium-frequency induction furnace or high temperature resistance furnace.
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