A starting glass for joule heating ceramic electric smelting furnace suitable for power reactor high-level liquid waste glass solidification and preparation and application

Abstract

The application belongs to the technical field of high-level liquid waste treatment, and provides a starting glass for a joule heating ceramic electric smelting furnace for glass solidification of high-level liquid waste of a power reactor, and preparation and application thereof.The starting glass comprises the following components in mass fraction: SiO2 35-55%, B2O3 9-15%, Na2O 6-14%, Li2O 1-3%, Al2O3 3-6%, CaO 5-8.3%, MgO 0.3-2.08%, BaO 1.03-3.13%, V2O5 0.2-2.3%, Sb2O5 0.3-2%, ZrO2 1-3%, La2O3 3-6%, CeO2 0.3-1.8%, and MoO3 1-2.8%. The starting glass provided by the application ensures the safety of starting and replacement of the joule heating ceramic electric smelting furnace in the process of glass solidification of high-level liquid waste of the power reactor.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high-level liquid waste treatment, and particularly relates to a starting glass for a joule heating ceramic electric smelting furnace for glass solidification of high-level liquid waste of a power reactor and preparation and application. BACKGROUND

[0002] The spent fuel used by a nuclear power plant is a mixture with very complex composition from a chemical point of view, mainly including the following four components, such as uranium oxide, plutonium oxide, fission products (FP) and minor actinides, which have the characteristics of complex composition, containing more than 40 elements, more than 100 isotopes, strong radioactivity, high biological toxicity, long half-life and the like.

[0003] Specifically, the high-level liquid waste of the power reactor contains more than 40 components, mainly containing alkali metals, lanthanide elements, fission elements (30-70 elements), and the content of Al2O3 is 5-20wt%; the total content of 'yellow phase' elements such as sulfur and molybdenum is low, less than 2wt%; the total content of noble metals such as Ru, Rh and Pd is less than 3wt%.

[0004] The existing commercial spent fuel reprocessing plants in the world all use glass solidification to treat high-level liquid waste, and the process of glass solidification is to mix high-level liquid waste with glass material in a certain proportion, and then melt at high temperature (900-1200 DEG C) by using a joule heating ceramic electric smelting furnace to obtain stable glass or glass-like solid.

[0005] When the joule heating ceramic electric smelting furnace is used for glass solidification, starting glass needs to be used to start and clean the joule heating ceramic electric smelting furnace. However, the existing technology does not involve the starting glass for the joule heating ceramic electric smelting furnace for solidification of high-level liquid waste of the power reactor. SUMMARY

[0006] Therefore, the present application aims to provide a starting glass for a joule heating ceramic electric smelting furnace for glass solidification of high-level liquid waste of a power reactor and preparation and application. The starting glass provided by the present application can be used for starting and cleaning the joule heating ceramic electric smelting furnace for glass solidification of high-level liquid waste of a power reactor.

[0007] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0008] The present application provides a starting glass for a joule heating ceramic electric smelting furnace for glass solidification of high-level liquid waste of a power reactor, which comprises the following components in mass fraction:

[0009] SiO2 35-55%, B2O3 9-15%, Na2O 6-14%, Li2O 1-3%, Al2O3 3-6%, CaO 5-8.3%, MgO 0.3-2.08%, BaO 1.03-3.13%, V2O5 0.2-2.3%, Sb2O5 0.3-2%, ZrO2 1-3%, La2O3 3-6%, CeO2 0.3-1.8%, MoO3 1-2.8%.

[0010] The application further provides a preparation method of the starting glass for the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor.

[0011] The components are ground and mixed to obtain mixed powder;

[0012] The mixed powder is sequentially subjected to melting and pouring to obtain the starting glass for the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor.

[0013] Preferably, the temperature of the melting is 1150-1300 DEG C, and the time is 3-5 h.

[0014] The application further provides application of the starting glass for the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor or the starting glass obtained by the preparation method in treatment of high-level liquid waste of a power reactor.

[0015] The application provides a starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor, which comprises the following components in mass fraction: SiO2 35-55%, B2O3 9-15%, Na2O 6-14%, Li2O 1-3%, Al2O3 3-6%, CaO 5-8.3%, MgO 0.3-2.08%, BaO 1.03-3.13%, V2O5 0.2-2.3%, Sb2O5 0.3-2%, ZrO2 1-3%, La2O3 3-6%, CeO2 0.3-1.8%, and MoO3 1-2.8%. The starting glass provided by the application can ensure the basic performance of the joule heating ceramic electric smelting furnace, such as electrical performance and viscosity performance, to meet the requirements of the joule heating ceramic electric smelting furnace, and the component design in the replacement process will not affect the fluctuation of the final product components in the solidification process of the joule heating ceramic electric smelting furnace, that is, the components of the starting glass and the glass solidification product containing high-level liquid waste of a power reactor change little. It can be seen that the starting glass provided by the application can ensure the safety of the joule heating ceramic electric smelting furnace in the high-level liquid waste glass solidification process of a power reactor. DETAILED DESCRIPTION

[0016] The application provides a starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor, which comprises the following components in mass fraction:

[0017] SiO2 35-55%, B2O3 9-15%, Na2O 6-14%, Li2O 1-3%, Al2O3 3-6%, CaO 5-8.3%, MgO 0.3-2.08%, BaO 1.03-3.13%, V2O5 0.2-2.3%, Sb2O5 0.3-2%, ZrO2 1-3%, La2O3 3-6%, CeO2 0.3-1.8%, MoO3 1-2.8%.

[0018] In the application, the raw materials used in the application are preferably commercially available products.

[0019] The starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor provided by the application comprises SiO2 in a mass fraction of 35-55%, preferably 40-52%, and further preferably 45-50%.

[0020] The starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor provided by the application comprises B2O3 in a mass fraction of 9-15%, preferably 10-14%, and further preferably 11-13%.

[0021] The starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor provided by the application comprises Na2O in a mass fraction of 6-14%, preferably 8-12%.

[0022] The starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor provided by the application comprises Li2O in a mass fraction of 1-3%, preferably 1.47-2.52%.

[0023] The starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor provided by the application comprises Al2O3 in a mass fraction of 3-6%, preferably 4-5.5%.

[0024] The starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor provided by the application comprises CaO in a mass fraction of 5-8.3%, preferably 6-8%, and further preferably 6.5-7.5%.

[0025] The starting glass for a joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor provided by the application comprises MgO in a mass fraction of 0.3-2.08%, preferably 1-2%.

[0026] The starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor comprises 1.03-3.13% of BaO in mass fraction, preferably 1.5-2.5%.

[0027] The starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor comprises 0.2-2.3% of V2O5 in mass fraction, preferably 1-2%.

[0028] The starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor comprises 0.3-2% of Sb2O5 in mass fraction, preferably 0.8-1.8%.

[0029] The starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor comprises 1-3% of ZrO2 in mass fraction, preferably 1.5-2.5%.

[0030] The starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor comprises 3-6% of La2O3 in mass fraction, preferably 5-6%.

[0031] The starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor comprises 0.3-1.8% of CeO2 in mass fraction, preferably 0.8-1.6%.

[0032] The starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor comprises 1-2.8% of MoO3 in mass fraction, preferably 1.5-2.5%.

[0033] The application further provides a preparation method of the starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor.

[0034] The components are ground and mixed to obtain mixed powder;

[0035] The mixed powder is sequentially subjected to melting and pouring to obtain the starting glass for the Joule heating ceramic electric smelting furnace for the high-level liquid waste glass solidification of the power reactor.

[0036] The components are ground and mixed to obtain mixed powder.

[0037] The application does not make specific limitation on the parameters of the grinding and mixing, as long as the materials can be fully mixed. After the grinding and mixing, the application preferably further comprises sieving, and the number of sieving is preferably 3 times.

[0038] After the mixed powder is obtained, the mixed powder is sequentially subjected to melting and pouring to obtain the start-up glass for the joule heating ceramic electric smelting furnace for the high-level liquid waste glassification of the power reactor.

[0039] In the present application, the temperature of the melting is preferably 1150-1300℃, and the time is preferably 3-5h.

[0040] The present application does not make specific limitation to the properties of the start-up glass for the joule heating ceramic electric smelting furnace for the high-level liquid waste glassification of the power reactor obtained by pouring, which can be set according to the actual situation; specifically, when the start-up glass is applied to the start-up of the joule heating ceramic electric smelting furnace for the high-level liquid waste glassification of the power reactor, it is preferably poured into a micro-bead shape, and the particle size of the micro-bead start-up glass is preferably 0.5-5mm; when the start-up glass is used for performance testing, it is preferably poured into a block shape, and then subjected to annealing treatment; the temperature of the annealing treatment is preferably 450-550℃, and the holding time is preferably 1.5-3h.

[0041] The present application also provides the application of the start-up glass for the joule heating ceramic electric smelting furnace for the high-level liquid waste glassification of the power reactor or the start-up glass for the joule heating ceramic electric smelting furnace for the high-level liquid waste glassification of the power reactor obtained by the preparation method to the treatment of the high-level liquid waste of the power reactor.

[0042] In the present application, the high-level liquid waste of the power reactor contains more than forty components, mainly containing alkali metals, lanthanide elements, and fissile elements (30-70th elements), wherein the content of Al2O3 is 5-20wt%; the total content of "yellow phase" elements such as sulfur and molybdenum is low, less than 2wt%; the total content of noble metals such as Ru, Rh, and Pd is less than 3wt%.

[0043] The present application does not make specific limitation to the operation of applying the start-up glass for the joule heating ceramic electric smelting furnace for the high-level liquid waste glassification of the power reactor to the treatment of the high-level liquid waste of the power reactor, which can be set according to the actual situation.

[0044] The start-up glass for the joule heating ceramic electric smelting furnace for the high-level liquid waste glassification of the power reactor, the preparation and application provided by the present application will be described in detail below in combination with examples, but they should not be understood as limiting the protection scope of the present application.

[0045] The components of the start-up glass in the examples and comparative examples are shown in Table 1.

[0046] Table 1 Components of the start-up glass in the examples and comparative examples

[0047] No. Oxide Example 1 Example 2 Example 3 Example 4 Comparative Example 1 SiO2 35 55 47 52 40 2 B2O3 15 12 11 12 11 3 Na2O 14 11 8 6 15 4 Li2O 3 1.47 2.01 2.52 3.2 5 Al2O3 6 3 5.3 4.2 3.5 6 CaO 8.3 5 7.5 6.8 9 7 MgO 2.08 0.3 1.5 1.8 2.5 8 BaO 2.02 3.13 1.99 1.58 2.5 9 [V2O5] 2.3 0.2 1.9 1.6 1.1 10 Sb2O5 2 0.3 1.8 1.6 1.2 11 Zr02 3 1 2.3 1.6 1.6 12 La2O3 6 3 5.7 5.2 4.7 13 CeO2 0.3 1.8 1.6 1.2 1.5 14 MoO3 1 2.8 2.4 1.9 3.2 Total 100 100 100 100 100

[0048] The preparation method of the start-up glass suitable for the joule heating ceramic electric smelting furnace for the power reactor high-level liquid waste glass solidification is as follows:

[0049] 1) The raw materials were weighed according to the formula in Table 1 and the total weight was calculated, and the materials were ground, mixed and sieved three times to fully mix and evenly distribute the materials.

[0050] 2) The mixed batch was placed in a platinum crucible, then the crucible was placed in a high-temperature furnace, and the batch was melted at 1300 DEG C for 5 hours with stirring by a stainless steel rod. After the melting was completed, the glass block was poured into an annealing furnace at 500 DEG C for 3 hours to obtain a block-shaped start-up glass for performance testing.

[0051] The resistivity of the block-shaped start-up glass was measured by the method of GB / T 41708-2022, the viscosity of the block-shaped start-up glass was measured by ASTM C965-96, the crystallization rate of the block-shaped start-up glass was measured by the method of JY / T 0587-2020, the liquidus of the block-shaped start-up glass was measured by the method of ASTM C829-81(2010), the element leaching rate of the block-shaped start-up glass was measured by the methods of EJ 1186-2005 and ASTM 1220-17, and the results are shown in Table 2.

[0052] Table 2 Performance test results of the start-up glass obtained in the examples and comparative examples

[0053]

[0054] As can be seen from Table 2, the resistivity, viscosity and liquidus of the obtained start-up glass meet the requirements of the joule heating ceramic electric smelting furnace operation, and can ensure the basic process performance of the joule heating ceramic electric smelting furnace operation. The crystallization rate and element leaching rate of the start-up glass can ensure the long-term stability of the glass sample during deep geological disposal.

[0055] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered within the scope of protection of the present application.

Claims

1. A starter glass suitable for use in a Joule-heated ceramic electric melting furnace for glass solidification of high-level waste liquid in power stacks, characterized in that, It is composed of the following components with mass fraction: SiO2 35~55%, B2O3 9~15%, Na2O 6~14%, Li2O 1~3%, Al2O3 3~6%, CaO 5~8.3%, MgO 0.3~2.08%, BaO 1.03~3.13%, V2O5 0.2~2.3%, Sb2O5 0.3~2%, ZrO2 1~3%, La2O3 3~6%, CeO2 0.3~1.8%, MoO3 1~2.8%; The preparation method of the starting glass for the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor comprises the following steps: The components are ground and mixed to obtain a mixed powder; The mixed powder is sequentially subjected to melting and pouring to obtain the starting glass for the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor; The melting temperature is 1150~1300℃, and the time is 3~5h; When the starting glass is applied to the starting of the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor, it is poured into a micro-bead shape, and the particle size of the micro-bead-shaped starting glass is 0.5~5mm; When the starting glass is used for performance testing, it is poured into a block shape, and then subjected to annealing treatment; the annealing treatment temperature is 450~550℃, and the holding time is 1.5~3h.

2. The method of producing a start-up glass for a joule-heated ceramic electric melter for the vitrification of high-level liquid waste for a nuclear reactor, according to claim 1, characterized in that, The components are ground and mixed to obtain a mixed powder; The mixed powder is sequentially subjected to melting and pouring to obtain the starting glass for the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor; The melting temperature is 1150~1300℃, and the time is 3~5h; When the starting glass is applied to the starting of the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor, it is poured into a micro-bead shape, and the particle size of the micro-bead-shaped starting glass is 0.5~5mm; When the starting glass is used for performance testing, it is poured into a block shape, and then subjected to annealing treatment; the annealing treatment temperature is 450~550℃, and the holding time is 1.5~3h.

3. The starting glass for the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor of claim 1 or prepared by the preparation method of claim 2 for the joule heating ceramic electric smelting furnace for high-level liquid waste glass solidification of a power reactor in the treatment of high-level liquid waste of a power reactor. ​

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