Preparation, regeneration and application of a chelating microfiltration membrane

Patent metadata

Field	Value
Publication number	US-10870083-B2
Application number	US-201715749098-A
Country	US
Kind code	B2
Filing date	Jun 15, 2017
Priority date	Jan 16, 2017
Publication date	Dec 22, 2020
Grant date	Dec 22, 2020

Abstract

A polyvinylidene fluoride (PVDF) casting membrane solution is shaped as a flat sheet membrane by thermally induced phase separation (TIPS), the PVDF membrane is defluorinated with an alkaline potassium permanganate solution, and then the carbon chain is extended with glycidyl methacrylate (GMA) as the graft monomer, and finally the nucleophilic substitution is carried out between melamine and GMA to produce a chelating microfiltration membrane for capturing and enriching heavy metals with high flux and high capacity.

First claim

What is claimed is:

1. A preparation method of a chelating microfiltration membrane, comprising:
A. preparing a polyvinylidene fluoride flat sheet membrane: adding 70-90 parts of a solvent into a reactor, then adding 4-22 parts of a pore-forming agent and 6-16 parts of polyvinylidene fluoride, then dissolving completely to form a casting membrane solution; stirring and reacting the casting membrane solution for 1-44 h in the reactor, wherein the reaction temperature is controlled at 50-100° C.; wherein the casting membrane solution, after being settled and defoamed, is shaped as a diaphragm by employing a thermally induced phase separation process; soaking the diaphragm in distilled water for 1-3 h, and finally drying to produce a polyvinylidene fluoride PVDF flat sheet membrane;
B. defluorination: adding the polyvinylidene fluoride flat sheet membrane obtained in step A and a low concentration alkaline potassium permanganate solution to the reactor, wherein a mass ratio of the flat sheet membrane and the alkaline potassium permanganate solution is 1:20-1:50, with a temperature controlled at 10-100° C., performing the reaction for 1-25 h, and then washing and drying to obtain a defluorinated flat sheet membrane;
C. grafting glycidyl methacrylate: adding the deflourinated flat sheet membrane obtained in step B and a solution of glycidyl methacrylate at a concentration of 0.5-5% to the reactor, wherein a mass ratio of the deflourinated flat sheet membrane and the solution of glycidyl methacrylate is 1:20-1:50, then adding an initiator and a polymerization inhibitor, wherein the temperature is controlled at 10-120° C., and the reaction is performed for 1-25 h, and then washing and drying to obtain a grafted flat sheet membrane;
D. melamine modification: adding the grafted flat sheet membrane obtained in step C and a solution of melamine at a concentration of 0.1-5.0% to the reactor, wherein a mass ratio of the grafted flat sheet membrane and the solution of melamine is 1:20-1:50, with the temperature controlled at 10-120° C., performing the reaction for 1-36 h, and then washing and drying.

2. The preparation method of a chelating microfiltration membrane according to claim 1 , wherein the solvent in step A is one selected from the group consisting of N-methyl pyrrolidone, N,N-dimethyl acetamide, trimethylolpropane, dimethyl phthalate, and triethyl phosphate.

3. The preparation method of a chelating microfiltration membrane according to claim 2 , wherein the pore-forming agent in step A is one selected from the group consisting of polyethylene glycol and polyvinyl pyrrolidone.

4. The preparation method of a chelating microfiltration membrane according to claim 3 , wherein a mass fraction of the alkaline potassium permanganate solution in step B is 0.5-5%.

5. The preparation method of a chelating microfiltration membrane according to claim 4 , wherein the solvent in the solution of glycidyl methacrylate in step C is one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol and toluene.

6. The preparation method of a chelating microfiltration membrane according to claim 5 , wherein the initiator in step C is one selected from the group consisting of 2,2-azoisobutyronitrile, ammonium persulfate, potassium persulfate, and benzoyl peroxide, with a concentration of 0.01-0.05%.

7. The preparation method of a chelating microfiltration membrane according to claim 6 , wherein the polymerization inhibitor in step C is one selected from the group consisting of methylhydroquinone, p-hydroxyanisole, and 2-tert-butylhydroquinone, with a concentration of 0.01-0.05%.

8. The preparation method of a chelating microfiltration membrane according to claim 1 , further comprising a regeneration process including soaking the chelating microfiltration membrane in a solution of hydrochloric acid, nitric acid or sulfuric acid at 0.001-1.0 M for 1-72 h and then soaking and washing in deionized water for 1-72 h.

Assignees

• Nanjing University

Inventors

• Liu Fuqiang
• Zhang Yanhong
• Song Li
• Zhao Wei
• Zhu Changqing
• Ling Chen
• Li Aimin

Classifications

• B01D71/34 Primary

  Polyvinylidene fluoride · CPC title

• B01D67/0013

  Casting processes · CPC title

• B01D67/00931

  by introduction of specific groups after membrane formation, e.g. by grafting · CPC title

• B01D67/00113

  Pretreatment of the casting solutions, e.g. thermal treatment or ageing · CPC title

• B01D67/009

  with wave-energy, particle-radiation or plasma · CPC title