阅读说明：本技术 一种蒽醌超滤膜其及制备方法 (Anthraquinone ultrafiltration membrane and preparation method thereof ) 是由 严滨 叶茜 许美兰 曾孟祥 于 2020-06-17 设计创作，主要内容包括：本发明属于废水处理技术领域,具体是一种蒽醌超滤膜及其制备方法,按重量份数计,由以下各组分组成的铸膜液制备而成,15～40份聚氯乙烯、0.07～1份蒽醌改性聚硅氧烷、2～15份成孔剂、0.5～2份热稳定剂、1～3份交联剂、1～2份氧化镁、0.2～0.8份过氧化二异丙苯和50～80份有机溶剂。本发明综合了超滤膜和蒽醌化合物两种材料的优势,对含氮废水,尤其是对含偶氮染料和硝酸盐的废水具有较好的过滤脱氮作用,而且可多次循环使用。(The invention belongs to the technical field of wastewater treatment, and particularly relates to an anthraquinone ultrafiltration membrane and a preparation method thereof, wherein the anthraquinone ultrafiltration membrane is prepared from, by weight, 15-40 parts of polyvinyl chloride, 0.07-1 part of anthraquinone modified polysiloxane, 2-15 parts of pore-forming agent, 0.5-2 parts of heat stabilizer, 1-3 parts of crosslinking agent, 1-2 parts of magnesium oxide, 0.2-0.8 part of dicumyl peroxide and 50-80 parts of organic solvent. The invention integrates the advantages of ultrafiltration membrane and anthraquinone compound, has better filtering and denitrification effect on nitrogen-containing wastewater, especially wastewater containing azo dye and nitrate, and can be recycled for many times.)

1. An anthraquinone ultrafiltration membrane is characterized by being prepared from, by weight, 15-40 parts of polyvinyl chloride, 0.07-1 part of anthraquinone modified polysiloxane, 2-15 parts of pore-forming agent, 0.5-2 parts of heat stabilizer, 1-3 parts of cross-linking agent, 1-2 parts of magnesium oxide, 0.2-0.8 part of dicumyl peroxide and 50-80 parts of organic solvent.

2. The anthraquinone ultrafiltration membrane of claim 1, wherein the degree of polymerization of the polyvinyl chloride is 800-2000.

3. The anthraquinone ultrafiltration membrane according to claim 1, wherein the anthraquinone-modified polysiloxane is obtained by reacting 9, 10-anthraquinone-2-sulfonyl chloride and amino vinyl polysiloxane.

4. The anthraquinone ultrafiltration membrane of claim 3, wherein the amino vinyl polysiloxane has a general structural formula of R¹SiMe₂O(SiOMe₂)_a(SiOMeR_N)_b(SiOMeVi)_cSiMe₂R¹Wherein R is¹Selected from methyl, vinyl or hydroxy, Me is methyl, R_NIs 3-aminopropyl or N-2-aminoethyl-3-aminopropyl, Vi is ethenyl, a is more than or equal to 20 and less than or equal to 200, b is more than or equal to 3 and less than or equal to 9, and c is more than or equal to 2 and less than or equal to 7.

5. The anthraquinone ultrafiltration membrane according to claim 3, wherein the ratio of the mole number of the 9, 10-anthraquinone-2-sulfonyl chloride to the mole number of amino groups in the aminovinyl polysiloxane is 1: 1-3.

6. The anthraquinone ultrafiltration membrane of claim 1, wherein the pore former is selected from one or more of polyvinylpyrrolidone, zinc chloride, polyethylene glycol, tributyl citrate and calcium chloride.

7. The anthraquinone ultrafiltration membrane of claim 1, wherein said heat stabilizer is selected from one or more of calcium zinc stabilizer, barium zinc stabilizer and organic tin stabilizer.

8. The anthraquinone ultrafiltration membrane of claim 1, wherein the crosslinker is selected from one or more of diallyl maleate, ethylene glycol dimethyl allyl ester, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isonitrile uraurate, triallyl nitrile uraurate, tetraethylene glycol dimethacrylate and dipropylene glycol diacrylate.

9. A method for preparing an anthraquinone ultrafiltration membrane according to any one of claims 1 to 8, which comprises the following steps,

step one, preparing a casting solution: preparing raw materials of each component, accurately weighing each component, sequentially adding the raw materials into a container, stirring and dissolving the raw materials uniformly at 25-50 ℃, and removing bubbles;

step two, forming: and (2) placing the membrane casting solution obtained in the first step into a hollow fiber spinning spray head, spinning into a fiber membrane at the spinning temperature of 45-85 ℃ and the spinning speed of 20-60 m/min, immersing the fiber membrane in deionized water coagulation bath at 10-35 ℃ for 30 seconds-3 minutes after 0.5-1 second in air, then entering a baking tunnel furnace at 175-190 ℃ for 2-7 minutes, then immersing the fiber membrane in deionized water coagulation bath at 10-35 ℃ for 30 seconds-2 minutes, stretching according to the stretching ratio of 2-5, immersing the fiber membrane in 25-50 wt% of glycerol aqueous solution for 5 minutes-3 hours, taking out and airing to obtain the anthraquinone ultrafiltration membrane.

Technical Field

The invention belongs to the technical field of wastewater treatment, and relates to an anthraquinone ultrafiltration membrane and a preparation method thereof.

Background

The ultrafiltration membrane is a microporous filtration membrane with consistent pore size specification and the rated pore size range of less than 0.01 micron. Solute molecules smaller than the pore size can be screened out by applying a suitable pressure to one side of the membrane to separate particles having a molecular weight greater than 500 daltons (atomic mass units) and a particle size greater than 10 nanometers.

The anthraquinone compound can effectively promote and improve the microbial degradation rate of the nitrogen-containing wastewater containing azo dyes, nitrates and the like, and has potential great application significance and value. However, no combination of an ultrafiltration membrane and an anthraquinone compound for treating nitrogen-containing wastewater has been reported.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide an anthraquinone ultrafiltration membrane.

The invention also aims to provide a preparation method of the anthraquinone ultrafiltration membrane.

The technical scheme of the invention is as follows:

an anthraquinone ultrafiltration membrane is prepared from, by weight, 15-40 parts of polyvinyl chloride, 0.07-1 part of anthraquinone modified polysiloxane, 2-15 parts of pore-forming agent, 0.5-2 parts of heat stabilizer, 1-3 parts of cross-linking agent, 1-2 parts of magnesium oxide, 0.2-0.8 part of dicumyl peroxide and 50-80 parts of organic solvent. In the present invention, the organic solvent may be one or more selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), and N, N-dimethylacetamide (DMAc).

Preferably, the degree of polymerization of the polyvinyl chloride is 800-2000.

Preferably, the anthraquinone-modified polysiloxane is obtained by reacting 9, 10-anthraquinone-2-sulfonyl chloride and amino vinyl polysiloxane.

More preferably, the amino vinyl polysiloxane has a structural general formula of R¹SiMe₂O(SiOMe₂)_a(SiOMeR_N)_b(SiOMeVi)_cSiMe₂R¹Wherein R is¹Selected from methyl, vinyl or hydroxy, Me is methyl, R_NIs 3-aminopropyl or N-2-aminoethyl-3-aminopropyl, Vi is ethenyl, a is more than or equal to 20 and less than or equal to 200, b is more than or equal to 3 and less than or equal to 9, and c is more than or equal to 2 and less than or equal to 7.

More preferably, the ratio of the mole number of the 9, 10-anthraquinone-2-sulfonyl chloride to the mole number of amino groups in the amino vinyl polysiloxane is 1: 1-3.

The method for reacting 9, 10-anthraquinone-2-sulfonyl chloride with amino vinyl polysiloxane comprises the following steps: adding amino vinyl polysiloxane, an acid-binding agent and tetrahydrofuran into a container in an environment of 0-5 ℃, stirring for dissolving, dropwise adding a tetrahydrofuran solution of 9, 10-anthraquinone-2-sulfonyl chloride, continuously stirring for 2-10 hours after dropwise adding, heating to 20-40 ℃, continuously stirring for reacting for 3-10 hours, filtering, and removing low-boiling-point substances from filtrate to obtain the anthraquinone modified polysiloxane. The acid-binding agent can be triethylamine, triethanolamine, ammonium carbonate, sodium carbonate or potassium carbonate, and the molar ratio of the acid-binding agent to the 9, 10-anthraquinone-2-sulfonyl chloride is 1.1-1.3: 1.

Preferably, the pore-forming agent is selected from one or more of polyvinylpyrrolidone, zinc chloride, polyethylene glycol, tributyl citrate and calcium chloride.

Preferably, the heat stabilizer is one or more selected from calcium zinc stabilizer, barium zinc stabilizer and organic tin stabilizer.

Preferably, the crosslinking agent is selected from one or more of diallyl maleate, ethylene glycol dimethyl allyl ester, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isonitrile uraurate, triallyl nitrile uraurate, tetraethylene glycol dimethacrylate and dipropylene glycol diacrylate. In a more preferred embodiment, the crosslinking agent is selected from one or more of diallyl maleate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isonitrile uraurate and triallyl nitrile uraurate.

A method for preparing an anthraquinone ultrafiltration membrane according to any one of the above embodiments, comprising the steps of,

step one, preparing a casting solution: preparing raw materials of each component, accurately weighing each component, sequentially adding the raw materials into a container, stirring and dissolving the raw materials uniformly at 25-50 ℃, and removing bubbles;

step two, forming: and (2) placing the membrane casting solution obtained in the first step into a hollow fiber spinning spray head, spinning into a fiber membrane at the spinning temperature of 45-85 ℃ and the spinning speed of 20-60 m/min, immersing the fiber membrane in deionized water coagulation bath at 10-35 ℃ for 30 seconds-3 minutes after 0.5-1 second in air, then entering a baking tunnel furnace at 175-190 ℃ for 2-7 minutes, then immersing the fiber membrane in deionized water coagulation bath at 10-35 ℃ for 30 seconds-2 minutes, stretching according to the stretching ratio of 2-5, immersing the fiber membrane in 25-50 wt% of glycerol aqueous solution for 5 minutes-3 hours, taking out and airing to obtain the anthraquinone ultrafiltration membrane.

The invention has the beneficial effects that: according to the invention, the anthraquinone modified polysiloxane is added into the membrane casting solution of the PVC ultrafiltration membrane, and by utilizing the incompatibility of the polysiloxane and the PVC material, the anthraquinone modified polysiloxane can migrate and enrich to the surface of the PVC material, so that the anthraquinone content on the surface of the PVC is higher, and in the crosslinking process of the PVC, vinyl groups in polysiloxane molecules can participate in crosslinking, and the anthraquinone modified polysiloxane is fixed on the surface of the ultrafiltration membrane in a chemical manner.

Detailed Description

The technical solution of the present invention is further illustrated and described by the following detailed description.

Unless otherwise specified, the parts in the following examples are parts by weight.