CN112174195A - Carbon-coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof - Google Patents
Carbon-coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof Download PDFInfo
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- 229910052722 tritium Inorganic materials 0.000 title claims abstract description 89
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 title claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 5
- 230000035755 proliferation Effects 0.000 title description 4
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims abstract description 54
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 43
- 239000012298 atmosphere Substances 0.000 claims abstract description 30
- 230000001681 protective effect Effects 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 238000003860 storage Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 55
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000009395 breeding Methods 0.000 claims description 19
- 230000001488 breeding effect Effects 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 9
- 239000001307 helium Substances 0.000 claims description 9
- 229910052734 helium Inorganic materials 0.000 claims description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052754 neon Inorganic materials 0.000 claims description 7
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000002062 proliferating effect Effects 0.000 claims description 2
- 238000005253 cladding Methods 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 20
- 238000005260 corrosion Methods 0.000 abstract description 14
- 239000000919 ceramic Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 239000008188 pellet Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910010699 Li5FeO4 Inorganic materials 0.000 description 1
- 229910011638 LiCrO2 Inorganic materials 0.000 description 1
- 229910010584 LiFeO2 Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- High Energy & Nuclear Physics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a 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 a carbon source gas; (3) obtaining C-coated Li after gas-solid separation2TiO3A tritium breeder. The preparation device system comprises a storage bin, a fluidized bed coating device, a tail gas treatment device and a product collection 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 a C-coated Li2TiO3Tritium breeder, preparation method and preparation device system thereof.
Background
Deuterium (D) -tritium (T) nuclear fusion energy (D + T → He + n +17.6MeV) is considered to be one of important ways for solving the energy crisis of human beings due to the advantages of safety, cleanness, high efficiency and the like. Tritium fuel, however, is naturally less abundant and must be contained by neutron bombardment6Material of Li for tritium fuel: (1n+6Li→4He +3T +4.78 MeV). Over decades of development, Li is now present2TiO3The microsphere is 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.
With the continuous and intensive research, people gradually find that Li is preferred in the actual service environment2TiO3The 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 Li5FeO4，LiCrO2，LiFeO2Isooxide corrosion layer, deterioration of mechanical properties of the cladding structure material, especially in He-H2In 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.
The most important reason for the formation of the corrosion layer is Li2TiO3The Li and O elements in the steel matrix have higher affinity with Fe, Cr, Ni and other elements in the steel matrix, a fragile and porous (or crack) oxide corrosion layer is generated in a high-temperature (500-900 ℃) service environment, and meanwhile, the elements of the steel matrix diffuse to a contact interface to cause the segregation of the components in the matrix, thereby further deteriorating the mechanical property of the steel matrix. In addition, Fe element in the steel matrix also enters Li by diffusion2TiO3Crystal lattice and grain boundary, and reduced grain growthThe long activation energy, in a long-time service environment, the crystal grains grow abnormally, so that the compressive strength of the microspheres is reduced and crushed, and the potential safety hazard of the collapse of a ball bed exists.
Based on this, the Japanese atomic energy mechanism is 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.
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.
CN108751975A discloses a method for preparing tritium-proliferated ceramic pellets in a fusion reactor solid blanket, which has mild conditions, can complete two processes of pelletizing and curing simultaneously in the process of sedimentation, simplifies the purification and transfer processes of pellet embryo bodies, and ensures that the obtained product has high sphericity, uniform particle size, high porosity and mechanical strength and is convenient for industrial production. However, the tritium breeding ceramic pellets are in direct contact with cladding materials during use, and stability of the tritium breeding agent is affected.
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.
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 a 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 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 a carbon source gas;
(3) obtaining 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 subsequently introduced carbon source gas is prevented.
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 nitrogen, argon, helium or neon, and typical but non-limiting combinations include a combination of nitrogen and argon, a combination of argon and helium, a combination of helium and neon, a combination of nitrogen, argon and helium, 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 C layer can be smoothly coated.
Preferably, the mixing in step (2) is performed by introducing the carbon source gas 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 gas-solid separation method in step (3) 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 the combination of at least two of nitrogen, argon, helium or neon;
(2) on the basis of continuously carrying out the step (1), introducing a carbon source gas into 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 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) obtaining C-coated Li after gravity settling, centrifugal settling or filtering2TiO3A tritium breeder.
In a second aspect, the present invention provides a C-coated Li prepared by the preparation method of the first aspect2TiO3Tritium breeder, said C coated Li2TiO3The thickness of the layer C of the tritium proliferator is not less than 1nm, and may be, for example, 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm or 5nm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In the present invention, the 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 surface is provided with a corrosion-resistant and stable C shell, 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 film isolates 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 present invention provides a method for preparing C-coated Li2TiO3The device system for the tritium breeder comprises a storage bin, a fluidized bed coating device, a tail gas treatment device and a product collection device;
the storage bin is used for providing Li for the fluidized bed coating device2TiO3Particles;
the fluidized bed coating device is used for mixing Li in protective atmosphere2TiO3Reacting the particles with a carbon source gas to obtain C-coated Li2TiO3A tritium proliferating agent;
the tail gas treatment device is used for removing tail gas generated in the fluidized bed coating device;
the product collecting device is used for collecting the C-coated Li generated in the fluidized bed coating device2TiO3A tritium breeder.
Compared with the prior art, the invention has the following beneficial effects:
(1) the inert C film of 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 C film of 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) preparation of 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 schematic diagram of the process for preparing C-coated Li according to the present invention2TiO3A device system for tritium breeders;
FIG. 2 is a C-coated Li obtained by the preparation method provided in example 12TiO3EDS profile of tritium breeder;
FIG. 3 is a 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 tail gas treatment device; 4-product collection 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 present invention provides a method for preparing C-coated Li as shown in FIG. 12TiO3The device system of tritium breeder, the device system includes feed bin 1, fluidized bed cladding device 2, tail gas processing apparatus 3 and product collection device 4.
In the present invention, the storage bin 1 is used for providing Li for the fluidized bed coating device 22TiO3Particles; the fluidized bed coating device 2 is used for mixing Li in protective atmosphere2TiO3Reacting the particles with a carbon source gas to obtain C-coated Li2TiO3A tritium breeder, specifically, the fluidized bed coating device 2 is a fluidized bed; the tail gas treatment device 3 is used for treating tail gas generated in the fluidized bed coating device, and specifically, the tail gas treatment device 3 is a conventional compensation ignition device; the product collecting device 4 is used for collecting the C-coated Li generated in the fluidized bed coating device2TiO3Tritium breeder, specifically, product collection device 4 is the storage tank.
Example 1
This example provides a 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 mixing temperature of the granules in the protective atmosphere is 700 ℃, and the mixing time is 30 min; the gas introducing speed of the carbon source gas is 125 mL/min;
(3) obtaining C-coated Li after gravity settling2TiO3A tritium breeder.
FIG. 2 is a view of the C-coated Li obtained by the preparation method provided in this example2TiO3EDS profile of tritium breeder with C content up to 12 at.%.
FIG. 3 is a view of the C-coated Li obtained by the preparation method provided in this example2TiO3In the SEM image of the tritium breeding agent, as can be seen from FIG. 3, the surface of the crystal grain of the microsphere is uniformly coated with a layer of nano C film.
The preparation method provided in this example can obtain C-coated Li2TiO3The thickness of the C layer of the tritium breeding agent is 2 nm.
Example 2
This example provides a 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 nitrogen;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas ethane into Li2TiO3The mixing temperature of the granules in the protective atmosphere is 800 ℃, and the mixing time is 45 min; the gas introducing speed of the carbon source gas is 160 mL/min;
(3) obtaining C-coated Li after centrifugal sedimentation2TiO3A tritium breeder.
The C-coated Li obtained in this example2TiO3The thickness of the C film of the tritium breeder is 2.5nm, and the obtained C is coated with Li2TiO3The 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 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 helium;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas ethylene into Li2TiO3The mixing temperature of the granules in the protective atmosphere is 600 ℃, and the mixing time is 15 min; the gas introducing speed of the carbon source gas is 85 mL/min;
(3) filtering to obtain C-coated Li2TiO3A tritium breeder.
The C-coated Li obtained in this example2TiO3The thickness of the C film of the tritium breeder is 1.5nm, and the obtained C is coated with Li2TiO3The 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-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 neon;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas propylene into Li2TiO3Mixing the granules in a protective atmosphere at 900 deg.C for 1 min; the gas introducing speed of the carbon source gas is 200 mL/min;
(3) obtaining C-coated Li after gravity settling2TiO3A tritium breeder.
The C-coated Li obtained in this example2TiO3The thickness of the C film of the tritium breeder is 1nm, and the obtained C is coated with Li2TiO3The 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 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 argon;
(2) on the basis of continuously carrying out the step (1), introducing carbon source gas acetylene into Li2TiO3The mixing temperature of the granules in the protective atmosphere is 500 ℃, and the mixing time is 60 min; the gas introducing speed of the carbon source gas is 50 mL/min;
(3) obtaining C-coated Li after centrifugal sedimentation2TiO3A tritium breeder.
The C-coated Li obtained in this example2TiO3The thickness of the C film of the tritium breeder is 3nm, and the obtained C is coated with Li2TiO3Elemental constitution of tritium breedersAnd the micro-morphology is similar to that of example 1, and therefore, the description thereof is omitted.
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) introducing nitrogen into Li on the basis of continuous operation of the step (1)2TiO3The mixing temperature of the granules in the protective atmosphere 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 12TiO3The 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 low-activation steel after coating a C layer.
It can be seen that the inert 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; the inert C film of 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; preparation of 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. 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 a carbon source gas;
(3) obtaining 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 of step (1) comprises any one of nitrogen, 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.
5. The production method according to any one of claims 1 to 4, wherein the carbon source gas of step (2) comprises any one of methane, ethane, ethylene, acetylene or propylene or a combination of at least two thereof.
6. The production method according to any one of claims 1 to 5, wherein the carbon source gas in the step (2) is introduced at a gas flow rate of 50 to 200 mL/min.
7. The process of any one of claims 1 to 6, wherein the gas-solid separation in step (3) 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 the combination of at least two of nitrogen, argon, helium or neon;
(2) on the basis of continuously carrying out the step (1), introducing a carbon source gas into 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 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) obtaining C-coated Li after gravity settling, centrifugal settling or filtering2TiO3A tritium breeder.
9. C-coated Li prepared by the preparation method according to any one of claims 1 to 82TiO3Tritium proliferator characterized in that said C coats Li2TiO3The thickness of the C layer of the tritium breeding agent is more than or equal to 1 nm.
10. For preparing C-coated Li2TiO3The device system for the tritium breeder is characterized by comprising a storage bin, a fluidized bed coating device, a tail gas treatment device and a product collection device;
the storage bin is used for providing Li for the fluidized bed coating device2TiO3Particles;
the fluidized bed coating device is used for mixing Li in protective atmosphere2TiO3Reacting the particles with a carbon source gas to obtain C-coated Li2TiO3A tritium proliferating agent;
the tail gas treatment device is used for removing tail gas generated in the fluidized bed coating device;
the product collecting device is used for collecting the C-coated Li generated in the fluidized bed coating device2TiO3A tritium breeder.
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| 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 |
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