Metal samarium production device and method
阅读说明：本技术 金属钐生产装置及方法 (Metal samarium production device and method ) 是由 刘玉宝 张先恒 赵二雄 苗旭晨 陈国华 董岳阳 刘冉 康佳 于兵 黄海涛 杨鹏飞 于 2020-07-03 设计创作，主要内容包括：本发明公开了一种金属钐生产装置及方法。该金属钐生产装置包括炉体、炉盖、坩埚支撑装置、坩埚、坩埚中心加热体、坩埚中心加热体电极、套筒、收集器、加热控制系统和真空冷却充气系统；所述加热控制系统设置为能够分步多次对坩埚中心加热体的加热温度进行控制,以避免镧渣与坩埚粘连；所述真空冷却充气系统设置为能够对炉体的内部进行抽真空操作,且能够对炉体的内部进行快速降温,并能够向炉体内部充入惰性气体。本发明的金属钐生产装置可以有效避免镧渣与坩埚粘连。(The invention discloses a device and a method for producing metal samarium. The samarium metal production device comprises a furnace body, a furnace cover, a crucible supporting device, a crucible center heating body electrode, a sleeve, a collector, a heating control system and a vacuum cooling and inflating system; the heating control system is arranged to control the heating temperature of the heating body at the center of the crucible step by step for multiple times so as to avoid the lanthanum slag from being adhered to the crucible; the vacuum cooling and inflating system is arranged to be capable of vacuumizing the interior of the furnace body, rapidly cooling the interior of the furnace body and inflating inert gas into the furnace body. The production device of metal samarium can effectively avoid the adhesion of lanthanum slag and the crucible.)
1. A samarium metal production device is characterized by comprising a furnace body, a furnace cover, a crucible supporting device, a crucible central heating body electrode, a sleeve, a collector, a heating control system and a vacuum cooling and inflating system; the crucible supporting device, the crucible center heating body, the sleeve and the collector are all arranged in the furnace body; the crucible center heating body electrode, the heating control system and the vacuum cooling and inflating system are all arranged outside the furnace body;
the top end of the furnace body is open; the furnace cover is arranged at the top end of the furnace body; the crucible supporting device is welded on the inner side wall of the furnace body; the crucible supporting device and the bottom end of the inner wall of the furnace body are provided with a certain distance; the crucible is arranged above the crucible supporting device and is used for containing a lanthanum and samarium oxide mixed material block; a crucible center heating body is arranged on the crucible supporting device; the crucible center heating body penetrates through the center of the bottom wall of the crucible and extends upwards into the crucible to heat the lanthanum and samarium oxide mixed material block in the crucible; a central hole attached to the crucible central heating body is reserved in the central part of the bottom wall of the crucible, so that the crucible central heating body can penetrate through the bottom wall of the crucible; the crucible center heating body is electrically connected with the crucible center heating body electrode; a sleeve is arranged above the crucible; the collector cover is arranged at the top end of the sleeve; the sleeve is used for supporting and connecting the collector; the collector is used for collecting and condensing samarium steam escaping in the heating process;
the heating control system is arranged to control the heating temperature of the heating body at the center of the crucible step by step for multiple times so as to avoid the lanthanum slag from being adhered to the crucible; one output end of the heating control system is electrically connected with the electrode of the crucible center heating body, so that the control of the crucible center heating body is realized; the other output end of the heating control system is connected with the controlled end of the heating body in the center of the crucible;
the vacuum cooling and inflating system is arranged to be capable of vacuumizing the interior of the furnace body, rapidly cooling the interior of the furnace body and inflating inert gas into the furnace body.
2. The samarium production apparatus of claim 1, wherein the heating control system comprises a control cabinet, a temperature controller disposed within the control cabinet, and a power supply disposed within the control cabinet.
3. The samarium production apparatus of claim 1, wherein the vacuum cooling aeration system comprises a gas circulation cooling apparatus, a vacuum system, and an aeration system; the gas circulating cooling device, the vacuum system and the inflation system are respectively arranged to be capable of independently operating and are not mutually influenced when independently operating;
a vacuum extraction valve is arranged between the gas circulating cooling device and the vacuum system; an inflation valve is arranged between the gas circulating cooling device and the inflation system;
the gas circulating cooling device is arranged to be capable of introducing cooling gas into the furnace body;
the vacuum system is communicated with a pipeline in the gas circulating cooling device and is used for vacuumizing; the vacuum system comprises a vacuum exhaust tube and a vacuum exhaust device arranged at the tail end of the vacuum exhaust tube; the vacuum air exhaust valve is arranged on the vacuum air exhaust pipe;
the gas charging system is communicated with the other pipeline in the gas circulating cooling device and is used for charging inert gas into the furnace body; the inflation system comprises an inflation pipeline, an inflation valve and an inflation device; the gas charging device adopts a steel cylinder filled with inert gas.
4. The apparatus for producing metallic samarium of claim 3 further comprising an air cooling apparatus;
the gas circulating cooling device comprises a circulating gas outlet pipe arranged at the upper part of the side wall of the furnace body and a circulating gas inlet pipe arranged at the lower part of the side wall of the furnace body; and the air cooling device is respectively connected with the circulating air outlet pipe and the circulating air inlet pipe.
5. The apparatus of claim 4, in which the air cooling means comprises an exhaust fan, a heat exchanger, and an exhaust fan; the air inlet end of the exhaust fan is communicated with the circulating air outlet pipe; the air outlet end of the exhaust fan is communicated with the air inlet end of the heat exchanger; an exhaust fan is connected with the air outlet end of the heat exchanger; the air outlet end of the exhaust fan is communicated with the circulating air inlet pipe.
6. The samarium production apparatus of claim 5, wherein the heat exchanger comprises a bellows and a cooling water tube coiled outside the bellows; the cooling water pipe is arranged in such a way that circulating cooling water is introduced into the cooling water pipe;
the circulating air outlet pipe is communicated with the air cooling device and the vacuum system; a gas circulation cooling air inlet valve is arranged at an air inlet of the air cooling device and can be closed when the vacuum system operates;
the air outlet end of the air cooling device is communicated with the circulating air inlet pipe, the air outlet end of the air cooling device is communicated with the inflation pipeline, and the inflation valve is arranged on the inflation pipeline.
7. The samarium production apparatus of claim 1 further comprising a plurality of temperature detection devices for detecting the temperature inside the crucible, the temperature detection devices being disposed at different positions on the upper portion of the mixed lanthanum and samarium oxide block; the output end of the temperature detection device is connected with the input end of the heating control system; the temperature detection device adopts a B-type platinum-rhodium thermocouple temperature sensor.
8. The apparatus for producing metallic samarium of claim 1 further comprising an external heating body and a heat shield;
the outer heating body is sleeved outside the crucible; the controlled end of the external heating body is connected with one output end of the heating control system; the bottom end of the external heating body is arranged on the crucible supporting device;
the outer heating body is a spiral heating pipe;
the external heating body is electrically connected with an electrode of the external heating body; the external heating body electrode is electrically connected with the heating control system;
and a heat shield is arranged on the outer side of the outer heating body and is set to reduce the outward radiation of heat of the outer heating body in the heating process.
9. A method for producing metal samarium by using the metal samarium production apparatus of any one of claims 1 to 8, comprising the steps of:
(1) the first stage is as follows: material preparation
Grinding a massive lanthanum ingot into lanthanum scraps of 0.5-5 mm by using a planer or a milling machine, uniformly mixing the lanthanum scraps and samarium oxide powder by using a V-shaped mixer, and pressing the uniformly mixed powder by using a four-column press to obtain a cylindrical material block with the diameter of 5-15 cm and the thickness of 2-8 cm and a truncated cone-shaped material block with the upper part with the diameter of 2-8 cm, the lower part with the diameter of 5-15 cm and the thickness of 2-8 cm;
(2) and a second stage: charging furnace
Paving a layer of truncated cone-shaped material blocks at the bottom of the crucible, enabling one end with a small diameter to face downwards, uniformly placing cylindrical material blocks on the upper part, placing a sleeve and a collector, covering a furnace cover for vacuumizing operation, and enabling the vacuum degree to reach 10-1～3×10-1When Pa is needed, high-purity argon is filled to the relative vacuum degree of-0.10-0.01 MPPa, and then the vacuum is pumped again to 10-1～3×10-1Pa below;
(3) and a third stage: reduction of
Under the condition of continuous vacuum pumping, the lanthanum and samarium oxide mixed material block is sequentially heated according to the following heating method:
a) heating from 15-25 ℃ to 250-450 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 20-80 min;
b) heating to 550-750 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 50-150 min;
c) heating to 750-950 ℃ at a heating rate of 8-12 ℃/min, and keeping the temperature for 50-150 min;
d) heating to 900-1050 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 100-200 min;
e) heating to 1050-1350 ℃ at a heating rate of 3-7 ℃/min, and preserving heat for 300-500 min;
f) heating to 1300-1500 ℃ at a heating rate of 3-7 ℃/min, and keeping the temperature for 50-150 min;
g) heating to 1400-1600 ℃ at a heating rate of 3-7 ℃/min, and keeping the temperature for 50-150 min;
(4) a fourth stage: cooling and tapping
Keeping the high vacuum state for cooling, when the temperature is reduced to 900-1100 ℃, opening an inflation valve, filling high-purity argon until the relative vacuum degree is-0.05-0.01 MPa, then starting a gas circulating cooling device for forced air cooling for 20-40 min, namely reducing the temperature to 80-120 ℃, and stopping the forced air cooling; opening a furnace cover after vacuum breaking, taking out the collector, taking out the crucible, inverting, taking out lanthanum slag, and taking out the lanthanum slag for 5-25 min; the yield of the obtained product is more than or equal to 85 percent.
10. A method for producing metal samarium by using the metal samarium production apparatus of any one of claims 1 to 8, comprising the steps of:
(1) the first stage is as follows: material preparation
Grinding a massive lanthanum ingot into lanthanum scraps of 1-3mm by using a planer or a milling machine, uniformly mixing the lanthanum scraps and samarium oxide powder by using a V-shaped mixer, performing compression molding on the uniformly mixed powder by using a four-column press machine, and pressing into a cylindrical material block with the diameter of 8-12 cm and the thickness of 4-6 cm and a truncated cone-shaped material block with the upper part diameter of 4-6 cm, the lower part diameter of 8-12 cm and the thickness of 4-6 cm;
(2) and a second stage: charging furnace
Paving a layer of round table-shaped material blocks at the bottom of the crucible, enabling one end with a small diameter to face downwards, uniformly placing cylindrical material blocks on the upper part, placing a sleeve and a collector, covering a furnace cover for vacuumizing operation, and enabling the vacuum degree to reach 1.5 × 10-1～2.5×10-1When Pa is needed, high-purity argon is filled to the relative vacuum degree of-0.06 to-0.04 MPa, and then the vacuum is pumped again to 1.5 × 10-1～2.5×10-1Pa below;
(3) and a third stage: reduction of
Under the condition of continuous vacuum pumping, the lanthanum and samarium oxide mixed material block is sequentially heated according to the following heating method:
a) heating from 15-25 ℃ to 350-400 ℃ at a heating rate of 9-10 ℃/min, and keeping the temperature for 30-50 min;
b) heating to 650-700 ℃ at a heating rate of 9-10 ℃/min, and keeping the temperature for 60-90 min;
c) heating to 850-900 ℃ at the heating rate of 8-9 ℃/min, and keeping the temperature for 60-90 min;
d) heating to 980-1000 ℃ at a heating rate of 6-8 ℃/min, and preserving heat for 150-180 min;
e) heating to 1150-1300 ℃ at a heating rate of 6-7 ℃/min, and keeping the temperature for 360-480 min;
f) heating to 1380-1450 ℃ at a heating rate of 5-6 ℃/min, and keeping the temperature for 60-100 min;
g) heating to 1480-1550 ℃ at the heating rate of 5-6 ℃/min, and keeping the temperature for 60-100 min;
(4) a fourth stage: cooling and tapping
Keeping the high vacuum state for cooling, when the temperature is reduced to 950-1050 ℃, opening an inflation valve, filling high-purity argon to the relative vacuum degree of-0.04-0.02 MPa, starting a gas circulating cooling device for forced air cooling for 25-35 min, namely reducing the temperature to 95-105 ℃, and stopping the forced air cooling; opening a furnace cover after vacuum breaking, taking out the collector, taking out the crucible, inverting, taking out lanthanum slag, and taking out the lanthanum slag for 15-20 min; the yield of the obtained product is more than or equal to 88 percent.
Technical Field
The invention relates to a device and a method for producing metal samarium.
Background
The rare earth metal is widely applied to various functional materials, such as high-performance rare earth permanent magnet materials, magnetostrictive materials, magnetic refrigeration materials, rare earth hydrogen storage materials, rare earth luminescent materials and the like. However, without a rare earth raw material of sufficient purity, it is impossible to produce a functional material having excellent properties. The new rare earth material produced by high-purity rare earth metal and the compound thereof plays an important role in modern high and new technology and military technology.
The high-purity metal samarium can be used for producing a magnetic material samarium cobalt (Sm-Co) alloy and can also be used for absorbing thermal neutrons in a nuclear reactor.
CN109055768A discloses a vacuum furnace for preparing high-purity metal samarium and a method for preparing the high-purity metal samarium by using the vacuum furnace; the vacuum furnace for preparing high-purity samarium metal comprises a condensation crucible, a crucible and a separator, wherein the condensation crucible, the separator and the crucible are positioned in the vacuum furnace and sequentially comprise the condensation crucible, the separator and the crucible from top to bottom, and the separator is positioned in the middle of the crucible or above the crucible; the method utilizes the characteristic that vapor pressure of metal samarium is higher than vapor pressure of metal lanthanum and the like, and utilizes phase-change heat of rare earth metal vapor to ensure that the metal samarium is subjected to multiple times of evaporation and condensation in a separator to separate impurities with low vapor pressure, thereby preparing the high-purity metal samarium at one time. However, the above method is prone to problems of uneven heating, difficult discharge and low production efficiency.
Because of the high vapor pressure of the rare earth metal Sm, early researchers adopted the traditional method of oxide metal thermal reduction when preparing samarium metal, but the results were unsatisfactory. High-activity alkaline earth metal and alkali metal are used as reducing agents in the aspect of metal thermal reduction of samarium oxide, but pure metal samarium cannot be obtained; lanthanum is adopted as a reducing agent to obtain relatively pure metal samarium, and the yield is relatively high.
However, the following problems generally exist in the actual operation process when lanthanum is used as a reducing agent to produce samarium metal: 1) in the heating process, only the outer wall of the crucible is heated, and the material block in the crucible is not uniformly heated, so that the reduction distillation time is long; 2) after the production of the metal samarium is finished, the metal samarium is naturally cooled during cooling, the cooling speed is slow, the waste of cooling time is caused, and the efficiency is low; 3) lanthanum slag is easy to adhere to a crucible, so that the problems of difficult discharging, high labor intensity of manual discharging and the like are caused, and the production efficiency is low.
Therefore, in order to solve the above technical problems, a new apparatus and method for producing samarium metal are needed.
Disclosure of Invention
In view of this, an object of the present invention is to provide a samarium producing apparatus, which can effectively prevent lanthanum slag from adhering to a crucible. The invention also aims to provide a production method of metal samarium, which can effectively avoid lanthanum slag from being adhered to a crucible, improve the cooling rate of a furnace body and greatly shorten the discharging time.
The invention adopts the following technical scheme to achieve the purpose.
The invention provides a samarium metal production device, which comprises a furnace body, a furnace cover, a crucible supporting device, a crucible central heating body electrode, a sleeve, a collector, a heating control system and a vacuum cooling and inflating system, wherein the furnace body is arranged on the furnace cover; the crucible supporting device, the crucible center heating body, the sleeve and the collector are all arranged in the furnace body; the crucible center heating body electrode, the heating control system and the vacuum cooling and inflating system are all arranged outside the furnace body;
the top end of the furnace body is open; the furnace cover is arranged at the top end of the furnace body; the crucible supporting device is welded on the inner side wall of the furnace body; the crucible supporting device and the bottom end of the inner wall of the furnace body are provided with a certain distance; the crucible is arranged above the crucible supporting device and is used for containing a lanthanum and samarium oxide mixed material block; a crucible center heating body is arranged on the crucible supporting device; the crucible center heating body penetrates through the center of the bottom wall of the crucible and extends upwards into the crucible to heat the lanthanum and samarium oxide mixed material block in the crucible; a central hole attached to the crucible central heating body is reserved in the central part of the bottom wall of the crucible, so that the crucible central heating body can penetrate through the bottom wall of the crucible; the crucible center heating body is electrically connected with the crucible center heating body electrode; a sleeve is arranged above the crucible; the collector cover is arranged at the top end of the sleeve; the sleeve is used for supporting and connecting the collector; the collector is used for collecting and condensing samarium steam escaping in the heating process;
the heating control system is arranged to control the heating temperature of the heating body at the center of the crucible step by step for multiple times so as to avoid the lanthanum slag from being adhered to the crucible; one output end of the heating control system is electrically connected with the electrode of the crucible center heating body, so that the control of the crucible center heating body is realized; the other output end of the heating control system is connected with the controlled end of the heating body in the center of the crucible;
the vacuum cooling and inflating system is arranged to be capable of vacuumizing the interior of the furnace body, rapidly cooling the interior of the furnace body and inflating inert gas into the furnace body.
According to the samarium production device, preferably, the heating control system comprises a control cabinet, a temperature controller arranged in the control cabinet and a power supply arranged in the control cabinet.
According to the samarium production device, preferably, the vacuum cooling and aerating system comprises a gas circulating cooling device, a vacuum system and an aerating system; the gas circulating cooling device, the vacuum system and the inflation system are respectively arranged to be capable of independently operating and are not mutually influenced when independently operating;
a vacuum extraction valve is arranged between the gas circulating cooling device and the vacuum system; an inflation valve is arranged between the gas circulating cooling device and the inflation system;
the gas circulating cooling device is arranged to be capable of introducing cooling gas into the furnace body;
the vacuum system is communicated with a pipeline in the gas circulating cooling device and is used for vacuumizing; the vacuum system comprises a vacuum exhaust tube and a vacuum exhaust device arranged at the tail end of the vacuum exhaust tube; the vacuum air exhaust valve is arranged on the vacuum air exhaust pipe;
the gas charging system is communicated with the other pipeline in the gas circulating cooling device and is used for charging inert gas into the furnace body; the inflation system comprises an inflation pipeline, an inflation valve and an inflation device; the gas charging device adopts a steel cylinder filled with inert gas.
According to the samarium production device, preferably, the samarium production device further comprises an air cooling device;
the gas circulating cooling device comprises a circulating gas outlet pipe arranged at the upper part of the side wall of the furnace body and a circulating gas inlet pipe arranged at the lower part of the side wall of the furnace body; and the air cooling device is respectively connected with the circulating air outlet pipe and the circulating air inlet pipe.
According to the samarium production device, preferably, the air cooling device comprises an exhaust fan, a heat exchanger and an exhaust fan; the air inlet end of the exhaust fan is communicated with the circulating air outlet pipe; the air outlet end of the exhaust fan is communicated with the air inlet end of the heat exchanger; an exhaust fan is connected with the air outlet end of the heat exchanger; the air outlet end of the exhaust fan is communicated with the circulating air inlet pipe.
According to the samarium production device of the present invention, preferably, the heat exchanger comprises an air box and a cooling water pipe coiled outside the air box; the cooling water pipe is arranged in such a way that circulating cooling water is introduced into the cooling water pipe;
the circulating air outlet pipe is communicated with the air cooling device and the vacuum system; a gas circulation cooling air inlet valve is arranged at an air inlet of the air cooling device and can be closed when the vacuum system operates;
the air outlet end of the air cooling device is communicated with the circulating air inlet pipe, the air outlet end of the air cooling device is communicated with the inflation pipeline, and the inflation valve is arranged on the inflation pipeline.
According to the samarium production device disclosed by the invention, preferably, the samarium production device further comprises a plurality of temperature detection devices for detecting the temperature inside the crucible, wherein the temperature detection devices are arranged at different positions on the upper part of the lanthanum and samarium oxide mixed material block; the output end of the temperature detection device is connected with the input end of the heating control system; the temperature detection device adopts a B-type platinum-rhodium thermocouple temperature sensor.
According to the samarium production device, preferably, the samarium production device further comprises an external heating body and a heat shield;
the outer heating body is sleeved outside the crucible; the controlled end of the external heating body is connected with one output end of the heating control system; the bottom end of the external heating body is arranged on the crucible supporting device;
the outer heating body is a spiral heating pipe;
the external heating body is electrically connected with an electrode of the external heating body; the external heating body electrode is electrically connected with the heating control system;
and a heat shield is arranged on the outer side of the outer heating body and is set to reduce the outward radiation of heat of the outer heating body in the heating process.
The invention also provides a method for producing the metal samarium by adopting the metal samarium production device, which comprises the following steps:
(1) the first stage is as follows: material preparation
Grinding a massive lanthanum ingot into lanthanum scraps of 0.5-5 mm by using a planer or a milling machine, uniformly mixing the lanthanum scraps and samarium oxide powder by using a V-shaped mixer, and pressing the uniformly mixed powder by using a four-column press to obtain a cylindrical material block with the diameter of 5-15 cm and the thickness of 2-8 cm and a truncated cone-shaped material block with the upper part with the diameter of 2-8 cm, the lower part with the diameter of 5-15 cm and the thickness of 2-8 cm;
(2) and a second stage: charging furnace
Paving a layer of truncated cone-shaped material blocks at the bottom of the crucible, enabling one end with a small diameter to face downwards, uniformly placing cylindrical material blocks on the upper part, placing a sleeve and a collector, covering a furnace cover for vacuumizing operation, and enabling the vacuum degree to reach 10-1～3×10-1When Pa is needed, high-purity argon is filled to the relative vacuum degree of-0.10 to-0.01 MPa, and then the vacuum is pumped again to 10 DEG-1～3×10-1Pa below;
(3) and a third stage: reduction of
Under the condition of continuous vacuum pumping, the lanthanum and samarium oxide mixed material block is sequentially heated according to the following heating method:
a) heating from 15-25 ℃ to 250-450 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 20-80 min;
b) heating to 550-750 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 50-150 min;
c) heating to 750-950 ℃ at a heating rate of 8-12 ℃/min, and keeping the temperature for 50-150 min;
d) heating to 900-1050 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 100-200 min;
e) heating to 1050-1350 ℃ at a heating rate of 3-7 ℃/min, and preserving heat for 300-500 min;
f) heating to 1300-1500 ℃ at a heating rate of 3-7 ℃/min, and keeping the temperature for 50-150 min;
g) heating to 1400-1600 ℃ at a heating rate of 3-7 ℃/min, and keeping the temperature for 50-150 min;
(4) a fourth stage: cooling and tapping
Keeping the high vacuum state for cooling, when the temperature is reduced to 900-1100 ℃, opening an inflation valve, filling high-purity argon until the relative vacuum degree is-0.05-0.01 MPa, then starting a gas circulating cooling device for forced air cooling for 20-40 min, namely reducing the temperature to 80-120 ℃, and stopping the forced air cooling; opening a furnace cover after vacuum breaking, taking out the collector, taking out the crucible, inverting, taking out lanthanum slag, and taking out the lanthanum slag for 5-25 min; the yield of the obtained product is more than or equal to 85 percent.
The invention also provides a method for producing the metal samarium by adopting the metal samarium production device, which comprises the following steps:
(1) the first stage is as follows: material preparation
Grinding a massive lanthanum ingot into lanthanum scraps of 1-3mm by using a planer or a milling machine, uniformly mixing the lanthanum scraps and samarium oxide powder by using a V-shaped mixer, performing compression molding on the uniformly mixed powder by using a four-column press machine, and pressing into a cylindrical material block with the diameter of 8-12 cm and the thickness of 4-6 cm and a truncated cone-shaped material block with the upper part diameter of 4-6 cm, the lower part diameter of 8-12 cm and the thickness of 4-6 cm;
(2) and a second stage: charging furnace
Paving a layer of round table-shaped material blocks at the bottom of the crucible, enabling one end with a small diameter to face downwards, uniformly placing cylindrical material blocks on the upper part, placing a sleeve and a collector, covering a furnace cover for vacuumizing operation, and enabling the vacuum degree to reach 1.5 × 10-1～2.5×10-1When Pa is needed, high-purity argon is filled to the relative vacuum degree of-0.06 to-0.04 MPa, and then the vacuum is pumped again to 1.5 × 10-1～2.5×10-1Pa below;
(3) and a third stage: reduction of
Under the condition of continuous vacuum pumping, the lanthanum and samarium oxide mixed material block is sequentially heated according to the following heating method:
a) heating from 15-25 ℃ to 350-400 ℃ at a heating rate of 9-10 ℃/min, and keeping the temperature for 30-50 min;
b) heating to 650-700 ℃ at a heating rate of 9-10 ℃/min, and keeping the temperature for 60-90 min;
c) heating to 850-900 ℃ at the heating rate of 8-9 ℃/min, and keeping the temperature for 60-90 min;
d) heating to 980-1000 ℃ at a heating rate of 6-8 ℃/min, and preserving heat for 150-180 min;
e) heating to 1150-1300 ℃ at a heating rate of 6-7 ℃/min, and keeping the temperature for 360-480 min;
f) heating to 1380-1450 ℃ at a heating rate of 5-6 ℃/min, and keeping the temperature for 60-100 min;
g) heating to 1480-1550 ℃ at the heating rate of 5-6 ℃/min, and keeping the temperature for 60-100 min;
(4) a fourth stage: cooling and tapping
Keeping the high vacuum state for cooling, when the temperature is reduced to 950-1050 ℃, opening an inflation valve, filling high-purity argon to the relative vacuum degree of-0.04-0.02 MPa, starting a gas circulating cooling device for forced air cooling for 25-35 min, namely reducing the temperature to 95-105 ℃, and stopping the forced air cooling; opening a furnace cover after vacuum breaking, taking out the collector, taking out the crucible, inverting, taking out lanthanum slag, and taking out the lanthanum slag for 15-20 min; the yield of the obtained product is more than or equal to 88 percent.
The production device of metal samarium can effectively avoid the adhesion of lanthanum slag and the crucible. The production method of the metal samarium can effectively avoid the lanthanum slag from being adhered to the crucible, improve the cooling rate of the furnace body and shorten the discharging time.
Drawings
Fig. 1 is a schematic structural view of a samarium producing apparatus of the present invention.
Fig. 2 is a schematic structural diagram of an air cooling device according to the present invention.
Fig. 3 is a schematic structural view of another samarium production apparatus according to the present invention.
The reference numerals are explained below:
1-furnace cover; 2-furnace body; 3-a gas circulation cooling device; 31-an exhaust fan; 32-a heat exchanger; 33-an exhaust fan; 4-a vacuum system; 5-circulating air inlet pipe; 6-circulating an air outlet pipe; 7-vacuum extraction valve; 8-gas circulation cooling intake valve; 9-a heat shield; 10-external heating body; 11-crucible support means; 12-a central heating body of the crucible; 13-a collector; 14-a sleeve; 15-a crucible; a 16-lanthanum and samarium oxide mixed material block; 17-external heater electrode; 18-a crucible central heater electrode; 19-a heating control system; 20-vacuum air extraction pipe; 21-gas circulation cooling gas outlet valve; 22-an inflation conduit; 23-a gas-filled valve; 25-inflation system.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
< apparatus for producing metallic samarium >
The invention provides a samarium production device which comprises a furnace body, a furnace cover, a crucible supporting device, a crucible central heating body electrode, a sleeve, a collector, a heating control system and a vacuum cooling and inflating system. Optionally, an air cooling device, a temperature detection device, an external heating body and/or a heat shield are also included.
In the invention, the crucible supporting device, the crucible center heating body, the sleeve and the collector are arranged in the furnace body. The heating body electrode, the heating control system and the vacuum cooling and inflating system in the center of the crucible are all arranged outside the furnace body.
In the present invention, the top end of the furnace body is open. The furnace cover is arranged at the top end of the furnace body. The crucible supporting device is welded on the inner side wall of the furnace body. The crucible supporting device and the bottom end of the inner wall of the furnace body are provided with a certain distance. The crucible is arranged above the crucible supporting device and is used for containing a lanthanum and samarium oxide mixed material block. The crucible supporting device is provided with a crucible center heating body. The central heating body of the crucible penetrates through the central part of the bottom wall of the crucible and extends upwards into the crucible to heat the lanthanum and samarium oxide mixed material block in the crucible. A middle hole attached to the central heating body of the crucible is reserved in the central part of the bottom wall of the crucible, and therefore the central heating body of the crucible can penetrate through the bottom wall of the crucible. The crucible center heating body is connected with the crucible center heating body electrode in an electric connection mode. A sleeve is arranged above the crucible. The collector cover is arranged at the top end of the sleeve. The sleeve is used for supporting and connecting the collector. The collector is used for collecting and condensing samarium steam escaping in the heating process. The central heating body of the crucible can ensure that heat is diffused from the central part of the crucible to the periphery, and the lanthanum and samarium oxide mixed material block in the crucible can be uniformly heated.
In the present invention, preferably, the crucible center heating body is in a circular truncated cone shape or a cone shape, and the cross-sectional area of the crucible center heating body is sequentially increased from top to bottom (the upper part is thin and the lower part is thick), so that smooth discharging can be ensured. More preferably, the crucible center heating body is in a circular truncated cone shape, and the cross-sectional area of the crucible center heating body is sequentially increased from top to bottom (the upper part is thin and the lower part is thick), so that smooth discharging can be ensured.
In the present invention, preferably, the sleeve has a circular truncated cone shape or a conical shape; the cross section area of the sleeve is increased from top to bottom (the upper part is small and the lower part is large); the bottom end of the sleeve is matched with the top end of the crucible, and the top end of the sleeve is matched with the shape of the collector. More preferably, the sleeve is in the shape of a circular truncated cone; the cross section area of the sleeve is increased from top to bottom (the upper part is small and the lower part is large); the bottom end of the sleeve is matched with the top end of the crucible, and the top end of the sleeve is matched with the shape of the collector.
In the invention, the heating control system is arranged to control the heating temperature of the heating body in the center of the crucible step by step for multiple times so as to avoid the adhesion of lanthanum slag and the crucible. One output end of the heating control system is electrically connected with the electrode of the crucible center heating body, so that the control of the crucible center heating body is realized; the other output end of the heating control system is connected with the controlled end of the heating body in the center of the crucible.
In the present invention, the electrical connection may be a wire, or may be other electrical connection.
In the invention, the vacuum cooling and inflating system is arranged to vacuumize the interior of the furnace body, quickly cool the interior of the furnace body and fill inert gas into the furnace body.
The production device of metal samarium can effectively avoid the adhesion of lanthanum slag and the crucible. In addition, the metal samarium production device can improve the cooling rate of the furnace body and greatly shorten the discharging time.
In the present invention, the heating control system may include a control cabinet, a temperature controller disposed within the control cabinet, and a power source disposed within the control cabinet. The temperature controller is preferably a temperature controller of the prior art. Preferably, the temperature controller includes a temperature acquisition unit, a temperature control unit, and a voltage control unit. Wherein the acquisition unit can acquire temperature-detecting device's detected signal to feed back detected signal to the temperature control unit. The temperature control unit is capable of outputting a drive signal. The voltage control unit can generate corresponding driving voltage according to the driving signal output by the temperature control unit, and then controls the heating temperature of the central heating body and/or the outer heating body of the crucible.
In the present invention, the vacuum cooling aeration system may include a gas circulation cooling device, a vacuum system, and an aeration system. The gas circulation cooling device, the vacuum system and the inflation system are respectively arranged to be capable of independently operating and are not affected when the gas circulation cooling device, the vacuum system and the inflation system are independently operated. A vacuum extraction valve is arranged between the gas circulation cooling device and the vacuum system. An inflation valve is arranged between the gas circulating cooling device and the inflation system. The gas circulation cooling device is arranged on the side wall of the furnace body and used for introducing cooling gas into the furnace body. The vacuum system is communicated with a pipeline in the gas circulation cooling device and is used for vacuumizing operation. Preferably, the vacuum system comprises a vacuum exhaust tube and a vacuum exhaust device connected and arranged at the end of the vacuum exhaust tube. The vacuum air exhaust valve is arranged on the vacuum air exhaust pipe. The gas charging system is communicated with another pipeline in the gas circulating cooling device and is used for charging inert gas into the furnace body. The inflation system comprises an inflation pipeline, an inflation valve and an inflation device. The gas charging device can adopt a steel cylinder filled with inert gas, and can also adopt other gas charging devices. Preferably, the gas charging device is a steel cylinder containing inert gas. The steel cylinder is filled with high-purity argon or argon.
In the invention, the samarium metal production device can also comprise an air cooling device.
In the present invention, the gas circulation cooling device preferably includes a circulation outlet pipe communicated with the upper portion of the side wall of the furnace body, a circulation inlet pipe communicated with the lower portion of the side wall of the furnace body, and an air cooling device connected to the circulation outlet pipe and the circulation inlet pipe, respectively.
In the present invention, the air cooling device preferably includes an exhaust fan, a heat exchanger, and an exhaust fan. The air inlet end of the exhaust fan is communicated with the circulating air outlet pipe; the air outlet end of the exhaust fan is communicated with the air inlet end of the heat exchanger; an exhaust fan is connected with the air outlet end of the heat exchanger; the air outlet end of the exhaust fan is communicated with the circulating air inlet pipe.
In the present invention, the heat exchanger preferably includes an air box and a cooling water pipe coiled outside the air box; the cooling water pipe is arranged in a way that circulating cooling water is introduced into the cooling water pipe.
In the invention, the circulating air outlet pipe is communicated with the air cooling device; the circulating air outlet pipe is communicated with the vacuum system; the communication may be achieved by a three-way joint. The air inlet of the air cooling device is provided with a gas circulation cooling air inlet valve, and the gas circulation cooling air inlet valve can be closed when the vacuum system operates, so that the gas circulation cooling air inlet valve and the vacuum system are not influenced by each other.
In the invention, the air outlet end of the air cooling device is communicated with the circulating air inlet pipe; the air outlet end of the air cooling device is communicated with the inflation pipeline; the communication may be achieved by a three-way joint. The inflation valve is arranged on the inflation pipeline, and the gas circulation cooling device and the inflation system can be prevented from being influenced by controlling the on-off of the inflation valve.
In the invention, the samarium metal production device can also comprise a temperature detection device. And a plurality of temperature detection devices for detecting the internal temperature of the crucible are arranged at different positions on the upper part of the lanthanum and samarium oxide mixed material block. The output end of the temperature detection device is connected with the input end of the heating control system.
In the invention, the temperature detection device can adopt a thermocouple sensor, and preferably adopts a B-type platinum-rhodium thermocouple temperature sensor. The B-type thermocouple is a noble metal thermocouple, the diameter of a thermocouple wire is specified to be bai0.5mm, the allowable deviation is minus 0.015mm, the famous du-meaning chemical components of a positive electrode (BP) of the B-type thermocouple are platinum-rhodium alloy, wherein the rhodium content is 30%, the platinum content is 70%, a negative electrode (BN) of the B-type thermocouple is platinum-rhodium alloy, and the B-type thermocouple is commonly called a double platinum-rhodium thermocouple because the rhodium content is 6%. The thermocouple has the maximum long-term use temperature of 1600 ℃ and the maximum short-term use temperature of 1800 ℃, and can be completely suitable for temperature detection in the invention. The thermocouple sensors are distributed at different positions on the upper part of the material block, so that the uniformity of the monitored temperature can be ensured.
The samarium production device can also comprise an external heating body and a heat shield. The setting of outer heating body can further improve the even degree that lanthanum and samaric oxide mixing material piece heated. In addition, the central heating body and the outer heating body of the crucible are respectively controlled by a heating control system, so that the heating temperature of the lanthanum and samarium oxide mixed material block is more uniform, and the heating speed is higher. The temperature detection device feeds back temperature information to the heating control system, and matches the output power of the central heating body and the outer heating body of the crucible according to the feedback.
In the invention, the external heating body is sleeved outside the crucible. The controlled end of the external heating body is connected with the other output end of the heating control system. The bottom end of the external heating body is arranged on the crucible supporting device. Preferably, the outer heating body is arranged as a coiled heating tube. The external heating body is connected with the external heating body electrode in an electric connection mode. The external heating body electrode is electrically connected with the heating control system. The electrical connection mode may be a wire or other electrical connection modes.
In the invention, the heat shield is arranged on the outer side of the outer heating body and is used for reducing the outward radiation of heat in the heating process of the outer heating body.
< method for producing metallic samarium >
The invention provides a method for producing metal samarium, which comprises the following steps: (1) the first stage is as follows: preparing materials; (2) and a second stage: charging; (3) and a third stage: reduction; (4) a fourth stage: and (6) cooling and discharging.
In the step (1), the massive lanthanum ingot is ground into lanthanum scraps by a planer or a milling machine, the lanthanum scraps and the samarium oxide powder are uniformly mixed by a V-shaped mixer, the uniformly mixed powder is pressed by a four-column press to be pressed into a cylindrical material block and a round table material block. The size of the lanthanum dust is preferably 0.5-5 mm, and more preferably 1-3 mm. The size of the cylindrical mass is preferably: the diameter is 5-15 cm, and the thickness is 2-8 cm; the size of the cylindrical mass is more preferably: the diameter is 8-12 cm and the thickness is 4-6 cm. The size of the cylindrical mass is preferably: the diameter of the upper part is 2-8 cm, the diameter of the lower part is 5-15 cm, and the thickness is 2-8 cm; the size of the cylindrical mass is more preferably: the diameter of the upper part is 4-6 cm, the diameter of the lower part is 8-12 cm, and the thickness is 4-6 cm. According to an embodiment of the invention, a block lanthanum ingot is ground into lanthanum scraps of 0.5-5 mm by a planer or a milling machine, the lanthanum scraps and samarium oxide powder are uniformly mixed by a V-shaped mixer, the uniformly mixed powder is pressed by a four-column press machine to form a cylindrical material block with the diameter of 5-15 cm and the thickness of 2-8 cm and a truncated cone-shaped material block with the upper part with the diameter of 2-8 cm and the lower part with the diameter of 5-15 cm and the thickness of 2-8 cm.
In the step (2), a layer of truncated cone-shaped material blocks is paved at the bottom of the crucible firstly, the end with small diameter faces downwards, the cylindrical material blocks are evenly placed on the upper part, the sleeve and the collector are placed, the furnace cover is covered for vacuumizing operation, and the vacuum degree reaches 10-1～3×10-1When Pa is needed, high-purity argon is filled to the relative vacuum degree of-0.10 to-0.01 MPa, and then the vacuum is pumped again to 10 DEG-1～3×10-1Preferably, a layer of truncated cone-shaped material blocks is paved at the bottom of the crucible, the end with the small diameter faces downwards, the cylindrical material blocks are evenly placed at the upper part, a sleeve and a collector are placed, a furnace cover is covered, the vacuumizing operation is carried out, and the vacuum degree reaches 1.5 × 10-1～2.5×10-1When Pa is needed, high-purity argon is filled to-0.06-0.04 MPa, and then the vacuum is pumped again to 1.5 × 10-1～2.5×10-1Pa or less. More preferably, a layer of truncated cone-shaped material blocks is paved at the bottom of the crucible firstly, one end with small diameter faces downwards, cylindrical material blocks are evenly placed at the upper part of the crucible, a sleeve and a collector are placed, and the furnace is coveredThe cover is vacuumized to reach a vacuum degree of 1.8 × 10-1～2.2×10-1When Pa is needed, high-purity argon is filled to the relative vacuum degree of-0.055 to-0.045 MPa, and then the vacuum is pumped again to 1.8 × 10-1～2.2×10-1Pa or less.
In the step (3), under the condition of continuous vacuum pumping, the lanthanum and samarium oxide mixed material block is sequentially heated according to the following heating method:
a) heating from 15-25 ℃ to 250-450 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 20-80 min;
b) heating to 550-750 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 50-150 min;
c) heating to 750-950 ℃ at a heating rate of 8-12 ℃/min, and keeping the temperature for 50-150 min;
d) heating to 900-1050 ℃ at a heating rate of 6-10 ℃/min, and keeping the temperature for 100-200 min;
e) heating to 1050-1350 ℃ at a heating rate of 3-7 ℃/min, and preserving heat for 300-500 min;
f) heating to 1300-1500 ℃ at a heating rate of 3-7 ℃/min, and keeping the temperature for 50-150 min;
g) heating to 1400-1600 ℃ at a heating rate of 3-7 ℃/min, and keeping the temperature for 50-150 min.
In the step (3) of the present invention, the temperature increase rate in a) is preferably 8 to 10 ℃/min, and more preferably 9 to 10 ℃/min. a) The heat preservation time in (3) is preferably 30-60 min, and more preferably 30-50 min.
In the step (3), the heating rate in b) is preferably 8-10 ℃/min, and more preferably 9-10 ℃/min. b) The heat preservation time in (3) is preferably 60-120 min, and more preferably 60-90 min.
In the step (3), the temperature rise rate in c) is preferably 8-10 ℃/min, and more preferably 8-9 ℃/min. c) The heat preservation time in (3) is preferably 60-120 min, and more preferably 60-90 min.
In the step (3) of the present invention, the temperature increase rate in d) is preferably 5 to 8 ℃/min, and more preferably 6 to 8 ℃/min. d) The heat preservation time in (3) is preferably 120-180 min, and more preferably 150-180 min.
In the step (3), the temperature rise rate in e) is preferably 5-8 ℃/min, and more preferably 6-7 ℃/min. e) The heat preservation time in (3) is preferably 360-500 min, and more preferably 360-480 min.
In the step (3) of the present invention, the temperature increase rate in f) is preferably 5 to 8 ℃/min, more preferably 5 to 6 ℃/min. f) The heat preservation time in (3) is preferably 60-120 min, and more preferably 60-100 min.
In the step (3) of the present invention, the temperature increase rate in g) is preferably 5 to 8 ℃/min, more preferably 5 to 6 ℃/min. g) The heat preservation time in (3) is preferably 60-120 min, and more preferably 60-100 min.
Preferably, under the condition of continuous vacuum pumping, the temperature of the lanthanum and samarium oxide mixed material block is sequentially increased according to the following temperature increasing method:
a) heating from 15-25 ℃ to 300-400 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature for 30-60 min;
b) heating to 600-700 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature for 60-120 min;
c) heating to 800-900 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature for 60-120 min;
d) heating to 950-1000 ℃ at a heating rate of 5-8 ℃/min, and keeping the temperature for 120-180 min;
e) heating to 1100-1300 ℃ at a heating rate of 5-8 ℃/min, and keeping the temperature for 360-500 min;
f) heating to 1350-1450 ℃ at a heating rate of 5-8 ℃/min, and preserving heat for 60-120 min;
g) heating to 1455-1550 ℃ at a heating rate of 5-8 ℃/min, and keeping the temperature for 60-120 min.
More preferably, under the condition of continuous vacuum pumping, the lanthanum and samarium oxide mixed material blocks are sequentially heated according to the following seven-stage heating method:
a) heating from 15-25 ℃ to 350-400 ℃ at a heating rate of 9-10 ℃/min, and keeping the temperature for 30-50 min;
b) heating to 650-700 ℃ at a heating rate of 9-10 ℃/min, and keeping the temperature for 60-90 min;
c) heating to 850-900 ℃ at the heating rate of 8-9 ℃/min, and keeping the temperature for 60-90 min;
d) heating to 980-1000 ℃ at a heating rate of 6-8 ℃/min, and preserving heat for 150-180 min;
e) heating to 1150-1300 ℃ at a heating rate of 6-7 ℃/min, and keeping the temperature for 360-480 min;
f) heating to 1380-1450 ℃ at a heating rate of 5-6 ℃/min, and keeping the temperature for 60-100 min;
g) heating to 1480-1550 ℃ at a heating rate of 5-6 ℃/min, and keeping the temperature for 60-100 min.
In the step (4), cooling is carried out under a high vacuum state, when the temperature is reduced to 900-1100 ℃, an inflation valve is opened, high-purity argon is filled to-0.05-0.01 MPa, then a gas circulation cooling device is started to carry out forced air cooling for 20-40 min, namely, the temperature is reduced to 80-120 ℃, and the forced air cooling is stopped; opening the furnace cover after vacuum breaking, taking out the collector, taking out the crucible, and inverting the crucible to easily take out the lanthanum slag, wherein the lanthanum slag is taken out for 5-25 min; the yield of the obtained product is more than or equal to 85 percent. Preferably, cooling is carried out under a high vacuum state, when the temperature is reduced to 920-1080 ℃, an inflation valve is opened, high-purity argon is filled to-0.045-0.025 MPa, then a gas circulating cooling device is started to carry out forced air cooling for 25-35 min, namely, the temperature is reduced to 95-105 ℃, and the forced air cooling is stopped; opening the furnace cover after vacuum breaking, taking out the collector, taking out the crucible, and inverting the crucible to easily take out the lanthanum slag, wherein the lanthanum slag is taken out for 10-20 min; the yield of the obtained product is more than or equal to 87 percent. More preferably, the cooling is carried out under a high vacuum state, when the temperature is reduced to 950-1050 ℃, the inflation valve is opened, high-purity argon is filled to-0.04-0.02 MPa, then the gas circulating cooling device is started to carry out forced air cooling for 25-35 min, namely, the temperature is reduced to 95-105 ℃, and the forced air cooling is stopped; opening the furnace cover after vacuum breaking, taking out the collector, taking out the crucible, and inverting the crucible to easily take out the lanthanum slag, wherein the lanthanum slag is taken out for 15-20 min; the yield of the obtained product is more than or equal to 88 percent.
The production method of the metal samarium can effectively avoid the lanthanum slag from being adhered to the crucible, can improve the cooling rate of the furnace body and greatly shorten the discharging time.