CN114160554A - 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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- CN114160554A CN114160554A CN202111372574.8A CN202111372574A CN114160554A CN 114160554 A CN114160554 A CN 114160554A CN 202111372574 A CN202111372574 A CN 202111372574A CN 114160554 A CN114160554 A CN 114160554A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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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 is carried out according to 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 dosage of the ternary carbonic acid eutectic molten salt and the treatment temperature, the purpose of efficiently treating the cobalt-containing cation exchange resin is realized on the basis of greatly reducing the dosage 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 treating waste resins include cement curing, incineration, pyrolysis, and the like. Because of the lack of proper adhesion between cement binder and resin beads, there are often problems of low capacity, large increase in capacity of cured bodies, high leaching rate of nuclides, etc. when resin waste is treated by cement curing methods. Although conventional pyrolysis or incineration minimizes the volume of waste, radionuclides escape into the air as exhaust gases are emitted. Therefore, when waste resin is treated, the waste resin is thoroughly treated by following the principle of waste minimization, and the radionuclide is effectively trapped and 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 and are difficult to fix in the existing method for treating the cation exchange waste 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;
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.
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 to 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 1.6 wt% to 2.4 wt%.
Further limiting, the content of radioactive elements in the waste cation exchange resin containing radioactive elements in the step 1 is 2 wt%.
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 up to 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 content of Co in the waste cation exchange resin containing Co is 2 wt%;
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 a Co content of 2 wt% in the example is obtained by simulation according to the following steps:
step (1): weigh 0.4g of anhydrous CoCl2Fully dissolved and then fixed to 50mL to prepare CoCl with the concentration of 0.0615mol/L2Aqueous solution to simulate the liquid containingRadionuclide wastewater;
step (2): fully infiltrating cation exchange resin (nuclear grade 732 type cation exchange resin produced by Hangzhou resin factory, which has a structure of styrene-divinylbenzene copolymer with sulfonic functional group on benzene ring) for 2h by using 1mol/LHCl solution, and then washing the cation resin by using deionized water for 7-8 times until the pH value of the solution is 7; secondly, 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 operation of the first step and the second step for 3-5 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 2 wt%.
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. it can be seen from FIG. 1 that the cation exchange resin was oxidized at 800 ℃ for 2h, and that the waste salt contained NaK3(SO4)2This indicates the SO produced2Is effectively absorbed by the carbonic acid molten salt 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 radioactive nuclide 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, Germany2+Detecting the content, wherein the detection parameters are as follows: the power was 1150W, the rinsing was 20s, the wavelength was 10s, the short wavelength 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 of 95.64%, the cobalt rejection efficiency is 97.3%, and most of the cobalt is still retained in the molten salt.
Claims (9)
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;
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.
2. The method for treating the waste cation exchange resin containing the radioactive elements by using the ternary eutectic carbonate molten salt according to claim 1, wherein the mass ratio of lithium carbonate to sodium carbonate to potassium carbonate in the ternary eutectic salt mixture in the step 1 is 1: (0.78-1.16): (0.89 to 1.33).
3. The method for treating the waste cation exchange resin containing the radioactive elements by using the ternary eutectic carbonate molten salt according to claim 2, wherein the mass ratio of lithium carbonate to sodium carbonate to potassium carbonate in the ternary eutectic salt mixture in the step 1 is 1: 0.97: 1.11.
4. the method for treating the waste cation exchange resin containing the radioactive elements by using the ternary eutectic molten carbonate salt according to claim 1, wherein the mass ratio of the ternary eutectic salt mixture to the waste cation exchange resin containing the radioactive elements in the step 1 is (0.8-1.2): 1.
5. the method for treating the waste cation exchange resin containing the radioactive elements by using the ternary eutectic molten carbonate salt according to claim 4, wherein the mass ratio of the ternary eutectic salt mixture to the waste cation exchange resin containing the radioactive elements in the step 1 is 1: 1.
6. the method for treating the waste cation exchange resin containing the radioactive elements by using the ternary carbonic acid eutectic molten salt as claimed in claim 1, wherein the waste cation exchange resin containing the radioactive elements in the step 1 is waste cation exchange resin containing Co.
7. The method for treating the waste cation exchange resin containing the radioactive elements by using the ternary carbonic acid eutectic molten salt as claimed in claim 1, wherein the content of the radioactive elements in the waste cation exchange resin containing the radioactive elements in the step 1 is 1.6-2.4 wt%.
8. The method for treating the waste cation exchange resin containing the radioactive elements by using the ternary carbonic acid eutectic molten salt as claimed in claim 1, wherein the content of the radioactive elements in the waste cation exchange resin containing the radioactive elements in the step 1 is 2 wt%.
9. The method for treating the waste cation exchange resin containing the radioactive elements by using the ternary carbonic acid eutectic molten salt as claimed in claim 1, wherein in the step 2, the mixture obtained after the step 1 is heated at 800 ℃ for 2h to complete the treatment of the waste cation exchange resin containing the radioactive elements.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4145396A (en) * | 1976-05-03 | 1979-03-20 | Rockwell International Corporation | Treatment of organic waste |
| US20140378734A1 (en) * | 2013-06-21 | 2014-12-25 | Hitachi-Ge Nuclear Energy, Ltd. | Radioactive Organic Waste Treatment Method and System |
| JP2019084496A (en) * | 2017-11-07 | 2019-06-06 | 株式会社東芝 | Waste liquid treatment method and waste liquid treatment apparatus |
| 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 |
| JP2021032590A (en) * | 2019-08-19 | 2021-03-01 | 株式会社東芝 | Method and device for treating ion exchange resin |
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- 2021-11-18 CN CN202111372574.8A patent/CN114160554B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4145396A (en) * | 1976-05-03 | 1979-03-20 | Rockwell International Corporation | Treatment of organic waste |
| US20140378734A1 (en) * | 2013-06-21 | 2014-12-25 | Hitachi-Ge Nuclear Energy, Ltd. | Radioactive Organic Waste Treatment Method and System |
| JP2019084496A (en) * | 2017-11-07 | 2019-06-06 | 株式会社東芝 | Waste liquid treatment method and waste liquid treatment apparatus |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| X.-Z. WANG ET AL: "《Study on the destruction process of cationic exchange resins treated by Li2CO3-Na2CO3-K2CO3molten salt》", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
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