NL2036905B1 - Basic glass for solidifying high-level radioactive liquid waste, preparation method, use, and solidification method for high-level radioactive liquid waste - Google Patents
Basic glass for solidifying high-level radioactive liquid waste, preparation method, use, and solidification method for high-level radioactive liquid waste Download PDFInfo
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- 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
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- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
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- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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Abstract
Provided is basic glass for solidifying high—level radioactive liquid waste, a preparation method, and a solidification method for high—level radioactive liquid waste. The basic glass for solidifying high—level radioactive liquid waste of the present invention includes, in percentage by mass, the following components: 28%—60% of SiOz, 12%—25% of B203, 9%—30% of Nazû, 2.l%—2.7% of Lizo, 4%— 6% of Alxh, 5%—6.5% of CaO, O.l%—O.5% of MgO, l.0%—l.8% of BaO, l.5%—2.5% of Vflk and O.l%—l% of Sbflk. According to the present invention, a crystallization. rate is lower than 5vol% by reducing an introduction amount of alkaline earth metals, such that the basic glass for solidifying high—level radioactive liquid waste has desirable crystallization resistance, and can satisfy the requirements of a Joule furnace process; and contents of Nazo and LizO in the basic glass are increased, no Naflkflh crystal is precipitated, and Mo is desirably accommodated.
Description
BASIC GLASS FOR SOLIDIFYING HIGH-LEVEL RADIOACTIVE LIQUID
WASTE, PREPARATION METHOD, USE, AND SOLIDIFICATION METHOD
FOR HIGH-LEVEL RADIOACTIVE LIQUID WASTE
[01] The present invention relates to the technical field of treatment and disposal of radioactive waste, and in particular to basic glass for solidifying high-level radioactive liquid waste, a preparation method, a use, and a solidification method for high-level radioactive liquid waste.
[02] Spent fuel used in a nuclear power plant is a mixture having extremely complex chemical components, mainly includes the following four types of components: uranium oxide, (oxide) plutonium, a fission product (FP), and a minor actinide element, for example, has complex components, contains more than 40 elements and more than 100 isotopes, and features strong radioactivity, high biological toxicity, and long half-life period.
[03] High-level radioactive liquid waste is treated through glass solidification in an existing commercial spent fuel treatment plant in the world. Glass solidification is a process that the high-level radioactive liquid waste and glass frit are mixed in a certain proportion, and is subjected to high-temperature (900°C-1200°C) melting to obtain stable glass or a glass-like solid.
[04] With different burn-up depth, cooling time and a post- treatment process of the spent fuel, components of the high- level radicactive liquid waste finally sent to a link of glass solidification is also different. In view of this, different solidified body formulas should be designed according to characteristics of different liquid waste components, such that different basic glass components should be obtained to accommodate or “wrap” all elements in the high-level radioactive liquid waste, so as to satisfy leaching resistance and avoid generation of “yellow phase”, and further satisfy the requirements of a subsequent glass solidification process, such as a Joule furnace process and a cold crucible process, so as to avoid the phenomenon of crystallization blocking. A yellow phase is a crystal phase (i.e. a second phase is not desired) spontaneously precipitated during formation (including cooling) of a solidified body. With a yellow color, the yellow phase is named as “yellow phase”, which mainly includes S, Mo, Cr, and radioactive elements Sr, Cs and other elements. The “yellow phase” has extremely poor chemical stability, and is extremely easy to dissolve in water, resulting in leaching of radioactive elements Sr and Cs out of control.
[05] An existing glass solidified body contains a large amount of alkaline earth metal oxides introduced by basic glass, such as CaO, Ba0 and FeO, so as to accommodate insoluble elements in the high-level radioactive liquid waste, but during cooling, the alkaline earth metal oxide and S10; easily form a pyroxene crystal phase such as Ca (Ba,
Fe)Si04, of which a volume crystallization rate reaches 20%, or even higher.
[06] Furthermore, with the requirements for a crystallization rate during a subsequent Joule furnace “freeze-thawing” discharge process, extremely high requirements for crystallization resistance of the glass solidified body are put forward. That is, after 28 days of insulation at different temperatures between 700°C and 950°C, the volume crystallization rate is required to be less than 5%. However, the «crystallization rate of the glass solidified body at present reaches 20% or more. As a result, process problems such as discharge blockage are easily caused, resulting in an incapability to smoothly treat the high-level radioactive liquid waste.
[07] In view of the above, an objective of the present invention is to provide basic glass for solidifying high- level radioactive liquid waste, a preparation method, a use, and a solidification method for high-level radioactive liquid waste. After the high-level radioactive liquid waste is solidified by the basic glass for solidifying high-level radioactive liquid waste according to the present invention, a crystallization rate of an obtained high-level radioactive liquid waste glass solidified body is low.
[08] In order to achieve the above objective of invention, the present invention provides the following technical solution:
[09] the present invention provides basic glass for solidifying high-level radioactive liquid waste. The basic glass includes, in percentage by mass, the following components:
[10] 283-60% of 510;, 12%-25% of B203, 9%-30% of Na:0, 2.12- 2.7% of Liz0, 4%-6% of Al:0:3, 5%-6.5% of Cal, 0.1%-0.53 of
MgO, 1.0%-1.8% of BaO, 1.5%-2.53 of V;0s, and 0.1%-1% of
SD20s5.
[11] The present invention further provides a preparation method for the basic glass for solidifying high-level radioactive liquid waste of the technical solution described above. The preparation method includes:
[12] weighing the components of the basic glass for solidifying high-level radioactive liquid waste of the technical solution described above in corresponding percentage by mass, and grinding and mixing the components to obtain mixed powder; and
[13] sequentially melting and subsequently treating the mixed powder to obtain the basic glass for solidifying high- level radioactive liquid waste.
[14] Preferably, a melting temperature is 1300°C-1400°C, and insulation time is 2 h-3 h.
[15] The present invention further provides a use of the basic glass for solidifying high-level radioactive liquid waste of the technical solution described above in solidification of the high-level radioactive liquid waste.
[16] The present invention further provides a solidification method for high-level radioactive liquid waste. The method includes:
[17] mixing the high-level radioactive liquid waste and basic glass to obtain a mixed ingredient; and
[18] sequentially melting, pouring and annealing the mixed ingredient to solidifying the high-level radioactive liquid waste, where
[19] the basic glass is basic glass for solidifying high- level radioactive liquid waste of the technical solution described above.
[20] Preferably, a mass ratio of the high-level radioactive liquid waste to the basic glass is 18:82-22:78.
[21] Preferably, a melting temperature is 1150°C-1200°C, and insulation time is 2 h-3 h.
[22] Preferably, the casting is carried out in a mold, and a temperature of the mold is 380°C-420°C.
[23] Preferably, an annealing temperature is 500°C-550°C, and insulation time is 1.5 h-2.5 h.
[24] The present invention provides basic glass for solidifying high-level radicactive liquid waste. The basic glass includes, in percentage by mass, the following components: 28%-60% of Si0:, 12%-25% of B203, 9%-30% of Na:0, 2.18-2.7% of Li:0, 43-63 of Al203, 5%-6.5% of CaO, 0.1%-0.5% of MgO, 1.0%-1.8% of BaO, 1.5%-2.5% of V20;, and 0.1%-1% of
Sb20s.
[25] Beneficial effects:
[26] (1) Reduction in crystallization performance
[27] In order to reduce precipitation of pyroxene crystal phases such as Ca (Mg, Ba, Fe)SiO4, introduction amounts of oxides such as CaO, MgO and BaO are reduced in the basic glass for solidifying high-level radioactive liquid waste of the present invention, so as to avoid appearance of double liquid phases at a high temperature and avoid occurrence of spontaneous crystallization induced by an interface effect at a low temperature of the double liquid phases, i.e. avoid appearance of pyroxene crystals.
[28] (2) Achievement of accommodation capability
[29] Most of important structural units in a high-level 5 radioactive liquid waste glass solidified body after the high-level radioactive liquid waste is solidified by the basic glass are [S104], [BOs] and [AlO:47] tetrahedra. Oxides such as Na:0, Li:0, CaO, MgO and BaO are introduced into the basic glass for solidifying high-level radioactive liquid waste of the present invention such that chemical bonds between tetrahedral structural units can be broken to generate non-bridge oxygen atoms, and the non-bridge oxygen atoms carry negative charges; and the charges of the non- bridge oxygen atoms are balanced by corresponding cations, for example, by means of two Nat or Lit, or one Ca?t or Mg2* or Ba?2+, The oxides Na:0, Lis0, CaO, MgO and BaO are introduced, such that a glass network of a high-level radioactive liquid waste glass solidified body is weaken, and since Nat, Li*, Ca?+, Mg?+ or Ba?t is large, a large cavity can be generated in the glass network, and the glass network can expand.
[30] In the present invention, due to the requirement of reducing crystallization performance, the introduction amount of alkaline earth metal oxide is appropriately reduced, such that the introduction amount of alkali metal oxides such as Naz0 and Li:0 is increased. Particularly, chemical bonds between [SiO4], [BOs] and [AlO:7] are broken through Na;0 to form a large number of cavities, so as to accommodate insoluble element “Mo” in the high-level radioactive liquid waste, i.e. avoid generation of a “yellow phase”, such that leaching resistance of the solidified body satisfies the requirement.
[31] Data of the example shows that a crystallization rate is lower than bvol4 by reducing an introduction amount of alkaline earth metal, such that the basic glass for solidifying high-level radioactive liquid waste of the present invention has desirable crystallization resistance,
and can satisfy the requirements of a Joule furnace process; and contents of Na:0 and Li:0 in the basic glass are increased, no Na:MoO; crystal is precipitated, and Mo element is desirably accommodated. Further, the basic glass for solidifying high-level radioactive liquid waste according to the present invention satisfies design requirements of components when accommodation capacity is 20wt3 for high- level radioactive liquid waste having burn-up consumption of 5.5 GWd/tU.
[32] The present invention provides basic glass for solidifying high-level radioactive liquid waste. The basic glass includes, in percentage by mass, the {following components:
[33] 28%-60% of Si0;, 12%-25% of B:03, 9%-30% of Nap0, 2.1%- 2.7% of Liz0, 42-63 of Al:0:, 5%-6.5% of CaO, 0.1%-0.5% of
MgO, 1.03-1.8% of Ba0, 1.5%-2.5% of V20s, and 0.1%-1% of
Sb20s.
[34] In the present invention, unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.
[35] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 282-603 of Si0:, which is preferably 503-608.
[36] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 12%-25% of B:03, which is preferably 12%-20%, and is further preferably 123-153.
[37] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 9%-30% of Na:0, which is preferably 94-154, and is further preferably 9%-13%.
[38] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 2.1%-2.7% of Lis0, which is preferably
: 2.2%-2.6%, and is further preferably 2.4%-2.5%.
[39] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 4%-6% of Als03, which is preferably 4.5%-5.5%.
[40] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 5%-6.5% of CaO, which is preferably 5.5%-6.5%.
[41] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 0.1%-0.5% of MgO, which is preferably 0.13-0.44.
[42] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 1.0%-1.8% of BaO, which is preferably 1.2%-1.6%, and is further preferably 1.4%.
[43] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 1.5%-2.5% of V:0s, which is preferably 1.6%-2.2%.
[44] The basic glass for solidifying high-level radioactive liquid waste according to the present invention includes, in percentage by mass, 0.13-1% of Sb0s, which is preferably 0.3%-0.9%, and is further preferably 0.6%-0.8%.
[45] In the present invention, the properties of the basic glass for solidifying high-level radioactive liquid waste are preferably powder-shaped or microbead-shaped, the powder-shaped base glass for solidifying high-level radioactive liquid waste has a particle size preferably less than 75 microns, and the microbead-shaped basic glass for solidifying high-level radioactive liquid waste has a particle size preferably ranging from 1 mm to 3 mm.
[46] The present invention further provides a preparation method for the basic glass for solidifying high-level radioactive liquid waste of the technical solution described above. The preparation method includes:
[47] weigh the components of the basic glass for solidifying high-level radioactive liquid waste of the technical solution described above in corresponding percentage by mass, and grind and mix the components to obtain mixed powder; and
[48] sequentially melt and subsequently treat the mixed powder to obtain the basic glass for solidifying high-level radioactive liquid waste.
[49] According to the present invention, components of the basic glass for solidifying high-level radioactive liquid waste of the technical solution described above are weighed in corresponding percentage by mass, and then ground and mixed to obtain mixed powder.
[50] In the present invention, grinding and mixing parameters include: an apparatus is preferably a corundum pot; a grinding medium is preferably an agate ball, and the agate ball has a diameter preferably ranging from 0.5 cm to 1 cm; and a ratio of the material to the ball is preferably 1:2, and grinding time is preferably greater than 1 h.
[51] After the grinding and mixing, the present invention preferably further includes screening. The number of times of screening is preferably 3 times.
[52] After the mixed powder is obtained, the mixed powder is sequentially melted and subsequently treated in the present invention to obtain the basic glass for solidifying high-level radioactive liquid waste.
[53] In the present invention, a melting temperature is preferably 1300°C-1400°C, which is further preferably 1350°C; and insulation time is preferably 2 h-3 h.
[54] In the present invention, when the basic glass for solidifying high-level radioactive liquid waste is preferably powder-shaped, the subsequent Treatment preferably sequentially includes water quenching and grinding. In the present invention, a reagent for water quenching is preferably water, and a temperature of the water is preferably less than or equal to 50°C. In the present invention, the grinding parameters are not specifically limited as long as a particle size of the basic glass for solidifying the powder-shaped high-level radioactive liquid waste finally obtained may be less than 75 microns.
[55] In the present invention, when the basic glass for solidifying high-level radicactive liquid waste is preferably microbead-shaped, the operation of the subsequent treatment is not specifically limited in the present invention as long as the microbead-shaped basic glass for solidifying high-level radioactive liquid waste having a particle size ranging from 1 mm to 3 mm may be obtained.
[56] The present invention further provides a use of the basic glass for solidifying high-level radioactive liquid waste of the technical solution described above in solidification of the high-level radioactive liquid waste.
[57] The present invention further provides a solidification method for high-level radioactive liquid waste. The method includes:
[58] mixing the high-level radioactive liquid waste and basic glass to obtain a mixed ingredient; and
[59] sequentially melting, pouring and annealing the mixed ingredient to solidifying the high-level radioactive liquid waste, where
[60] the basic glass is basic glass for solidifying high- level radioactive liquid waste of the technical solution described above.
[61] According to the present invention, the high-level radioactive liquid waste and the basic glass are mixed to obtain a mixed ingredient.
[62] In the present invention, the high-level radioactive liquid waste is preferably high-level radioactive liquid waste having a burn-up of 5.5 GWd/tU. In the present invention, a mass ratio of the high-level radioactive liquid waste to the basic glass is preferably 18:82-22:78, which is further preferably 2:8. The mixing manner is not specifically limited in the present invention as long as the high-level radioactive liquid waste and the basic glass may be sufficiently mixed.
[63] After the mixed ingredient is obtained, the mixed ingredient is sequentially melted, cast and annealed in the present invention to solidify the high-level radioactive liquid waste.
[64] In the present invention, a melting temperature is preferably 1150°C-1200°C, and insulation time is preferably 2 h-3 h.
[65] In the present invention, the casting is carried out in a mold, and a temperature of the mold is 380°C-420°C, which is further preferably 400°C.
[66] In the present invention, an annealing temperature is 500°C-550°C, and insulation time is 1.5 h-2.5 h, which is further preferably 2 h.
[67] After the annealing, the present invention further includes: naturally cool a material obtained after the annealing to a room temperature.
[68] In the present invention, the material obtained after the annealing and the cooling is named as a high-level radioactive liquid waste glass solidified body.
[69] The basic glass for solidifying high-level radicactive liquid waste, the preparation method, the use, and the solidification method for high-level radioactive liquid waste according to the present invention are described in detail below in combination with the examples, but the examples should not be construed as limiting the scope of protection of the present invention.
[70] Example
[71] The formulas of basic glass for solidifying high- level radioactive liquid waste in the examples and the comparative example are shown in Table 1.
[72] Table 1 Formulas of basic glass for solidifying high- level radioactive liquid waste in examples and comparative example
Serial Example | Example | Example | Example | Example | Comparative number oxide 1 2 3 4 5 Example 1 3 Mao 14 12 mn les Je 45 sel
BR
[73] It may be seen from Table 1 that in the basic glass for solidifying high-level radioactive liquid waste of
Example 1, an introduction amount of alkaline earth metal is reduced, and the total of CaO+MgO+Ba0 is 6.3wt2. 5 [74] The preparation method for the basic glass for solidifying high-level radioactive liquid waste in the examples and the comparative example includes:
[75] 1) calculate a formula of glass batch according to glass components and percentage by mass, weigh raw materials according to an ingredient list, calculate a total weight, and carry out grinding, mixing and screening for three times to fully and uniformly mix the materials to obtain mixed powder; and
[76] 2) place the uniformly mixed powder into a platinum crucible, then place the crucible inte a high-temperature furnace, carry out feeding repeatedly for high-temperature melting of 1350°C, clarify a mixture for 2.5 h, stir the mixture with a stainless steel thin rod, and carry out water quenching, drying and grinding after melting is completed to obtain powder-shaped basic glass for solidifying high- level radioactive liquid waste for later use.
[77] A solidification method for high-level radioactive liquid waste includes:
[78] 1) Uniformly mix basic glass (80wt%) for solidifying high-level radioactive liquid waste and simulated high-level radioactive liquid waste (20wt3) of a power reactor to prepare a solidified body batch.
[79] Simulated high-level radicactive liquid waste having burn-up of 5.5 GWd/tU and cooled for 8 years is selected as the simulated high-level radioactive liquid waste of the power reactor, contains forty or above components, mainly includes alkali metals, lanthanides and fission elements (30-70 elements), and includes about 10wt%-12Zwt% of noble metals Rul, Rh, Pd and Swt%-12wt% of insoluble element Mo0:.
[80] 2) Add the solidified body batch into a platinum crucible, place the crucible at 1150°C for insulation for 2h, and stir the solidified body batch repeatedly during the period to promote clarification and homogenization of the solidified body.
[81] 3) after melting is completed, cast a clarified and homogenized molten liquid into a mold at 400°C, solidify and shape the molten liquid, transfer the molten liquid into a muffle furnace, anneal the molten liquid for 2 h at 530°C, and then cool the molten liquid to a room temperature along with the muffle furnace to solidify the simulated high-level radioactive liquid waste of the power reactor, where a material obtained by cooling is named as a simulated liquid waste glass solidified body.
[82] The obtained simulated liquid waste glass solidified body is crushed into slivers, and the slivers are placed into a gradient furnace to test a liquidus temperature of the slivers.
[83] The simulated liquid waste glass solidified body is ground into powder (less than 75 microns), placed into the crucible, and insulated for 28 days at a temperature about 20°C below the liquidus temperature, and a crystallization rate is analyzed by means of X-RAY diffraction.
[84] Components of the simulated liquid waste glass solidified body are analyzed, and then a formula of “accommodation capacity (3)=content (WLS) of oxides introduced by high-level radioactive liquid waste in glass solidified body/total oxides {wt3}% is calculated.
[85] Results are shown in table 2.
[86] Table 2 Liquidus temperature and crystallization rate of simulated liquid waste glass solidified body obtained in
Examples 1-5 and Comparative Example 1
Glass Liquidus ne [rp ie mse capacity (%) phase rate (vol$) body (°C)
Example 3 | 20 | 820 3.1 20 20 850 RuO:+CaSiO4 22.5
Example 1
[87] It may be seen from Table 2 that a crystalline phase of the simulated liguid waste glass solidified body only contains the noble metal RuUO; inherited from the raw material and a durable phase CaMoO4, and does not contain diopside
CaSiO4 precipitated in the comparative example, which indicates that in the present invention, crystallization of the diopside is well inhibited by reducing the content of alkaline earth metals (CaOtMgO+Ba0). Specifically, in the basic glass for solidifying high-level radioactive liquid waste according to Example 1, the introduction amount of the alkaline earth metals is reduced, the total of Ca0+MgO+Ba0 is 6.3 wt %, and a crystalline phase of the simulated liquid waste glass solidified body only contains the noble metal
RuO: inherited from the raw material and the durable phase
CaMoO4. However, in the basic glass for solidifying high- level radioactive liquid waste according to Comparative
Example 1, the total of CaOtMgO+BaO0 is 15wt%, and two crystalline phases of “Ru0:+CaSi0.,” are precipitated in the crystalline phase of the simulated liquid waste glass solidified body, and the crystallization rate reaches 22.5vol4. The reason is that the alkaline earth metal is high, such that the high crystallization rate has adverse effects on the subsequent production process, such as the problem of blocking a discharge pipe. Since the simulated liquid waste glass solidified body obtained by the basic glass for solidifying high-level radioactive liquid waste according to the present invention does not contain diopside
CaSiO4 precipitated in the comparative example, it is indicated that in the present invention, reduction in crystallization of the diopside is well inhibited by reducing the content of the alkaline earth metals.
[88] Secondly, the crystalline phase of the simulated liquid waste glass solidified body contains the durable phase CaMoOQ4, but does not contain Na:Mo0O4 having high water solubility, which indicates that introduction of Na:0 has an effect of breaking a network, provides a sufficient cavity, effectively ensures accommodation of Mo element, improves leaching resistance of the simulated liquid waste glass solidified body, and satisfies the requirement of chemical stability of the liquid waste glass solidified body.
Further, it may be seen from Table 2 that after the simulated liquid waste glass solidified body obtained in Example 1 is insulated at 800°C for 28 days, an overall crystallization rate is only 3.4vol%, which satisfies the requirements for the crystallization rate in the Joule furnace process, and also satisfies the requirements for the crystallization rate of product glass in EJ1186. Finally, according to the basic glass for solidifying high-level radioactive liquid waste of the present invention, the introduction amount of alkaline earth metals (CaO+MgO+Ba0) is reduced, and the content of Na:O0 is further increased, such that when the accommodation capacity is 20wt3 for the simulated high-level radioactive liquid waste having burn-up of 5.5 GWd/tU, the simulated liquid waste glass solidified body has excellent accomodation performance on Mo element, and moreover, the crystallization rate of the simulated liquid waste glass solidified body is lower than bvol % and has excellent crystallization resistance, which can satisfy the requirements of the Joule furnace process.
[89] What are described above are merely the preferred embodiments of the present invention, it should be pointed out that those of ordinary skill in the art can further make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also fall within the scope of protection of the present invention.
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| CN112624608A (en) * | 2020-12-18 | 2021-04-09 | 中国建筑材料科学研究总院有限公司 | Borosilicate glass curing substrate and preparation method and application thereof |
| CN115057618A (en) * | 2022-03-04 | 2022-09-16 | 中国科学院上海光学精密机械研究所 | Borosilicate cured glass, preparation method and application thereof |
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| CN112624608A (en) * | 2020-12-18 | 2021-04-09 | 中国建筑材料科学研究总院有限公司 | Borosilicate glass curing substrate and preparation method and application thereof |
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