CN113371725A - Method for treating radioactive waste molecular sieve - Google Patents
Method for treating radioactive waste molecular sieve Download PDFInfo
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- CN113371725A CN113371725A CN202110557724.6A CN202110557724A CN113371725A CN 113371725 A CN113371725 A CN 113371725A CN 202110557724 A CN202110557724 A CN 202110557724A CN 113371725 A CN113371725 A CN 113371725A
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- molecular sieve
- radioactive waste
- cesium
- molecular sieves
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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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
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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
- G21F9/34—Disposal of solid waste
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention belongs to the technical field of radioactive waste treatment, and relates to a method for treating a radioactive waste molecular sieve. The processing method comprises the following steps: (1) mixing a radioactive waste molecular sieve containing cesium, an aluminum source and sodium hydroxide in water, and then reacting under stirring to form a sol mixture containing cesium, silica and alumina; (2) and adding the sol mixture containing cesium, silicon and aluminum oxide into a high-pressure reaction kettle for hydrothermal reaction to obtain cesium type analcime crystals. The method for treating the radioactive waste molecular sieves can treat the radioactive waste molecular sieves simply, quickly, with low treatment cost and stable final products, and directly converts the waste molecular sieves into pollucite by a hydrothermal method.
Description
Technical Field
The invention belongs to the technical field of radioactive waste treatment, and relates to a method for treating a radioactive waste molecular sieve.
Background
The molecular sieve has a large specific surface and rich pore structures, and the rich specific surface and the rich pore structures enable the molecular sieve to have a good adsorption effect, and meanwhile, the molecular sieve is acid-resistant, alkali-resistant and has good selective adsorption, so the molecular sieve is widely applied to the aspect of environmental management.
The molecular sieve is also greatly applied to the treatment of radioactive wastewater. Various molecular sieves have strong adsorption capacity on cesium, and the molecular sieves are widely applied to removing cesium in cesium-containing waste liquid with low concentration, such as the nuclear accidents of the san li island and the fukushima of Japan.
However, after adsorption is completed, cesium can also diffuse out through the pores of the molecular sieve, so that the cesium-containing molecular sieve cannot be directly disposed.
The current approach to the radioactive spent molecular sieves is high temperature vitrification and the use of barium blocking to prevent diffusion of cesium. However, the molecular sieve is vitrified at high temperature and high pressure, and cesium is easily volatilized at high temperature in the vitrification process; good results can be obtained when waste molecular sieves are mixed into borate glass and the voids are filled with barium to block the diffusion of cesium, however, the volume of radioactive waste is increased and the disposal cost is also greatly increased.
Just because the cesium-containing waste molecular sieves are difficult to treat, the existing treatment technology for radioactive waste molecular sieves still has a great problem, so that the existing radioactive waste molecular sieves are in a temporary storage state, and the use of the molecular sieves is reduced as much as possible in the actual radioactive waste treatment process. For example, the large quantities of waste molecular sieves produced in fukushima, japan, have not been reasonably disposed of.
Therefore, the treatment technology of the radioactive waste molecular sieve becomes a great problem restricting the further use of the molecular sieve, and the research on the reasonable treatment technology of the cesium-containing waste molecular sieve is not slow.
Disclosure of Invention
The invention aims to provide a method for treating radioactive waste molecular sieves, which can treat the radioactive waste molecular sieves simply, quickly, with low treatment cost and stable treatment final products, and directly convert the waste molecular sieves into pollucite by utilizing a hydrothermal method.
To achieve this object, in a basic embodiment, the present invention provides a method for treating a radioactive waste molecular sieve, the method comprising the steps of:
(1) mixing a radioactive waste molecular sieve containing cesium, an aluminum source and sodium hydroxide in water, and then reacting under stirring to form a sol mixture containing cesium, silica and alumina;
(2) and adding the sol mixture containing cesium, silicon and aluminum oxide into a high-pressure reaction kettle for hydrothermal reaction to obtain cesium type analcime crystals.
In a preferred embodiment, the invention provides a method for treating radioactive waste molecular sieves, wherein in the step (1), the molecular sieve is selected from one or more of clinoptilolite, mordenite, a ZSM type molecular sieve, a Y type molecular sieve, an X type molecular sieve and an A type molecular sieve.
In a preferred embodiment, the present invention provides a method for treating radioactive waste molecular sieves, wherein in the step (1), the aluminum source is selected from aluminum hydroxide and/or aluminum chloride.
In a preferred embodiment, the invention provides a method for treating radioactive waste molecular sieves, wherein in the step (1), the mass ratio of the radioactive waste molecular sieves containing cesium, an aluminum source and sodium hydroxide is 1:0.01-0.5: 0.2-1.
In a preferred embodiment, the present invention provides a method for treating radioactive waste molecular sieves, wherein in the step (1), the reaction temperature is 0-100 ℃, the reaction time is 10-120min, and the stirring speed is 100-2000 rpm.
In a preferred embodiment, the invention provides a method for treating radioactive waste molecular sieves, wherein in the step (2), the high-pressure reaction kettle is a polytetrafluoroethylene-lined high-pressure reaction kettle.
In a preferred embodiment, the present invention provides a method for treating radioactive waste molecular sieves, wherein in the step (2), the temperature of the hydrothermal reaction is 110-.
The method has the advantages that the radioactive waste molecular sieves can be simply and quickly treated by the method, the treatment cost is low, the final product is stable, and the waste molecular sieves are directly converted into pollucite by a hydrothermal method.
The invention utilizes the cesium-containing waste molecular sieves as a silicon source and an aluminum source, and cesium loaded on the molecular sieves as a cesium source to synthesize the pollucite. The pollucite belongs to a analcime type molecular sieve, has stable structure, is not easy to damage, has small aperture, and can ensure that cesium can be safely sealed in the molecular sieve framework, thereby achieving the aim of safely disposing cesium-containing waste molecular sieves.
Drawings
Fig. 1 is an XRD detection pattern of pollucite obtained in example 1.
FIG. 2 is the scanning electron microscopy atlas of pollucite obtained in example 1.
Detailed Description
The following examples further illustrate specific embodiments of the present invention.
Example 1: treatment of waste molecular sieves with simulated radioactivity
(1) Adding Y molecular sieve into cesium-containing solution, and fully adsorbing to load Cs+In an amount of 150mg/g, to simulate a cesium-containing radioactive waste molecular sieve, which is sufficiently dried.
(2) Putting the cesium-containing Y molecular sieve obtained in the step (1), aluminum hydroxide and sodium hydroxide into ultrapure water, wherein the mass ratio of the cesium-containing Y molecular sieve to the aluminum hydroxide is as follows: aluminum hydroxide: sodium hydroxide: after fully stirring (500rpm), the mixture reacts at room temperature for 120min to form a sol with uniform distribution.
(3) And (3) adding the sol obtained in the step (2) into a polytetrafluoroethylene lining high-pressure reaction kettle, carrying out hydrothermal reaction at 150 ℃ and 0.5Mpa for 48h, stopping the reaction, and centrifuging to obtain the cesium analcime crystal.
(4) Taking the cesium type analcime crystal sample obtained in the step (3) to carry out XRD detection (instrument model: Pasnaki Sharpe, CuK)αVoltage: 40kv, current: 40mA, scanning speed: 4 degree/min, measuring angle of 10-80 degree and scanning electron microscope detection, the results are respectively shown in figure 1 and figure 2.
As can be seen from FIG. 1, the generated cesium type analcime crystal has a good pollucite structure, and is in close agreement with a pollucite XRD standard card, which shows that the treatment method of the present invention can completely hydrothermally convert radioactive waste molecular sieves containing cesium into pollucite.
As can be seen from fig. 2, the produced cesium type analcime crystal, i.e., the synthesized cesium type analcime has a better microstructure, the produced pollucite is in an irregular spherical shape, the particles are clear, and no obvious impurities are present.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (7)
1. A method for treating radioactive waste molecular sieves is characterized by comprising the following steps:
(1) mixing a radioactive waste molecular sieve containing cesium, an aluminum source and sodium hydroxide in water, and then reacting under stirring to form a sol mixture containing cesium, silica and alumina;
(2) and adding the sol mixture containing cesium, silicon and aluminum oxide into a high-pressure reaction kettle for hydrothermal reaction to obtain cesium type analcime crystals.
2. The processing method according to claim 1, characterized in that: in the step (1), the molecular sieve is selected from one or more of clinoptilolite, mordenite, a ZSM type molecular sieve, a Y type molecular sieve, an X type molecular sieve and an A type molecular sieve.
3. The processing method according to claim 1, characterized in that: in the step (1), the aluminum source is selected from aluminum hydroxide and/or aluminum chloride.
4. The processing method according to claim 1, characterized in that: in the step (1), the mass ratio of the radioactive waste molecular sieve containing cesium to the aluminum source to the sodium hydroxide is 1:0.01-0.5: 0.2-1.
5. The processing method according to claim 1, characterized in that: in the step (1), the reaction temperature is 0-100 ℃, the reaction time is 10-120min, and the stirring speed is 100-2000 rpm.
6. The processing method according to claim 1, characterized in that: in the step (2), the high-pressure reaction kettle is a high-pressure reaction kettle added with a polytetrafluoroethylene lining.
7. The processing method according to claim 1, characterized in that: in the step (2), the temperature of the hydrothermal reaction is 110-.
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Citations (10)
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| US3959172A (en) * | 1973-09-26 | 1976-05-25 | The United States Of America As Represented By The United States Energy Research And Development Administration | Process for encapsulating radionuclides |
| CN102897787A (en) * | 2012-10-22 | 2013-01-30 | 天津工业大学 | Synthesis method of rho type molecular sieve with narrow particle size distribution |
| CN104528746A (en) * | 2014-12-04 | 2015-04-22 | 西南科技大学 | Preparation method of microcrystalline pollucite |
| CN105617982A (en) * | 2016-02-24 | 2016-06-01 | 清华大学 | Inorganic adsorbent for removing 110mAg in radioactive water and preparing method thereof |
| CN107311193A (en) * | 2017-08-16 | 2017-11-03 | 西南科技大学 | A kind of preparation method of pollucite tiny balloon |
| CN108417286A (en) * | 2018-03-14 | 2018-08-17 | 清华大学 | A method of it impregnates and prepares simulation pollucite source core |
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| CN112742346A (en) * | 2020-12-25 | 2021-05-04 | 济南大学 | Adsorbing material for capturing radioactive element iodine |
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2021
- 2021-05-21 CN CN202110557724.6A patent/CN113371725B/en active Active
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| CN102897787A (en) * | 2012-10-22 | 2013-01-30 | 天津工业大学 | Synthesis method of rho type molecular sieve with narrow particle size distribution |
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| CN109859875A (en) * | 2019-01-16 | 2019-06-07 | 中国辐射防护研究院 | A kind of decontamination solution prosecutor method of Spent Radioactive lubricating oil |
| CN109704351A (en) * | 2019-03-05 | 2019-05-03 | 西南科技大学 | A kind of low temperature of pollucite exempts to calcine preparation method |
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