CN110436465B - Industrial production method for enriching boron-10 boron carbide - Google Patents
Industrial production method for enriching boron-10 boron carbide Download PDFInfo
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Abstract
An industrial production method for enriching boron-10 boron carbide belongs to the field of chemical synthesis. The method is invented for mainly solving the problems of low yield and high cost of the existing method for preparing the enriched boron-10 boron carbide. Mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2Respectively metered by a flowmeter and fully mixed in a static mixer to form Ar-10BF3‑CH4‑H2And heating the mixed gas by a heater, feeding the heated mixed gas into a plasma reaction chamber, instantaneously heating and ionizing the mixed gas under the induction of a high-frequency power supply, and condensing the mixed gas on the wall of the plasma reaction chamber to generate boron-10-enriched boron carbide powder. The scraper plates scrape the boron-10-enriched boron carbide powder off from the wall of the device, the boron-10-enriched boron carbide powder is conveyed to the boron-10-enriched boron carbide storage tank by the screw conveyor, the ultrasonic waves continuously act on the plasma reaction chamber, and the mixed gas comes out from the boron-10-enriched boron carbide storage tank and is absorbed by the absorption tower. Its advantages are high output rate and low cost.
Description
The technical field is as follows:
the invention belongs to the field of chemical synthesis, and particularly relates to a method for producing boron-10-enriched boron Carbide (CVD) by using a Chemical Vapor Deposition (CVD) method10B4C) Powder technology.
Background art:
natural boron (B) has two stable isotopes, i.e.10B and11b, 19.78% and 80.22% abundance, respectively. Wherein the content of the first and second substances,10b has a thermal neutron absorption cross-section of up to 3837 targets11The weight of the fruit is 7.67 times that of the fruit multiplied by 10, which is 5.12 times that of the fruit multiplied by 10, and10the absorption spectrum of B is wide, strong secondary radiation is not generated after neutrons are absorbed, and the post-treatment is easy. And boron carbide (B)4C) As neutron absorbing material, its absorption capacity depends mainly on10B content, so as to enrich boron-10 boron carbide: (10B4C) Substitute for natural abundance boron carbide (B)4C) The total material consumption can be greatly reduced, and the neutron absorption efficiency is improved. Selecting fast reactor (fast reactor for short)10Boron carbide pellets with the B abundance of 92 percent are used as the core control rod material, but the current Chinese experiment is fastThe control rod assembly of the reactor does not have localization conditions, mainly depends on Russian import, and realizes localization of the control rod of the fast reactor, the core of which is high enriched boron-10 boron carbide10B4C) And (3) development.
Preparation of boron-10-enriched boron carbide10B4C) Firstly, the boron isotope is separated and purified. In the existing separation and purification methods, the chemical exchange rectification method and the low-temperature rectification method of boron trifluoride realize industrial production scale, and the obtained product is mainly boron trifluoride (boron trifluoride) enriched with boron-1010BF3) And boron trifluoride enriched with boron-11: (11BF3) Therefore, it is10B4C is prepared by10BF3Is used as a starting material. In the currently published literature, boron-10-enriched boron carbide (B)10B4C) The preparation of (A) is usually based on the preparation route of natural abundance boron carbide, but because of the natural abundance boron carbide10BF3The preparation cost is very high due to the complex process and long process for the starting raw material.
The carbothermic method is the most mature process route for industrially preparing boron carbide at present, and natural boric acid is usually adopted as a raw material. If the boron-boron trifluoride enriched catalyst is applied to the preparation of boron-10-enriched boron carbide, boron-10-boron trifluoride is enriched firstly10B4C) There are two main methods for preparing boron-10-enriched boric acid, namely organic esterification and inorganic hydrolysis. The carbothermic reduction process is that under the high temperature and inert atmosphere, carbon black or petroleum coke is reacted with boron-10-enriched boric acid to prepare boron-10-enriched boron carbide (10B4C) In that respect The reduction process is carried out at high temperature (2100-2300 deg.C), boron oxide is largely evaporated and decomposed to lose, and at least 29% -33% of boron source is lost in the production process. In view of enriching boron-10 boron trifluoride10BF3) The price is very expensive, obviously, the carbothermic method is not suitable for preparing enriched boron-10 boron carbide10B4C）。
The magnesiothermic reduction method usually uses simple substance carbon and natural boron oxide as reaction raw materials, if the simple substance carbon and the natural boron oxide are applied to the enrichment of boron-10 boron carbide (B)10B4C) Starting with boron-10 trifluorideThe raw materials are firstly prepared into boron-10-enriched boric acid and then dehydrated to generate boron-10-enriched boron oxide. In the magnesium thermal reduction process, boron-10-enriched boron oxide reacts with magnesium to generate elemental boron-10 and magnesium oxide, and the elemental boron-10 and elemental carbon are synthesized into boron-10-enriched boron carbide (B)10B4C) In that respect It has the problems that: the loss of boron source is high and the product purity is low.
The direct synthesis method of boron powder is characterized by that the boron-10 powder and carbon powder are directly synthesized into boron-10 enriched boron carbide10B4C) In that respect The boron powder has complex preparation process and high production cost.
Direct cracking method: firstly, boron trifluoride is synthesized into trimethyl borate or trialkylboron, and then the trimethyl borate or the trialkylboron is cracked at high temperature. The method has no report of industrial production at present.
Vapor deposition methods, including Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD). Chemical vapor deposition is a process for preparing ultrafine powders based on the chemical reaction of vapors of volatile metal compounds. The method can be classified into a thermal chemical vapor reaction method, a laser induced vapor deposition method (LICVD), and a plasma vapor deposition method (PCVD).
A commonly used reaction precursor for boron carbide is BCI3-CH4-H2、B2H6-CH4-H2、B5H9-CH4And the like. Although satisfactory performance can be obtained from powders synthesized by chemical vapor deposition, the low yield of the method itself, and the high cost associated with the requirement for equipment and gas phase raw materials, have not been widely adopted in industrial production.
At present, no boron-10 enriched boron trifluoride one-step method for producing boron-10 enriched boron carbide (B)10B4C) Mature, high-efficiency and low-cost industrial production technology. The existing Chemical Vapor Deposition (CVD) method for producing boron-10-enriched boron carbide has low yield and high cost, and is not suitable for industrial production.
The invention content is as follows:
the invention aims to solve the technical problem of providing an industrial production method for enriching boron-10 boron carbideA process comprising enriching boron-10-enriched boron trifluoride10BF3) One-step method for producing enriched boron-10 boron carbide10B4C) Has the advantages of high yield, good quality and low cost, and is enriched with boron-10 boron carbide (B)10B4C) The method lays a solid foundation for wide application in the fields of nuclear industry, national defense military industry and the like.
The above object is achieved by: mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2Respectively metered by a flowmeter and fully mixed in a static mixer to form Ar-10BF3-CH4- H2Heating the mixed gas by a heater, introducing the heated mixed gas into a plasma reaction chamber, instantaneously heating and ionizing the mixed gas under the induction of a high-frequency power supply, and condensing the mixed gas on the wall of the plasma reaction chamber to generate boron-10-enriched boron carbide (B:)10B4C) And (3) powder. The scraper plate is used for enriching boron-10 boron carbide10B4C) The powder is scraped off from the wall and is conveyed to a boron-10 enriched boron carbide (B)10B4C) The storage tank, the ultrasonic wave acts on the plasma reaction chamber in succession, plays and vibrates the effect. The mixed gas is enriched with boron-10 boron carbide10B4C) And (4) discharging from the storage tank, and absorbing in an absorption tower.
The invention adopts a continuous plasma CVD method, and the specific process is as follows: replacing the process system with high-purity nitrogen until the oxygen content is less than 1ppm, and replacing the system with Ar gas until the nitrogen content is less than 0.01%. The system is pressurized to 50Kpa (G) -100 Kpa (G) by Ar gas, and the system pressure is automatically adjusted by a pressure adjusting valve to be maintained. Mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2Respectively measured by a flowmeter, fully mixed in a static mixer for 3-10 seconds, the temperature of the raw material mixture is 298-318 k (the outlet temperature of the static mixer), and formed Ar-10BF3-CH4- H2The mixed gas is heated to 473k-533k by the heater and enters the plasma reaction chamber, the mixed gas is instantaneously heated and ionized under the induction of a high-frequency power supply (heated by an induction coil of the plasma reaction chamber),Ar-10BF3-CH4- H2the temperature of the mixed gas is 1240k-1360k, after the heating is finished, coolant is introduced into a jacket of the plasma reaction chamber, and boron-10 enriched boron carbide is generated by condensation on the wall of the plasma reaction chamber10B4C) Powder, scraping the boron-10-enriched boron carbide powder from the wall of the device by a scraper plate, conveying the boron-10-enriched boron carbide powder to a boron-10-enriched boron carbide storage tank by a screw conveyor, and continuously acting ultrasonic waves on a plasma reaction chamber to play a role of oscillation. And the boron-10-enriched boron carbide product is extracted from a discharge pipeline at the bottom of the boron-10-enriched boron carbide storage tank. Mixed gas (Ar, HF, CH) after reaction4、H2) And the mixed gas flows out of the mixed gas pipeline of the boron-10-enriched boron carbide storage tank, is pumped to an absorption tower by a compressor and is absorbed by calcium carbonate aqueous solution.
In the raw material mixed gas, the molar ratio of the raw material components is as follows:10BF3：CH4=3.5-4.5:1；Ar：（10BF3+CH4）=1-3:100；H2：CH41: 2-3; the high frequency power supply frequency was 1.45 GHz. And electrifying the induction coil by using a high-frequency power supply.
The coolant in the cooling jacket of the plasma reaction chamber can be cooling medium such as cooling brine, circulating water and the like. The temperature of the inner wall of the plasma reaction chamber is not higher than 60 ℃. The ultrasonic power is 200-450 kw.
The enriched boron-10 boron carbide prepared by the method is continuously produced (10B4C) The powder has a granularity of 0.1-0.3 μm, a product purity of over 99.9 percent and a yield of over 99 percent.
The production system structure used by the process is as follows: comprises that10BF3Storage tank, CH4Storage tank, Ar storage tank, H2A storage tank is arranged in the storage tank,10BF3storage tank, CH4Storage tank, Ar storage tank, H2The storage tanks are respectively provided with pipelines connected with the inlet of the static mixer, the outlet of the static mixer is provided with a pipeline connected with the material inlet of the heater, the material outlet of the heater is provided with a pipeline connected with the feed inlet of the plasma reaction chamber, the discharge outlet of the plasma reaction chamber is provided with a pipeline connected with the boron-10 enriched boron carbide storage tank, and the boron-10 enriched boron carbide storage tank is provided with a product enriched boron-10 boron carbide tapping lines with valves installed on the product tapping lines; the boron-10-enriched boron carbide storage tank is also connected with a mixed gas pipeline, the other end of the mixed gas pipeline is connected with the inlet of a compressor, and the outlet of the compressor is connected with the inlet of the absorption tower through a pipeline.
The plasma reaction chamber is a cylindrical reactor made of 316L stainless steel and comprises an inner wall and an outer wall, a jacket is arranged between the inner wall and the outer wall, the inner surface of the inner wall is plated with a gold or silver coating, and the outer wall is provided with a coolant inlet and a coolant outlet which are communicated with the jacket; an induction coil is wound outside the outer wall, a screw conveyor is arranged inside the plasma reaction chamber, a scraper is fixed on a screw of the screw conveyor, and the screw conveyor drives the scraper to rotate through the screw; the outer edge of the scraper is in contact with the inner surface of the inner wall. The scraper and the screw conveyor are both made of carbon fiber composite materials, and the surfaces of the scraper and the screw conveyor are plated with gold or silver coatings.
It is also possible to use boron trifluoride (BF) in natural abundance3) As a raw material instead of enriched boron-10 boron trifluoride10BF3) Boron trifluoride (BF) in natural abundance3) And enriched boron-10 boron trifluoride10BF3) The quantity of the boron carbide powder is completely consistent, the natural abundance boron carbide powder prepared by the method is continuously produced, the granularity is 0.1-0.3 mu m, the product purity is more than 99.9 percent, and the yield is more than 99 percent.
The invention has the advantages that: the invention adopts an original continuous extraction Chemical Vapor Deposition (CVD) method and uses Ar-10BF3-CH4- H2The mixed gas is taken as a raw material, and boron-10 enriched boron carbide (boron carbide) is continuously produced and extracted in a plasma reaction chamber10B4C) And (3) powder. The method has the greatest advantage that the method can continuously produce and extract the enriched boron-10 boron carbide ((B))10B4C) Powder, high yield, low cost, and the prepared boron-10-enriched boron carbide10B4C) The granularity of the powder is 0.1-0.3 μm, the purity of the product is more than 99.9 percent, and the yield is more than 99 percent.
Description of the drawings:
FIG. 1 is a production flow diagram of the present invention.
The specific implementation mode is as follows:
referring to fig. 1, the structure of the process flow system is as follows: comprises that10BF3Storage tank 1, CH4Storage tank 2, Ar storage tank 3, H2The storage tank (4) is provided with a storage tank,10BF3storage tank 1, CH4Storage tank 2, Ar storage tank 3, H2The storage tank 4 is respectively provided with a pipeline connected with an inlet of the static mixer 5, an outlet of the static mixer is provided with a pipeline connected with a material inlet of the heater 6, a material outlet of the heater is provided with a pipeline connected with a feed inlet of the plasma reaction chamber 7, a discharge hole of the plasma reaction chamber is provided with a pipeline connected with a boron-10-enriched boron carbide storage tank 8, the boron-10-enriched boron carbide storage tank is provided with a product boron-10-enriched boron carbide discharge pipeline 9, and the product boron discharge pipeline is provided with a valve; the boron-10-enriched boron carbide storage tank is also connected with a mixed gas pipeline 10, the other end of the mixed gas pipeline is connected with an inlet of a compressor 11, and an outlet of the compressor is connected with an inlet of an absorption tower 12 through a pipeline.
The plasma reaction chamber is a cylindrical reactor made of 316L stainless steel, and comprises an inner wall 71 and an outer wall 72, a jacket 73 is arranged between the inner wall and the outer wall, the inner surface of the inner wall is plated with a gold or silver coating, and the outer wall is provided with a coolant inlet and a coolant outlet which are communicated with the jacket; an induction coil 74 is wound outside the outer wall, a screw conveyor 75 is arranged inside the plasma reaction chamber, a scraper 76 is fixed on a screw of the screw conveyor, and the screw conveyor drives the scraper to rotate through the screw during operation; the outer edge of the scraper is in contact with the inner surface of the inner wall. The scraper and the screw conveyor are both made of carbon fiber composite materials, and the surfaces of the scraper and the screw conveyor are plated with gold or silver coatings.
Mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2Respectively metered by a flowmeter and fully mixed in a static mixer to form Ar-10BF3-CH4- H2Heating the mixed gas by a heater, introducing the heated mixed gas into a plasma reaction chamber, instantaneously heating and ionizing the mixed gas under the induction of a high-frequency power supply, and condensing the mixed gas on the wall of the plasma reaction chamber to generate boron-10-enriched boron carbide (B:)10B4C) And (3) powder. The scraper plate is used for enriching boron-10 boron carbide10B4C) Powder fromThe wall of the vessel is scraped off and is conveyed to the boron-10 enriched boron carbide (by a screw conveyer)10B4C) The storage tank, the ultrasonic wave acts on the plasma reaction chamber in succession, plays and vibrates the effect. The mixed gas is enriched with boron-10 boron carbide10B4C) And (4) discharging from the storage tank, and absorbing in an absorption tower.
The invention adopts a continuous plasma CVD method, and the specific process is as follows: replacing the process system with high-purity nitrogen until the oxygen content is less than 1ppm, and replacing the system with Ar gas until the nitrogen content is less than 0.01%. The system is pressurized to 50Kpa (G) -100 Kpa (G) by Ar gas, and the system pressure is automatically adjusted by a pressure adjusting valve to be maintained. Mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2Respectively measured by a flowmeter, fully mixed in a static mixer for 3-10 seconds, the temperature of the raw material mixture is 298-318 k (the outlet temperature of the static mixer), and formed Ar-10BF3-CH4- H2The mixed gas is heated to 473k-533k by the heater and enters the plasma reaction chamber, the mixed gas is instantaneously heated and ionized (heated by the induction coil of the plasma reaction chamber) under the induction of the high-frequency power supply, Ar-10BF3-CH4- H2The temperature of the mixed gas is 1240k-1360k, after the heating is finished, coolant is introduced into a jacket of the plasma reaction chamber, and boron-10 enriched boron carbide is generated by condensation on the wall of the plasma reaction chamber10B4C) Powder, scraping the boron-10-enriched boron carbide powder from the wall of the device by a scraper plate, conveying the boron-10-enriched boron carbide powder to a boron-10-enriched boron carbide storage tank by a screw conveyor, and continuously acting ultrasonic waves on a plasma reaction chamber to play a role of oscillation. And the boron-10-enriched boron carbide product is extracted from a discharge pipeline at the bottom of the boron-10-enriched boron carbide storage tank. Mixed gas (Ar, HF, CH) after reaction4、H2) And the mixed gas flows out of the mixed gas pipeline of the boron-10-enriched boron carbide storage tank, is pumped to an absorption tower by a compressor and is absorbed by calcium carbonate aqueous solution.
In the raw material mixed gas, the molar ratio of the raw material components is as follows:10BF3：CH4=3.5-4.5:1；Ar：（10BF3+CH4）=1-3:100；H2：CH41: 2-3; the high frequency power supply frequency was 1.45 GHz. The induction coil is energized using a high frequency power supply.
The coolant in the cooling jacket of the plasma reaction chamber can be cooling medium such as cooling brine, circulating water and the like. The temperature of the inner wall of the plasma reaction chamber is not higher than 60 ℃. The ultrasonic power is 200-450 kw.
The enriched boron-10 boron carbide prepared by the method is continuously produced (10B4C) The powder has a granularity of 0.1-0.3 μm, a product purity of over 99.9 percent and a yield of over 99 percent.
It is also possible to use boron trifluoride (BF) in natural abundance3) As a raw material instead of enriched boron-10 boron trifluoride10BF3) Boron trifluoride (BF) in natural abundance3) And enriched boron-10 boron trifluoride10BF3) The quantity of the boron carbide powder is completely consistent, the natural abundance boron carbide powder prepared by the method is continuously produced, the granularity is 0.1-0.3 mu m, the product purity is more than 99.9 percent, and the yield is more than 99 percent.
Example 1, the process system was purged with high purity nitrogen to an oxygen content of less than 1ppm and then purged with Ar gas until the nitrogen content was less than 0.01%. The system is pressurized to 50Kpa (G) by Ar gas, and the system pressure is automatically adjusted by a pressure adjusting valve to be maintained. Mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2After being respectively measured by a flowmeter, the molar ratio of the raw material components is as follows:10BF3：CH4=3.75:1；Ar：（10BF3+CH4）=1.5:100；H2：CH4=2.2: 1; mixing in a static mixer for 4 seconds at a raw material mixture temperature of 303k to form Ar-10BF3-CH4- H2The mixed gas is heated to 497k by the heater and enters the plasma reaction chamber, and the mixed gas is instantaneously heated and ionized under the induction of the high-frequency power supply, Ar-10BF3-CH4- H2The mixed gas temperature is 1240k, after heating, the coolant is introduced into the jacket of the plasma reaction chamber, the temperature of the inner wall of the plasma reaction chamber is 35 ℃, and the mixed gas is arranged in the plasma reaction chamberCondensation on the wall of the vessel to produce boron-10 enriched boron carbide10B4C) Powder, scraping the boron-10-enriched boron carbide powder from the wall of the device by a scraper plate, conveying the boron-10-enriched boron carbide powder to a boron-10-enriched boron carbide storage tank by a screw conveyor, and continuously acting ultrasonic waves with the power of 300 kw on a plasma reaction chamber to play a role of oscillation. And the boron-10-enriched boron carbide product is extracted from a discharge pipeline at the bottom of the boron-10-enriched boron carbide storage tank. Mixed gas (Ar, HF, CH) after reaction4、H2) And (3) discharging from a mixed gas pipeline of the boron-10-enriched boron carbide storage tank, pumping the mixed gas to an absorption tower by a compressor, and performing absorption treatment by using a calcium carbonate aqueous solution.
The enriched boron-10 boron carbide prepared by the method is continuously produced (10B4C) Powder with a particle size of 0.12 μm, a product purity of 99.95% and a yield of 99.4%.
Example 2, the process system was purged with high purity nitrogen to an oxygen content of less than 1ppm and then purged with Ar gas until the nitrogen content was less than 0.01%. The system is pressurized to 80Kpa (G) by Ar gas, and the pressure of the system is automatically adjusted by a pressure adjusting valve to maintain the pressure of the system. Mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2The molar ratio of (A) to (B) is:10BF3：CH4=4.15:1；Ar：（10BF3+CH4）=2.5:100；H2：CH4=2.6: 1; mixing in a static mixer for 6 seconds at a raw material mixture temperature of 318k to form Ar-10BF3-CH4- H2The mixed gas is heated to 522k by a heater and enters a plasma reaction chamber, the mixed gas is instantaneously heated and ionized under the induction of a high-frequency power supply, Ar-10BF3-CH4- H2The temperature of the mixed gas is 1300k, after the heating is finished, the coolant is introduced into a jacket of the plasma reaction chamber, the temperature of the inner wall of the plasma reaction chamber is 45 ℃, and boron-10 enriched boron carbide (boron carbide) is generated by condensation on the wall of the plasma reaction chamber10B4C) Powder, scraping the boron-10-enriched boron carbide powder from the wall of the device by a scraper plate, conveying the powder to a boron-10-enriched boron carbide storage tank by a screw conveyor, and continuously acting ultrasonic waves with the power of 380 kw on a plasma reactionAnd the chamber plays a role in oscillation. And the boron-10-enriched boron carbide product is extracted from a discharge pipeline at the bottom of the boron-10-enriched boron carbide storage tank. Mixed gas (Ar, HF, CH) after reaction4、H2) And (3) discharging from a mixed gas pipeline of the boron-10-enriched boron carbide storage tank, pumping the mixed gas to an absorption tower by a compressor, and performing absorption treatment by using a calcium carbonate aqueous solution.
The enriched boron-10 boron carbide prepared by the method is continuously produced (10B4C) The powder has the granularity of 0.19 mu m, the product purity of 99.98 percent and the yield of 99.6 percent.
Example 3, the process system was purged with high purity nitrogen to an oxygen content of less than 1ppm and then purged with Ar gas until the nitrogen content was less than 0.01%. The system is pressurized to 100Kpa (G) by Ar gas, and the system pressure is automatically adjusted by a pressure adjusting valve to be maintained. Mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2After being respectively measured by a flowmeter, the molar ratio of the raw material components is as follows:10BF3：CH4=4.5:1；Ar：（10BF3+CH4）=3:100；H2：CH41: 3; mixing in a static mixer for 10 seconds at a raw material mixture temperature of 318k to form Ar-10BF3-CH4- H2The mixed gas is heated to 533k by a heater and enters a plasma reaction chamber, the mixed gas is instantaneously heated and ionized under the induction of a high-frequency power supply, Ar-10BF3-CH4- H2The temperature of the mixed gas is 1360k, coolant is introduced into a jacket of the plasma reaction chamber after the heating is finished, the temperature of the inner wall of the plasma reaction chamber is 60 ℃, and boron-10 enriched boron carbide (boron carbide) is generated by condensation on the wall of the plasma reaction chamber10B4C) Powder, scraping the boron-10-enriched boron carbide powder from the wall of the device by a scraper plate, conveying the powder to a boron-10-enriched boron carbide storage tank by a screw conveyor, and continuously acting ultrasonic waves with the power of 450kw on a plasma reaction chamber to play a role of oscillation. And the boron-10-enriched boron carbide product is extracted from a discharge pipeline at the bottom of the boron-10-enriched boron carbide storage tank. Mixed gas (Ar, HF, CH) after reaction4、H2) From enriched boron-10 boron carbide storage tankThe mixed gas comes out of the mixed gas pipeline, is pumped to an absorption tower by a compressor and is absorbed and treated by calcium carbonate aqueous solution.
The enriched boron-10 boron carbide prepared by the method is continuously produced (10B4C) Powder with a particle size of 0.3 μm, a product purity of 99.93% and a yield of 99.2%.
Example 4, the process system was purged with high purity nitrogen to an oxygen content of less than 1ppm and then purged with Ar gas until the nitrogen content was less than 0.01%. The system was pressurized to 70kpa (g) with Ar gas and maintained at this system pressure with automatic adjustment by a pressure regulator valve. BF mixing the raw material3、CH4With auxiliary gases Ar, H2After being respectively measured by a flowmeter, the molar ratio of the raw material components is as follows: BF (BF) generator3：CH4=3.5:1；Ar：（BF3+CH4）=1:100；H2：CH4=2.6: 1; mixing thoroughly in a static mixer for 3 seconds at a feed mixture temperature of 298k to form Ar-BF3-CH4- H2Heating the mixed gas to 473k by a heater, introducing the mixed gas into a plasma reaction chamber, and instantaneously heating and ionizing the mixed gas under the induction of a high-frequency power supply to obtain Ar-BF3-CH4- H2The temperature of the mixed gas is 1240k, after the heating is finished, the coolant is introduced into a jacket of the plasma reaction chamber, the temperature of the inner wall of the plasma reaction chamber is 48 ℃, and boron-10 enriched boron carbide is generated by condensation on the wall of the plasma reaction chamber10B4C) Powder, scraping the boron-10-enriched boron carbide powder from the wall of the device by a scraper plate, conveying the boron-10-enriched boron carbide powder to a boron-10-enriched boron carbide storage tank by a screw conveyor, and continuously acting ultrasonic waves with the power of 200 kw on a plasma reaction chamber to play a role of oscillation. And the boron-10-enriched boron carbide product is extracted from a discharge pipeline at the bottom of the boron-10-enriched boron carbide storage tank. The mixed gas after reaction comes out from the mixed gas pipeline of the boron-10-enriched boron carbide storage tank, is pumped to an absorption tower by a compressor and is absorbed and treated by calcium carbonate aqueous solution.
The enriched boron-10 boron carbide prepared by the method is continuously produced (10B4C) Powder with a granularity of 0.1 μm, a product purity of 99.92% and a yield of 99.2%.
Claims (6)
1. An industrial production method for enriching boron-10 boron carbide is characterized in that: the continuous plasma CVD method is adopted, and the specific process is as follows: replacing the process system with high-purity nitrogen until the oxygen content is less than 1ppm, and replacing the system with Ar gas until the nitrogen content is less than 0.01%; pressurizing the system to 50Kpa (G) -100 Kpa (G) by using Ar gas, and automatically adjusting the pressure by using a pressure adjusting valve to maintain the system pressure; mixing the raw materials10BF3、CH4With auxiliary gases Ar, H2Respectively metered by a flowmeter and fully mixed in a static mixer to form Ar-10BF3-CH4-H2The mixed gas is heated to 473k-533k by the heater and enters the plasma reaction chamber, the mixed gas is instantaneously heated and ionized under the induction of the high-frequency power supply, Ar-10BF3-CH4-H2The temperature of the mixed gas is 1240k-1360k, after heating, coolant is introduced into a jacket of the plasma reaction chamber, boron-10-enriched boron carbide powder is generated by condensation on the wall of the plasma reaction chamber, the boron-10-enriched boron carbide powder is scraped off from the wall by a scraper plate and is sent to a boron-10-enriched boron carbide storage tank by a screw conveyer, and ultrasonic waves continuously act on the plasma reaction chamber to play a role of oscillation; the boron-10-enriched boron carbide product is extracted from a discharge pipeline at the bottom of the boron-10-enriched boron carbide storage tank; the reacted mixed gas is discharged from a mixed gas pipeline of a boron-10-enriched boron carbide storage tank and pumped to an absorption tower by a compressor to be absorbed by calcium carbonate aqueous solution.
2. The industrial production method for boron-10-enriched boron carbide according to claim 1, wherein: the mixing time of the materials in the static mixer is 3 seconds to 10 seconds, and the temperature of the raw material mixture is 298k to 318 k.
3. The industrial production method for boron-10-enriched boron carbide according to claim 1, wherein: the molar ratio of the raw material components is as follows:10BF3：CH4＝3.5-4.5:1；Ar：(10BF3+CH4)＝1-3:100；H2：CH4＝2-3:1。
4. the industrial production method for boron-10-enriched boron carbide according to claim 1, wherein: the temperature of the inner wall of the plasma reaction chamber is not higher than 60 ℃.
5. The industrial production method for boron-10-enriched boron carbide according to claim 1, wherein: the inner surface of the inner wall of the plasma reaction chamber is plated with a gold or silver coating, and the surfaces of the scraper and the screw conveyer are plated with gold or silver coatings.
6. The industrial production method for boron-10-enriched boron carbide according to claim 1, wherein: with boron trifluoride (BF) in natural abundance3) As a raw material instead of enriched boron-10 boron trifluoride10BF3) Boron trifluoride (BF) in natural abundance3) And enriched boron-10 boron trifluoride10BF3) The number of the same is identical.
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| US5300951A (en) * | 1985-11-28 | 1994-04-05 | Kabushiki Kaisha Toshiba | Member coated with ceramic material and method of manufacturing the same |
| CN108046268A (en) * | 2017-12-12 | 2018-05-18 | 江西瑞合精细化工有限公司 | The method that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder |
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| US5300951A (en) * | 1985-11-28 | 1994-04-05 | Kabushiki Kaisha Toshiba | Member coated with ceramic material and method of manufacturing the same |
| CN108046268A (en) * | 2017-12-12 | 2018-05-18 | 江西瑞合精细化工有限公司 | The method that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder |
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