Phosphoric acid derivative-modified resin and method for preparing the same

Abstract

The application relates to a phosphoric acid derivative modified resin and a preparation method thereof, and comprises the following steps: S1, mixing styrene, divinylbenzene, benzoyl peroxide, isooctane, polyvinyl alcohol and water, stirring to form a ball, and reacting at high temperature to obtain resin white balls; S2, mixing and swelling the resin white balls with dichloroethane, adding chloromethyl ether and ZnCl2 to react to obtain resin chloro balls; S3, mixing and swelling the resin chloro balls with butyl phthalate, adding hexamethylenetetramine to react, and adjusting the pH to alkaline to obtain resin amine balls; S4, mixing and swelling the resin amine balls with disodium ethylenediaminetetraacetate, adding formaldehyde, monobutyl phosphoric acid and concentrated hydrochloric acid to react to obtain alpha interception resin, i.e. the phosphoric acid derivative modified resin. Compared with the prior art, the alpha interception resin prepared by the application has a plutonium adsorption capacity of greater than 0.20 mmol / g in 5-8 mol / L nitric acid waste liquid, a distribution coefficient of greater than 1000, and high-efficiency plutonium recovery.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment materials technology, and in particular to a phosphate derivative modified resin and its preparation method. Background Technology

[0002] The nuclear industry is a high-tech strategic industry and an important cornerstone of national security. During the nuclear fuel cycle, spent fuel reprocessing involves a large amount of radioactivity, approximately 10... 9 Radioactive waste containing Bq / L plutonium (Pu) requires the development of new waste treatment materials to address the discharge issue. In a 6–8 mol / L nitric acid solution, the Pu in the radioactive waste produced during production primarily exists as Pu(NO3)6. 2- Since the waste liquid exists in this form, the first step in the waste liquid treatment process is to reduce the Pu content to below 17.4 μg / L. In order to achieve such a high adsorption efficiency, it is necessary to design and develop a selective adsorption resin with a large capacity for Pu.

[0003] Chelating resins are a class of functional polymer materials with chelating groups attached to a polymer backbone. Specific metal ions and metal ion complexes form stable multidentate complexes with chelating resins, thereby achieving the separation and enrichment of metal ions. According to the type of chelating group, chelating resins can be classified into styrene type, imine carboxylic acid type, Schiff base type, salicylic acid type, 8-hydroxyquinoline type, geminal aminooxime type, and aminophosphonic acid type, etc.

[0004] Currently, there are two main synthetic routes for preparing chelating resins both domestically and internationally: First, synthesizing monomers containing chelating groups and then polymerizing them to obtain chelating resins; second, attaching functional groups with chelating effects to a polymer resin matrix. The vast majority of chelating resins are synthesized using the second method. The adsorption performance of the resin is directly related to the control of the conditions during resin synthesis and the amount of reagents added. Summary of the Invention

[0005] The purpose of this invention is to provide a phosphoric acid derivative modified resin and its preparation method to solve the problem of waste liquid discharge, so that the Pu content in the waste liquid is reduced to below 17.4 μg / L during the waste liquid treatment process.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] One of the technical solutions of the present invention is to provide a method for preparing a phosphate derivative modified resin, comprising the following steps:

[0008] S1. Styrene, divinylbenzene, benzoyl peroxide, isooctane, polyvinyl alcohol and water are mixed and stirred to form beads. The mixture is then reacted at high temperature to obtain resin white beads.

[0009] S2. Mix the resin white balls obtained in step S1 with chloromethyl ether to swell, then add ZnCl2 to react and obtain resin chlorine balls;

[0010] S3. Mix the resin chlorine balls obtained in step S2 with butyl phthalate to swell, then add hexamethylenetetramine to react, adjust the pH to alkaline, and obtain resin amine balls.

[0011] S4. Mix the resin amine balls obtained in step S3 with disodium ethylenediaminetetraacetate and swell them. Then add formaldehyde, monobutyl phosphate, and concentrated hydrochloric acid to react and obtain α-interceptor resin, which is the phosphate derivative modified resin.

[0012] In step S1, the reaction process of the resin white spheres is as follows:

[0013]

[0014] In step S2, the structural formula of the resin chlorine ball is:

[0015]

[0016] Furthermore, in step S1, the ratio of styrene, divinylbenzene, benzoyl peroxide, isooctane, polyvinyl alcohol, and water is 50g:6.9g:0.5g:56g:1g:200mL.

[0017] Furthermore, in step S1, the temperature at which the spheres are formed by stirring is 50–70°C. Specifically, the high-temperature reaction is carried out at 60–80°C for 4 hours, then the temperature is raised to 70–90°C for aging for 8 hours, and finally the temperature is dried at 70–90°C for 8 hours.

[0018] Furthermore, in step S2, the ratio of resin white balls, chloromethyl ether, and ZnCl2 is 2g: (11-12)mL: (1-2)g.

[0019] Furthermore, in step S2, the swelling time is 1–2 h, the reaction temperature is 50–70 °C, and the reaction time is 20–30 h.

[0020] Furthermore, in step S3, the ratio of resin chlorine beads, butyl phthalate, and hexamethylenetetramine is 1g:4mL:(0.5~1)g.

[0021] Furthermore, in step S3, the swelling time is 1–2 h, the reaction temperature is 50–70 °C, the reaction time is 10–20 h, and the pH is adjusted to 9–10.

[0022] Furthermore, in step S4, the ratio of resin amine balls, disodium ethylenediaminetetraacetate, formaldehyde, monobutyl phosphate, and concentrated hydrochloric acid is 1g:1g:1g:(1-3)g:(0.5-1)mL.

[0023] Furthermore, in step S4, the swelling time is 1–2 h, the reaction temperature is 85–95 °C, and the reaction time is 24 h.

[0024] The second technical solution of this invention is to provide a phosphate derivative modified resin, based on the preparation method described in one of the above technical solutions.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The α-interceptor resin prepared by the preparation method of the present invention can efficiently recover Pu from 5-8 mol / L nitric acid waste liquid, with a Pu adsorption capacity greater than 0.20 mmol / g and a partition coefficient greater than 1000, thereby reducing the Pu content in the wastewater to below 17.4 μg / L, providing a new material for the treatment of radioactive waste liquid.

[0027] (2) The polystyrene resin (PS-DVB) used in this invention has higher radiation stability. The chloromethylated resin is an extractant that is easy to dechlorinate under alkaline conditions. Furthermore, substances containing phosphate groups have high affinity and selectivity for uranium and Pu. Therefore, phosphate groups are the active groups of the α-interceptor resin of this invention. Attached Figure Description

[0028] Figure 1 This describes a partial synthesis process of the phosphate derivative-modified resin of the present invention. The small spherical shapes represent the polymer backbone. Detailed Implementation

[0029] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0030] Unless otherwise specified, the raw materials or processing techniques used in the following embodiments and comparative examples are all conventional commercially available raw materials or conventional processing techniques in the art.

[0031] Example 1:

[0032] 1.0 g of polyvinyl alcohol was added to a three-necked flask containing 200 mL of deionized water and heated to 65 °C until the polyvinyl alcohol was completely dissolved to obtain an aqueous solution. 50.0 g of styrene, 6.9 g of divinylbenzene (63% purity), 0.5 g of benzoyl peroxide, and 56.0 g of isooctane were mixed evenly and added to the above polyvinyl alcohol aqueous solution. After stirring to form uniformly sized beads, the temperature was slowly raised to 75 °C and reacted for 4 h. Then the temperature was raised to 80 °C and aged for 8 h. After the reaction was completed, the copolymer was boiled and dried at 90 °C for 8 h for later use to obtain resin white beads.

[0033] 20.0 g of resin white beads were added to a 250 mL three-necked flask, followed by 120.0 g of chloromethyl ether (111.73 mL). After swelling for 1.5 h, stirring was started, the oil bath temperature was raised to 60 °C, and 14.0 g of anhydrous ZnCl2 was added. The mixture was stirred and refluxed for 24 h to obtain resin chloride beads. After the reaction was completed, the resin chloride beads were filtered out and washed with plenty of water until neutral.

[0034] Add 20.0 g of resin chlorine beads to a 250 mL three-necked flask, and add 80 mL of butyl phthalate to swell for 1 h. Add 18.0 g of hexamethylenetetramine, start stirring, and react at 55 °C for 16 h. Adjust the pH to 9. After the reaction is complete, the resin amine beads are obtained, washed with ethanol, and then washed with water until neutral. Set aside for later use.

[0035] 20.0 g of resin amine beads were added to a 250 mL three-necked flask, followed by 20.0 g of disodium ethylenediaminetetraacetate solution to swell for 1 h. Then, 20 g of formaldehyde, 20.0 g of monobutyl phosphate, and 15 mL of concentrated hydrochloric acid were added. The mixture was stirred and reacted at 95 °C for 24 h. After the reaction was completed, the resin was washed with ethanol and then with water until neutral to obtain α-interceptor resin, which is the phosphate derivative modified resin.

[0036] Figure 1 This describes the synthesis process of resin amine spheres and α-interceptor resin in the synthesis of phosphate derivative modified resin.

[0037] The final α-interceptor resin exhibited an adsorption capacity of 0.20 mmol / g for Pu in 7.0 mol / L nitric acid wastewater, and could adsorb radioactive materials with an activity of approximately 10. 9 The Pu content in radioactive waste liquid containing Bq / L metallic Pu decreased to below 17.4 μg / L.

[0038] Example 2:

[0039] Add 1g of polyvinyl alcohol to a three-necked flask containing 200mL of deionized water and heat to 55℃ until the polyvinyl alcohol is completely dissolved to obtain an aqueous solution. Mix 50.0g of styrene, 6.9g of divinylbenzene (purity 63%), 0.5g of benzoyl peroxide and 56.0g of isooctane evenly and add to the above polyvinyl alcohol aqueous solution. Stir to form uniformly sized beads, then slowly heat to 78℃ and react for 4h. Then heat to 85℃ and age for 8h. After the reaction is completed, boil the copolymer and dry it at 80℃ for 8h for later use.

[0040] Add 20.0 g of white globules to a 250 mL three-necked flask, then add 120.0 g of chloromethyl ether (111.73 mL). After swelling for 1.5 h, start stirring, heat the oil bath to 50 °C, and add 14.0 g of anhydrous ZnCl2. Stir and reflux for 24 h. After the reaction is complete, filter out the resin and wash with plenty of water until neutral.

[0041] Add 20.0 g of chloroform to a 250 mL three-necked flask, then add 80 mL of butyl phthalate to swell for 1 h. Add 13.8 g of hexamethylenetetramine, start stirring, and react at 60 °C for 16 h. Adjust the pH to 10. After the reaction is complete, wash with ethanol and water until neutral, then set aside for later use.

[0042] 20.0 g of amine spheres were added to a 250 mL three-necked flask, followed by 20.0 g of disodium ethylenediaminetetraacetate solution to swell for 1 h. Then, 20 g of formaldehyde, 47.5 g of monobutyl phosphate, and 10 mL of concentrated hydrochloric acid were added. The mixture was stirred and reacted at 95 °C for 24 h. After the reaction was completed, the resin was washed with ethanol and then with water until neutral to obtain α-interceptor resin, which is the phosphate derivative modified resin.

[0043] The final α-interceptor resin exhibited an adsorption capacity of 0.24 mmol / g for Pu in 7.0 mol / L nitric acid wastewater, and could adsorb radioactive materials with an activity of approximately 10. 9 The Pu content in radioactive waste liquid containing Bq / L metallic Pu decreased to below 17.4 μg / L.

[0044] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. The application of a phosphate derivative-modified resin in the recovery of plutonium from radioactive waste, characterized in that, The preparation method of the phosphoric acid derivative modified resin includes the following steps: S1. Styrene, divinylbenzene, benzoyl peroxide, isooctane, polyvinyl alcohol and water are mixed and stirred to form beads. The mixture is then reacted at high temperature to obtain resin white beads. S2. Mix the resin white balls obtained in step S1 with chloromethyl ether to swell, then add ZnCl2 to react and obtain resin chlorine balls; S3. Mix the resin chlorine balls obtained in step S2 with butyl phthalate to swell, then add hexamethylenetetramine to react, adjust the pH to alkaline, and obtain resin amine balls. S4. Mix the resin amine balls obtained in step S3 with disodium ethylenediaminetetraacetate and swell them. Then add formaldehyde, monobutyl phosphite, and concentrated hydrochloric acid to react and obtain α-interceptor resin, which is a phosphate derivative modified resin. In step S1, the ratio of styrene, divinylbenzene, benzoyl peroxide, isooctane, polyvinyl alcohol, and water is 50 g: 6.9 g: 0.5 g: 56 g: 1 g: 200 mL; the temperature for stirring to form beads is 50~70℃; the high-temperature reaction is specifically carried out by reacting at 60~80℃ for 4 h, then aging at 70~90℃ for 8 h, and finally drying at 70~90℃ for 8 h. In step S2, the ratio of resin white balls, chloromethyl ether, and ZnCl2 is 2 g : (11~12) mL : (1~2) g; the swelling time is 1~2 h, the reaction temperature is 50~70℃, and the reaction time is 20~30 h. In step S3, the ratio of resin chlorine balls, butyl phthalate, and hexamethylenetetramine is 1 g: 4 mL: (0.5~1) g; the swelling time is 1~2 h, the reaction temperature is 50~70℃, the reaction time is 10~20 h, and the pH is adjusted to 9~10. In step S4, the ratio of resin amine balls, disodium ethylenediaminetetraacetate, formaldehyde, monobutyl phosphite, and concentrated hydrochloric acid is 1 g: 1 g: 1 g: (1~3) g: (0.5~1) mL; the swelling time is 1~2 h; the reaction temperature is 85~95℃; and the reaction time is 24 h.

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