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CN-122006672-A - Preparation method, product and application of magnetic cadmium ion imprinted polymer

CN122006672ACN 122006672 ACN122006672 ACN 122006672ACN-122006672-A

Abstract

The invention belongs to the technical field of electroplating solution purification, and relates to a preparation method, a product and application of a magnetic cadmium ion imprinted polymer, wherein the preparation method adopts a solvothermal method to prepare ferroferric oxide magnetic nanoparticles; the preparation method comprises the steps of carrying out surface amination modification on magnetic particles by using a silane coupling agent, carrying out surface amination modification on the magnetic particles by using cadmium ions as templates, constructing a imprinted polymer layer on the surfaces of the magnetic particles subjected to amination modification by using polyethyleneimine and glutamic acid in the presence of a cross-linking agent, eluting the templates of cadmium ions, and obtaining the magnetic cadmium ion imprinted polymer.

Inventors

  • CHEN CHEN
  • CHENG JIHUA
  • JI HAI
  • YAO YILIN
  • LIU MINGJU
  • ZHANG HAIJIN
  • ZHANG QI

Assignees

  • 中国航空工业集团公司金城南京机电液压工程研究中心

Dates

Publication Date
20260512
Application Date
20260317

Claims (9)

  1. 1. A preparation method of a magnetic cadmium ion imprinted polymer is characterized by comprising the following steps of (1) preparing ferroferric oxide magnetic nano particles by a solvothermal method, (2) carrying out surface amination modification on the magnetic particles obtained in the step (1) by using a silane coupling agent, (3) constructing an imprinted polymer layer on the surfaces of the magnetic particles subjected to amination modification by taking cadmium ions as templates through the reaction of polyethyleneimine and glutamic acid in the presence of a cross-linking agent, and (4) eluting the template cadmium ions to obtain the magnetic cadmium ion imprinted polymer.
  2. 2. The preparation method according to claim 1, wherein the reactants of the solvothermal method in the step (1) comprise ferric trichloride hexahydrate, sodium citrate and anhydrous sodium acetate, the solvent is ethylene glycol, the reaction temperature is 185-200 ℃, the reaction time is 10-14 hours, and the saturated magnetization intensity of the ferroferric oxide nano particles is more than 43 emu/g.
  3. 3. The method according to claim 1, wherein the silane coupling agent in the step (2) is aminopropyl triethoxysilane.
  4. 4. The method according to claim 1, wherein the crosslinking agent in the step (3) is ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and the mass ratio of the polyethylenimine to glutamic acid is (2-4): 1.
  5. 5. A magnetic cadmium ion imprinted polymer prepared by the preparation method of any one of claims 1-4.
  6. 6. The magnetic cadmium ion imprinted polymer according to claim 5, wherein the particle size distribution of the prepared magnetic cadmium ion imprinted polymer is 780-900 nm, the saturation magnetization is not less than 43 emu/g, the adsorption capacity of the magnetic cadmium ion imprinted polymer to Cu2 + is not less than 27 mg/g, the adsorption capacity to Cd2 + is not more than 3 mg/g, and the selectivity coefficient of Cu2 + /Cd² + is not less than 15.
  7. 7. A method of purifying a cyanide-free electrolytic cadmium plating solution using the magnetic cadmium ion-imprinted polymer according to claim 6, comprising the steps of: S1, preparing a magnetic cadmium ion imprinted polymer; S2, pretreating the magnetic cadmium ion imprinted polymer prepared in the step S1; S3, contacting the pretreated magnetic cadmium ion imprinted polymer with a cyanide-free electroplating cadmium solution to be purified in an adsorption reactor, and adsorbing and removing heavy metal impurity ions in the solution; S4, carrying out solid-liquid separation on the mixed solution processed in the step S3 through a high gradient magnetic separator to obtain purified electroplating solution and an adsorption saturated magnetic material; And S5, regenerating the magnetic material with saturated adsorption obtained in the step S4 by using acid liquor, and returning the regenerated material to the step S3 for recycling.
  8. 8. The method according to claim 6, wherein in the step S3, the addition amount of the magnetic cadmium ion imprinted polymer is 3-12 g/L plating solution, the flow rate during contact is 1-5 BV/h, the contact time is 1.5-4.5 hours, the operation temperature is 15-65 ℃, and the pH range is 2.5-10.5.
  9. 9. The method according to claim 6, wherein in step S5, the acid solution for regeneration is a nitric acid solution of 0.8-1.2 mol/L, and the regeneration treatment time is 45-75 minutes.

Description

Preparation method, product and application of magnetic cadmium ion imprinted polymer Technical Field The invention belongs to the technical field of electroplating liquid purification, and particularly relates to a preparation method, a product and application of a magnetic cadmium ion imprinted polymer. Background The cyanide-free cadmium electroplating process has become a mainstream process due to the environment-friendly characteristic, but in the actual production process, metal impurity ions such as copper, iron, nickel and the like can be continuously accumulated in the plating solution. The existence of the impurities can cause the problems of darkening, pitting, brittleness increase and the like of the plating layer, and seriously affect the quality of the plating layer. In the prior art, the treatment is generally carried out by a low-current electrolytic method, a masking agent method or an ion exchange resin method. The small-current electrolytic method has long treatment period and high energy consumption, and can only partially remove certain metal impurities, the masking agent method can only temporarily inhibit the influence of the impurities and can not fundamentally remove the impurity ions, and the common chelating resin such as iminodiacetic acid, sulfhydryl and the like has the problems that the binding capacity of functional groups and the impurity ions is severely interfered, the selectivity is poor and the cadmium ions are co-adsorbed, so that the loss of main salt is caused. It should be noted that the cyanide-free cadmium plating solution generally contains relatively high concentration complexing agents such as EDTA, NTA and the like, and the complexing agents and impurity ions form stable complexes, so that the conventional adsorption material is difficult to effectively remove impurities. In addition, the existing adsorption material generally has the problems of poor regeneration performance, difficult solid-liquid separation and the like. Therefore, developing a novel purification material and method which can remove impurities with high selectivity under a strong complexing environment and is easy to separate and recycle is a technical problem to be solved in the field. Disclosure of Invention The invention aims to provide a preparation method, a product and application of a magnetic cadmium ion imprinted polymer, and aims to solve the long-standing technical problems in the purification process of cyanide-free electroplating cadmium solution, including the problems that the main salt cadmium ions are lost due to poor impurity ion removal selectivity, the traditional purification material is invalid under the strong complexing agent environment, the solid-liquid separation and material recovery operations are complicated, the service life of an adsorption material is short, the regeneration is difficult, the purification process adaptability is narrow and the like. Technical proposal A preparation method of a magnetic cadmium ion imprinted polymer comprises the following steps of (1) preparing ferroferric oxide magnetic nano particles by a solvothermal method, (2) carrying out surface amination modification on the magnetic particles obtained in the step (1) by using a silane coupling agent, (3) taking cadmium ions as templates, constructing an imprinted polymer layer on the surfaces of the magnetic particles subjected to amination modification through the reaction of polyethyleneimine and glutamic acid in the presence of a cross-linking agent, and (4) eluting the template cadmium ions to obtain the magnetic cadmium ion imprinted polymer. Further, the reactants of the solvothermal method in the step (1) comprise ferric trichloride hexahydrate, sodium citrate and anhydrous sodium acetate, the solvent is ethylene glycol, the reaction temperature is 185-200 ℃, the reaction time is 10-14 hours, and the saturated magnetization intensity of the ferroferric oxide magnetic nanoparticles is more than 43 emu/g. Further, in the step (2), the silane coupling agent is aminopropyl triethoxysilane. Further, the cross-linking agent in the step (3) is ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and the mass ratio of the polyethyleneimine to the glutamic acid is (2-4): 1. The magnetic cadmium ion imprinted polymer prepared by the preparation method. Further, the particle size distribution of the prepared magnetic cadmium ion imprinted polymer is 780-900 nm, the saturation magnetization is more than or equal to 43 emu/g, the adsorption capacity of the magnetic cadmium ion imprinted polymer to Cu2 + is more than or equal to 27 mg/g, the adsorption capacity to Cd2 + is less than or equal to 3 mg/g, and the selectivity coefficient of Cu2 +/Cd²+ is more than or equal to 15. A method for purifying a cyanide-free electroplating cadmium solution by using a magnetic cadmium ion imprinted polymer, which comprises the following steps: S1, preparing a magnetic cadmium ion imprinted polymer;