CN114160554B - Method for treating waste cation exchange resin containing radioactive elements by using ternary carbonic acid eutectic molten salt - Google Patents
Method for treating waste cation exchange resin containing radioactive elements by using ternary carbonic acid eutectic molten salt Download PDFInfo
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Abstract
A method for treating waste cation exchange resin containing radioactive elements by using ternary carbonic acid eutectic molten salt. The invention belongs to the field of waste resin treatment. The invention aims to solve the technical problems that the radionuclide is discharged by waste gas and is difficult to fix in the existing method for treating the cation exchange waste resin. The method of the invention comprises the following steps: step 1: uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate to obtain a ternary eutectic salt mixture, and then adding waste cation exchange resin containing radioactive elements to continuously and uniformly mix; step 2: and (3) heating the mixture obtained in the step (1) at the temperature of 750-850 ℃ for 1.5-2.5 h to finish the treatment of the waste cation exchange resin containing the radioactive elements. According to the invention, through comprehensive regulation and control of the usage amount and the treatment temperature of the ternary carbonic acid eutectic molten salt, the purpose of efficiently treating the cobalt-containing cation exchange resin is realized on the basis of greatly reducing the usage amount of the ternary carbonic acid eutectic molten salt, most of cobalt is still retained in the molten salt, and the treatment effect is obvious.
Description
Technical Field
The invention belongs to the field of waste resin treatment, and particularly relates to a method for treating waste cation exchange resin containing radioactive elements by using ternary carbonic acid eutectic molten salt.
Background
Cationic resins are widely used in the nuclear industry to remove radioactive contaminants. Resins loaded with radionuclides cannot be regenerated and reused and they should be handled reasonably to minimize environmental hazards.
Common methods for disposing of waste resins include cement curing, incineration, pyrolysis, and the like. Due to the lack of proper adhesion between cement binder and resin beads, the problems of low containment capacity, large volume increase of cured bodies, high nuclide leaching rate and the like exist when resin waste is treated by a cement curing method. Although conventional pyrolysis or incineration minimizes the volume of waste, radionuclides escape into the air as exhaust gases are emitted. Therefore, when the waste resin is treated, the waste resin is not only thoroughly treated by following the principle of waste minimization, but also the radionuclide is effectively trapped and the escape is reduced.
Disclosure of Invention
The invention provides a method for treating waste cation exchange resin containing radioactive elements by using ternary carbonic acid eutectic molten salt, which aims to solve the technical problems that radioactive nuclides are discharged by waste gas in an entrainment mode and are difficult to fix in the conventional method for treating the waste cation exchange resin.
The method for treating the waste cation exchange resin containing the radioactive elements by using the ternary carbonic acid eutectic molten salt comprises the following steps of:
step 1: uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate to obtain a ternary eutectic salt mixture, and then adding waste cation exchange resin containing radioactive elements to continuously and uniformly mix;
and 2, step: and (2) heating the mixture obtained in the step (1) at the temperature of 750-850 ℃ for 1.5-2.5 h to finish the treatment of the waste cation exchange resin containing the radioactive elements.
Further limiting, in the ternary eutectic salt mixture in the step 1, the mass ratio of lithium carbonate to sodium carbonate to potassium carbonate is 1: (0.78-1.16): (0.89-1.33).
Further limiting, in the ternary eutectic salt mixture in the step 1, the mass ratio of lithium carbonate to sodium carbonate to potassium carbonate is 1:0.97:1.11.
further limiting, the mass ratio of the ternary eutectic salt mixture to the waste cation exchange resin containing radioactive elements in the step 1 is (0.8-1.2): 1.
further limiting, the mass ratio of the ternary eutectic salt mixture to the waste cation exchange resin containing radioactive elements in the step 1 is 1:1.
further, the waste cation exchange resin containing radioactive elements in the step 1 is waste cation exchange resin containing Co.
Further limiting, the content of the radioactive element in the waste cation exchange resin containing the radioactive element in the step 1 is 1.6wt% to 2.4wt%.
Further limiting, the content of radioactive elements in the waste cation exchange resin containing radioactive elements in the step 1 is 2wt%.
Further limiting, the mixture obtained after the step 1 is heated and treated at 800 ℃ for 2h in the step 2, and the treatment of the waste cation exchange resin containing the radioactive elements is completed.
Compared with the prior art, the invention has the following remarkable effects:
the invention utilizes the characteristic that carbonate in molten carbonate can react with cobalt in the cobalt-containing cation exchange resin and oxidize the carbonate into cobaltosic oxide, uses ternary eutectic carbonate molten salt to oxidize the cobalt-containing cation exchange resin, converts the cobalt into cobaltosic oxide with good thermal stability, and realizes the purpose of efficiently treating the cobalt-containing cation exchange resin on the basis of greatly reducing the dosage of the ternary eutectic carbonate molten salt and comprehensively regulating and controlling the treatment temperature, the oxidation is carried out for 2 hours at 800 ℃, the oxidation efficiency is as high as 95.64 percent, the interception efficiency of the cobalt is 97.3 percent, and most of the cobalt is still retained in the molten salt.
Drawings
FIG. 1 is an XRD pattern of the treated product of comparative example 1;
FIG. 2 is a thermogravimetric plot of a cation exchange resin without ion exchange;
figure 3 is the XRD pattern of the product after treatment of example 1.
Detailed Description
Example 1, the method for treating the waste cation exchange resin containing radioactive elements by using the ternary carbonic acid eutectic molten salt of the embodiment comprises the following steps:
step 1: lithium carbonate, sodium carbonate and potassium carbonate are mixed according to the mass ratio of 1:0.97:1.11, uniformly mixing to obtain a ternary eutectic salt mixture, and then adding waste cation exchange resin containing Co to continuously and uniformly mix; the mass ratio of the ternary eutectic salt mixture to the waste Co-containing cation exchange resin is 1:1; the Co content of the Co-containing waste cation exchange resin is 2wt%;
step 2: and (3) heating the mixture obtained in the step (1) at 800 ℃ for 2h to finish the treatment of the waste Co cation exchange resin.
The waste cation exchange resin with the Co content of 2wt% in the embodiment is obtained by simulation according to the following steps:
step (1): weigh 0.4g of anhydrous CoCl 2 Fully dissolved and then fixed to 50mL to prepare CoCl with the concentration of 0.0615mol/L 2 Aqueous solutions to simulate wastewater containing radionuclides;
step (2): (1) fully infiltrating cation exchange resin (nuclear grade 732 type cation exchange resin produced by Hangzhou optical resin factory, which is styrene-divinylbenzene copolymer with sulfonic functional group on benzene ring) with 1mol/LHCl solution for 2h, and then washing the cation resin with deionized water for 7-8 times until the pH value of the solution is 7; (2) fully soaking the cation exchange resin for 2 hours by using 1mol/LNaOH solution, and then washing the cation exchange resin for 7-8 times by using deionized water until the pH value of the solution is 7; repeating the operations of the steps (1) to (2) for 3 to 5 times, and then storing the cation exchange resin in a wet state to obtain the pretreated cation exchange resin;
and (3): and (3) putting 5mL of the solution obtained in the step (1) and 2g of the pretreated cation exchange resin obtained in the step (2) into a 10mL centrifuge tube, shaking at the temperature of 25 ℃ for 48h at the rotating speed of 120r/min to complete ion exchange, and then drying the ion-exchanged resin at the temperature of 101 ℃ for 12h to obtain the waste cation exchange resin with the Co content of 2wt%.
Comparative example 1: this example differs from example 1 in that: the resin to be treated is cation exchange resin which is not subjected to ion exchange (nuclear grade 732 type cation exchange resin produced by Hangzhou optical resin factory, and the structure of the resin is styrene-divinylbenzene copolymer with sulfonic functional group on benzene ring).
The XRD pattern of the treated product of comparative example 1 is shown in FIG. 1, and it can be seen from FIG. 1 that the cation exchange resin was oxidized at 800 ℃ for 2 hours, and that the waste salt includes NaK 3 (SO 4 ) 2 This indicates the SO produced 2 Is effectively absorbed by the molten carbonate and is converted into stable inorganic substances.
The thermogravimetric curve of the cation exchange resin without ion exchange is shown in FIG. 2. It can be seen from FIG. 2 that the cation exchange resin is effectively destroyed by oxidation at 800 ℃ for 2 h.
The XRD pattern of the treated product of example 1 of the present invention is shown in FIG. 3. From FIG. 3, it can be seen that cobaltosic oxide exists in the form of cobalt. In conclusion, the ternary carbonate eutectic salt molten salt method is a method for effectively treating the cobalt-containing cation exchange resin and intercepting the radionuclide cobalt.
The inductively coupled plasma ICP was used to measure the Co content of the treated product of example 1 using an inductively coupled plasma emission instrument, sammer Feishel, germany 2+ Detecting the content, wherein the detection parameters are as follows: the power was 1150W, the washing was 20s, the long wave was 10s, the short wave was 5s, and the measurement was repeated 3 times for each sample. The results show that oxidation at 800 ℃ for 2h has an oxidation efficiency as high as 95.64%, the cobalt rejection efficiency is 97.3%, and most of the cobalt is still retained in the molten salt.
Claims (1)
1. A method for treating waste cation exchange resin containing radioactive elements by using ternary carbonic acid eutectic molten salt is characterized by comprising the following steps:
step 1: uniformly mixing lithium carbonate, sodium carbonate and potassium carbonate to obtain a ternary eutectic salt mixture, and then adding waste cation exchange resin containing radioactive elements to continuously and uniformly mix; the mass ratio of lithium carbonate, sodium carbonate and potassium carbonate in the ternary eutectic salt mixture is 1:0.97:1.11, the mass ratio of the ternary eutectic salt mixture to the waste cation exchange resin containing radioactive elements is 1:1, the waste cation exchange resin containing the radioactive elements is waste cation exchange resin containing Co, and the content of the radioactive elements in the waste cation exchange resin containing the radioactive elements is 2wt%;
step 2: and (3) heating the mixture obtained in the step (1) at 800 ℃ for 2h to finish the treatment of the waste cation exchange resin containing the radioactive elements.
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| US4145396A (en) * | 1976-05-03 | 1979-03-20 | Rockwell International Corporation | Treatment of organic waste |
| EP2819125B1 (en) * | 2013-06-21 | 2018-08-08 | Hitachi-GE Nuclear Energy, Ltd. | Radioactive organic waste treatment method and system |
| JP6845119B2 (en) * | 2017-11-07 | 2021-03-17 | 株式会社東芝 | Waste liquid treatment method and waste liquid treatment equipment |
| JP2021032590A (en) * | 2019-08-19 | 2021-03-01 | 株式会社東芝 | Method and device for treating ion exchange resin |
| CN110665548A (en) * | 2019-09-12 | 2020-01-10 | 哈尔滨工程大学 | Method for treating cation exchange resin by molten salt oxidation technology |
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