CN114984930A - Resin for separating Sr-90 in high-acid medium and preparation method thereof - Google Patents
Resin for separating Sr-90 in high-acid medium and preparation method thereof Download PDFInfo
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- CN114984930A CN114984930A CN202210681248.3A CN202210681248A CN114984930A CN 114984930 A CN114984930 A CN 114984930A CN 202210681248 A CN202210681248 A CN 202210681248A CN 114984930 A CN114984930 A CN 114984930A
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- butylcyclohexyl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The invention discloses a preparation method of resin which is resistant to high acid, has high selectivity and high adsorption capacity and is used for separating Sr-90 in a high-acid medium, and the resin. The preparation method of the resin comprises the following steps: the CG-71 crude resin is fully removed of impurities on the surface and fully activated, and then the activated CG-71 base resin is vacuum-impregnated by 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution. The resin prepared by the method can be used for separating Sr-90 resin, has higher Sr-90 adsorption rate in a high-acid medium than that of the prior art, and has higher specificity.
Description
Technical Field
The invention relates to a preparation method of resin for separating radioactive materials and application of the resin, in particular to a preparation method of the resin which is resistant to high acid, has high selectivity and high adsorption capacity and is used for separating Sr-90 in a high-acid medium.
Background
In the process of utilizing and developing nuclear energy, a large amount of radioactive waste liquid with high radioactivity, high toxicity and high acidity can be generated, wherein Sr-90 is one of radioactive nuclides which are mainly concerned in the post-treatment of spent fuel due to high fission yield, strong radioactivity and high heat release amount, and if the Sr-90 can be effectively recovered, the radioactive intensity can be reduced, the volume of the waste liquid can be reduced, and the separated and purified Sr-90 has important applications in the fields of military, medical research and the like.
The Sr-90 separating and purifying method mainly comprises an evaporation concentration method [1], a solvent extraction method [2], a chemical precipitation method [3], an ion exchange method [4] and the like, but has certain disadvantages, such as large energy consumption and high cost of the evaporation concentration method; the solvent extraction method is easy to generate secondary pollution; the chemical precipitation method has low recovery rate and is easy to generate secondary pollution; the ion exchange method is easy to be pulverized and bonded and difficult to be regenerated. In contrast, the currently used solid-phase extraction method is a recognized "green and clean" method due to the advantages of high adsorption capacity, high selectivity, good hydrodynamic properties, no secondary pollution and the like [5 ]. However, the separation materials used in the current solid phase extraction methods have poor stability in high acid media, and mainly have the following problems: 1. the high acid environment has more strict requirements on the structural stability of the resin material, and the commercial organic polymer is not resistant to high acid and has poorer structural stability; 2. the functional group of the solid phase extraction resin is easy to protonate under the high acid environment, so that the separation performance is reduced, and the selective separation of target nuclide is difficult to realize. The currently commercial strontium resin is model SR-B-100-A resin produced by Triskem of France, and the highest adsorption rate can reach 60% under a high-acid environment when the strontium resin is used for separating Sr-90, and the attached figure 4 shows that the strontium resin has a high adsorption rate.
Disclosure of Invention
The invention provides a preparation method and application of a Sr-90 separating resin material, which can overcome the defects of the prior art and has higher adsorption rate in a high-acid environment.
The preparation method of the resin for separating Sr-90 from the high-acid medium comprises the following steps: fully removing impurities on the surface of CG-71 crude resin, fully activating the surface of the resin by using methanol to react with the resin, preparing a 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution, adding the 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution into the activated CG-71 base resin, and performing vacuum impregnation to saturate 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 at the surface sites of the CG-71 base resin, thereby obtaining the resin for separating Sr-90 in a high-acid medium.
The preferable preparation method of the resin for separating Sr-90 from the high-acid medium comprises the following steps:
a, adding ultrapure water into CG-71 crude resin, fully shaking in a constant-temperature shaker at 25 ℃, removing water, pouring methanol on the resin to cover the solid surface, allowing the methanol to flow through a filter cake under the action of gravity, removing the methanol by suction filtration after the methanol does not flow down, repeating the steps for more than three times until the pH of the filtered water is less than 7 and the filtered methanol is clear and transparent, then carrying out reduced pressure rotary evaporation on the resin at 60 ℃ to remove the methanol, carrying out vacuum drying treatment on the resin at 40 ℃,
b, preparing 1 mol/L4, 4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution, adding 40ml ethanol solution into 10g of CG-71-based resin after treatment, then adding 5g of 1 mol/L4, 4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution, slowly and fully stirring the system, removing ethanol at 50 ℃ under reduced pressure until the weight is constant on a balance, and then carrying out rotary evaporation to fully remove ethanol; after the resin was sufficiently dried in a vacuum oven at 50 ℃ and taken out, the impregnation treatment was repeated three times again in the manner described above.
The resin prepared by the method can be used for separating Sr-90 resin, has higher Sr-90 adsorption rate in a high-acid medium than that of the prior art, and has higher specificity.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the strontium resin prepared by the method. A, B has a particle size of 400 μm and C, D has a particle size of 75 μm.
FIG. 2 is a Scanning Electron Microscope (SEM) image of strontium resin prepared by the method after soaking for 24h under different acidity. In the figure: a is the initial resin, and B, C, D, E, F has corresponding acid degrees of 1M, 2M, 4M, 6M and 8M respectively.
FIG. 3 is a graph showing the results of adsorption experiments of commercial strontium resins at different acidity levels.
FIG. 4 is a graph showing the results of adsorption experiments at different acidity for resins prepared by the process of the present invention.
FIG. 5 is a graph showing the results of an ion selectivity experiment for resins prepared by the method of the present invention.
Detailed Description
The following is a specific embodiment of the present invention.
1) Purification of CG-71 based resin:
weighing 10g CG-71 crude resin in a 100mL centrifuge tube, adding 50mL ultrapure water, shaking in a constant temperature shaker at 25 ℃ for 30min, and then filtering in a Buchner funnel to remove water. 40mL of methanol was poured over the filter cake to cover the surface of the filter cake and allowed to flow through the filter cake under gravity. When the methanol does not flow down, the methanol is completely removed by suction filtration. The filter cake was then transferred to a 100mL centrifuge tube and the above procedure was repeated three more times until the pH of the filtered water was <7 and the filtered methanol was clear and transparent. The resin was then transferred to a 250mL flask and 100mL of methanol was added and the methanol removed by rotary evaporation at 60 ℃ under reduced pressure until the weight was constant on a balance and then rotary evaporated for an additional period of time to allow the methanol to be completely removed. Removing the device, putting the sample into a vacuum drying oven, drying at 40 deg.C for 24 hr or more, taking out, and weighing for use.
2) Impregnation treatment of resin
A1 mol/L ethanol solution of 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 was prepared and stirred on a magnetic stirrer so that 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 was completely dissolved in ethanol. 10g of purified CG-71 based resin was weighed into a 100mL round bottom flask, 40mL of ethanol solution was added, and 5g of 1 mol/L4, 4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 was added. The flask was placed on a magnetic stirrer, stirred slowly for 24h then removed, ethanol removed at 50 ℃ under reduced pressure (9 mbar or less in this experiment) until constant weight on a balance, and then rotary evaporated for a period of time to ensure complete removal; and drying the product in a vacuum drying oven at 50 ℃ for 24h, taking out the product and weighing the product for later use.
Repeating the previous step three times to obtain the CG-71-based strontium resin after physical vacuum impregnation.
The method adopts CG-71-based resin and 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 as substrates, the synthetic method is simple and convenient, and the obtained resin is a large-particle-size spherical material, is high in acid resistance, high in adsorption capacity and high in selectivity on strontium.
The tests and results relating to the resins prepared by the process of the invention are as follows:
(1) characterization of morphology and particle size of strontium resin
As can be seen from figure 1, according to the synthesis method established by the patent, the novel CG-71-based strontium resin is in a uniform spherical structure, the surface has obvious mesoporous shape, and the surface area of the spherical resin is the largest, which is beneficial to improving the exchange capacity; strontium resins with different particle sizes can be obtained by controlling synthesis conditions, and the method is favorable for being applied to practical column experimental separation.
(2) Acid resistance characterization of strontium resins
Fig. 2 is an image of a resin surface enlarged by 40000 times, a is not subjected to acid treatment, concentrations of nitric acids corresponding to B, C, D, E, F are respectively 1M, 2M, 4M, 6M and 8M, the surface is not subjected to obvious morphological change after oscillation for 24h, table 1 shows TOC content of strontium resin after being soaked for 24h under different acidity, the acidity changes from 0.05M to 8M, and the TOC value is stabilized at 0.17ppm to 0.22 ppm.
Table 1 shows the TOC content data of the strontium resin prepared by the method after being soaked for 24 hours under different acidity.
In the table: DCH18C6 bicyclohexane and 18-crown-6
DB18C6 dibenzo 18-crown-6
DtBuCH18C64,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6
(3) Adsorption experiment result of strontium resin
Fig. 3 and 4 are graphs showing experimental results of commercial resins and resins prepared according to the present invention at different acidity and different initial concentrations, respectively. It can be seen from the figure that the adsorption rate of the synthetic resin is gradually increased with the increase of the nitric acid concentration, the synthetic resin still has strong adsorption effect on strontium under the strong acid environment of 12M, the adsorption rate is stabilized at about 80% when the nitric acid concentration is 7M-12M, and the adsorption rate of the commercial strontium resin produced by the French Triskem company is 60% under high acid (FIG. 3); compared with commercial strontium resin, the resin prepared by the method provided by the invention has the advantages that the strontium adsorption rate and the strontium adsorption capacity are obviously improved, and the home-made substitution is expected.
(4) Ion selectivity test results of strontium resin
As is clear from fig. 5, adsorption experiments were carried out for a plurality of elements such as alkali metals, alkaline earth metals, and transition metals in the periodic table. It can be seen that the strontium resin material synthesized by the method has adsorption effect on Sr and Pb only in 8M nitric acid, Mn in 7M nitric acid, Cd in 6M nitric acid, Ba in 2-4M nitric acid and Tl in 0.01-3M nitric acid, and the material synthesized by the method has high specific selectivity on strontium.
Claims (3)
1. A preparation method of resin for separating Sr-90 from high-acid medium is characterized in that: fully removing impurities on the surface of CG-71 crude resin, fully activating the surface of the resin by using methanol to react with the resin, preparing a 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution, adding the 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution into the activated CG-71 base resin, and performing vacuum impregnation to saturate 4,4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 at the surface sites of the CG-71 base resin, thereby obtaining the resin for separating Sr-90 in a high-acid medium.
2. The method of claim 1 for preparing resin for the separation of Sr-90 in a high acid medium, wherein:
a, adding ultrapure water into CG-71 crude resin, fully shaking in a constant-temperature shaker at 25 ℃, removing water, pouring methanol on the resin to cover the solid surface, allowing the methanol to flow through a filter cake under the action of gravity, removing the methanol by suction filtration after the methanol does not flow down, repeating the steps for more than three times until the pH of the filtered water is less than 7 and the filtered methanol is clear and transparent, then carrying out reduced pressure rotary evaporation on the resin at 60 ℃ to remove the methanol, carrying out vacuum drying treatment on the resin at 40 ℃,
b, preparing 1 mol/L4, 4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution, adding 40ml ethanol solution into 10g of CG-71-based resin after treatment, then adding 5g of 1 mol/L4, 4 '(5') bis (tert-butylcyclohexyl) -18-crown-6 ethanol solution, slowly and fully stirring the system, removing ethanol at 50 ℃ under reduced pressure until the weight is constant on a balance, and then carrying out rotary evaporation to fully remove ethanol; after the resin was sufficiently dried in a vacuum oven at 50 ℃ and taken out, the impregnation treatment was repeated three times again in the manner described above.
3. The resin prepared by the method of claim 1 or 2 for the separation of Sr-90 in a high acid medium.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210681248.3A CN114984930A (en) | 2022-06-16 | 2022-06-16 | Resin for separating Sr-90 in high-acid medium and preparation method thereof |
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| CN202210681248.3A CN114984930A (en) | 2022-06-16 | 2022-06-16 | Resin for separating Sr-90 in high-acid medium and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116262627A (en) * | 2023-03-21 | 2023-06-16 | 兰州大学 | Separating from waste liquid 90 Sr is obtained 90 Y method and system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4835107A (en) * | 1986-10-21 | 1989-05-30 | Arch Development Corp. | Method for the concentration and separation of actinides from biological and environmental samples |
| US6511603B1 (en) * | 2000-10-24 | 2003-01-28 | Arch Development Corp. | Alkaline earth cation extraction from acid solution |
| CN1429391A (en) * | 2000-04-14 | 2003-07-09 | Pg研究基金会公司 | Method for isolating and purifying 90Y from 90 strontium in multi-curie quantities |
| CN104805286A (en) * | 2015-04-22 | 2015-07-29 | 浙江大学 | Polymer-based supramolecular adsorbent, preparation method and application thereof |
| CN105478097A (en) * | 2015-12-25 | 2016-04-13 | 北京大学 | Strontium-yttrium separation resin as well as preparation and application thereof |
-
2022
- 2022-06-16 CN CN202210681248.3A patent/CN114984930A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4835107A (en) * | 1986-10-21 | 1989-05-30 | Arch Development Corp. | Method for the concentration and separation of actinides from biological and environmental samples |
| CN1429391A (en) * | 2000-04-14 | 2003-07-09 | Pg研究基金会公司 | Method for isolating and purifying 90Y from 90 strontium in multi-curie quantities |
| US6511603B1 (en) * | 2000-10-24 | 2003-01-28 | Arch Development Corp. | Alkaline earth cation extraction from acid solution |
| CN104805286A (en) * | 2015-04-22 | 2015-07-29 | 浙江大学 | Polymer-based supramolecular adsorbent, preparation method and application thereof |
| CN105478097A (en) * | 2015-12-25 | 2016-04-13 | 北京大学 | Strontium-yttrium separation resin as well as preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴述超;曹颁;董利明;胡勇平;楼培定;郑存江;: "锶特效树脂萃取-色谱耦合热电离同位素质谱法测定海水中锶同位素研究", 中国无机分析化学 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116262627A (en) * | 2023-03-21 | 2023-06-16 | 兰州大学 | Separating from waste liquid 90 Sr is obtained 90 Y method and system |
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