CN-116983961-B - Phosphoric acid derivative modified resin and preparation method thereof

CN116983961BCN 116983961 BCN116983961 BCN 116983961BCN-116983961-B

Abstract

The invention relates to a phosphoric acid derivative modified resin and a preparation method thereof, wherein the preparation method comprises the following steps of S1, mixing styrene, divinylbenzene, benzoyl peroxide, isooctane and polyvinyl alcohol with water, stirring to form ball beads, reacting at high temperature to obtain resin white balls, S2, mixing and swelling the resin white balls with dichloroethane, adding chloromethyl ether and ZnCl 2 for reaction to obtain resin chlorine balls, S3, mixing and swelling the resin chlorine balls with butyl phthalate, adding hexamethylenetetramine for reaction, adjusting pH to be alkaline to obtain resin amine balls, and S4, mixing and swelling the resin amine balls with disodium ethylenediamine tetraacetate, adding formaldehyde, monobutyl phosphate and concentrated hydrochloric acid for reaction to obtain alpha-interception resin, namely the phosphoric acid derivative modified resin. Compared with the prior art, the alpha interception resin prepared by the invention has the advantages that the adsorption capacity of the alpha interception resin to plutonium from 5-8 mol/L nitric acid waste liquid is more than 0.20mmol/g, the distribution coefficient is more than 1000, and the plutonium is efficiently recovered.

Inventors

XU DAN
CUI WENXING
GONG WEI
YANG XIUYU
GUO ZHICHAO
ZHU YINGXI

Assignees

中核四0四有限公司

Dates

Publication Date: 20260508
Application Date: 20230717

Claims (1)

1. The application of the phosphoric acid derivative modified resin in recovering plutonium from radioactive waste liquid is characterized in that the preparation method of the phosphoric acid derivative modified resin comprises the following steps: s1, mixing styrene, divinylbenzene, benzoyl peroxide, isooctane and polyvinyl alcohol with water, stirring to form beads, and reacting at high temperature to obtain resin white balls; s2, mixing and swelling the resin white ball obtained in the step S1 with chloromethyl ether, and then adding ZnCl 2 for reaction to obtain a resin chlorine ball; S3, mixing and swelling the resin chlorine ball obtained in the step S2 with butyl phthalate, adding hexamethylenetetramine for reaction, and adjusting pH to be alkaline to obtain resin amine balls; s4, mixing and swelling the resin amine balls obtained in the step S3 with disodium ethylenediamine tetraacetate, and then adding formaldehyde, monobutyl phosphite and concentrated hydrochloric acid for reaction to obtain alpha interception resin, namely phosphoric acid derivative modified resin; In the step S1, the proportion 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 that firstly, the beads react at 60-80 ℃ for 4-h, then the beads are heated to 70-90 ℃ for aging 8 h, and finally, the beads are dried at 70-90 ℃ for 8 h; In the S2 step, the proportion of the resin white ball, chloromethyl ether and ZnCl 2 is 2g (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 the S3 step, the ratio of the resin chlorine ball to the butyl phthalate to the hexamethylene tetramine is 1g to 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 regulated to 9-10; In the S4 step, the proportion of the resin amine balls, the disodium ethylenediamine tetraacetate, the formaldehyde, the monobutyl phosphite and the concentrated hydrochloric acid is 1 g to 1 g (1-3 g to 0.5-1 mL, the swelling time is 1-2 h, the reaction temperature is 85-95 ℃, and the reaction time is 24h.

Description

Phosphoric acid derivative modified resin and preparation method thereof Technical Field The invention relates to the technical field of wastewater treatment materials, in particular to phosphoric acid derivative modified resin and a preparation method thereof. Background The nuclear industry is a high-tech strategic industry, is a national security important foundation stone, and in the nuclear fuel circulation process, the post-treatment of spent fuel involves a large amount of radioactive waste liquid with the activity of about 10 9 Bq/L of metallic plutonium (Pu), so that a new waste liquid treatment material needs to be developed for solving the waste liquid discharge problem. In a nitric acid solution of 6-8 mol/L, pu in radioactive waste liquid in production mainly exists in the form of Pu (NO 3)62-), the Pu content needs to be reduced to below 17.4 mug/L in the waste liquid treatment process, and in order to achieve high adsorption efficiency, a selective adsorption resin with large capacity for Pu needs to be designed and developed. The chelate resin is a functional polymer material with a chelate group connected to a polymer skeleton, and specific metal ions and metal ion complexes form stable polydentate complexes with the chelate resin to realize separation and enrichment of metal ions, and the chelate resin can be classified into a styrene type, an iminocarboxylic acid type, a Schiff base type, a salicylic acid type, an 8-hydroxyquinoline type, an amidoxime type, an aminophosphonic acid type and the like according to the type of the chelate group. At present, the chelate resin is mainly prepared by 2 synthetic routes at home and abroad, namely firstly, synthesizing a monomer containing a chelate group, and then polymerizing to prepare the chelate resin, and secondly, connecting a functional group with a chelate effect on a polymer resin matrix. Most of the chelate resin synthesis is carried out by the second method. The adsorption performance of the resin is directly related to the condition control of the resin synthesis process and the addition amount of the reagent. Disclosure of Invention The invention aims to solve the problem of waste liquid discharge and provides a phosphoric acid derivative modified resin and a preparation method thereof, so that the Pu content in the waste liquid treatment process is reduced to below 17.4 mug/L. The aim of the invention can be achieved by the following technical scheme: one of the technical schemes of the invention is to provide a preparation method of phosphoric acid derivative modified resin, which comprises the following steps: s1, mixing styrene, divinylbenzene, benzoyl peroxide, isooctane and polyvinyl alcohol with water, stirring to form beads, and reacting at high temperature to obtain resin white balls; s2, mixing and swelling the resin white ball obtained in the step S1 with chloromethyl ether, and then adding ZnCl 2 for reaction to obtain a resin chlorine ball; S3, mixing and swelling the resin chlorine ball obtained in the step S2 with butyl phthalate, adding hexamethylenetetramine for reaction, and adjusting pH to be alkaline to obtain resin amine balls; S4, mixing and swelling the resin amine balls obtained in the step S3 with disodium ethylenediamine tetraacetate, and then adding formaldehyde, monobutyl phosphate and concentrated hydrochloric acid for reaction to obtain alpha interception resin, namely the phosphoric acid derivative modified resin. In the step S1, the reaction procedure of the resin white ball is as follows: in the step S2, the structural formula of the resin chlorine ball is as follows: Further, in the step S1, the ratio of styrene, divinylbenzene, benzoyl peroxide, isooctane, polyvinyl alcohol and water is 50g:6.9g:0.5g:56g:1g:200mL. Further, in the step S1, the temperature for stirring to form the ball is 50-70 ℃, the high-temperature reaction is specifically carried out for 4 hours at 60-80 ℃, then the temperature is raised to 70-90 ℃ for aging for 8 hours, and finally the ball is dried for 8 hours at 70-90 ℃. In the step S2, the proportion of the resin white ball, chloromethyl ether and ZnCl 2 is 2g (11-12) mL (1-2). Further, in the step S2, the swelling time is 1-2 hours, the reaction temperature is 50-70 ℃, and the reaction time is 20-30 hours. In the step S3, the ratio of the resin chlorine ball, the butyl phthalate and the hexamethylenetetramine is 1g:4mL (0.5-1 g). Further, in the step S3, 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 the step S4, the proportion of the resina amine balls, the disodium ethylenediamine tetraacetate, the formaldehyde, the monobutyl phosphate and the concentrated hydrochloric acid is 1g to 1g (1-3 g) (0.5-1 mL). Further, in the step S4, the swelling time is 1-2 h, the reaction temperature is 85-95 ℃ and the reaction time is 24h. The second technical scheme of the invention is to provide a phosphoric