CN112174196A - TiN/C coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof - Google Patents
TiN/C coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof Download PDFInfo
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- C01G23/003—Titanates
- C01G23/005—Alkali titanates
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
- C01B21/0763—Preparation from titanium, zirconium or hafnium halides
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Abstract
The invention provides TiN/C coated Li2TiO3A tritium breeder, a preparation method and a preparation device system thereof are disclosed, wherein the preparation method comprises the following steps: (1) make Li2TiO3The particles are in a fluidized state in a protective atmosphere; (2) mixing Li on the basis of the continuous operation of the step (1)2TiO3Particles and carbon source gas to obtain C-coated Li2TiO3Particles; (3) mixing the C-coated Li obtained in the step (2) on the basis of continuous operation of the step (1)2TiO3Particles, titanium source gas and nitrogen source gas; (4) obtaining TiN/C coated Li after gas-solid separation2TiO3A tritium breeder. The device system comprisesThe device 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 Li2TiO3Corrosion to cladding material, and raising the content of lithium-base ceramic tritium breeder in He-H2/H2Stability 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 TiN/C coated Li2TiO3Tritium breeder, preparation method and preparation device system thereof.
Background
In the field of nuclear fusion, Li2TiO3The microsphere is one of candidate materials of the solid tritium breeding cladding, and has excellent performances of high Li density, good tritium release performance, high compressive strength, good moisture resistance and the like. However, with the development of research, Li is found in the actual service process2TiO3The microspheres can erode the cladding material, forming a brittle oxide erosion layer, which deteriorates the mechanical properties of the cladding material. Especially in He-H2In the atmosphere of cleaning, the corrosion phenomenon is more obvious, and great potential safety hazard is caused to the long-term stable operation of the nuclear reactor.
The corrosion phenomenon occurs mainly due to Li2TiO3Li and O elements in the microspheres and Fe, Cr, Ni and other elements in the steel-based cladding material have higher affinity, a fragile and porous oxide corrosion layer is generated in a service environment of 500-900 ℃, and meanwhile, the elements of the steel-based cladding material diffuse to a contact interface to cause component segregation in the matrix, so that the mechanical property of the steel matrix is further deteriorated.
In addition, Fe element in the steel-based cladding material also enters Li through diffusion2TiO3The crystal lattice and the crystal boundary reduce the crystal grain growth activation energy, and in a long-time service environment, the crystal grains grow abnormally, so that the compressive strength of the microspheres is reduced, and further the potential safety hazard of the collapse of a ball bed exists.
To solve this problem, the Japanese atomic energy mechanism was designed to have Er2O3Coated RAFM Steel (Fusion Eng. Des.87(2012)1777 and 1787), by design of Er2O3The coating layer creates a barrier layer between the microsphere and the steel substrate, and blocks Li2TiO3And 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.
CN106630985A discloses a nanostructured lithium orthosilicate ceramic pellet for tritium breeding and a preparation method thereof, which comprises the steps of firstly preparing precursor powder with uniform particle size by a solvothermal method, then obtaining a lithium ceramic pellet blank with uniform microstructure by wet forming, and finally obtaining the nanostructured lithium orthosilicate ceramic pellet by a two-step sintering mode. The lithium orthosilicate ceramic prepared by the invention has high purity and good sphericity, the grain size reaches the nanometer level, the pores are small, the distribution is uniform, and the irradiation resistance, the mechanical property and the tritium release performance of the tritium propagation ceramic can be improved. However, the lithium orthosilicate ceramic pellets are in direct contact with the cladding material during use, which affects the stability of the tritium breeder.
CN108911735A discloses a high sphericity tritium breeder nanostructured lithium titanate ceramic pellet and a preparation method thereof, the preparation method adopts a premixed liquid composed of a high molecular dispersant and deionized water and precursor powder to prepare a slurry with good fluidity, the obtained slurry is further subjected to wet forming and high-temperature sintering to obtain a nano-structured lithium titanate ceramic pellet with high sphericity, which is not only beneficial to filling of a tritium breeder pellet bed and recovery of residual lithium, but also can increase pellet stacking density to obtain a high-lithium density tritium breeder, and can further reduce thermal stress and irradiation cracking conditions of the tritium breeder and prolong the service life of the tritium breeder. However, the invention also has the problem that the lithium titanate ceramic pellets are in direct contact with the cladding material in the use 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 higher 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 breeding agent and the cladding material and prevent the tritium breeding agent from directly contacting with the cladding material becomes a problem to be solved urgently in the prior art of the tritium breeding cladding module in the nuclear fusion reactor.
Disclosure of Invention
The invention aims to provide TiN/C coated Li2TiO3Tritium breeder, method and apparatus system for its preparation, which overcomes Li2TiO3Corrosion to cladding material, and raising the content of lithium-base ceramic tritium breeder in He-H2/H2Stability in an O environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a TiN/C coated Li2TiO3A method of preparing a tritium proliferator, the method comprising the steps of:
(1) make Li2TiO3The particles are in a fluidized state in a protective atmosphere;
(2) mixing Li on the basis of the continuous operation of the step (1)2TiO3Particles and carbon source gas to obtain C-coated Li2TiO3Particles;
(3) mixing the C-coated Li obtained in the step (2) on the basis of continuous operation of the step (1)2TiO3Particles, titanium source gas and nitrogen source gas;
(4) obtaining TiN/C coated Li after gas-solid separation2TiO3A tritium breeder.
In the present invention, the fluidization state in the step (1) is such that not only Li2TiO3The particles are uniformly distributed in the reaction space, and the air in the reaction space is removed, so that the reaction between the oxygen in the air and the carbon source gas entering subsequently is prevented; step (2) said Li2TiO3The particles capture carbon atoms released by the decomposition reaction of the carbon source gas in a fluidized state, thereby forming Li2TiO3Forming a uniform carbon film on the surface of the particles; the C-coated Li of step (3)2TiO3Depositing a TiN film on the particles in a fluidized state to obtain TiN/C coated Li2TiO3The composite core-shell structure of (A) is an advanced tritium breeding agent.
Preferably, the Li in the step (1)2TiO3The particles are spherical or spheroidal in shape.
Preferably, the Li2TiO3The particles have an equivalent diameter of 0.1 to 1.2mm, and may be, for example, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.1mm or 1.2mm, but are not limited to the values listed, and other values not listed in the range of values are equally applicable.
In the present invention, when said Li is2TiO3When the particles are spherical in shape, the equivalent diameter is Li2TiO3The actual particle size of the particles; when said Li is2TiO3When the particles are spheroidal in shape, the equivalent diameter is Li2TiO3The average particle size of the particles.
Preferably, the gas in the protective atmosphere in step (1) comprises any one or a combination of at least two of argon, helium or neon, 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 is2TiO3The particles keep a fluidized state, and can isolate oxygen in the environment, so that the subsequent TiN/C film layer can be smoothly coated.
Preferably, the mixing method of step (2)In the formula (II) is that the carbon source gas is introduced into the Li2TiO3The particles are in a protective atmosphere.
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 unrecited values within the range of values are equally 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 carbon source gas in step (2) 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 (2) 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 mixing in the step (3) is performed in a manner that the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li2TiO3The 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 C-coated Li from different inlets at the same time2TiO3The particles are in a protective atmosphere so that the C coats the Li2TiO3A TiN film layer is formed on the surface of the particles.
Preferably, the temperature of the mixing in step (3) 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 unrecited values within the range of values are equally 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 titanium source gas in the step (3) 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-.
Preferably, the nitrogen source gas in step (3) is nitrogen.
Preferably, the titanium source gas is introduced in step (3) 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 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 equally applicable.
Preferably, the gas-solid separation method in step (4) comprises any one or a combination of at least two of gravity settling, centrifugal settling or filtration, and typical but non-limiting combinations include a combination of gravity settling and centrifugal settling, a combination of centrifugal settling and filtration, a combination of gravity settling and filtration, or a combination of gravity settling, centrifugal settling and filtration.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) making spherical or spheroidal Li with equivalent diameter of 0.1-1.2mm2TiO3The 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), introducing a carbon source gas into Li2TiO3The particles are in protective atmosphere to obtain C-coated Li2TiO3Particles; the mixing temperature is 500-900 ℃, and the mixing time is more than or equal to 1 min; 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 50-200 mL/min;
(3) on the basis of continuously performing the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the C-coated Li2TiO3The mixing temperature is 500-900 ℃ in the protective atmosphere of the particles, and the mixing time is more than or equal to 1 min; the titanium source gas is formed by gasifying titanium dichloride at the high temperature of 400-800 ℃, and the gas speed is 50-200 mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50-200 mL/min;
(4) obtaining TiN/C coated Li after gravity settling, centrifugal settling or filtering2TiO3A tritium breeder.
In a second aspect, the present invention provides a TiN/C coated Li prepared by the preparation method of the first aspect2TiO3Tritium breeder, said TiN/C coated Li2TiO3The tritium breeder has TiN as outer layer, C as middle layer and Li as inner layer2TiO3Microspheres of (2)。
In the present invention, the TiN/C coated Li2TiO3The tritium breeder departs from the traditional idea of creating a barrier layer by depositing an oxide coating on a cladding material by depositing Li2TiO3The TiN and C shells with corrosion resistance and good stability are constructed on the surfaces, 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 TiN and C films isolate the tritium breeder from H in the scavenging gas2/H2The 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 TiN/C coated Li2TiO3The 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 device2TiO3Particles;
the fluidized bed coating device is firstly used for mixing Li in protective atmosphere2TiO3Reacting the particles with a carbon source gas to obtain C-coated Li2TiO3Particles, then mixing C-coated Li in protective atmosphere2TiO3Reacting the particles, titanium source gas and nitrogen source gas to obtain TiN/C coated Li2TiO3A 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 TiN/C coated Li generated in the fluidized bed coating device2TiO3A 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 TiN/C film in the present invention blocks Li2TiO3The 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 TiN/C film in the present invention blocks Li2TiO3Tritium breeder and H in sweep gas2/H2The direct contact of O obviously improves the stability of the proliferation agent in the cladding;
(3) the invention prepares TiN/C coated Li2TiO3The tritium breeding agent has the advantages of simple method, uniform coating layer, controllable thickness, low cost and easy large-scale batch production.
Drawings
FIG. 1 is a process for preparing TiN/C coated Li according to the present invention2TiO3A device system for tritium breeders;
FIG. 2 is TiN/C coated Li obtained by the preparation method provided in example 12TiO3EDS profile of tritium breeder;
FIG. 3 is TiN/C coated Li obtained by the preparation method provided in example 12TiO3SEM 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 explained by the following 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 TiN/C coated Li as shown in figure 12TiO3The 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 present invention, the storage bin 1 is used for providing Li for the fluidized bed coating device 22TiO3Particles; the fluidized bed coating apparatus 2 is first used to mix Li in a protective atmosphere2TiO3The particles are mixed with a carbon source gas,obtaining C-coated Li after reaction2TiO3Particles, then mixing C-coated Li in protective atmosphere2TiO3Reacting the particles, titanium source gas and nitrogen source gas to obtain TiN/C coated Li2TiO3A 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 TiN/C coated Li generated in the fluidized bed coating device 22TiO3A 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 TiN/C coated Li2TiO3The 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 0.6mm2TiO3The particles are in a fluidized state in a protective atmosphere of argon;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas methane into Li2TiO3The particles are in protective atmosphere to obtain C-coated Li2TiO3Particles; the mixing temperature is 800 deg.C, and the mixing time is 30 min; the gas introducing speed of the carbon source gas is 125 mL/min;
(3) on the basis of continuously performing the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the C-coated Li2TiO3The mixing temperature of the granules in the protective atmosphere is 700 ℃, and the mixing time is 30 min; 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 125 mL/min; the nitrogen source gas is nitrogen, and the gas speed is 125 mL/min;
(4) obtaining TiN/C coated Li after gravity settling2TiO3A tritium breeder.
FIG. 2 is a view of TiN/C coated Li obtained by the preparation method provided in this example2TiO3EDS diagram of tritium breeder, wherein TiN content reaches 12.3 at.%, and C content reaches 12 at.%.
FIG. 3 is a view of TiN/C coated Li obtained by the preparation method provided in this example2TiO3The SEM image of the tritium breeder shows that a layer of nano TiN/C 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 TiN/C coated Li2TiO3The 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 0.9mm2TiO3The particles are in a fluidized state in a protective atmosphere of helium;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas ethane into Li2TiO3The particles are in protective atmosphere to obtain C-coated Li2TiO3Particles; the mixing temperature is 700 deg.C, and the mixing time is 45 min; the gas introducing speed of the carbon source gas is 160 mL/min;
(3) on the basis of continuously performing the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the C-coated Li2TiO3The mixing temperature of the granules in the protective atmosphere is 800 ℃, and the mixing time is 45 min; the titanium source gas is formed by gasifying titanium dichloride at a high temperature of 700 ℃, the carrier gas is helium, and the gas speed is 160 mL/min; the nitrogen source gas is nitrogen, and the gas speed is 160 mL/min;
(4) obtaining TiN/C coated Li after centrifugal sedimentation2TiO3A tritium breeder.
TiN/C-coated Li obtained in example2TiO3The 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 3
This example provides a TiN/C coated Li2TiO3The 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 0.3mm2TiO3The particles are in a fluidized state in a protective atmosphere of neon;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas ethylene into Li2TiO3The particles are in protective atmosphere to obtain C-coated Li2TiO3Particles; the mixing temperature is 600 ℃, and the mixing time is 15 min; the gas introducing speed of the carbon source gas is 85 mL/min;
(3) on the basis of continuously performing the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the C-coated Li2TiO3The mixing temperature of the granules in the protective atmosphere is 600 ℃, and the mixing time is 15 min; 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 85 mL/min; the nitrogen source gas is nitrogen, and the gas speed is 85 mL/min;
(4) filtering to obtain TiN/C coated Li2TiO3A tritium breeder.
TiN/C-coated Li obtained in example2TiO3The 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 TiN/C coated Li2TiO3The 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 1.2mm2TiO3The particles are in a fluidized state in a protective atmosphere of argon;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas propylene into Li2TiO3The particles are in protective atmosphere to obtain C-coated Li2TiO3Particles; the temperature of mixing is 900 ℃, mixingThe mixing time is 1 min; the gas introducing speed of the carbon source gas is 200 mL/min;
(3) on the basis of continuously performing the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the C-coated Li2TiO3Mixing the granules in a protective atmosphere at 900 deg.C for 1 min; 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 200 mL/min; the nitrogen source gas is nitrogen, and the gas speed is 200 mL/min;
(4) obtaining TiN/C coated Li after gravity settling2TiO3A tritium breeder.
TiN/C-coated Li obtained in example2TiO3The 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 example provides a TiN/C coated Li2TiO3The 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 0.1mm2TiO3The particles are in a fluidized state in a protective atmosphere of helium;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas acetylene into Li2TiO3The particles are in protective atmosphere to obtain C-coated Li2TiO3Particles; mixing at 500 deg.C for 60 min; the gas introducing speed of the carbon source gas is 50 mL/min;
(3) on the basis of continuously performing the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the C-coated Li2TiO3The mixing temperature of the granules in the protective atmosphere is 500 ℃, and the mixing time is 60 min; 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 50 mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50 mL/min;
(4) obtaining TiN/C coated Li after centrifugal sedimentation2TiO3A tritium breeder.
TiN/C-coated Li obtained in example2TiO3The 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.
Comparative example 1
This comparative example provides Li2TiO3A 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 0.6mm2TiO3The 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 Li2TiO3The particles are in a protective atmosphere; the mixing temperature is 700 deg.C, and the mixing time is 30 min; 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 125 mL/min; the nitrogen source gas is nitrogen, and the gas speed is 125 mL/min;
(3) treated Li obtained after gravity settling2TiO3A tritium breeder.
Treated Li obtained in this comparative example2TiO3The tritium breeder is not coated with a TiN film layer, so that the TiN/C coated Li provided by the invention can be seen2TiO3The tritium breeder needs to be coated with a TiN layer on the basis of coating the C layer, and the coating sequence of the C layer and the TiN layer cannot be converted.
Comparative example 2
This comparative example provides Li2TiO3A 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 0.6mm2TiO3The particles are in a fluidized state in a protective atmosphere of argon;
(2) introducing nitrogen into Li on the basis of continuous operation of the step (1)2TiO3The particles are locatedThe mixing temperature is 700 ℃, and the mixing time is 30 min; the gas introducing speed of the nitrogen is 125 mL/min;
(3) obtaining Li after gravity settling2TiO3A tritium breeder.
Li obtained in example 1 and comparative example 22TiO3The 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 12TiO3Low activation steel with tritium breeder showed no significant corrosion, but was loaded with Li from comparative example 12TiO3The low activation steel of tritium breeder found obvious corrosion, indicating Li2TiO3The tritium breeder obviously inhibits the corrosion of the low-activation steel after coating the TiN/C layer.
It can be seen that the inert TiN/C film in the present invention hinders Li2TiO3The 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 TiN/C film in the present invention blocks Li2TiO3Tritium breeder and H in sweep gas2/H2The direct contact of O obviously improves the stability of the proliferation agent in the cladding; the invention prepares TiN/C coated Li2TiO3The 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 (10)
1. TiN/C coated Li2TiO3A process for the preparation of a tritium breeder, characterized in that it comprises the following steps:
(1) make Li2TiO3The particles are in a fluidized state in a protective atmosphere;
(2) mixing Li on the basis of the continuous operation of the step (1)2TiO3Particles and carbon source gas to obtain C-coated Li2TiO3Particles;
(3) mixing the C-coated Li obtained in the step (2) on the basis of continuous operation of the step (1)2TiO3Particles, titanium source gas and nitrogen source gas;
(4) obtaining TiN/C coated Li after gas-solid separation2TiO3A tritium breeder.
2. The production method according to claim 1, wherein the Li of step (1)2TiO3The shape of the particles is spherical or spheroidal;
preferably, the Li2TiO3The equivalent diameter of the particles is 0.1-1.2 mm.
3. The method according to claim 1 or 2, 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 thereof.
4. The production method according to any one of claims 1 to 3, wherein the mixing in step (2) is performed by passing the carbon source gas through the Li2TiO3The particles are in a protective atmosphere;
preferably, the temperature of the mixing in the step (2) is 500-900 ℃;
preferably, the mixing time of the step (2) is more than or equal to 1 min;
preferably, the carbon source gas in step (2) comprises any one or a combination of at least two of methane, ethane, ethylene, acetylene or propylene;
preferably, the carbon source gas in the step (2) is introduced at a gas flow rate of 50-200 mL/min.
5. Preparation according to any one of claims 1 to 4The method is characterized in that the mixing mode in the step (3) is that the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li2TiO3The particles are in a protective atmosphere;
preferably, the temperature of the mixing in the step (3) is 500-900 ℃;
preferably, the mixing time of the step (3) is more than or equal to 1 min;
preferably, the titanium source gas in the step (3) is a gas formed by high-temperature gasification of 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 the step (1);
preferably, the temperature of the high-temperature gasification is 400-800 ℃;
preferably, the nitrogen source gas in step (3) is nitrogen.
6. The production method according to any one of claims 1 to 5, wherein the titanium source gas in the step (3) is introduced at a gas flow rate of 50 to 200 mL/min;
preferably, the nitrogen source gas in the step (3) is introduced at a gas flow rate of 50-200 mL/min.
7. The process of any one of claims 1 to 6, wherein the gas-solid separation in step (4) comprises any one or a combination of at least two of gravity settling, centrifugal settling or filtration.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) making spherical or spheroidal Li with equivalent diameter of 0.1-1.2mm2TiO3The 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), introducing a carbon source gas into Li2TiO3The particles are in protective atmosphere to obtain C-coated Li2TiO3Particles; the mixing temperature is 500-900 ℃, and the mixing time is more than or equal to 1 min; 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 50-200 mL/min;
(3) on the basis of continuously performing the step (1), respectively and independently introducing a titanium source gas and a nitrogen source gas into the C-coated Li2TiO3The mixing temperature is 500-900 ℃ in the protective atmosphere of the particles, and the mixing time is more than or equal to 1 min; the titanium source gas is formed by gasifying titanium dichloride at the high temperature of 400-800 ℃, and the gas speed is 50-200 mL/min; the nitrogen source gas is nitrogen, and the gas speed is 50-200 mL/min;
(4) obtaining TiN/C coated Li after gravity settling, centrifugal settling or filtering2TiO3A tritium breeder.
9. TiN/C coated Li prepared by the preparation method according to any one of claims 1 to 82TiO3A tritium breeding agent characterized in that the TiN/C-coated Li2TiO3The tritium breeder has TiN as outer layer, C as middle layer and Li as inner layer2TiO3The microspheres of (1).
10. Is used for preparing TiN/C coated Li2TiO3The device system for the tritium breeder is characterized by comprising 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 device2TiO3Particles;
the fluidized bed coating device is firstly used for mixing Li in protective atmosphere2TiO3Reacting the particles with a carbon source gas to obtain C-coated Li2TiO3Particles, then mixing C-coated Li in protective atmosphere2TiO3Reacting the particles, titanium source gas and nitrogen source gas to obtain TiN/C coated Li2TiO3Tritium boosterA reproductive 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 TiN/C coated Li generated in the fluidized bed coating device2TiO3A tritium proliferating agent;
the tail gas treatment device is used for removing tail gas generated in the fluidized bed coating device.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115305442A (en) * | 2022-08-26 | 2022-11-08 | 核工业西南物理研究院 | Surface modified tritium proliferation agent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228130A (en) * | 1998-02-04 | 1999-08-24 | Nuclear Fuel Ind Ltd | Lithium ceramic granule and its production |
| EP1138650A1 (en) * | 2000-03-31 | 2001-10-04 | Ngk Insulators, Ltd. | Method of manufacturing lithium titanate pebbles |
| CN105449187A (en) * | 2015-12-20 | 2016-03-30 | 华南理工大学 | Preparation method of high-performance co-doped lithium titanate electrode material |
| CN106252623A (en) * | 2016-08-26 | 2016-12-21 | 深圳博磊达新能源科技有限公司 | A kind of carbon-nitrogen doped lithium titanate electrode material, preparation method and application |
| CN108807884A (en) * | 2018-05-31 | 2018-11-13 | 中国科学院过程工程研究所 | A kind of system and method for lithium ion battery negative material carbon coating modification |
-
2020
- 2020-09-28 CN CN202011045490.9A patent/CN112174196B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228130A (en) * | 1998-02-04 | 1999-08-24 | Nuclear Fuel Ind Ltd | Lithium ceramic granule and its production |
| EP1138650A1 (en) * | 2000-03-31 | 2001-10-04 | Ngk Insulators, Ltd. | Method of manufacturing lithium titanate pebbles |
| CN105449187A (en) * | 2015-12-20 | 2016-03-30 | 华南理工大学 | Preparation method of high-performance co-doped lithium titanate electrode material |
| CN106252623A (en) * | 2016-08-26 | 2016-12-21 | 深圳博磊达新能源科技有限公司 | A kind of carbon-nitrogen doped lithium titanate electrode material, preparation method and application |
| CN108807884A (en) * | 2018-05-31 | 2018-11-13 | 中国科学院过程工程研究所 | A kind of system and method for lithium ion battery negative material carbon coating modification |
Non-Patent Citations (2)
| Title |
|---|
| 赵崴巍等: "氚增殖包层结构材料阻氚涂层技术研究现状", 《中国核科学技术进展报告（第二卷）》 * |
| 雷永泉 等: "《新能源材料》", 31 December 2000 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115305442A (en) * | 2022-08-26 | 2022-11-08 | 核工业西南物理研究院 | Surface modified tritium proliferation agent and preparation method thereof |
| CN115305442B (en) * | 2022-08-26 | 2023-09-19 | 核工业西南物理研究院 | Surface modified tritium breeder and preparation method thereof |
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