CN117658460A - Base glass for curing high-level waste liquid, preparation method and application thereof, and curing method of high-level waste liquid - Google Patents
Base glass for curing high-level waste liquid, preparation method and application thereof, and curing method of high-level waste liquid Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 105
- 239000002927 high level radioactive waste Substances 0.000 title claims abstract description 101
- 239000006121 base glass Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001723 curing Methods 0.000 title abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000007711 solidification Methods 0.000 claims description 13
- 230000008023 solidification Effects 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 abstract description 24
- 230000008025 crystallization Effects 0.000 abstract description 24
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000002901 radioactive waste Substances 0.000 abstract description 6
- 239000011521 glass Substances 0.000 description 21
- 235000019353 potassium silicate Nutrition 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- 239000002699 waste material Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 4
- 229910052637 diopside Inorganic materials 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002915 spent fuel radioactive waste Substances 0.000 description 4
- 229910004762 CaSiO Inorganic materials 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229910000439 uranium oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
- G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
- G21F9/305—Glass or glass like matrix
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention belongs to the technical field of radioactive waste treatment and disposal, and provides base glass for curing high-level radioactive waste liquid, a preparation method and a curing method of the high-level radioactive waste liquid. The invention discloses base glass for curing high-level radioactive waste liquid, which comprises the following components in percentage by mass: siO (SiO) 2 28～60％，B 2 O 3 12～25％，Na 2 O9～30％，Li 2 O 2.1～2.7％，Al 2 O 3 4～6％，CaO 5～6.5％，MgO 0.1～0.5％，BaO1.0～1.8％，V 2 O 5 1.5～2.5％，Sb 2 O 5 0.1 to 1 percent. The invention reduces the introduction amount of alkaline earth metal, has crystallization rate lower than 5vol percent, has good crystallization resistance and can meet the requirements of a Joule furnace process; increasing Na content in the base glass 2 O、Li 2 O content, no Na 2 MoO 4 And the crystal is separated out, so that good inclusion of Mo is realized.
Description
Technical Field
The invention relates to the technical field of radioactive waste treatment and disposal, in particular to base glass for curing high-level radioactive waste liquid, a preparation method and application thereof, and a curing method of the high-level radioactive waste liquid.
Background
Spent fuel used in nuclear power plants is a very complex mixture from a chemical standpoint. Spent fuel mainly comprises four components such as uranium oxide, (oxidized) plutonium, fission Products (FP), and minor actinides; has the characteristics of complex components, more than 40 elements, more than 100 isotopes, strong radioactivity, high biotoxicity, long half-life and the like.
The method is characterized in that the high-level waste liquid is treated in the internationally existing commercial spent fuel post-treatment plant in a glass solidification mode, and the glass solidification process is a process of mixing the high-level waste liquid with glass materials according to a certain proportion, and obtaining stable glass or glass-like solid after melting at a high temperature (900-1200 ℃).
Because the spent fuel has different burning depth, cooling time and post-treatment process, the components of the high-level waste liquid finally fed into the glass solidification link are different, different solidified body formulas are designed according to the characteristics of different waste liquid components, so that different basic glass components are obtained to contain or 'wrap' all elements in the high-level waste liquid, the leaching resistance is met, the generation of 'yellow phase' is avoided, and meanwhile, the requirements of the subsequent glass solidification process, such as a Joule furnace, a cold crucible process and the like, are also met, so that the occurrence of crystallization blocking phenomenon is avoided. The yellow phase is a crystal phase spontaneously precipitated (i.e., the second phase is not expected to appear) in the formation process of the solidified body (including the cooling process), and is named as "yellow phase" because the yellow phase is yellow in color and mainly contains S, mo, cr, radioactive elements Sr, cs and the like. The yellow phase has extremely poor chemical stability, is easy to dissolve in water, and causes leaching of radioactive elements Sr and Cs to be out of control.
The components of the existing glass solidified body contain a large amount of alkaline earth metal oxides, such as CaO, baO, feO, etc. introduced by the base glass to realize the inclusion of indissolvable elements in the high-level radioactive waste liquid, but the alkaline earth metal oxides are easy to be combined with SiO in the cooling process 2 Forming Ca (Ba, fe) SiO 4 The volume crystallization rate of the isosbestic stone crystalline phase reaches 20 percent and even higher.
In addition, because of the crystallization rate requirement of the subsequent Joule furnace 'freeze thawing' discharging process, namely, the crystallization resistance of the glass solidified body is highly required, namely, the volume crystallization rate requirement is less than 5 percent after the glass solidified body is respectively insulated for 28 days at different temperatures between 700 ℃ and 950 ℃. However, the crystallization rate of the existing glass solidified body reaches 20% or more, so that the technical problems of unloading blockage and the like are easily caused, and the treatment of high-level waste liquid cannot be smoothly realized.
Disclosure of Invention
In view of the above, the invention aims to provide a base glass for curing high-level waste liquid, a preparation method and application thereof, and a curing method of the high-level waste liquid. After the high-level waste liquid is solidified by the base glass for solidifying the high-level waste liquid, the crystallization rate of the obtained high-level waste liquid glass solidified body is low.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides base glass for curing high-level radioactive waste liquid, which comprises the following components in percentage by mass:
SiO 2 28～60％，B 2 O 3 12～25％，Na 2 O 9～30％，Li 2 O 2.1～2.7％，Al 2 O 3 4～6％，CaO 5～6.5％，MgO 0.1～0.5％，BaO 1.0～1.8％，V 2 O 5 1.5～2.5％，Sb 2 O 5 0.1～1％。
the invention also provides a preparation method of the base glass for curing the high-level radioactive waste liquid, which comprises the following steps:
the components and the corresponding mass fractions of the base glass for curing the high-level waste liquid are weighed according to the technical scheme, and then are ground and mixed to obtain mixed powder;
and (3) sequentially carrying out melting and subsequent treatment on the mixed powder to obtain the base glass for solidifying the high-level radioactive waste liquid.
Preferably, the melting temperature is 1300-1400 ℃, and the heat preservation time is 2-3 h.
The invention also provides application of the base glass for curing the high-level waste liquid in curing the high-level waste liquid.
The invention also provides a method for solidifying the high-level radioactive waste liquid, which comprises the following steps:
mixing the high-level waste liquid with the base glass to obtain a mixed ingredient;
sequentially melting, casting and annealing the mixed ingredients to realize solidification of the high-level waste liquid;
the base glass is the base glass for curing the high-level waste liquid according to the technical scheme.
Preferably, the mass ratio of the high-level radioactive waste liquid to the base glass is 18: 82-22: 78.
preferably, the melting temperature is 1150-1200 ℃, and the heat preservation time is 2-3 h.
Preferably, the casting is performed in a mold having a temperature of 380 to 420 ℃.
Preferably, the annealing temperature is 500-550 ℃ and the heat preservation time is 1.5-2.5 h.
The invention provides base glass for curing high-level radioactive waste liquid, which comprises the following components in percentage by mass: siO (SiO) 2 28～60％，B 2 O 3 12～25％，Na 2 O 9～30％，Li 2 O 2.1～2.7％，Al 2 O 3 4～6％，CaO 5～6.5％，MgO 0.1～0.5％，BaO 1.0～1.8％，V 2 O 5 1.5～2.5％，Sb 2 O 5 0.1～1％。
The beneficial effects are that:
(1) Reduction of devitrification Performance
To reduce Ca (Mg, ba, fe) SiO 4 The invention reduces the introduction amount of oxide such as CaO, mgO, baO by the base glass for solidifying the high-level radioactive waste liquid, so as to avoid the occurrence of high Wen Shishuang liquid phase, and simultaneously avoid the occurrence of spontaneous crystallization induced by interface effect at low temperature of double liquid phases, namely, the occurrence of pyroxene crystals.
(2) Implementation of containment capability
The most important structural units in the high-level waste liquid glass solidified body obtained by solidifying the high-level waste liquid by the base glass are [ SiO ] 4 ]、[BO 4 - ]、[AlO 4 - ]Tetrahedra. The base glass for curing the high-level radioactive waste liquid of the invention introduces Na 2 O、Li 2 O, caO, mgO, baO, which breaks the chemical bonds between these tetrahedral building blocks, produces unbridged oxygen atoms, which are negatively charged; the charge of the unbridged oxygen atom being balanced by the corresponding cation, e.g. by 2 Na + Or Li (lithium) + Or 1 Ca 2+ Or Mg (Mg) 2+ Or Ba (Ba) 2+ . Introducing the above oxide Na 2 O、Li 2 O, caO, mgO, baO the glass network of the high-level waste liquid glass solidified body is weakened due to Na + 、Li + 、Ca 2+ 、Mg 2+ Or Ba (Ba) 2+ Larger, larger cavities may be created in the glass network and the glass network expanded.
In the invention, due to the requirement of reduced crystallization performance, the introduction amount of alkaline earth metal oxide is reduced properly, thus increasing alkali metal Na 2 O、Li 2 The amount of oxide such as O introduced, especially Na 2 O breaking [ SiO ] 4 ]、[BO 4 - ]、[AlO 4 - ]The chemical bonds between the two components form a large number of cavities so as to realize the inclusion of insoluble element Mo in the high-level radioactive waste liquid, namely, the generation of yellow phase is avoided, and the leaching resistance of the solidified body meets the requirement.
The data of the examples show that: the basic glass for curing the high-level radioactive waste liquid has good crystallization resistance by reducing the introduction amount of alkaline earth metal and the crystallization rate of less than 5vol percent, and can meet the requirements of a Joule furnace process; increasing Na content in glass 2 O、Li 2 O content, no Na 2 MoO 4 The crystal is separated out, and the good inclusion of Mo element is realized. In addition, the base glass for curing the high-level waste liquid provided by the invention aims at the high-level waste liquid with the burnup of 5.5GWd/tU, and when the content of the high-level waste liquid is 20wt%, the components meet the design requirements.
Detailed Description
The invention provides base glass for curing high-level radioactive waste liquid, which comprises the following components in percentage by mass:
SiO 2 28～60％，B 2 O 3 12～25％，Na 2 O 9～30％，Li 2 O 2.1～2.7％，Al 2 O 3 4～6％，CaO 5～6.5％，MgO 0.1～0.5％，BaO 1.0～1.8％，V 2 O 5 1.5～2.5％，Sb 2 O 5 0.1～1％。
in the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
The base glass for curing the high radioactive waste liquid provided by the invention comprises 28-60% of SiO by mass percent 2 Preferably 50 to 60%.
The base glass for curing the high radioactive waste liquid provided by the invention comprises 12-25% by mass of B 2 O 3 Preferably 12 to 20%, more preferably 12 to 15%.
The base glass for curing the high-level radioactive waste liquid provided by the invention comprises 9-30% of Na by mass 2 O is preferably 9 to 15%, more preferably 9 to 13%.
The base glass for curing the high-level radioactive waste liquid provided by the invention comprises 2.1-2.7% of Li by mass percent 2 O is preferably 2.2 to 2.6%, more preferably 2.4 to 2.5%.
The base glass for curing the high radioactive waste liquid provided by the invention comprises 4-6% of Al by mass percent 2 O 3 Preferably 4.5 to 5.5%.
The base glass for curing the high-level radioactive waste liquid provided by the invention comprises 5-6.5% of CaO by mass percent, preferably 5.5-6.5%.
The base glass for curing the high-level radioactive waste liquid provided by the invention comprises 0.1-0.5% of MgO, preferably 0.1-0.4% of MgO.
The base glass for curing the high-level radioactive waste liquid provided by the invention comprises 1.0-1.8% of BaO by mass, preferably 1.2-1.6% and more preferably 1.4%.
The base glass for curing the high-level radioactive waste liquid provided by the invention comprises 1.5-2.5% of V by mass percent 2 O 5 Preferably 1.6 to 2.2%.
The base glass for curing the high-level radioactive waste liquid provided by the invention comprises 0.1-1% by mass of Sb 2 O 5 Preferably 0.3 to 0.9%, more preferably 0.6 to 0.8%.
In the present invention, the basic glass for curing the high level waste liquid is preferably in the form of powder or microbeads; the particle size of the powdery base glass for curing the high-level waste liquid is preferably less than 75 micrometers, and the particle size of the base glass for curing the micro-bead-shaped high-level waste liquid is preferably 1-3 mm.
The invention also provides a preparation method of the base glass for curing the high-level radioactive waste liquid, which comprises the following steps:
the components and the corresponding mass fractions of the base glass for curing the high-level waste liquid are weighed according to the technical scheme, and then are ground and mixed to obtain mixed powder;
and (3) sequentially carrying out melting and subsequent treatment on the mixed powder to obtain the base glass for solidifying the high-level radioactive waste liquid.
According to the technical scheme, the components and the corresponding mass fractions of the base glass for curing the high-level waste liquid are weighed, and then ground and mixed to obtain the mixed powder.
In the present invention, the parameters of the milling mixture include: the equipment is preferably a corundum tank; the grinding medium is preferably agate balls, and the diameter of the agate balls is preferably 0.5-1 cm; the ball ratio is preferably 1:2, preferably > 1 hour.
After the grinding and mixing, the invention preferably further comprises sieving, wherein the sieving times are preferably 3 times.
After the mixed powder is obtained, the mixed powder is sequentially melted and subjected to subsequent treatment, so that the base glass for solidifying the high-level radioactive waste liquid is obtained.
In the present invention, the melting temperature is preferably 1300 to 1400 ℃, and more preferably 1350 ℃; the heat preservation time is preferably 2-3 hours.
In the present invention, when the base glass for curing high level waste liquid is preferably in a powder form, the subsequent treatment preferably includes water quenching and grinding in order. In the present invention, the water quenching agent is preferably water, and the temperature of the water is preferably equal to or less than 50 ℃. The parameters of the grinding are not particularly limited in the present invention, so long as the particle size of the finally obtained powdery base glass for curing the high level radioactive waste is less than 75 μm.
In the present invention, when the base glass for curing high level waste liquid is preferably in the form of microbeads, the operation of the subsequent treatment is not particularly limited as long as the base glass for curing high level waste liquid having a particle size of 1 to 3mm can be obtained.
The invention also provides application of the base glass for curing the high-level waste liquid in curing the high-level waste liquid.
The invention also provides a method for solidifying the high-level radioactive waste liquid, which comprises the following steps:
mixing the high-level waste liquid with the base glass to obtain a mixed ingredient;
sequentially melting, casting and annealing the mixed ingredients to realize solidification of the high-level waste liquid;
the base glass is the base glass for curing the high-level waste liquid according to the technical scheme.
The invention mixes the high level waste liquid with the base glass to obtain the mixed ingredients.
In the present invention, the high level waste liquid is preferably high level waste liquid with a burnup of 5.5 GWd/tU. In the invention, the mass ratio of the high-level waste liquid to the base glass is preferably 18: 82-22: 78, further preferably 2:8. the mixing method is not particularly limited in the present invention, as long as the high level waste liquid and the base glass can be sufficiently mixed.
After the mixed ingredients are obtained, the mixed ingredients are sequentially melted, poured and annealed, so that the solidification of the high-level waste liquid is realized.
In the present invention, the melting temperature is preferably 1150-1200 ℃, and the holding time is preferably 2-3 hours.
In the present invention, the casting is preferably performed in a mold having a temperature of preferably 380 to 420 ℃, and more preferably 400 ℃.
In the present invention, the annealing temperature is preferably 500 to 550 ℃, and the holding time is preferably 1.5 to 2.5 hours, and more preferably 2 hours.
After the annealing, the invention further comprises the step of naturally cooling the material obtained by the annealing to room temperature.
In the invention, the material obtained after annealing and cooling is named as high-level waste liquid glass solidified body.
The base glass for curing high-level waste liquid, the preparation method and application thereof, and the method for curing high-level waste liquid according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Examples
The formulation of the base glass for curing high level waste liquid in examples and comparative examples is shown in Table 1.
Table 1 formulation of base glass for curing high level waste liquid in examples and comparative examples
| Sequence number | Oxide compound | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| 1 | SiO 2 | 52 | 54 | 55 | 56 | 58 | 53 |
| 2 | B 2 O 3 | 20 | 18 | 16 | 13.6 | 12 | 15.7 |
| 3 | Na 2 O | 14 | 12 | 11 | 12.3 | 9 | 4.5 |
| 4 | Li 2 O | 2.1 | 2.2 | 2.4 | 2.5 | 2.7 | 2.6 |
| 5 | Al 2 O 3 | 4 | 4.5 | 5 | 5.5 | 6 | 4.4 |
| 6 | CaO | 5 | 5.5 | 6.4 | 6.1 | 6.5 | 8 |
| 7 | MgO | 0.3 | 0.4 | 0.3 | 0.1 | 0.5 | 5.2 |
| 8 | BaO | 1 | 1.2 | 1.4 | 1.6 | 1.8 | 4.2 |
| 9 | V 2 O 5 | 1.5 | 1.6 | 1.7 | 1.9 | 2.5 | 1.8 |
| 10 | Sb 2 O 5 | 0.1 | 0.6 | 0.8 | 0.4 | 1 | 0.6 |
| Totalizing | 100 | 100 | 100 | 100 | 100 | 100 |
As can be seen from table 1: in the base glass for curing a high level waste liquid of example 1, the amount of alkaline earth metal introduced was reduced, and the total of CaO+MgO+BaO was 6.3wt%.
The preparation method of the base glass for curing the high-level radioactive waste liquid in the examples and the comparative examples comprises the following steps:
1) And (3) calculating a glass batch formula according to the glass components and the mass percentage, weighing the raw materials according to a batch table, adding the total weight, grinding, mixing and sieving for three times, and fully and uniformly mixing the materials to obtain the mixed powder.
2) Placing the uniformly mixed powder into a platinum crucible, then placing the crucible into a high-temperature furnace, charging for many times, melting at 1350 ℃ for clarifying for 2.5 hours, stirring with a stainless steel fine rod, and obtaining the powdery base glass for solidifying the high-level waste liquid after water quenching, drying and grinding after the melting.
The solidification method of the high-level radioactive waste liquid comprises the following steps:
1) And uniformly mixing the base glass (80 wt%) for curing the high-level waste liquid with the simulated power stack high-level waste liquid (20 wt%) to prepare the cured body batch.
The simulated power stack high-level discharge waste liquid is burnt 5.5GWd/tU, and cooled for 8 years, contains forty kinds of components, mainly contains alkali metal, lanthanide and fission element (30-70 elements), and contains about 10-12 wt% of noble metal RuO 2 Rh, pd and 9-12 wt% of indissolvable element MoO 3 Etc.
2) The solidified body batch is added into a platinum crucible, and is placed at 1150 ℃ for 2 hours of heat preservation, and is stirred for a plurality of times during the heat preservation, so as to promote clarification and homogenization of the solidified body.
3) Pouring the clarified and homogenized molten liquid into a mold at 400 ℃ after melting, transferring the molten liquid into a muffle furnace for annealing at 530 ℃ for 2 hours after solidification and shaping, and cooling the molten liquid to room temperature along with the furnace to realize solidification of simulated power stack high-level waste liquid; the cooled material was named simulated waste glass solidification.
The obtained simulated waste liquid glass solidified body is crushed into slag, and the slag is placed in a gradient furnace, and the liquidus temperature of the slag is tested.
The resulting simulated waste liquid glass solidified body was ground to a powder (less than 75 microns), placed in a crucible, incubated at a temperature of about 20 ℃ below the liquidus temperature for 28 days, and analyzed for crystallization rate by X-RAY diffraction.
The resulting simulated waste liquid glass solid was subjected to component analysis, and then "inclusion capacity (%) =oxide content (wt%)/total oxide (wt%)" introduced by the high-level waste liquid in the glass solid was calculated.
The results are shown in Table 2.
TABLE 2 liquidus temperatures and crystallization Rate of simulated waste liquid glass solid obtained in examples 1 to 5 and comparative example 1
As can be seen from Table 2, the crystalline phase of the resulting simulated waste liquid glass solid contains only the noble metal RuO inherited from the raw material 2 Durable phase CaMoO 4 Without comparative precipitated diopside CaSiO 4 In the invention, the content of alkaline earth metal (CaO+MgO+BaO) is reduced, so that the invention has good inhibition effect on reducing diopside crystallization, and the method specifically comprises the following steps: in the base glass for curing high level waste liquid provided in example 1, the amount of alkaline earth metal introduced was reduced, the total of CaO+MgO+BaO was 6.3% by weight, and the crystalline phase of the resulting simulated waste liquid glass cured product contained only noble metal RuO inherited from the raw material 2 Durable phase CaMoO 4 The method comprises the steps of carrying out a first treatment on the surface of the In the base glass for curing a high level waste liquid provided in comparative example 1, the total of CaO+MgO+BaO was 15% by weight, and "RuO" was precipitated in the crystal phase of the resulting simulated waste liquid glass solid 2 +CaSiO 4 "two crystalline phases and crystallization rate up to 22.5vol%, which is due to the higher alkaline earth metal, the higher crystallization rate adversely affects the subsequent production process, such as the problem of blockage of the discharge pipe. The simulated waste liquid glass solidified body obtained by utilizing the base glass for solidifying the high-level waste liquid provided by the invention does not contain diopside CaSiO precipitated in the comparative example 4 In the invention, the content of alkaline earth metal is reduced, so that the diopside crystallization is well inhibited.
Next, the resulting simulated waste liquid glass solid contains a durable phase CaMoO in the crystal phase 4 But does not contain Na with high water solubility 2 MoO 4 Description of Na 2 The introduction of O plays a role of breaking the net, provides a sufficient amount of cavities, effectively ensures the inclusion of Mo element, improves the leaching resistance of the obtained simulated waste liquid glass solidified body, and meets the requirement of chemical stability of the waste liquid glass solidified body. In addition, as can be seen from table 2, the simulated waste liquid glass solidified body obtained in example 1 has an overall crystallization rate of only 3.4vol% after being kept at 800 ℃ for 28 days, i.e. the requirement of the crystallization rate in the joule furnace process is met, and the requirement of the crystallization rate of the product glass in EJ1186 is also met. Finally, the base glass for curing the high radioactive waste liquid of the invention is prepared by reducing alkaline earthThe metal (CaO+MgO+BaO) is introduced in an amount to increase Na 2 The content of O aims at the simulated high-level waste liquid with the burnup of 5.5GWd/tU, when the content is 20wt%, the obtained simulated waste liquid glass solidified body has good inclusion for Mo element, and meanwhile, the crystallization rate is lower than 5vol%, so that the simulated waste liquid glass solidified body has good crystallization resistance and can meet the requirements of a Joule furnace process.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The base glass for curing the high-level waste liquid is characterized by comprising the following components in percentage by mass:
SiO 2 28～60％，B 2 O 3 12～25％，Na 2 O 9～30％，Li 2 O 2.1～2.7％，Al 2 O 3 4～6％，CaO 5～6.5％，MgO 0.1～0.5％，BaO 1.0～1.8％，V 2 O 5 1.5～2.5％，Sb 2 O 5 0.1～1％。
2. the method for preparing the base glass for curing the high-level radioactive waste liquid according to claim 1, which is characterized by comprising the following steps:
the components according to claim 1 and the corresponding mass fractions are weighed and then ground and mixed to obtain mixed powder;
and (3) sequentially carrying out melting and subsequent treatment on the mixed powder to obtain the base glass for solidifying the high-level radioactive waste liquid.
3. The preparation method according to claim 2, wherein the melting temperature is 1300-1400 ℃ and the holding time is 2-3 h.
4. The use of the base glass for curing high-level waste liquid according to claim 1 in curing high-level waste liquid.
5. The solidification method of the high-level radioactive waste liquid is characterized by comprising the following steps of:
mixing the high-level waste liquid with the base glass to obtain a mixed ingredient;
sequentially melting, casting and annealing the mixed ingredients to realize solidification of the high-level waste liquid;
the base glass is the base glass for curing the high-level waste liquid according to claim 1.
6. The method according to claim 5, wherein the mass ratio of the high-level waste liquid to the base glass is 18: 82-22: 78.
7. the method according to claim 5, wherein the melting temperature is 1150-1200 ℃ and the holding time is 2-3 h.
8. The curing process of claim 5, wherein the casting is performed in a mold having a temperature of 380 to 420 ℃.
9. The method according to claim 5, wherein the annealing temperature is 500-550 ℃ and the holding time is 1.5-2.5 h.
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