CN112174196B - TiN/C coated lithium titanate tritium proliferation agent, preparation method and preparation device system thereof - Google Patents
TiN/C coated lithium titanate tritium proliferation agent, preparation method and preparation device system thereof Download PDFInfo
- Publication number
- CN112174196B CN112174196B CN202011045490.9A CN202011045490A CN112174196B CN 112174196 B CN112174196 B CN 112174196B CN 202011045490 A CN202011045490 A CN 202011045490A CN 112174196 B CN112174196 B CN 112174196B
- Authority
- CN
- China
- Prior art keywords
- tio
- gas
- coated
- source gas
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21B—FUSION REACTORS
- G21B1/00—Thermonuclear fusion reactors
- G21B1/11—Details
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a TiN/C coated Li 2 TiO 3 Tritium breeder, preparation method and preparation device system thereof, wherein the preparation method comprises the following steps: (1) Causing Li to be 2 TiO 3 The particles are in a fluidization state in a protective atmosphere; (2) Mixing Li on the basis of the continuous progress of the step (1) 2 TiO 3 Particles and carbon source gas to obtain C-coated Li 2 TiO 3 Particles; (3) Mixing the C-coated Li obtained in the step (2) on the basis of continuous proceeding of the step (1) 2 TiO 3 Particles, titanium source gas and nitrogen source gas; (4) After gas-solid separation, tiN/C coated Li is obtained 2 TiO 3 Tritium breeder. The device system 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 invention overcomes the defects of Li 2 TiO 3 Corrosion to cladding material and promotion of the proliferation agent of lithium-based ceramic tritium in He-H 2 /H 2 Stability in O environment.
Description
Technical Field
The invention belongs to the technical field of nuclear fusion, relates to a preparation method of a nuclear shell structure advanced lithium-based ceramic tritium breeder, and in particular relates to a TiN/C coated Li 2 TiO 3 Tritium breeder, its preparation method and preparation device system.
Background
In the field of nuclear fusion, li 2 TiO 3 The microsphere is used as one of candidate materials of the solid tritium proliferation cladding, and has the excellent performances of high Li density, good tritium release performance, high compressive strength, good moisture resistance and the like. However, with the progressive development of research, it was found that Li 2 TiO 3 The microspheres can erode the cladding material to form a brittle oxide erosion layer, thereby deteriorating the mechanical properties of the cladding material. Especially in He-H 2 In the clean atmosphere, the corrosion phenomenon is more obvious, and causes a great potential safety hazard for long-term stable operation of the nuclear reactor.
The corrosion phenomenon occurs mainly due to Li 2 TiO 3 Li and O elements in the microspheres have larger affinity with Fe, cr, ni and other elements in the steel-based cladding material, a fragile and porous oxide corrosion layer is generated in the service environment at 500-900 ℃, and meanwhile, the elements of the steel-based cladding material diffuse to a contact interface to cause the segregation of components 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 by diffusion 2 TiO 3 The crystal lattice and crystal boundary reduce the activation energy of crystal grain growth, and in a long-time service environment, the crystal grains can grow abnormally, so that the compressive strength of the microsphere is reduced, and the potential safety hazard of collapse of the sphere is further caused.
To solve this problem, japanese atomic energy institutions were designed with Er 2 O 3 Coated RAFM steel (Fusion Eng. Des.87 (2012) 1777-1787) by design Er 2 O 3 The coating creates a barrier layer between the microspheres and the steel matrix, which hinders Li 2 TiO 3 And the element between the steel matrix diffuses and reacts, so that the safety of the cladding is improved. However, as the service time increases, the coating is easily removed due to the large thermal stress existing between the oxide and the RAFM steel substrate.
CN106630985a discloses a nano-structured lithium orthosilicate ceramic pellet for tritium proliferation and a preparation method thereof, wherein precursor powder with uniform particle size is prepared by a solvothermal method, then a lithium ceramic pellet biscuit with uniform microstructure is obtained by wet forming, and finally the nano-structured lithium orthosilicate ceramic pellet is obtained by a two-step sintering method. The lithium orthosilicate ceramic prepared by the method has high purity and good sphericity, has crystal grain size reaching nanometer level, small pores and uniform distribution, and is expected to improve the irradiation resistance, mechanical property and tritium release property of tritium proliferation ceramic at the same time. However, the lithium orthosilicate ceramic pellets are in direct contact with the cladding material during use, affecting the stability of the tritium breeder.
CN108911735a discloses a nano-structured lithium titanate ceramic pellet of a high sphericity tritium proliferation agent and a preparation method thereof, the preparation method adopts a premix solution composed of a high molecular dispersant and deionized water and precursor powder to prepare slurry with good fluidity, the obtained slurry is further subjected to wet forming and high-temperature sintering to obtain the nano-structured lithium titanate ceramic pellet with high sphericity, which is not only beneficial to filling of a tritium proliferation pellet bed and recovery of residual lithium, but also can increase the stacking density of the pellet to obtain the tritium proliferation agent with high lithium density, and can further reduce the thermal stress and irradiation cracking condition of the tritium proliferation agent and prolong the service life of the tritium proliferation agent. 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, and the phenomenon of corrosion of the cladding material is easy to cause.
CN108550404a discloses a fluid tritium proliferation ceramic composite material, which is formed by mixing liquid and solid phases, and can eliminate the magnetohydrodynamic resistance effect of the existing liquid metal or molten salt tritium proliferation agent and the corrosion effect on cladding structural materials, and can also eliminate the problems of low tritium release efficiency, low heat transfer, fragility, carrier gas channel blockage caused by lithium volatilization, and the like. However, the cost of the method is high, the large-scale batch production is difficult to realize, and the problem that the cladding material is corroded after long-term use cannot be fundamentally avoided due to the diffusion of elements between the tritium breeder and the cladding material.
Therefore, how to further design and optimize the barrier layer between the tritium breeder and the cladding material to prevent the tritium breeder from directly contacting with the cladding material becomes a problem to be solved by the tritium breeder cladding module in the nuclear fusion reactor at present.
Disclosure of Invention
The invention aims to provide a TiN/C coated Li 2 TiO 3 Tritium breeder, preparation method and preparation device system thereof, wherein the preparation method overcomes Li 2 TiO 3 Corrosion to cladding material and promotion of the proliferation agent of lithium-based ceramic tritium in He-H 2 /H 2 Stability in O environment.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a TiN/C coated Li 2 TiO 3 A method of preparing a tritium breeder, the method comprising the steps of:
(1) Causing Li to be 2 TiO 3 The particles are in a fluidization state in a protective atmosphere;
(2) Mixing Li on the basis of the continuous progress of the step (1) 2 TiO 3 Particles and carbon source gas to obtain C-coated Li 2 TiO 3 Particles;
(3) Mixing the C-coated Li obtained in the step (2) on the basis of continuous proceeding of the step (1) 2 TiO 3 Particles, titanium source gas and nitrogen source gas;
(4) After gas-solid separation, tiN/C coated Li is obtained 2 TiO 3 Tritium breeder.
In the present invention, the fluidization state of step (1) is such that not only Li 2 TiO 3 The particles are uniformly distributed in the reaction space, and air in the reaction space is removed, so that oxygen in the air is prevented from reacting with the carbon source gas which enters subsequently; step (2) the Li 2 TiO 3 The particles capture carbon atoms released by the decomposition reaction of the carbon source gas in a fluidized state, thereby forming Li 2 TiO 3 Forming a uniform carbon film on the surface of the particles; step (3) the C-coated Li 2 TiO 3 The particles are deposited with a layer of TiN film in a fluidized state, so that TiN/C coated Li is obtained 2 TiO 3 Advanced tritium breeder in the composite core-shell structure.
Preferably, the Li of step (1) 2 TiO 3 The particles are spherical or spheroid in shape.
Preferably, the Li 2 TiO 3 The equivalent diameter of the particles is 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 is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the present invention, when Li is 2 TiO 3 When the shape of the particles is spherical, the equivalent diameter is Li 2 TiO 3 The actual particle size of the particles; when the Li is 2 TiO 3 When the shape of the particles is sphere-like, the equivalent diameter is Li 2 TiO 3 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 typically, but not limited to, 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 2 TiO 3 The particles keep a fluidized state, can isolate oxygen in the environment, and are convenient for the smooth coating of the subsequent TiN/C film layer.
Preferably, the mixing in step (2) is performed by introducing the carbon source gas into the Li 2 TiO 3 The particles are in a protective atmosphere.
Preferably, the temperature of the mixing in the step (2) is 500 to 900 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, but the temperature is not limited to the values listed, and other values not listed in the range are applicable.
Preferably, the mixing time in the step (2) is not less than 1min, for example, 1min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the carbon source gas of step (2) comprises any one or a combination of at least two of methane, ethane, ethylene, acetylene or propylene, typically but not limited to combinations comprising methane and ethane, ethane and ethylene, ethylene and acetylene, acetylene and propylene, methane, ethane and ethylene, ethane, ethylene and acetylene, or ethylene, acetylene and propylene.
Preferably, the gas velocity of the carbon source gas in the step (2) is 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, but the present invention is not limited to the above values, and other values not listed in the above values are equally applicable.
Preferably, the mixing in the step (3) is performed by independently introducing the titanium source gas and the nitrogen source gas into the C-coated Li 2 TiO 3 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 C-coated Li from different inlets at the same time 2 TiO 3 The particles are in a protective atmosphere so that C coats Li 2 TiO 3 The surface of the particles forms a TiN film layer.
Preferably, the temperature of the mixing in the step (3) is 500 to 900 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, but the temperature is not limited to the values listed, and other values not listed in the range are applicable.
Preferably, the mixing time in the step (3) is not less than 1min, for example, 1min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the titanium source gas in the step (3) is a gas formed by gasifying titanium salt at a high temperature.
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).
The high-temperature gasification temperature is preferably 400 to 800 ℃, and may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, for example, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the nitrogen source gas in the step (3) is nitrogen.
Preferably, the gas velocity of the titanium source gas in the step (3) is 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, but the present invention is not limited to the above values, and other values not listed in the above values are equally applicable.
Preferably, the gas velocity of the nitrogen source gas in the step (3) is 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, but the present invention is not limited to the above values, and other values not listed in the above values are equally applicable.
Preferably, the method of gas-solid separation of step (4) comprises any one or a combination of at least two of gravity sedimentation, centrifugal sedimentation or filtration, typically but not limited to a combination of gravity sedimentation and centrifugal sedimentation, a combination of centrifugal sedimentation and filtration, a combination of gravity sedimentation and filtration, or a combination of gravity sedimentation, centrifugal sedimentation and filtration.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Spherical or spheroidic Li with equivalent diameter of 0.1-1.2mm 2 TiO 3 The particles are in a fluidization state in a protective atmosphere; the gas in the protective atmosphere comprises any one or a combination of at least two of argon, helium and neon;
(2) Introducing a carbon source gas into Li on the basis of continuous proceeding of the step (1) 2 TiO 3 In the protective atmosphere of the particles, the C-coated Li is obtained 2 TiO 3 Particles; the mixing temperature is 500-900 ℃, and the mixing time is more than or equal to 1min; the carbon source gas comprises any one or a combination of at least two of methane, ethane, ethylene, acetylene or propylene; the gas inlet speed of the carbon source gas is 50-200mL/min;
(3) On the basis of continuous proceeding of the step (1), the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li 2 TiO 3 In the protective atmosphere of the particles, the mixing temperature is 500-900 ℃, and the mixing time is more than or equal to 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;
(4) After gravity sedimentation, centrifugal sedimentation or filtration, the TiN/C coated Li is obtained 2 TiO 3 Tritium breeder.
In a second aspect, the present invention provides a TiN/C coated Li prepared by the preparation method according to the first aspect 2 TiO 3 Tritium breeder, the TiN/C coating Li 2 TiO 3 The tritium breeder is TiN as outer layer, C as intermediate layer and Li as inner layer 2 TiO 3 Is a microsphere of (a).
In the invention, the TiN/C coats Li 2 TiO 3 Tritium breeder eliminates the conventional thought of depositing oxide coating on cladding material to create barrier layer by depositing on Li 2 TiO 3 The surface is constructed with a corrosion-resistant and good-stability TiN and C shell, so that an inert protective layer is formed between the tritium proliferation agent and the cladding material to achieve the aim of corrosion prevention, and meanwhile, the hydrophobic TiN and C film isolate the tritium proliferation agent from H in the scavenging gas 2 /H 2 O is directly contacted to achieve the aim of improving the stability of the tritium breeder, thereby solving the key problems of cladding coating shedding and tritium breeder crushingThe problem is finally obtained, namely an advanced lithium-based ceramic tritium breeder.
In a third aspect, the present invention provides a method for preparing TiN/C coated Li 2 TiO 3 The device system of 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 bin is used for providing Li for the fluidized bed coating device 2 TiO 3 Particles;
the fluidized bed coating device is firstly used for mixing Li in a protective atmosphere 2 TiO 3 The particles react with carbon source gas to obtain C-coated Li 2 TiO 3 Particles, and then used for mixing C to coat Li in protective atmosphere 2 TiO 3 The particles, titanium source gas and nitrogen source gas react to obtain TiN/C coated Li 2 TiO 3 Tritium breeder;
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 device 2 TiO 3 Tritium breeder;
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 of the invention hinders Li 2 TiO 3 The tritium breeder is in direct contact with the cladding material, so that the diffusion and reaction between Li, O, fe, cr elements are fundamentally avoided, and the safety of the cladding material is obviously improved;
(2) The inert TiN/C film of the invention hinders Li 2 TiO 3 Tritium breeder and H in purge gas 2 /H 2 The direct contact of O remarkably improves the stability of the proliferation agent in the cladding;
(3) Preparation of TiN/C coated Li according to the invention 2 TiO 3 The tritium breeder has the advantages of simple method, uniform coating layer, controllable thickness, low cost and easy mass production.
Drawings
FIG. 1 shows a method for preparing TiN/C coated Li according to the present invention 2 TiO 3 A tritium breeder device system;
FIG. 2 is a TiN/C coated Li obtained by the preparation method provided in example 1 2 TiO 3 EDS diagram of tritium breeder;
FIG. 3 is a TiN/C coated Li obtained by the preparation method provided in example 1 2 TiO 3 SEM image of tritium breeder.
Wherein: 1-a storage bin; 2-a fluidized bed coating device; 3-titanium source gasification device; 4-a product collection device; 5-tail gas treatment device.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The present invention provides a method for preparing TiN/C coated Li as shown in FIG. 1 2 TiO 3 The device system of the tritium breeder comprises a storage bin 1, a fluidized bed coating device 2, a titanium source gasification device 3, a product collection device 4 and a tail gas treatment device 5.
In the present invention, the silo 1 is used for providing Li for the fluidized bed coating device 2 2 TiO 3 Particles; the fluidized bed coating device 2 is used for mixing Li in a protective atmosphere 2 TiO 3 The particles react with carbon source gas to obtain C-coated Li 2 TiO 3 Particles, and then used for mixing C to coat Li in protective atmosphere 2 TiO 3 The particles, titanium source gas and nitrogen source gas react to obtain TiN/C coated Li 2 TiO 3 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 TiN/C coated Li generated in the fluidized bed coating device 2 2 TiO 3 Tritium breeder, in particular, said product collection device4 is a storage tank; the tail gas treatment device 5 is used for treating the 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
The present embodiment provides a TiN/C coated Li 2 TiO 3 A method for preparing a tritium breeder, which is carried out in the device system shown in the figure 1 provided by the invention, comprises the following steps:
(1) Spherical Li having a particle diameter of 0.6mm 2 TiO 3 The particles are in a fluidization state in the protective atmosphere of argon;
(2) On the basis of continuously proceeding the step (1), introducing carbon source gas methane into Li 2 TiO 3 In the protective atmosphere of the particles, the C-coated Li is obtained 2 TiO 3 Particles; the mixing temperature is 800 ℃, and the mixing time is 30min; the gas inlet speed of the carbon source gas is 125mL/min;
(3) On the basis of continuous proceeding of the step (1), the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li 2 TiO 3 In the protective atmosphere of the particles, the mixing temperature is 700 ℃, 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;
(4) After gravity sedimentation, tiN/C coated Li is obtained 2 TiO 3 Tritium breeder.
FIG. 2 shows a TiN/C coated Li obtained by the preparation method of the present example 2 TiO 3 EDS plot of tritium breeder, wherein TiN content reaches 12.3at.% and C content reaches 12at.%.
FIG. 3 shows a TiN/C coated Li obtained by the preparation method of the present example 2 TiO 3 In the SEM image of tritium breeder, as can be seen from FIG. 3, the surface of the crystal grain of the microsphere is uniformly coated with a layer of nano TiN/C film.
Example 2
The present embodiment provides a TiN/C coated Li 2 TiO 3 Preparation of tritium breederThe preparation method is carried out in the device system shown in the figure 1, and comprises the following steps:
(1) Spherical Li-like particles having an average particle diameter of 0.9mm 2 TiO 3 The particles are in a fluidization state in protective atmosphere helium;
(2) Introducing carbon source gas ethane into Li on the basis of continuously carrying out the step (1) 2 TiO 3 In the protective atmosphere of the particles, the C-coated Li is obtained 2 TiO 3 Particles; the mixing temperature is 700 ℃, and the mixing time is 45min; the gas inlet speed of the carbon source gas is 160mL/min;
(3) On the basis of continuous proceeding of the step (1), the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li 2 TiO 3 In the protective atmosphere of the particles, the mixing temperature is 800 ℃, and the mixing time is 45min; 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 160mL/min; the nitrogen source gas is nitrogen, and the gas speed is 160mL/min;
(4) Centrifugal sedimentation to obtain TiN/C coated Li 2 TiO 3 Tritium breeder.
TiN/C coated Li obtained in this example 2 TiO 3 The elemental composition and microstructure of the tritium breeder are similar to those of example 1 and will not be described in detail herein.
Example 3
The present embodiment provides a TiN/C coated Li 2 TiO 3 A method for preparing a tritium breeder, which is carried out in the device system shown in the figure 1 provided by the invention, comprises the following steps:
(1) Spherical Li having a particle diameter of 0.3mm 2 TiO 3 The particles are in a fluidized state in protective atmosphere neon;
(2) Introducing carbon source gas ethylene into Li on the basis of continuously carrying out the step (1) 2 TiO 3 In the protective atmosphere of the particles, the C-coated Li is obtained 2 TiO 3 Particles; the mixing temperature is 600 ℃, and the mixing time is 15min; the carbon source gasThe air inlet speed of the body is 85mL/min;
(3) On the basis of continuous proceeding of the step (1), the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li 2 TiO 3 In the protective atmosphere of the 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;
(4) Filtering to obtain TiN/C coated Li 2 TiO 3 Tritium breeder.
TiN/C coated Li obtained in this example 2 TiO 3 The elemental composition and microstructure of the tritium breeder are similar to those of example 1 and will not be described in detail herein.
Example 4
The present embodiment provides a TiN/C coated Li 2 TiO 3 A method for preparing a tritium breeder, which is carried out in the device system shown in the figure 1 provided by the invention, comprises the following steps:
(1) Spherical Li-like particles having an average particle diameter of 1.2mm 2 TiO 3 The particles are in a fluidization state in the protective atmosphere of argon;
(2) Introducing carbon source gas propylene into Li on the basis of continuously carrying out the step (1) 2 TiO 3 In the protective atmosphere of the particles, the C-coated Li is obtained 2 TiO 3 Particles; the mixing temperature is 900 ℃, and the mixing time is 1min; the gas inlet speed of the carbon source gas is 200mL/min;
(3) On the basis of continuous proceeding of the step (1), the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li 2 TiO 3 In the protective atmosphere of the particles, the mixing temperature is 900 ℃, and the mixing time is 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;
(4) After gravity sedimentation, tiN/C coated Li is obtained 2 TiO 3 Tritium breeder。
TiN/C coated Li obtained in this example 2 TiO 3 The elemental composition and microstructure of the tritium breeder are similar to those of example 1 and will not be described in detail herein.
Example 5
The present embodiment provides a TiN/C coated Li 2 TiO 3 A method for preparing a tritium breeder, which is carried out in the device system shown in the figure 1 provided by the invention, comprises the following steps:
(1) Spherical Li having a particle diameter of 0.1mm 2 TiO 3 The particles are in a fluidization state in protective atmosphere helium;
(2) Introducing acetylene as a carbon source gas into Li on the basis of continuous proceeding of the step (1) 2 TiO 3 In the protective atmosphere of the particles, the C-coated Li is obtained 2 TiO 3 Particles; the mixing temperature is 500 ℃, and the mixing time is 60min; the gas inlet speed of the carbon source gas is 50mL/min;
(3) On the basis of continuous proceeding of the step (1), the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li 2 TiO 3 In the protective atmosphere of the particles, 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;
(4) Centrifugal sedimentation to obtain TiN/C coated Li 2 TiO 3 Tritium breeder.
TiN/C coated Li obtained in this example 2 TiO 3 The elemental composition and microstructure of the tritium breeder are similar to those of example 1 and will not be described in detail herein.
Comparative example 1
This comparative example provides a Li 2 TiO 3 A method for treating a tritium breeder, which is carried out in the device system shown in fig. 1 provided by the invention, comprises the following steps:
(1) Spherical Li having a particle diameter of 0.6mm 2 TiO 3 Particle atThe protective atmosphere argon is in a fluidization state;
(2) Independently introducing a titanium source gas and a nitrogen source gas into the Li on the basis of continuous progress of the step (1) 2 TiO 3 The particles are in a protective atmosphere; the mixing temperature is 700 ℃, 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) After gravity sedimentation, treated Li is obtained 2 TiO 3 Tritium breeder.
Treated Li obtained in this comparative example 2 TiO 3 The tritium breeder is not coated with TiN film layer, thus the TiN/C coated Li provided by the invention 2 TiO 3 The tritium breeder needs to be coated with the TiN layer on the basis of coating the C layer, and the coating sequence of the C layer and the TiN layer cannot be changed.
Comparative example 2
This comparative example provides a Li 2 TiO 3 A method for treating a tritium breeder, which is carried out in the device system shown in fig. 1 provided by the invention, comprises the following steps:
(1) Spherical Li having a particle diameter of 0.6mm 2 TiO 3 The particles are in a fluidization state in the protective atmosphere of argon;
(2) Introducing nitrogen into Li on the basis of continuous operation of the step (1) 2 TiO 3 In the protective atmosphere of the particles, the mixing temperature is 700 ℃, and the mixing time is 30min; the gas inlet speed of the nitrogen is 125mL/min;
(3) After gravity sedimentation, li is obtained 2 TiO 3 Tritium breeder.
Li obtained in example 1 and comparative example 2 2 TiO 3 Tritium breeder is respectively filled in a container of low-activation steel, heated to 650 ℃ under argon atmosphere and kept for 10 days, then the surface of the low-activation steel is analyzed and tested, and as a result, li obtained in the example 1 is filled 2 TiO 3 The low activation steels of tritium breeder did not show significant corrosion but were loaded with Li from comparative example 1 2 TiO 3 The low activation steel of tritium breeder found a significant corrosion phenomenon, indicating Li 2 TiO 3 The tritium breeder significantly inhibits corrosion of the low activation steel after coating the TiN/C layer.
It can be seen that the inert TiN/C film of the present invention blocks Li 2 TiO 3 The tritium breeder is in direct contact with the cladding material, so that the diffusion and reaction between Li, O, fe, cr elements are fundamentally avoided, and the safety of the cladding material is obviously improved; the inert TiN/C film of the invention hinders Li 2 TiO 3 Tritium breeder and H in purge gas 2 /H 2 The direct contact of O remarkably improves the stability of the proliferation agent in the cladding; preparation of TiN/C coated Li according to the invention 2 TiO 3 The tritium breeder has the advantages of simple method, uniform coating layer, controllable thickness, low cost and easy mass production.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (14)
1. TiN/C coated Li 2 TiO 3 A method for preparing a tritium breeder, the method comprising the steps of:
(1) Li with equivalent diameter of 0.1-1.2mm 2 TiO 3 The particles are in a fluidization state in a protective atmosphere;
(2) On the basis of continuously carrying out the step (1), introducing a carbon source gas into Li at a gas speed of 50-200mL/min 2 TiO 3 Mixing the particles in a protective atmosphere at 500-900 ℃ to obtain the C-coated Li 2 TiO 3 Particles;
(3) On the basis of continuously carrying out the step (1), independently introducing a titanium source gas and a nitrogen source gas into the C-coated Li at a gas speed of 50-200mL/min 2 TiO 3 Protection of the particlesMixing in the atmosphere at 500-900 ℃;
(4) After gas-solid separation, tiN/C coated Li is obtained 2 TiO 3 Tritium breeder.
2. The method according to claim 1, wherein the Li in the step (1) 2 TiO 3 The particles are spherical or spheroid in shape.
3. The method of claim 1, wherein the gas in the protective atmosphere of step (1) comprises any one or a combination of at least two of argon, helium, or neon.
4. The method according to claim 1, wherein the mixing time in step (2) is not less than 1min.
5. The method of claim 1, wherein the carbon source gas of step (2) comprises any one or a combination of at least two of methane, ethane, ethylene, acetylene, or propylene.
6. The method according to claim 1, wherein the mixing time in step (3) is not less than 1min.
7. The method according to claim 1, wherein the titanium source gas in the step (3) is a gas formed by gasifying titanium salt at a high temperature.
8. The method according to claim 7, wherein the titanium salt is titanium dichloride.
9. The method of claim 7, wherein the carrier gas for high temperature gasification is the gas in the protective atmosphere of step (1).
10. The method of claim 7, wherein the high temperature gasification is at a temperature of 400-800 ℃.
11. The method of claim 1, wherein the nitrogen source gas in step (3) is nitrogen.
12. The method of claim 1, wherein the method of gas-solid separation of step (4) comprises any one or a combination of at least two of gravity settling, centrifugal settling, or filtration.
13. The preparation method according to any one of claims 1 to 12, characterized in that the preparation method comprises the steps of:
(1) Spherical or spheroidic Li with equivalent diameter of 0.1-1.2mm 2 TiO 3 The particles are in a fluidization state in a protective atmosphere; the gas in the protective atmosphere comprises any one or a combination of at least two of argon, helium and neon;
(2) Introducing a carbon source gas into Li on the basis of continuous proceeding of the step (1) 2 TiO 3 In the protective atmosphere of the particles, the C-coated Li is obtained 2 TiO 3 Particles; the mixing temperature is 500-900 ℃, and the mixing time is more than or equal to 1min; the carbon source gas comprises any one or a combination of at least two of methane, ethane, ethylene, acetylene or propylene; the gas inlet speed of the carbon source gas is 50-200mL/min;
(3) On the basis of continuous proceeding of the step (1), the titanium source gas and the nitrogen source gas are respectively and independently introduced into the C-coated Li 2 TiO 3 In the protective atmosphere of the particles, the mixing temperature is 500-900 ℃, and the mixing time is more than or equal to 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;
(4) After gravity sedimentation, centrifugal sedimentation or filtration, the TiN/C coated Li is obtained 2 TiO 3 Tritium breeder.
14. TiN/C coated Li prepared by the method of any one of claims 1-13 2 TiO 3 Tritium breeder, characterized in that the TiN/C is coated with Li 2 TiO 3 The tritium breeder is TiN as outer layer, C as intermediate layer and Li as inner layer 2 TiO 3 Is a microsphere of (a).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011045490.9A CN112174196B (en) | 2020-09-28 | 2020-09-28 | TiN/C coated lithium titanate tritium proliferation agent, preparation method and preparation device system thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011045490.9A CN112174196B (en) | 2020-09-28 | 2020-09-28 | TiN/C coated lithium titanate tritium proliferation agent, preparation method and preparation device system thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112174196A CN112174196A (en) | 2021-01-05 |
| CN112174196B true CN112174196B (en) | 2023-06-23 |
Family
ID=73945651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011045490.9A Active CN112174196B (en) | 2020-09-28 | 2020-09-28 | TiN/C coated lithium titanate tritium proliferation agent, preparation method and preparation device system thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112174196B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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 |
|---|
| 氚增殖包层结构材料阻氚涂层技术研究现状;赵崴巍等;《中国核科学技术进展报告（第二卷）》;20111031;第2卷;217-228 * |
| 雷永泉 等."16.1.3 氚增殖材料简介".《新能源材料》.2000,(第1版),415-416. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112174196A (en) | 2021-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4917857A (en) | Process for producing metallic or ceramic hollow-sphere bodies | |
| CN108335760B (en) | Preparation method of high-uranium-loading-capacity dispersed fuel pellet | |
| US3264073A (en) | Novel metal microspheres and their manufacture | |
| CN101771146B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN110117732B (en) | Method for coating MgO protective layer on surface of hollow microsphere | |
| CN109848427A (en) | A method of it improving palladium and coats zirconium base hydrogen-absorbing material antitoxinization cyclical stability | |
| CN111724919B (en) | Coated fuel particle containing burnable poison coating layer, pellet, fuel element and preparation method thereof | |
| CN112174196B (en) | TiN/C coated lithium titanate tritium proliferation agent, preparation method and preparation device system thereof | |
| CN111013579A (en) | Limited-area carbon material loaded with palladium single atom or palladium nano-particles and preparation method thereof | |
| CN113526983A (en) | Composite high-temperature oxidation-resistant coating of graphite material for nuclear reactor and preparation method thereof | |
| CN112185592B (en) | C/TiN coated lithium orthosilicate tritium propagation agent, preparation method thereof and preparation device system | |
| CN112174195A (en) | Carbon-coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof | |
| CN108039467B (en) | Spongy silicon powder, preparation method thereof and lithium ion battery applying spongy silicon powder | |
| CN112174155A (en) | Carbon-coated lithium orthosilicate tritium breeder and preparation method and preparation device system thereof | |
| CN110976899A (en) | In-situ anchoring co-reduction preparation method of carbon-based supported metal sub-nanoparticles | |
| CN111484017A (en) | Method for preparing SiC nanoparticles based on silica microspheres @ C | |
| CN112185591B (en) | Titanium nitride coated lithium orthosilicate tritium proliferation agent and preparation method and preparation device system thereof | |
| CN112174156B (en) | TiN/C coated lithium orthosilicate tritium propagation agent and preparation method and preparation device system thereof | |
| CN103708419B (en) | Method for preparing of high-activity LiH microspheres through wet process | |
| CN107887582B (en) | Silicon/carbon powder composite material, preparation method thereof and battery cathode material | |
| KR101195448B1 (en) | Preparation method of sintered porous plate using spent nuclear fuel, and the sintered porous plate thereby | |
| CN108448077B (en) | Method for preparing Si/C composite material by using oil shale waste residues as raw materials | |
| Wang et al. | Metal Phosphide Anodes in Sodium‐Ion Batteries: Latest Applications and Progress | |
| CN114180560A (en) | Preparation method of coal-based graphene in molten salt system | |
| CN109573952B (en) | Porous metal oxide particle and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Floor 1-2, building 5, artificial intelligence Industrial Park, 266 Chuangyan Road, Qilin science and Technology Innovation Park, Nanjing, Jiangsu Province Applicant after: Zhongke Nanjing Green Manufacturing Industry Innovation Research Institute Applicant after: Institute of Process Engineering, Chinese Academy of Sciences Address before: Floor 1-2, building 5, artificial intelligence Industrial Park, 266 Chuangyan Road, Qilin science and Technology Innovation Park, Nanjing, Jiangsu Province Applicant before: Nanjing Green Manufacturing Industry Innovation Research Institute Institute of process engineering Chinese Academy of Sciences Applicant before: Institute of Process Engineering, Chinese Academy of Sciences |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |