A microwave sintering solidified body and solidification method for radioactive mud

Abstract

The present invention belongs to the technical field of radioactive nuclear waste treatment, and in particular to a microwave sintered solidified body for radioactive mud, comprising a simulated radioactive mud base material powder containing a glass former and a solidified body material; the simulated radioactive mud base material powder containing the glass former comprises 40-100 wt% by mass of a simulated radioactive mud base material raw material powder and 0-60 wt% by mass of a silicate glass particle raw material powder; the solidified body material comprises 40 wt% by mass of simulated radioactive mud and 60 wt% by mass of a silicate glass particle powder, the simulated radioactive mud comprises 60-100 wt% by mass of the simulated radioactive mud base material powder and 0-40 wt% by mass of a radionuclide or a simulated radionuclide; and the sintering process is adjusted by adjusting the formula composition of the silicate glass particles, the simulated radionuclide Nd2O3 and the simulated radioactive mud base material powder to achieve the purpose of rapidly treating the radioactive mud.

Description

Technical Field

[0001] The patent of this invention belongs to the technical field of radioactive nuclear waste treatment, and relates to a microwave sintering solidified body and solidification method for radioactive mud. Background Art

[0002] Nuclear energy is highly valued as a clean and renewable energy source, and its development has positive effects in many areas. However, it is accompanied by the challenge of radioactive waste disposal. Radioactive waste is generated throughout multiple links related to nuclear energy. Improper disposal of the medium- and high-level radioactive mud formed after treatment can cause serious consequences such as ecological disasters. The safe and effective disposal of radioactive mud is of great significance.

[0003] Current conventional practices for radioactive waste disposal and different solidification methods:

[0004] 1. Internationally, radionuclides are usually fixed in matrix materials to form solid bodies, which are then placed in disposal repositories for disposal and monitoring, which places high demands on the performance of the solid bodies.

[0005] 2. Cement solidification is commonly used for intermediate and low-level radioactive waste. It was developed early, has mature technology, wide application, simple treatment, large production capacity, and low cost. It can treat nuclear waste through various solidification processes. Asphalt solidification is suitable for a variety of wet wastes and powdered wastes and has advantages such as simple process.

[0006] 3. High-level radioactive waste is often treated by vitrification, ceramics, or glass-ceramics. Vitrification involves mixing relevant raw materials in proportion and then heating, melting, and cooling them to form a glass body. Ceramic curing utilizes high-temperature solid-phase reactions to allow radioactive nuclides to enter lattice sites, forming multiple mineral phases. Glass-ceramics curing involves combining radioactive waste with a specific glass matrix to precipitate ceramic crystals to form a solid body, combining the advantages of both glass and ceramic solid bodies.

[0007] The current sintering technologies for nuclear waste solidification include traditional Joule sintering technology, spark plasma sintering technology and microwave sintering technology. Among them, microwave heating is safer and more reliable than conventional heating, has strong environmental adaptability, and has many advantages such as selective heating, which is beneficial to improving material properties. However, there are no related invention reports on the process and method of quickly fixing radioactive mud using microwave sintering technology. Summary of the Invention

[0008] Based on this, it is necessary to provide a microwave sintering solidified body and solidification method for radioactive mud that can achieve rapid solidification of radioactive mud through microwave sintering technology to reduce the storage and processing time of radioactive waste, improve processing efficiency, and reduce environmental risks.

[0009] A microwave sintering solidified body for radioactive mud, comprising a simulated radioactive mud base material powder containing a glass former and a solidified body material;

[0010] The simulated radioactive mud base material powder containing the glass former comprises 40-100 wt% of simulated radioactive mud base material raw material powder and 0-60 wt% of silicate glass particle raw material powder;

[0011] The solidified material comprises 40 wt% of simulated radioactive mud and 60 wt% of silicate glass particle powder, wherein the simulated radioactive mud comprises 60-100 wt% of simulated radioactive mud base material powder and 0-40 wt% of radioactive nuclides or simulated radioactive nuclides.

[0012] A method for preparing a microwave sintering solidified body for radioactive mud, comprising:

[0013] S100: preparing simulated radioactive mud base material raw material powder;

[0014] S200: preparing silicate glass particle raw material powder;

[0015] S300: preparing a simulated radioactive mud base material powder containing a glass former by mixing the simulated radioactive mud base material powder obtained in step S100 with the silicate glass particle powder obtained in step S200 in a ratio of 40-100 wt % to 0-60 wt % by mass;

[0016] S400: The simulated radioactive mud base material raw material powder obtained in step S100 and radioactive nuclides or simulated radioactive nuclides are mixed in a mass percentage ratio of 60-100 wt%:0-40 wt% to prepare simulated radioactive mud, and then the silicate glass particle raw material powder obtained in step S200 and the simulated radioactive mud are mixed in a mass percentage ratio of 60 wt%:40 wt% to prepare a solidified material.

[0017] Furthermore, the preparation of the simulated radioactive mud base material powder includes:

[0018] S101: Take the raw materials in the following mass percentages: CaCO319.81 wt%, Mg(OH)22.25 wt%, Na2CO343.28 wt%, Al(OH)315.21 wt%, Fe2O37.31 wt%, SiO25.52 wt%, Cr2O33.97 wt%, NiO 1.70 wt%, and MoO30.89 wt%;

[0019] S102: The raw materials in step S101 are mixed and stirred. The raw materials are placed in a flask and 150% of the total weight of the raw materials is added with anhydrous ethanol, and the mixture is mixed and stirred for 3-5 hours using a mechanical stirrer;

[0020] S103: drying the mixed raw materials in a constant temperature oven at 105° C. for 24 to 36 hours;

[0021] S104: The dried raw materials are ball-milled in a ball mill for 3 to 5 hours to prepare a uniformly mixed simulated radioactive mud matrix raw material powder.

[0022] Furthermore, the preparation of the raw material powder for silicate glass particles includes:

[0023] S201: taking the raw materials in mass percentages of SiO261.44 wt%, CaO11.20 wt%, Na2O7.90 wt%, BaO5.82 wt%, MgO5.82 wt%, Al2O34.78 wt%, and V2O52.64 wt%;

[0024] S202: Place the raw materials in a flask and add 150% of the total weight of the raw materials in anhydrous ethanol, and mix and stir using a mechanical stirrer for 3-5 hours;

[0025] S203: drying the mixed raw materials in a constant temperature oven at 105° C. for 24 to 36 hours;

[0026] S204: placing the dried raw material in a microwave muffle furnace for sintering at a temperature of 800° C., and keeping the sintering temperature at 800° C. for 40 min;

[0027] S205: placing the pre-sintered raw materials in a ball mill for 3 to 5 hours to obtain silicate glass particle powder;

[0028] S206: The ball-milled powder is passed through a 200-mesh sieve to obtain silicate glass particle powder with a particle size of 75 μm.

[0029] Furthermore, the step S300 further includes:

[0030] S301: Mixing, grinding, and drying a mixture of a simulated radioactive mud base material and silicate glass particle powder, and placing the dried mixture into a ball mill for 3 to 5 hours;

[0031] S302: Place the mixed powder in a microwave muffle furnace and heat it to 1000°C at a heating rate of 20°C / min, then heat it to 1100~1300°C at a heating rate of 10°C / min, keep it at the target temperature for 40 minutes, and then naturally cool it to room temperature to obtain a SiO2-Na2O-Al2O3 curing system material.

[0032] Furthermore, the step S400 further includes:

[0033] S401: Mixing, grinding, and drying the simulated radioactive mud and silicate glass particle powder, and then placing the dried mixed powder into a ball mill for 3 to 5 hours;

[0034] S402: The mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, then heated to 1200°C at a heating rate of 10°C / min, kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 glass system solid body and a silicate apatite silicate glass ceramic solid body.

[0035] Furthermore, the ball mill is a planetary ball mill.

[0036] Furthermore, the simulated radioactive mud is chemically similar to An 3+ Similar radioactive mud or non-radioactive mud.

[0037] Technical effects and advantages of the present invention:

[0038] 1. The present invention utilizes microwave sintering technology to adjust the formula composition of silicate glass particles, simulated radioactive nuclides Nd2O3 and simulated radioactive mud base material powder, and adjusts the sintering process to achieve the purpose of rapidly treating radioactive mud. By combining X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), high-resolution transmission electron microscopy-selected electron diffraction (HRTEM-SAED) and chemical stability testing for analysis, a SiO2-Na2O-Al2O3 silicate solidified body substrate is selected, and the formula composition of the glass solidified body or glass-ceramic solidified body for solidifying the radionuclides in the radioactive mud or simulating radionuclides and the microwave sintering process are used to prepare a SiO2-Na2O-Al2O3 silicate glass solidified body material with high efficiency in fixing radionuclides and silicate apatite (A I x A II 10-x (BO4)6O2(A=Na, Ca and Nd)) glass ceramic solid body material;

[0039] 2. The present invention can realize the solidification treatment of simulated radioactive mud containing 32 wt% Nd2O3 in the SiO2-Na2O-Al2O3 silicate glass solidified material, and no other phases appear in the sample; the glass solidified body of simulated radioactive mud containing 30 wt% Nd2O3 is mainly composed of Si4O 11 6- The main structural unit is sheet silicate group, Si4O 11 6-The integration of sheet silicate groups and SiO2 three-dimensional network structural units exceeds 50%, showing an excellent glass polymerization degree. The SEM-EDS results show that the surface of the glass solid body of the simulated radioactive mud containing 30 wt% Nd2O3 is flat and smooth, and Al, Si, Na, Ca, O, and Nd elements are evenly distributed in the glass solid body without any element enrichment; HRTEM-SAED results show obvious disorder of the amorphous structure and amorphous diffraction rings. Therefore, the SiO2-Na2O-Al2O3 silicate glass solid can achieve efficient fixation of simulated radioactive mud containing 30 wt% Nd2O3, while having a large volume reduction ratio and excellent glass polymerization degree. The normalized leaching rates of Nd and Si elements (RLNd and RLSi) in a 90°C deionized water environment are less than 2.5 × 10-6 g·m-2·d-1 and 1 × 10-3 g·m-2·d-1, respectively. The glass solid has good chemical stability, meeting the expected requirements of the nuclear industry (1×10-2 g·m-2·d-1).

[0040] 3. Using the present invention, silica apatite (A I x A II 10-x In the (BO4)6O2 (A = Na, Ca and Nd)) glass ceramic solidification material, the solidification treatment of simulated radioactive mud containing 40 w% Nd2O3 can be achieved, and (Ca, Na) x Nd 10-x (SiO4)6O2 Ca-silicon oxyapatite and Na-silicon oxyapatite phases, and the XRD spectrum structure has a steamed bun peak, the solidified sample is silicon oxyapatite (A I x A II 10-x (BO4)6O2 (A = Na, Ca and Nd)) glass-ceramic materials, SEM-EDS results show that the solidified body of simulated radioactive mud containing 40 w% Nd2O3 has hollow tubular structures and needle-shaped crystals. Nd, Ca, Na, Si and O elements are rich in the needle-shaped tubular structures, and Al, Na, Si, O and a small amount of Nd are distributed on the surface of the glass structure except the residual interface of the needle-shaped tubular structure; Na+ and part of Nd3+ are mixed in the AnI site, forming a tetrahedral NaNd9(SiO4)6O2 crystal phase structure with the surrounding 9 oxygen atoms. Another Ca 2+ Replace A I Na + and Nd 3+ Occupy the AI ​​position, the rest of the Nd 3+ Occupies A IIPosition, with the surrounding 7 oxygen atoms to form a decahedral Ca2Nd8(SiO4)6O2 crystal structure, the tetrahedron and the decahedron through the SiO4 tetrahedron, an O(4) site and an O 2- The remaining small amount of Nd is fixed in the SiO2-Na2O-Al2O3 glass phase, and the Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass-ceramic solids have extremely high solid solubility. The Nd element is "confined" in the silicate apatite crystal structure, and the remaining Nd is fixed in the glass structure of the glass-ceramic. This fixing mechanism provides a second layer of protection for the fixation of the Nd element, making the normalized leaching rates of Nd and Si (RLNd and RLSi) in a deionized water environment at 90°C lower than 1.76 × 10-6 g·m-2·d-1 and 1 ×10-3 g·m-2·d-1, respectively. The glass-ceramic solid material has excellent chemical stability, meeting the expected requirements of the nuclear industry (1×10-2 g·m-2·d-1).

[0041] 4. By adopting the present invention, only the microwave sintering process is adjusted, and the simulated radioactive mud and silicate glass particles are pretreated to achieve vitrification and glass-ceramic treatment of 32 wt% and 40 wt% Nd2O3. The preparation process is simple, easy to apply in engineering, can be widely used in the solidification treatment of radioactive mud, and has strong usability. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figures 1 to 4 The XRD spectra of the SiO2-Na2O-Al2O3 solids obtained in Examples 1 to 5 of the present invention are as follows;

[0043] Figures 5 and 6 The XRD spectra of the Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass ceramic solids prepared in Examples 6 to 19 of the present invention are shown;

[0044] Figures 7 and 8 SEM images of SiO2-Na2O-Al2O3 solidified bodies obtained in Examples 9 and 11 of the present invention;

[0045] Figures 9-11 These are SEM images of Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass-ceramic solidified bodies obtained in Examples 12, 16 and 19 of the present invention. DETAILED DESCRIPTION

[0046] To facilitate understanding of the present invention, the present invention will be described more fully below with reference to the accompanying drawings. The accompanying drawings illustrate preferred embodiments of the present invention. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the present disclosure.

[0047] It should be noted that when an element is referred to as being "fixed to" another element, it may be directly attached to the other element or there may be an intermediate element. When an element is referred to as being "connected to" another element, it may be directly connected to the other element or there may be an intermediate element. The terms "vertical," "horizontal," "left," "right," and similar expressions used herein are for illustrative purposes only and do not represent the only implementation methods.

[0048] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which this invention pertains. The terms used herein are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0049] Example 1: A simulated radioactive mud base material powder containing a glass former, the simulated radioactive mud base material powder containing a glass former comprising a simulated radioactive mud base material raw material powder and a silicate glass particle raw material powder;

[0050] A method for preparing a simulated radioactive slurry base material powder containing a glass former, comprising:

[0051] S100: preparing simulated radioactive mud base material raw material powder;

[0052] S101: Take the raw materials in the following mass percentages: CaCO319.81 wt%, Mg(OH)22.25 wt%, Na2CO343.28 wt%, Al(OH)315.21 wt%, Fe2O37.31 wt%, SiO25.52 wt%, Cr2O33.97 wt%, NiO 1.70 wt%, and MoO30.89 wt%;

[0053] S102: The raw materials in step S101 are mixed and stirred. The raw materials are placed in a flask and 150% of the total weight of the raw materials is added with anhydrous ethanol, and the mixture is mixed and stirred for 3-5 hours using a mechanical stirrer;

[0054] S103: drying the mixed raw materials in a constant temperature oven at 105° C. for 24 to 36 hours;

[0055] S104: ball milling the dried raw materials in a ball mill for 3 to 5 hours to prepare a uniformly mixed simulated radioactive mud base material raw material powder;

[0056] S200: preparing silicate glass particle raw material powder;

[0057] S201: taking the raw materials in mass percentages of SiO261.44 wt%, CaO11.20 wt%, Na2O7.90 wt%, BaO5.82 wt%, MgO5.82 wt%, Al2O34.78 wt%, and V2O52.64 wt%;

[0058] S202: Place the raw materials in a flask and add 150% of the total weight of the raw materials in anhydrous ethanol, and mix and stir using a mechanical stirrer for 3-5 hours;

[0059] S203: drying the mixed raw materials in a constant temperature oven at 105° C. for 24 to 36 hours;

[0060] S204: placing the dried raw material in a microwave muffle furnace for sintering at a temperature of 800° C., and keeping the sintering temperature at 800° C. for 40 min;

[0061] S205: placing the pre-sintered raw materials in a ball mill for 3 to 5 hours to obtain silicate glass particle powder;

[0062] S206: Passing the ball-milled powder through a 200-mesh sieve to obtain silicate glass particle powder with a particle size of 75 μm;

[0063] S300: The simulated radioactive slurry base material powder obtained in step S100 and the silicate glass particles obtained in step S200 raw powder by mass percentage 100wt%: 0wt% ratio to prepare a simulated radioactive slurry base material powder containing a glass forming body, note sample number SG0;

[0064] S301: Mixing, grinding, and drying a mixture of a simulated radioactive mud base material and silicate glass particle powder, and placing the dried mixture into a ball mill for 3 to 5 hours;

[0065] S302: The mixed powder was placed in a microwave muffle furnace and heated to 1000 ° C at a heating rate of 20 ° C / min, and then heated to 1100 / 1200 / 1300 ° C at 10 ° C / min, and kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 curing system material;

[0066] Example 2:

[0067] The difference from the previous embodiment is that the simulated radioactive slurry base material powder in step S300 and the silicate glass particles raw material powder obtained in step S200 are prepared in a ratio of 70wt% by mass: 30wt% to obtain a simulated radioactive slurry base material powder containing a glass former, and the sample number is SG30;

[0068] Example 3:

[0069] The difference from the previous embodiment is that the simulated radioactive slurry base material powder in step S300 and the silicate glass particles raw material powder obtained in step S200 are prepared in a ratio of 60wt% by mass: 40wt% to obtain a simulated radioactive slurry base material powder containing a glass former, and the sample number is SG40;

[0070] Example 4:

[0071] The difference from the previous embodiment is that the simulated radioactive slurry base material powder in step S300 and the silicate glass particles raw material powder obtained in step S200 are prepared in a ratio of 50wt% by mass: 50wt% to obtain a simulated radioactive slurry base material powder containing a glass former, and the sample number is SG50;

[0072] Example 5:

[0073] The difference from the previous embodiment is that the simulated radioactive slurry base material powder in step S300 and the silicate glass particles raw material powder obtained in step S200 are prepared in a ratio of 40wt% by mass: 60wt% to obtain a simulated radioactive slurry base material powder containing a glass former, and the sample number is SG60;

[0074] The table of the simulated radioactive slurry base material powder containing glass formers prepared in Examples 1-5 is as follows:

[0075] Example

[0076] The difference from the previous embodiment is that a microwave sintering solidified body for radioactive mud includes simulated radioactive mud base material powder containing glass former and Nd2O3;

[0077] S400: Mixing the simulated radioactive mud base material powder obtained in Example 1 with Nd2O3 to prepare simulated radioactive mud;

[0078] S401: Mix, grind and dry the simulated radioactive mud base material powder and Nd2O3 raw material, and put the dried mixed powder into a ball mill for 3 to 5 hours;

[0079] S402: drying the mixed raw materials in a constant temperature oven at 105° C. for 24 to 36 hours;

[0080] The mass percentage ratio of the simulated radioactive mud base material powder to Nd2O3 is as follows:

[0081]

[0082] A SiO2-Na2O-Al2O3 silicate glass solid material is prepared by mixing 40 wt% of the simulated radioactive mud obtained in Example 1 and 60 wt% of the silicate glass particle powder obtained in step 200 of Example 1, and drying the mixture to obtain a mixed powder, which is recorded as sample number SG60-Nd5. The mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, then to 1200°C at a heating rate of 10°C / min, and maintained at the target temperature for 40 minutes. The mixture is then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 system glass solid material.

[0083] Example 7

[0084] The difference from the previous embodiment is that a SiO2-Na2O-Al2O3 silicate glass solid material is obtained, and 40 wt% of the simulated radioactive mud obtained in No. 2 and 60 wt% of the silicate glass particle powder obtained in Example 2 are taken, mixed and dried to obtain a mixed powder, recorded as sample number SG60-Nd10; the mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, and then heated to 1200°C at a heating rate of 10°C / min, and kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 system glass solid material.

[0085] Example 8:

[0086] The difference from the previous embodiment is that a SiO2-Na2O-Al2O3 silicate glass solidified material is prepared by mixing 40 wt% of the simulated radioactive mud obtained in Example 3 and 60 wt% of the silicate glass particle powder obtained in Example 2, and drying them to obtain a mixed powder, which is recorded as sample number SG60-Nd20. The mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, then to 1200°C at a heating rate of 10°C / min, and maintained at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 system glass solidified material.

[0087] Example 9:

[0088] The difference from the previous embodiment is that a SiO2-Na2O-Al2O3 silicate glass solidified material is prepared by mixing 40 wt% of the simulated radioactive mud obtained in Example 4 and 60 wt% of the silicate glass particle powder obtained in Example 2, and drying them to obtain a mixed powder, which is recorded as sample number SG60-Nd30. The mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, then to 1200°C at a heating rate of 10°C / min, and maintained at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 system glass solidified material.

[0089] Example 10

[0090] The difference from the previous embodiment is that a SiO2-Na2O-Al2O3 silicate glass solidified material is prepared by mixing 40 wt% of the simulated radioactive mud obtained in Example 5 and 60 wt% of the silicate glass particle powder obtained in Example 2, and drying them to obtain a mixed powder, which is recorded as sample number SG60-Nd31. The mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, then to 1200°C at a heating rate of 10°C / min, and maintained at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 system glass solidified material.

[0091] Example 11

[0092] The difference from the previous embodiment is that a SiO2-Na2O-Al2O3 silicate glass solidified material is prepared by mixing 40 wt% of the simulated radioactive mud obtained in Example 6 and 60 wt% of the silicate glass particle powder obtained in Example 2, and drying them to obtain a mixed powder, which is recorded as sample number SG60-Nd32. The mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, then to 1200°C at a heating rate of 10°C / min, and maintained at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 system glass solidified material.

[0093] Example 12

[0094] A silicate I x A II 10-x(BO4)6O2 (A = Na, Ca and Nd)) glass ceramic solid material, 40 wt% of the simulated radioactive mud obtained in No. 7 and 60 wt% of the silicate glass particle powder obtained in step S200 in Example 1 are taken, mixed and dried to obtain a mixed powder, recorded as sample number SG60-Nd33; the mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, and then heated to 1200°C at a heating rate of 10°C / min, and kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass ceramic solid material;

[0095] Example 13

[0096] The difference from the previous embodiment is that a silicate (A I x A II 10-x (BO4)6O2 (A = Na, Ca and Nd)) glass ceramic solid material, 40 wt% of the simulated radioactive mud obtained in No. 8 and 60 wt% of the silicate glass particle powder obtained in Example 2 are taken, mixed and dried to obtain a mixed powder, recorded as sample number SG60-Nd34; the mixed powder is placed in a microwave muffle furnace and heated to 1000 ℃ at a heating rate of 20 ℃ / min, and then heated to 1200 ℃ at 10 ℃ / min, kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass ceramic solid material.

[0097] Example 14

[0098] The difference from the previous embodiment is that a silicate (A I x A II 10-x (BO4)6O2 (A = Na, Ca and Nd)) glass ceramic solid material, 40 wt% of the simulated radioactive mud obtained in No. 9 and 60 wt% of the silicate glass particle powder obtained in Example 2 are taken, mixed and dried to obtain a mixed powder, recorded as sample number SG60-Nd35; the mixed powder is placed in a microwave muffle furnace and heated to 1000 ℃ at a heating rate of 20 ℃ / min, and then heated to 1200 ℃ at 10 ℃ / min, kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass ceramic solid material.

[0099] Example 15

[0100] The difference from the previous embodiment is that a silicate (A I x A II 10-x (BO4)6O2 (A = Na, Ca and Nd)) glass ceramic solid material, 40 wt% of the simulated radioactive mud obtained in Example 10 and 60 wt% of the silicate glass particle powder obtained in Example 2 were taken, mixed and dried to obtain a mixed powder, recorded as sample number SG60-Nd36; the mixed powder was placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, and then heated to 1200°C at a heating rate of 10°C / min, kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass ceramic solid materials.

[0101] Example 16

[0102] The difference from the previous embodiment is that a silicate (A I x A II 10-x (BO4)6O2 (A = Na, Ca and Nd)) glass ceramic solid material, 40 wt% of the simulated radioactive mud obtained according to No. 11 and 60 wt% of the silicate glass particle powder obtained in Example 2 were taken, mixed and dried to obtain a mixed powder, recorded as sample number SG60-Nd37; the mixed powder was placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, and then heated to 1200°C at a heating rate of 10°C / min, kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass ceramic solid materials.

[0103] Example 17

[0104] The difference from the previous embodiment is that a silicate (A I x A II 10-x(BO4)6O2 (A = Na, Ca and Nd)) glass ceramic solid material, 40 wt% of the simulated radioactive mud obtained according to No. 12 and 60 wt% of the silicate glass particle powder obtained in Example 2 were taken, mixed and dried to obtain a mixed powder, recorded as sample number SG60-Nd38; the mixed powder was placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, and then heated to 1200°C at a heating rate of 10°C / min, kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass ceramic solid materials.

[0105] Example 18

[0106] The difference from the previous embodiment is that a silicate (A I x A II 10-x (BO4)6O2 (A = Na, Ca and Nd)) glass ceramic solid material, 40 wt% of the simulated radioactive mud obtained according to No. 13 and 60 wt% of the silicate glass particle powder obtained in Example 2 were taken, mixed and dried to obtain a mixed powder, recorded as sample number SG60-Nd39; the mixed powder was placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, and then heated to 1200°C at a heating rate of 10°C / min, kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass ceramic solid materials.

[0107] Example 19

[0108] The difference from the previous embodiment is that a silicate (A I x A II 10-x A (BO4)6O2 (A = Na, Ca and Nd)) glass-ceramic solid material is prepared by mixing 40 wt% of the simulated radioactive mud obtained in Example 14 and 60 wt% of the silicate glass particle powder obtained in Example 2, mixing and drying to obtain a mixed powder, recorded as sample number SG60-Nd40; the mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, then heated to 1200°C at a heating rate of 10°C / min, and kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass-ceramic solid materials;

[0109] The solidified bodies in Examples 1-19 are described below with reference to the accompanying drawings;

[0110] from Figure 1-4 It can be seen from the XDR spectrum that SG50 and SG60 do not have too many obvious diffraction peaks, while Figure 4 It is concluded that when the sintering temperature is 1200 and 1300 degrees Celsius, SG50 and SG60 have no peaks, so no diffraction peaks will appear when the sintering temperature is 1200 degrees Celsius;

[0111] And through Figure 5 The XDR spectrum shows that when Nd2O3 is 30wt% or less, no diffraction peaks appear. Figure 6 It is shown in the figure that when the mass percentage of Nd2O3 is 31wt%-39wt%, no diffraction peaks appear at 31wt% and 32wt%. Therefore, the SiO2-Na2O-Al2O3 silicate glass solidification material can be used for the solidification treatment of simulated radioactive mud containing 32w% Nd2O3, and no other phases appear in the sample.

[0112] The main components of the glass solidified body of simulated radioactive mud containing 30 wt% Nd2O3 are Si4O 11 6- The main structural unit is sheet silicate group, Si4O 11 6- The sheet silicate group and SiO2 three-dimensional network structure unit are more than 50%, showing an excellent glass polymerization degree. Figure 7-8 The SEM-EDS results show that the surface of the glass solidified body of the simulated radioactive mud containing 30 wt% Nd2O3 is flat and smooth, and the elements Al, Si, Na, Ca, O, and Nd are evenly distributed in the glass solidified body without any element enrichment;

[0113] The solidification treatment of simulated radioactive mud containing 40w% Nd2O3 can be carried out by using silica apatite (A I x A II 10-x (BO4)6O2(A=Na, Ca and Nd)) glass ceramic solidification material, (Ca, Na) appeared from the sample x Nd 10-x (SiO4)6O2 Ca-silicon oxyapatite and Na-silicon oxyapatite phases, and the XRD spectrum structure has a steamed bun peak, the solidified sample is silicon oxyapatite (A I x A II 10-x (BO4)6O2(A=Na, Ca and Nd)) glass ceramic materials, such as Figure 9-11The SEM-EDS results show that the solidified body of the simulated radioactive mud containing 40 w% Nd2O3 has hollow tubular structures and needle-shaped crystals. Nd, Ca, Na, Si and O elements are rich in the needle-shaped tubular structures, while Al, Na, Si, O and a small amount of Nd are distributed on the surface of the glass structure of the residual interface except the needle-shaped tubular structure. Na+ and part of Nd3+ are mixed in the AnI site, forming a tetrahedral NaNd9(SiO4)6O2 crystal phase structure with the surrounding 9 oxygen atoms. Another Ca 2+ Replace A I Na + and Nd 3+ Occupy the AI ​​position, the rest of the Nd 3+ Occupies A II Position, with the surrounding 7 oxygen atoms to form a decahedral Ca2Nd8(SiO4)6O2 crystal structure, the tetrahedron and the decahedron through the SiO4 tetrahedron, an O(4) site and an O 2- They are interconnected to form a solid body; the remaining small amount of Nd element is fixed in the SiO2-Na2O-Al2O3 glass phase. The formed Ca2Nd8(SiO4)6O2 and NaNd9(SiO4)6O2 glass-ceramic solid bodies have extremely high solid solubility. The Nd element is "confined" in the silicate apatite crystal structure, and the remaining Nd is fixed in the glass structure of the glass-ceramic. This fixing mechanism provides a second layer of protection for the fixation of the Nd element.

[0114] The ball mill in the above embodiment can be a planetary ball mill or other existing ball mills, and the simulated radioactive mud has the same chemical properties as An 3+ Similar radioactive mud or non-radioactive mud;

[0115] In the above examples: the raw materials used are all commercially available products and are AR analytical grade reagents;

[0116] In the above embodiment: the mass percentage ratio is to mix the ingredients according to the percentage of the total mass set manually;

[0117] In the above embodiments, the process parameters (drying temperature, ball milling time, etc.) in each step are within a range of values, and are applicable as long as the operation objectives are met.

[0118] The present invention is not limited to the above embodiments, and all embodiments described in the present invention can be implemented and have the above good effects.

[0119] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0120] The above-described embodiments merely represent several embodiments of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A method for preparing a microwave sintered solidified body of radioactive mud, characterized in that: include S100: preparing simulated radioactive mud base material raw material powder; S200: preparing silicate glass particle raw material powder; S300: preparing a simulated radioactive mud base material powder containing a glass former by mixing the simulated radioactive mud base material raw material powder obtained in step S100 and the silicate glass particle powder obtained in step S200 at a mass percentage of 40-100 wt %: 0-60 wt %; S400: preparing simulated radioactive mud by mixing the simulated radioactive mud base material powder obtained in step S100 with radionuclides or simulated radionuclides in a mass ratio of 60-100 wt%:0-40 wt% to obtain simulated radioactive mud, and then preparing a solidified material by mixing the silicate glass particle powder obtained in step S200 with the simulated radioactive mud in a mass ratio of 60 wt%:40 wt% to obtain a solidified material; The preparation of the raw material powder for silicate glass particles comprises: S201: taking the raw materials in mass percentages of SiO261.44 wt%, CaO11.20 wt%, Na2O7.90 wt%, BaO5.82 wt%, MgO5.82 wt%, Al2O3 4.78 wt%, and V2O52.64 wt%; S202: Place the raw materials in a flask and add 150% of the total weight of the raw materials in anhydrous ethanol, and mix and stir using a mechanical stirrer for 3-5 hours; S203: drying the mixed raw materials in a constant temperature oven at 105° C. for 24 to 36 hours; S204: placing the dried raw material in a microwave muffle furnace for sintering at a temperature of 800° C., and keeping the sintering temperature at 800° C. for 40 min; S205: placing the pre-sintered raw materials in a ball mill for 3 to 5 hours to obtain silicate glass particle powder; S206: Passing the ball-milled powder through a 200-mesh sieve to obtain silicate glass particle powder with a particle size of 75 μm; The step S300 further includes: S301: Mixing, grinding, and drying a mixture of a simulated radioactive slurry base material powder and a silicate glass particle powder, and placing the dried mixture into a ball mill for 3 to 5 hours; S302: placing the mixed powder in a microwave muffle furnace and heating it to 1000°C at a heating rate of 20°C / min, then heating it to 1100-1300°C at a heating rate of 10°C / min, keeping it at the target temperature for 40 minutes, and then naturally cooling it to room temperature to obtain a SiO2-Na2O-Al2O3 curing system material; The step S400 further includes: S401: Mixing, grinding, and drying the simulated radioactive mud and silicate glass particle powder, and then placing the dried mixed powder into a ball mill for 3 to 5 hours; S402: The mixed powder is placed in a microwave muffle furnace and heated to 1000°C at a heating rate of 20°C / min, then heated to 1200°C at a heating rate of 10°C / min, kept at the target temperature for 40 minutes, and then naturally cooled to room temperature to obtain a SiO2-Na2O-Al2O3 glass system solid body and a silicate apatite silicate glass ceramic solid body.

2. The method for preparing a microwave sintered solidified body of radioactive slurry according to claim 1, characterized in that: The preparation of the simulated radioactive mud base material raw material powder comprises: S101: Take the raw materials in the following mass percentages: CaCO3 19.81 wt%, Mg(OH)2 2.25 wt%, Na2CO3 43.28 wt%, Al(OH)3 15.21 wt%, Fe2O3 7.31 wt%, SiO2 5.52 wt%, Cr2O3 3.97 wt%, NiO 1.70 wt%, and MoO3 0.89 wt%; S102: The raw materials in step S101 are mixed and stirred. The raw materials are placed in a flask and 150% of the total weight of the raw materials is added with anhydrous ethanol, and the mixture is mixed and stirred for 3-5 hours using a mechanical stirrer; S103: drying the mixed raw materials in a constant temperature oven at 105° C. for 24 to 36 hours; S104: The dried raw materials are ball-milled in a ball mill for 3 to 5 hours to prepare a uniformly mixed simulated radioactive mud matrix raw material powder.

3. The method for preparing a microwave sintered solidified body of radioactive mud according to claim 2, characterized in that: The ball mill is a planetary ball mill.

4. The method for preparing a microwave sintered solidified body of radioactive slurry according to any one of claims 2 to 3, characterized in that: The simulated radioactive mud is chemically similar to An 3+ Similar radioactive mud or non-radioactive mud.

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