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CN-122011269-A - Anion exchange resin and preparation method and application thereof

CN122011269ACN 122011269 ACN122011269 ACN 122011269ACN-122011269-A

Abstract

The application discloses an anion exchange resin and a preparation method and application thereof. The preparation method comprises the steps of mixing the vinyl tertiary amine, vinyl tertiary amine styrene, a cross-linking agent and an initiator to obtain an oil phase, mixing the oil phase and a water phase to disperse, heating for polymerization and solidification to obtain an intermediate, wherein the water phase comprises a dispersing agent, and mixing the intermediate and a quaternizing agent to carry out quaternization reaction to obtain the anion exchange resin. Compared with the traditional process, the preparation method has the advantages of simple operation steps and milder reaction conditions. The anion exchange resin prepared by the preparation method has high strength, is not easy to break, has good stability, has the ion exchange capacity remarkably superior to that of the traditional grafted resin, and has more superior adsorption performance. Even under extreme conditions such as strong acidity, the resin can still keep higher adsorption capacity, and shows good environmental adaptability.

Inventors

  • YE ZHI
  • Zhou Ruoyao
  • CAI JIANGUO

Assignees

  • 江苏海普功能材料有限公司

Dates

Publication Date
20260512
Application Date
20251217

Claims (10)

  1. 1. A method for preparing an anion exchange resin, comprising the steps of: mixing vinyl tertiary amine, vinyl tertiary amine styrene, a cross-linking agent and an initiator to obtain an oil phase; Mixing the oil phase with a water phase to disperse, heating, polymerizing and solidifying to prepare an intermediate, wherein the water phase comprises a dispersing agent; and mixing the intermediate with a quaternizing agent to carry out quaternization reaction to obtain the anion exchange resin.
  2. 2. The method for preparing an anion exchange resin according to claim 1, wherein the mass ratio of the tertiary vinyl amine to the tertiary vinyl amine styrene to the cross-linking agent to the initiator is 1 (0.2-0.5): 0.05-0.15): 0.01-0.02.
  3. 3. The method of preparing an anion exchange resin of claim 2, wherein the tertiary allylic amine comprises one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, N-diethylaminoethyl acrylate, N-dimethylallylamine, and N, N-diethylallylamine.
  4. 4. The method of preparing an anion exchange resin of claim 2, wherein the olefinic tertiary amine styrene comprises one or more of 4-dimethylaminostyrene and 2-dimethylaminostyrene.
  5. 5. The method for producing an anion exchange resin according to any one of claims 1 to 4, wherein one or more of the following conditions are satisfied: (1) The cross-linking agent comprises one or more of divinylbenzene and ethylene glycol dimethacrylate; (2) The initiator includes one or more of azobisisobutyronitrile and benzoyl peroxide.
  6. 6. The method of preparing an anion exchange resin of claim 1, wherein the aqueous phase satisfies one or more of the following conditions: (1) The dispersing agent comprises one or more of polyvinyl alcohol, biological gelatin and hydroxyethyl cellulose; (2) The aqueous phase further comprises a buffer system and an inorganic salt; Optionally, the buffer system comprises a mixed solution of sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of the sodium dihydrogen phosphate to the disodium hydrogen phosphate is (4-6): 1, and the pH value of the buffer system is 7.4-7.6; optionally, the inorganic salt comprises one or more of sodium chloride, calcium chloride, potassium chloride and magnesium chloride, and further optionally, the mass ratio of the buffer system, the inorganic salt and the dispersing agent in the water phase is 1 (0.05-0.25): 0.0075-0.02.
  7. 7. The method of preparing a resin according to claim 1, wherein one or more of the following conditions are satisfied: (1) The dispersing condition comprises that the temperature is 40-50 ℃ and the time is 1-2 hours; (2) The heating polymerization conditions comprise the temperature of 60-75 ℃ and the time of 4-16 hours; (3) The curing conditions comprise the temperature of 80-90 ℃ and the time of 1-3 hours; (4) Optionally, the purification includes extraction with an organic solvent including one or more of ethanol, methylal, and acetone.
  8. 8. The method for producing a resin according to claim 1, wherein the step of mixing the intermediate with a quaternizing agent to carry out a quaternization reaction comprises mixing the intermediate with the quaternizing agent in a polar organic solvent to carry out a quaternization reaction, wherein the mass ratio of the intermediate, the polar organic solvent and the quaternizing agent is 1 (2 to 4): 1.2 to 1.8; optionally, one or more of the following conditions are satisfied: (1) Optionally, the haloalkane comprises one or more of methyl iodide, methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl bromochloride and 1, 2-bromochloroethane; (2) The polar organic solvent comprises one or more of acetonitrile, dimethyl sulfoxide, dimethylformamide and dimethylacetamide; (3) The quaternization reaction is carried out at a temperature of 20-30 ℃ for 5-7 hours.
  9. 9. An anion exchange resin prepared by the method of any one of claims 1 to 8.
  10. 10. Use of an anion exchange resin according to claim 9 for the adsorption of noble metals from a liquid phase; optionally, the noble metal comprises one or more of gold, tungsten, and molybdenum; Optionally, the pH of the liquid phase is 1-2.

Description

Anion exchange resin and preparation method and application thereof Technical Field The application relates to the technical field of adsorption materials, in particular to anion exchange resin and a preparation method and application thereof. Background In the existing extraction technology of a plurality of noble metals (such as gold, tungsten and molybdenum), the adsorption resin method has remarkable convenience and environmental protection, and becomes a core direction for replacing the traditional technology, wherein the convenience is that the resin can be directly mixed and adsorbed with leaching liquid without modification of complex equipment, intermittent and continuous production is adapted, the adsorption equilibrium time is short (usually 2-6 h) and is far faster than that of the traditional cyanide method (24-72 h), and gold recovery and resin regeneration can be realized through acid washing, alkali washing or complexing agent elution in the follow-up process, the operation flow is simple, and the method is easy to integrate with the existing gold extraction technology. The environment protection performance is that the whole process does not need to use extremely toxic cyanide, the pollution risk of soil and water is avoided from the source, the resin can be reused, the solid waste is reduced, meanwhile, the problem of excessive consumption of reagents in the traditional zinc powder replacement method is avoided, and the comprehensive environment protection treatment cost is reduced. However, the current noble metal adsorption resin technology still has obvious short plates, namely, firstly, the design of a resin skeleton pore structure is unreasonable, the mass transfer efficiency of macroporous resin is low, the stability of mesoporous resin is insufficient, the diffusion resistance of gold complex ions (such as [ Au (CN) 2]-), tungstate ions, molybdate ions and the like is large, the treatment effect on high-viscosity leachate or fine particle ore pulp is poor, secondly, the stability of functional groups is weak, the functional groups are easy to fall off in a strong acid-base (such as pH <2 or pH > 12) or high-temperature (such as >60 ℃) leaching system, the service life of the resin is shortened, and thirdly, the adsorption efficiency on an ultralow-concentration gold solution (containing Au 3+ <1 ppm) is low, and the deep recovery requirement of industrial wastewater is difficult to meet. Disclosure of Invention Based on this, it is necessary to provide anion exchange resins, methods of making and uses thereof. In a first aspect, the present application provides a process for the preparation of an anion exchange resin comprising the steps of: mixing vinyl tertiary amine, vinyl tertiary amine styrene, a cross-linking agent and an initiator to obtain an oil phase; Mixing the oil phase with a water phase to disperse, heating, polymerizing and solidifying to prepare an intermediate, wherein the water phase comprises a dispersing agent; and mixing the intermediate with a quaternizing agent to carry out quaternization reaction to obtain the anion exchange resin. In some embodiments, the mass ratio of the tertiary vinyl amine to the tertiary vinyl amine styrene to the cross-linking agent to the initiator is 1 (0.2-0.5): 0.05-0.15): 0.01-0.02. In some embodiments, the tertiary olefinic amine includes one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, N-diethylaminoethyl acrylate, N-dimethylallylamine, and N, N-diethylallylamine. In some embodiments, the olefinic tertiary amine styrene includes one or more of 4-dimethylaminostyrene and 2-dimethylaminostyrene. In some embodiments, the crosslinking agent includes one or more of divinylbenzene and ethylene glycol dimethacrylate. In some embodiments, the initiator comprises one or more of azobisisobutyronitrile and benzoyl peroxide. In some embodiments, the aqueous phase satisfies one or more of the following conditions: (1) The dispersing agent comprises one or more of polyvinyl alcohol, biological gelatin and hydroxyethyl cellulose; (2) The aqueous phase further comprises a buffer system and an inorganic salt; Optionally, the buffer system comprises a mixed solution of sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the mass ratio of the sodium dihydrogen phosphate to the disodium hydrogen phosphate is (4-6): 1, and the pH value of the buffer system is 7.4-7.6; optionally, the inorganic salt comprises one or more of sodium chloride, calcium chloride, potassium chloride and magnesium chloride, and further optionally, the mass ratio of the buffer system, the inorganic salt and the dispersing agent in the water phase is 1 (0.05-0.25): 0.0075-0.02. In some embodiments, the dispersing conditions include a temperature of 40 ℃ to 50 ℃ for 1h to 2h. In some embodiments, the heating polymerization conditions include a temperature of 60 ℃ to 75 ℃ and a time of 4 hours to 16 hours. In some embodiments, the cu