CN112185592B - C/TiN coated lithium orthosilicate tritium propagation agent, preparation method thereof and preparation device system - Google Patents
C/TiN coated lithium orthosilicate tritium propagation agent, preparation method thereof and preparation device system Download PDFInfo
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Abstract
The invention provides a C/TiN coated Li 4 SiO 4 Tritium breederAnd a preparation method and a preparation device system thereof, wherein the preparation method comprises the following steps: (1) Make Li 4 SiO 4 The particles are in a fluidized state in a protective atmosphere; (2) Mixing Li on the basis of the continuous operation of the step (1) 4 SiO 4 Particles, titanium source gas and nitrogen source gas to obtain TiN coated Li 4 SiO 4 A particle; (3) Mixing the TiN coated Li obtained in the step (2) on the basis of continuously performing the step (1) 4 SiO 4 Particles and a carbon source gas; (4) Obtaining C/TiN coated Li after gas-solid separation 4 SiO 4 A tritium breeder. The device system comprises a storage bin, a fluidized bed coating device, a titanium source gasification device, a product collecting device and a tail gas treatment device. The invention overcomes the defect of Li 4 SiO 4 Corrosion to the cladding material and increase the content of the lithium-based ceramic tritium breeder in He-H 2 /H 2 Stability in an O environment.
Description
Technical Field
The invention belongs to the technical field of nuclear fusion, relates to a preparation method of an advanced lithium-based ceramic tritium breeder with a core-shell structure, and particularly relates to C/TiN coated Li 4 SiO 4 Tritium breeder, preparation method and preparation device system thereof.
Background
With the rapid development of human society, the world energy consumption will continue to increase, the energy crisis and the environmental crisis become global issues to be solved urgently, and the safe, clean and sustainable nuclear fusion energy draws attention as a final approach to solving the energy crisis. Among them, deuterium-tritium fusion has low difficulty, and is the fusion reaction most suitable for nuclear fusion power generation. Tritium is a radioactive isotope of hydrogen and is extremely low in nature, so fusion reactor deuterium-tritium fuel cycles typically use Li to proliferate tritium. Over decades of development, li is now present 4 SiO 4 The microspheres are selected as one of candidate materials of the solid tritium breeding cladding due to the excellent characteristics of high Li density, good tritium release performance, large compressive strength, good moisture resistance and the like.
However, with the development of the research, people gradually find that in the actual service environment, the preferable Li is 4 SiO 4 The microspheres can corrode the clad material, e.g., react with 316 stainless steel, IN625 steel, low activation ferritic martensitic steel RAFM, european-97 steel, or ARAA alloy steel to form brittle Li 5 FeO 4 ，LiCrO 2 ，LiFeO 2 Isooxide corrosion layer, deterioration of mechanical properties of the cladding structure material, especially in He-H 2 In the cleaning atmosphere, the corrosion phenomenon is more obvious, and great potential safety hazard is caused to the long-term stable operation of the nuclear reactor.
To solve this problem, the Japanese atomic energy mechanism was designed to have Er 2 O 3 Coated RAFM steel (Fusion eng. Des.87 (2012) 1777-1787), by design Er 2 O 3 The coating layer creates a barrier layer between the microsphere and the steel substrate, and blocks Li 4 SiO 4 And the element between the cladding and the steel matrix diffuses and reacts, so that the safety of the cladding is improved. However, as the service time increases, the coating is prone to peeling off due to the large thermal stress between the oxide and the RAFM steel substrate.
CN101510450A discloses a method for preparing a ceramic tritium breeder in a fusion reactor cladding, which comprises the steps of mixing and dissolving an organic monomer and a cross-linking agent which can generate free radical polymerization reaction with water or an organic solvent to prepare a premixed solution, then adding ceramic tritium breeder powder, defoaming, adding an initiator and a catalyst to prepare slurry, and dropping the slurry into a heated medium which is mutually exclusive with the solvent used by the slurry by using a dropping device. After the liquid drops enter the medium, the liquid drops form a small sphere, the shape is solidified and preserved in the descending process, and the small sphere is collected, washed, dried and sintered to prepare the tritium value increasing agent ceramic small sphere material. The formed blank has high strength and good toughness; the formed small balls have high sphericity, smooth surface and good uniformity; the shrinkage is small after drying and sintering, the size of the ball is easy to control, and the strength is high; the cost is low and the process is flexible. However, the ceramic tritium breeder is in direct contact with the cladding material during use, and the stability of the tritium breeder is affected.
CN108911735A discloses a high sphericity tritium breeder nanostructure lithium titanate ceramic pellet and a preparation method thereof, wherein a premixed liquid composed of a high molecular dispersant and deionized water and precursor powder are adopted to prepare a slurry with good fluidity, the obtained slurry is further subjected to wet forming and high-temperature sintering to obtain the nano structure lithium titanate ceramic pellet with high sphericity, filling of a tritium breeder pellet bed and recovery of residual lithium are facilitated, pellet stacking density can be increased, a tritium breeder with high lithium density is obtained, thermal stress and irradiation cracking conditions of the tritium breeder can be further reduced, and the service life of the tritium breeder is prolonged. However, the invention also has the problem that the lithium titanate ceramic pellets are in direct contact with the cladding material in the using process, so that the phenomenon of corrosion of the cladding material is easily caused.
CN108550404A discloses a fluid state tritium breeding ceramic composite material, which is formed by mixing a liquid phase and a solid phase, and can eliminate the magnetohydrodynamic resistance effect and the corrosion effect on cladding structure materials of the existing liquid metal or molten salt tritium breeding agent, and also can eliminate the problems of low tritium release efficiency, low heat transfer property, fragility, carrier gas channel blockage caused by lithium volatilization and the like. However, the method has high cost, is difficult to realize large-scale batch production, cannot fundamentally avoid element diffusion between the tritium breeder and the cladding material, and still has the problem of cladding material corrosion after long-term use.
Therefore, how to further design and optimize a barrier layer between the tritium breeder and the cladding material and prevent the tritium breeder from being directly contacted with the cladding material becomes a problem to be solved urgently in the prior art of the tritium breeder cladding module in the nuclear fusion reactor.
Disclosure of Invention
The invention aims to provide a C/TiN coated Li 4 SiO 4 Tritium breeder, method and apparatus system for its preparation, which overcomes Li 4 SiO 4 The corrosion of the cladding material is the same as that of the cladding materialThe method improves the content of the lithium-based ceramic tritium breeder in He-H 2 /H 2 Stability in an O environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a C/TiN coated Li 4 SiO 4 A method of preparing a tritium proliferator, the method comprising the steps of:
(1) Make Li 4 SiO 4 The particles are in a fluidized state in a protective atmosphere;
(2) Mixing Li on the basis of the continuous operation of the step (1) 4 SiO 4 Particles, titanium source gas and nitrogen source gas to obtain TiN coated Li 4 SiO 4 A particle;
(3) Mixing the TiN coated Li obtained in the step (2) on the basis of continuously performing the step (1) 4 SiO 4 Particles and a carbon source gas;
(4) Obtaining C/TiN coated Li after gas-solid separation 4 SiO 4 A tritium breeder.
In the present invention, the fluidization state in the step (1) is such that not only Li 4 SiO 4 The particles are uniformly distributed in the reaction space, and the air in the reaction space is removed, so that the reaction of oxygen in the air and the carbon source gas entering subsequently is prevented; step (2) said Li 4 SiO 4 The particles capture TiN deposited by the reaction of the titanium source gas and the nitrogen source gas in a fluidized state, so that the particles are in Li 4 SiO 4 Forming a uniform TiN film on the particle surface, and coating Li on the TiN in the step (3) 4 SiO 4 The particles capture carbon atoms released by the decomposition reaction of the carbon source gas in a fluidized state, so that Li is coated on TiN 4 SiO 4 A uniform carbon film is formed on the surface of the particles, and then the C/TiN coated Li is obtained 4 SiO 4 The composite core-shell structure of (A) is an advanced tritium breeding agent.
Preferably, the Li in the step (1) 4 SiO 4 The particles are spherical or spheroidal in shape.
Preferably, the Li 4 SiO 4 The particles have an equivalent diameter of 0.1 to 1.2mm, and may be, for example, 0.1mm, 0.2mm, 0.3mm, 0.4 mmmm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.1mm or 1.2mm, but not limited to the values listed, and other values not listed within the range of values are equally applicable.
In the present invention, when said Li is 4 SiO 4 When the particles are spherical in shape, the equivalent diameter is Li 4 SiO 4 The actual particle size of the particles; when the Li is 4 SiO 4 When the particles are spheroidal in shape, the equivalent diameter is Li 4 SiO 4 The average particle size of the particles.
Preferably, the gas in the protective atmosphere in step (1) comprises any one of argon, helium or neon or a combination of at least two of them, and typical but non-limiting combinations include a combination of argon and helium, a combination of helium and neon, a combination of argon and neon, or a combination of argon, helium and neon.
In the present invention, the protective atmosphere may be such that the Li is 4 SiO 4 The particles keep a fluidized state, and can isolate oxygen in the environment, so that the subsequent C/TiN film layer can be coated smoothly.
Preferably, the mixing in step (2) is performed by independently introducing the titanium source gas and the nitrogen source gas into the Li respectively 4 SiO 4 The particles are in a protective atmosphere.
In the invention, the titanium source gas and the nitrogen source gas are respectively and independently introduced into the Li from different inlets at the same time 4 SiO 4 The particles are in a protective atmosphere so that Li is present 4 SiO 4 A TiN film layer is formed on the surface of the particles.
Preferably, the temperature of the mixing in step (2) is 500-900 ℃, for example 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mixing time in step (2) is not less than 1min, for example, 1min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but is not limited to the recited values, and other non-recited values in the range are also applicable.
Preferably, the titanium source gas in the step (2) is a gas formed by high-temperature gasification of a titanium salt.
Preferably, the titanium salt is titanium dichloride.
Preferably, the carrier gas for high-temperature gasification is the gas in the protective atmosphere in step (1).
Preferably, the high temperature gasification temperature is 400-800 ℃, for example 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the nitrogen source gas in step (2) is nitrogen.
Preferably, the titanium source gas is introduced in step (2) at a flow rate of 50-200mL/min, such as 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, 100mL/min, 110mL/min, 120mL/min, 130mL/min, 140mL/min, 150mL/min, 160mL/min, 170mL/min, 180mL/min, 190mL/min or 200mL/min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the nitrogen source gas is introduced at a flow rate of 50-200mL/min, for example, 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, 100mL/min, 110mL/min, 120mL/min, 130mL/min, 140mL/min, 150mL/min, 160mL/min, 170mL/min, 180mL/min, 190mL/min, or 200mL/min in step (2), but is not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the mixing in step (3) is performed by introducing the carbon source gas into the TiN coated Li 4 SiO 4 The particles are in a protective atmosphere.
Preferably, the temperature of the mixing in step (3) is 500-900 deg.C, such as 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C or 900 deg.C, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mixing time in step (3) is not less than 1min, for example, 1min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but is not limited to the recited values, and other non-recited values within the range are also applicable.
Preferably, the carbon source gas in step (3) comprises any one or a combination of at least two of methane, ethane, ethylene, acetylene or propylene, and typical but non-limiting combinations include a combination of methane and ethane, a combination of ethane and ethylene, a combination of ethylene and acetylene, a combination of acetylene and propylene, a combination of methane, ethane and ethylene, a combination of ethane, ethylene and acetylene, or a combination of ethylene, acetylene and propylene.
Preferably, the carbon source gas in step (3) is introduced at a flow rate of 50-200mL/min, such as 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, 100mL/min, 110mL/min, 120mL/min, 130mL/min, 140mL/min, 150mL/min, 160mL/min, 170mL/min, 180mL/min, 190mL/min or 200mL/min, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the gas-solid separation method in step (4) comprises any one or combination of at least two of gravity settling, centrifugal settling or filtration, and typical but non-limiting combinations include gravity settling and centrifugal settling, centrifugal settling and filtration, gravity settling and filtration, or gravity settling, centrifugal settling and filtration.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Making spherical or spheroidal Li with equivalent diameter of 0.1-1.2mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere; the gas in the protective atmosphere comprises any one or a combination of at least two of argon, helium or neon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The particles are in a protective atmosphere to obtain TiN coated Li 4 SiO 4 Particles; the mixing temperature is 500-900 deg.C, and the mixing time is not less than 1min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 400-800 ℃, and the gas speed is 50-200mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50-200mL/min;
(3) On the basis of continuously carrying out the step (1), introducing a carbon source gas into the TiN coated Li 4 SiO 4 The mixing temperature of the particles in the protective atmosphere is 500-900 ℃, and the mixing time is more than or equal to 1min; the carbon source gas comprises any one or combination of at least two of methane, ethane, ethylene, acetylene or propylene; the gas introducing speed of the carbon source gas is 50-200mL/min;
(4) Obtaining the C/TiN coated Li after gravity settling, centrifugal settling or filtering 4 SiO 4 A tritium breeder.
In a second aspect, the present invention provides a C/TiN coated Li prepared by the method of the first aspect 4 SiO 4 Tritium breeder, said C/TiN coated Li 4 SiO 4 The tritium breeder has an outer layer of C, an intermediate layer of TiN and an inner portion of Li 4 SiO 4 The microspheres of (1).
In the invention, the C/TiN coated Li 4 SiO 4 The tritium breeder departs from the traditional idea of creating a barrier layer by depositing an oxide coating on a cladding material by depositing Li 4 SiO 4 The surface is provided with a corrosion-resistant and stable C and TiN shell, so that an inert protective layer is formed between the tritium breeder and the cladding material to achieve the purpose of corrosion resistance, and meanwhile, the hydrophobic C and TiN film isolates the tritium breeder from H in the scavenging gas 2 /H 2 The direct contact of O achieves the purpose of improving the stability of the tritium breeder, thereby solving the key problems of coating falling and tritium breeder breakage and finally obtaining the advanced lithium-based ceramic tritium breeder.
In a third aspect, the invention provides a method for preparing C/TiN coated Li 4 SiO 4 The device system for the tritium breeder comprises a storage bin, a fluidized bed coating device, a titanium source gasification device, a product collection device and a tail gas treatment device;
the storage bin is used for providing Li for the fluidized bed coating device 4 SiO 4 Particles;
the fluidized bed coating device is firstly used for mixing Li in protective atmosphere 4 SiO 4 Reacting the particles, titanium source gas and nitrogen source gas to obtain TiN coated Li 4 SiO 4 The particles are mixed with TiN coated Li in protective atmosphere 4 SiO 4 Reacting the particles with a carbon source gas to obtain C/TiN coated Li 4 SiO 4 A tritium proliferating agent;
the titanium source gasification device is used for providing titanium source gas for the fluidized bed coating device;
the product collecting device is used for collecting the C/TiN coated Li generated in the fluidized bed coating device 4 SiO 4 A tritium proliferating agent;
the tail gas treatment device is used for removing tail gas generated in the fluidized bed coating device.
Compared with the prior art, the invention has the following beneficial effects:
(1) The inert C/TiN film of the present invention hinders Li 4 SiO 4 The tritium breeder is directly contacted with the cladding material, so that the diffusion and reaction among Li, O, fe and Cr elements are fundamentally avoided, and the safety of the cladding material is remarkably improved;
(2) The inert C/TiN film of the present invention hinders Li 4 SiO 4 Tritium breeder and H in sweep gas 2 /H 2 The direct contact of O obviously improves the stability of the proliferation agent in the cladding;
(3) The invention prepares the C/TiN coated Li 4 SiO 4 The tritium breeder has the advantages of simple method, uniform coating layer, controllable thickness, low cost and easy large-scale batch production.
Drawings
FIG. 1 is a schematic diagram of Li coated with C/TiN for preparing the Li coated by the invention 4 SiO 4 A device system for tritium breeders;
FIG. 2 is a C/TiN coated Li obtained by the preparation method provided in example 1 4 SiO 4 EDS profile of tritium breeder;
FIG. 3 is a C/TiN coated Li obtained by the preparation method provided in example 1 4 SiO 4 SEM images of tritium proliferators.
Wherein: 1-a storage bin; 2-fluidized bed coating device; 3-a titanium source gasification device; 4-a product collection device; 5-tail gas treatment device.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The invention provides a method for preparing C/TiN coated Li as shown in figure 1 4 SiO 4 The device system of tritium breeder, the device system includes feed bin 1, fluidized bed cladding device 2, titanium source gasification equipment 3, product collection device 4 and tail gas processing apparatus 5.
In the invention, the stock bin 1 is used for providing Li for the fluidized bed coating device 2 4 SiO 4 Particles; the fluidized bed coating apparatus 2 is first used to mix Li in a protective atmosphere 4 SiO 4 Reacting the particles, titanium source gas and nitrogen source gas to obtain TiN coated Li 4 SiO 4 The particles are mixed with TiN coated Li in protective atmosphere 4 SiO 4 Reacting the particles with a carbon source gas to obtain C/TiN coated Li 4 SiO 4 A tritium breeder, specifically, the fluidized bed coating device 2 is a fluidized bed; the titanium source gasification device 3 is used for providing titanium source gas for the fluidized bed coating device 2, and specifically, the titanium source gasification device 3 is a conical fluidized bed; the product collecting device 4 is used for collecting the C/TiN coated Li generated in the fluidized bed coating device 2 4 SiO 4 A tritium breeder, specifically, the product collection device 4 is a storage tank; the tail gas treatment device 5 is used for treating tail gas generated in the fluidized bed coating device 2, and specifically, the tail gas treatment device 5 is a conventional compensation ignition device.
Example 1
This example provides a C/TiN coated Li 4 SiO 4 Preparation of tritium breedersThe preparation method is carried out in the device system provided by the invention and shown in the figure 1, and comprises the following steps:
(1) Spherical Li having a particle diameter of 0.6mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of argon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The particles are in protective atmosphere to obtain TiN coated Li 4 SiO 4 Particles; the mixing temperature is 700 deg.C, and the mixing time is 30min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 600 ℃, the carrier gas is argon, and the gas speed is 125mL/min; the nitrogen source gas is nitrogen, and the gas speed is 125mL/min;
(3) On the basis of continuously carrying out the step (1), introducing carbon source gas methane into the TiN coated Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 700 ℃, and the mixing time is 30min; the gas introducing speed of the carbon source gas is 125mL/min;
(4) Obtaining C/TiN coated Li after gravity settling 4 SiO 4 A tritium breeder.
FIG. 2 is a schematic view of the Li coated with C/TiN obtained by the preparation method provided in this example 4 SiO 4 EDS diagram of tritium breeder, wherein TiN content reaches 14.6at.%, and C content reaches 7.8at.%.
FIG. 3 is the Li coated with C/TiN obtained by the preparation method provided in this example 4 SiO 4 The SEM image of the tritium breeder shows that a layer of nano C/TiN film is uniformly coated on the surface of the crystal particles of the microsphere as shown in figure 3.
Example 2
This example provides a C/TiN coated Li 4 SiO 4 The preparation method of the tritium breeding agent is carried out in the device system provided by the invention and shown in the figure 1, and comprises the following steps:
(1) Spheroidal Li having an average particle diameter of 0.9mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of helium;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The particles are in a protective atmosphere to obtain TiN coated Li 4 SiO 4 A particle; the mixing temperature is 800 ℃, and the mixing time is 45min; the titanium source gas is formed by gasifying titanium dichloride at high temperature of 700 ℃, the carrier gas is helium, and the gas speed is 160mL/min; the nitrogen source gas is nitrogen, and the gas speed is 160mL/min;
(3) On the basis of continuously carrying out the step (1), introducing carbon source gas ethane into the TiN coated Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 800 ℃, and the mixing time is 45min; the gas introducing speed of the carbon source gas is 160mL/min;
(4) Obtaining C/TiN coated Li after centrifugal sedimentation 4 SiO 4 A tritium breeder.
The C/TiN coated Li obtained in this example 4 SiO 4 The elemental composition and the microscopic morphology of the tritium breeder are similar to those of example 1, and therefore are not described herein.
Example 3
This example provides a C/TiN coated Li 4 SiO 4 A preparation method of a tritium breeding agent, which is carried out in the device system provided by the invention and shown in figure 1, comprises the following steps:
(1) Spherical Li having a particle diameter of 0.3mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of neon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The particles are in a protective atmosphere to obtain TiN coated Li 4 SiO 4 Particles; the mixing temperature is 600 ℃, and the mixing time is 15min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 500 ℃, the carrier gas is neon, and the gas speed is 85mL/min; the nitrogen source gas is nitrogen, and the gas speed is 85mL/min;
(3) On the basis of continuously carrying out the step (1), introducing carbon source gas ethylene into the TiN coated Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 600 ℃, and the mixing time is 15min; the gas introducing speed of the carbon source gas is 85mL/min;
(4) Filtering to obtain the C/TiN coated Li 4 SiO 4 A tritium breeder.
The C/TiN coated Li obtained in this example 4 SiO 4 The element composition and the micro-morphology of the tritium breeder are similar to those of example 1, and therefore, the details are not repeated herein.
Example 4
This example provides a C/TiN coated Li 4 SiO 4 A preparation method of a tritium breeding agent, which is carried out in the device system provided by the invention and shown in figure 1, comprises the following steps:
(1) Spheroidal Li having an average particle diameter of 1.2mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of argon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The particles are in a protective atmosphere to obtain TiN coated Li 4 SiO 4 A particle; mixing at 900 deg.C for 1min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 800 ℃, the carrier gas is argon, and the gas speed is 200mL/min; the nitrogen source gas is nitrogen, and the gas speed is 200mL/min;
(3) On the basis of continuously carrying out the step (1), introducing carbon source gas propylene into the TiN coated Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 900 ℃, and the mixing time is 1min; the gas introduction speed of the carbon source gas is 200mL/min;
(4) Obtaining C/TiN coated Li after gravity settling 4 SiO 4 A tritium breeder.
The C/TiN coated Li obtained in this example 4 SiO 4 The element composition and the micro-morphology of the tritium breeder are similar to those of example 1, and therefore, the details are not repeated herein.
Example 5
This embodiment provides aC/TiN coated Li 4 SiO 4 The preparation method of the tritium breeding agent is carried out in the device system provided by the invention and shown in the figure 1, and comprises the following steps:
(1) Spherical Li having a particle diameter of 0.1mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of helium;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The particles are in protective atmosphere to obtain TiN coated Li 4 SiO 4 A particle; the mixing temperature is 500 ℃, and the mixing time is 60min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 400 ℃, the carrier gas is helium, and the gas speed is 50mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50mL/min;
(3) On the basis of continuously carrying out the step (1), introducing carbon source gas acetylene into the TiN coated Li 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 500 ℃, and the mixing time is 60min; the gas introducing speed of the carbon source gas is 50mL/min;
(4) Obtaining C/TiN coated Li after centrifugal sedimentation 4 SiO 4 A tritium breeder.
The C/TiN coated Li obtained in this example 4 SiO 4 The elemental composition and the microscopic morphology of the tritium breeder are similar to those of example 1, and therefore are not described herein.
Comparative example 1
This comparative example provides Li 4 SiO 4 A method for treating a tritium breeding agent, wherein the method is carried out in the device system shown in figure 1, and the method comprises the following steps:
(1) Spherical Li having a particle diameter of 0.6mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere of argon;
(2) Introducing nitrogen into Li on the basis of continuous execution of the step (1) 4 SiO 4 The mixing temperature of the granules in the protective atmosphere is 700 ℃, and the mixing time is 30min; the introduction speed of the nitrogen is125mL/min；
(3) Obtaining Li after gravity settling 4 SiO 4 A tritium breeder.
Li obtained in example 1 and comparative example 2 4 SiO 4 The tritium proliferator was filled in each container of low activation steel, heated to 650 ℃ under an argon atmosphere and kept at that temperature for 10 days, and then the surface of the low activation steel was analyzed and tested, and as a result, it was found that the container was filled with Li obtained in example 1 4 SiO 4 Low activation steel with tritium breeder showed no significant corrosion, but was loaded with Li from comparative example 1 4 SiO 4 Obvious corrosion phenomenon is found in the low-activation steel of the tritium breeder, which indicates that Li 4 SiO 4 The tritium breeder obviously inhibits the corrosion of low-activation steel after coating a C/TiN layer.
It can be seen that the inert C/TiN film in the present invention hinders Li 4 SiO 4 The tritium breeder is directly contacted with the cladding material, so that the diffusion and reaction among Li, O, fe and Cr elements are fundamentally avoided, and the safety of the cladding material is remarkably improved; the inert C/TiN film of the present invention blocks Li 4 SiO 4 Tritium breeder and H in sweep gas 2 /H 2 The direct contact of O obviously improves the stability of the proliferation agent in the cladding; the invention prepares the C/TiN coated Li 4 SiO 4 The tritium breeding agent has the advantages of simple method, uniform coating layer, controllable thickness, low cost and easy large-scale batch production.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (14)
1. C/TiN coated Li 4 SiO 4 A process for the preparation of a tritium breeder, characterized in that it comprises the following steps:
(1) Making spherical or spheroidal Li with equivalent diameter of 0.1-1.2mm 4 SiO 4 Particles in a protective gasThe atmosphere is in a fluidized state;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The particles are in protective atmosphere to obtain TiN coated Li 4 SiO 4 A particle; the mixing temperature is 500-900 deg.C, and the mixing time is more than or equal to 1min;
(3) On the basis of continuously carrying out the step (1), introducing a carbon source gas into the TiN coated Li 4 SiO 4 The mixing temperature of the particles in the protective atmosphere is 500-900 ℃, and the mixing time is more than or equal to 1min;
(4) Obtaining C/TiN coated Li after gas-solid separation 4 SiO 4 A tritium breeder.
2. The method according to claim 1, wherein the gas in the protective atmosphere in step (1) comprises any one of argon, helium or neon or a combination of at least two of them.
3. The production method according to claim 1, wherein the titanium source gas in the step (2) is a gas formed by high-temperature gasification of a titanium salt.
4. The method according to claim 3, wherein the titanium salt is titanium dichloride.
5. The method according to claim 3, wherein the carrier gas for high-temperature gasification is a gas in the protective atmosphere in step (1).
6. The method according to claim 3, wherein the high-temperature gasification temperature is 400 to 800 ℃.
7. The method according to claim 1, wherein the nitrogen source gas in the step (2) is nitrogen.
8. The preparation method according to claim 1, wherein the introduction gas rate of the titanium source gas in the step (2) is 50 to 200mL/min.
9. The method according to claim 1, wherein the nitrogen source gas in the step (2) is introduced at a flow rate of 50 to 200mL/min.
10. The method according to claim 1, wherein the carbon source gas of step (3) comprises any one of methane, ethane, ethylene, acetylene or propylene or a combination of at least two of them.
11. The method according to claim 1, wherein the carbon source gas in the step (3) is introduced at a flow rate of 50 to 200mL/min.
12. The method of claim 1, wherein the gas-solid separation in step (4) comprises any one or a combination of at least two of gravity settling, centrifugal settling and filtration.
13. The method of any one of claims 1-12, comprising the steps of:
(1) Making spherical or spheroidal Li with equivalent diameter of 0.1-1.2mm 4 SiO 4 The particles are in a fluidized state in a protective atmosphere; the gas in the protective atmosphere comprises any one of argon, helium or neon or a combination of at least two of the argon, the helium or the neon;
(2) On the basis of continuously carrying out the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the Li 4 SiO 4 The particles are in protective atmosphere to obtain TiN coated Li 4 SiO 4 A particle; the mixing temperature is 500-900 deg.C, and the mixing time is not less than 1min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 400-800 ℃, and the gas speed is 50-200mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50-200mL/min;
(3) Continuously advancing in the step (1)On the basis of line, carbon source gas is introduced into the TiN coated Li 4 SiO 4 The mixing temperature of the particles in the protective atmosphere is 500-900 ℃, and the mixing time is more than or equal to 1min; the carbon source gas comprises any one or combination of at least two of methane, ethane, ethylene, acetylene or propylene; the gas introducing speed of the carbon source gas is 50-200mL/min;
(4) Obtaining the C/TiN coated Li after gravity settling, centrifugal settling or filtering 4 SiO 4 A tritium breeder.
14. C/TiN-coated Li prepared by the preparation method as described in any one of claims 1 to 13 4 SiO 4 A tritium breeding agent characterized in that the C/TiN-coated Li 4 SiO 4 The tritium breeder is C as the outer layer, tiN as the middle layer and Li as the inner layer 4 SiO 4 The microspheres of (1).
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