CN103111196A - Preparation method of nanofiltration membrane - Google Patents
Preparation method of nanofiltration membrane Download PDFInfo
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- CN103111196A CN103111196A CN2013100678180A CN201310067818A CN103111196A CN 103111196 A CN103111196 A CN 103111196A CN 2013100678180 A CN2013100678180 A CN 2013100678180A CN 201310067818 A CN201310067818 A CN 201310067818A CN 103111196 A CN103111196 A CN 103111196A
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Abstract
The invention discloses a preparation method of a nanofiltration membrane, and particularly relates to a preparation method of a PVA (Polyvinyl Acetate)-Polypiperazine-amide nanofiltration membrane doped with acyl-chloride-modified nano-TiO2 particles. The preparation method of the nanofiltration membrane comprises the steps of adding organically-modificed nano-TiO2 particles with benzoyl chloride groups into an organic trimesoyl chloride (TMC) solution to be dispersed into a solution, and then, enabling the solution to contact with an aqueous solution containing piperazine (PIP) and polyving alcohol (PVA) to be subjected to interfacial polymerization reaction to obtain an organic nano-modification composite nanofiltration membrane. The preparation method has the advantages that under the 1MPa operating pressure on the prepared membrane, water flux is obviously enhanced, meanwhile, high salt rejection to sodium sulfate is displayed, the rejection ratio of the sodium chloride is 50.4%, and different separation capabilities to univalent salt and divalent salt are represented; and the acyl-chloride-modified nano-TiO2 particles can favorably disperse in an organic phase, and assists an aqueous phase in forming a uniform membrane structure in the interfacial polymerization reaction.
Description
Technical field
The present invention relates to a kind of preparation technology of composite membrane, specifically refer to a kind of preparation method of acyl chlorides modified Nano TiO2 particle hydridization PVA-polypiperazine-amide nanofiltration membrane.
Background technology
NF membrane is the new membrane isolation technics between ultrafiltration and counter-infiltration.Its technical characterstic is to realize selectively seeing through dissolved constituent by sterically hindered and electrostatic interaction, and operating system pressure is well below reverse osmosis process (operating pressure is generally 0.4-1MPa), NF membrane to divalent ion and molecular weight greater than the rejection of 200 solute greater than 90%, and to the rejection of monovalent ion and low molecular weight solutes generally lower than 50%, thereby can realize Selective Separation to material.
At present, improving one's methods of NF membrane mainly contained new monomer development, surface modification, add the aspects such as organic molecule and interpolation inorganic particulate.In recent years, the technology of preparing of inorganic nano material reaches its maturity, and its use also increases gradually.Inorganic nano material and hydrophilic organics hydrophilicity are also become one of research direction for the flux Study of Lifting of interfacial polymerization NF membrane jointly.
Using inorganic particle in interfacial polymerization, is generally to say that inorganic nano-particle adds in organic phase.Common nano-titania particle surface adds in organic phase with a large amount of hydroxyls, and the hydrophily of hydroxyl can affect the dispersion effect of nano particle in organic phase, and this will have influence on the performance of NF membrane.After organically-modified, TiO
2Nanoparticle surface is with functional group, and the dispersive property in organic solvent improves simultaneously.After titanium dioxide nano-particle adds the organic phase of interfacial polymerization, in interfacial polymerization process can with monomer reaction, thereby obtain a kind of nano modification film between organic phase and inorganic phase with covalent bonds, the residual hydroxyl hydrophilic radical of simultaneously organically-modified nanoparticle surface also can improve the film properties after film forming.
Polyvinyl alcohol (PVA) structure belongs to strict line style, stable chemical nature, and it is highly hydrophilic that the carboxyl on strand has it.Add aqueous phase to participate in interface polymerization reaction PVA, can improve the hydrophily of diffusion barrier, then improve the water flux of NF membrane.
Summary of the invention
The present invention is directed to the less deficiency of present organic nanofiltration membrane flux, add hydrophilic polyethene alcohol (PVA) and a kind of organic chloride modified nano-titanium dioxide particle to carry out modification to NF membrane in the NF membrane preparation process, proposed a kind of preparation method of acyl chlorides modified Nano TiO2 particle hydridization PVA-polypiperazine-amide nanofiltration membrane.
The present invention is achieved by the following technical programs:
A kind of preparation method of NF membrane, its feature comprises the following steps:
(1) configuration quality concentration is 0.1% ~ 0.3% pyromellitic trimethylsilyl chloride (TMC) organic phase solution, and wherein solvent is IsoparG, then adds a certain amount of through TMC modified Nano TiO
2Particle, ultrasonic dispersion 1 hour is made into mass concentration and is 0.005% ~ 0.2% unit for uniform suspension;
(2) the polysulfones support membrane being put into mass concentration is that 0.1% ~ 0.5% piperazine (PIP) aqueous solution soaked 30 ~ 180 seconds, wherein contains mass concentration and be 0.01% ~ 0.2% middle molecular weight polyvinyl alcohol and mass concentration and be 0.01% dodecyl sodium sulfate (SDS); In the present invention, the molecular weight of described middle molecular weight polyvinyl alcohol is 60000 ~ 70000;
Unnecessary solution is removed in the polysulfones support membrane rubber rollers roll extrusion of (3) soaking through piperazine solution;
(4) after solution was done, the organic phase solution of completing with firm ultrasonic dispersion contacted 10 ~ 120 seconds;
(5) film that said process is made is put into the vacuum drying oven of 70 ~ 90 ℃ and was kept 10 ~ 15 minutes, dry getting final product.
As preferably, the benzoyl chlorination modified nano-titanium dioxide in the preparation method of above-mentioned a kind of NF membrane is with two kinds of groups: phenyl ring and chlorobenzoyl chloride group.
Beneficial effect: with the nano-TiO of chlorobenzoyl chloride group
2Form amido link with piperazine reaction in interface polymerization reaction, form rock-steady structure, difficult drop-off can improve the mechanical strength of NF membrane simultaneously, simultaneously keep original to the divalent salts equipment with high desalinization in, the existence of nano particle can improve the film pure water flux.And this preparation method is simple, and operation is easily gone.
The specific embodiment
The present invention will be further described below in conjunction with example, but protection scope of the present invention is not limited to this:
Embodiment 1
Configuration quality concentration is 0.2% pyromellitic trimethylsilyl chloride (TMC) organic phase solution, and wherein solvent is IsoparG; Configuration quality concentration is 0.2% the piperazine aqueous solution, then adding mass concentration is 0.05% middle molecular weight polyvinyl alcohol (PVA), the polysulfones support membrane is put into the piperazine aqueous solution soaked 120 seconds, wherein then use rubber rollers roll extrusion polysulfones support membrane, remove unnecessary solution; After solution is done, contact 20 seconds with organic phase solution; The vacuum drying oven of this film being put into 80 ℃ kept 12 minutes, and drying makes the hydridization Nano filtering composite membrane.With the initial performance of aqueous sodium persulfate solution, sodium-chloride water solution, the PEG-200 aqueous solution and the PEG-400 aqueous solution test membrane under 1MPa pressure of 2000ppm, this film is to Na
2SO
4Be respectively 98.4% and 53.2% with the salt rejection rate of NaCl, the removal efficiency rate of PEG-200 and PEG-400 is respectively 91.0% and 98.8%, flux is 65.47 L/h/m
2
Embodiment 2
Configuration quality concentration is 0.2% pyromellitic trimethylsilyl chloride (TMC) organic phase solution, and wherein solvent is IsoparG, then adds a certain amount of TMC modified nano-titanium dioxide particle, and ultrasonic dispersion 1 hour is made into mass concentration and is 0.005% unit for uniform suspension; Configuration quality concentration is 0.2% the piperazine aqueous solution, then adding mass concentration is 0.05% middle molecular weight polyvinyl alcohol (PVA), the polysulfones support membrane is put into the piperazine aqueous solution soaked 120 seconds, wherein then use rubber rollers roll extrusion polysulfones support membrane, remove unnecessary solution; After solution was done, the organic phase solution of completing with firm ultrasonic dispersion contacted 20 seconds; The vacuum drying oven of this film being put into 80 ℃ kept 12 minutes, and drying makes the hydridization Nano filtering composite membrane and tests, and diaphragm is to Na
2SO
4Be respectively 98.5% and 51.8% with the salt rejection rate of NaCl, the removal efficiency rate of PEG-200 and PEG-400 is respectively 90.8% and 98.6%, flux is 92.36L/h/m
2
Embodiment 3-4
Change the molecular weight of polyvinyl alcohol (PVA) in aqueous phase solution, the method for operating that other steps are identical with embodiment 1, preparation composite membrane and test obtain result such as following table:
Embodiment 5-8
Change the mass concentration of polyvinyl alcohol (PVA) contained in aqueous phase solution, the method for operating that other steps are identical with embodiment 1, preparation composite membrane and test obtain result such as following table:
Embodiment 9-14 changes the mass concentration of the contained TMC modified nano-titanium dioxide particle of organic phase solution, the method for operating that other steps are identical with embodiment 2, and preparation composite membrane and test obtain result such as following table:
The present invention will be with the organic modified nano TiO of chlorobenzoyl chloride group
2Particle adds in pyromellitic trimethylsilyl chloride (TMC) organic solution and is dispersed into uniform solution, then with contain the aqueous solution of piperazine (PIP) with polyvinyl alcohol (PVA) and contact and interface polymerization reaction occurs make organic nano modification composite nanometer filtering film.The composite nanometer filtering film that utilizes this method to prepare is compared unmodified polypiperazine-amide composite nanometer filtering film, and water flux obviously increases (106.66 L/m under the operating pressure of 1MPa
2.h), simultaneously sodium sulphate having been shown very high salt rejection rate (98.7%), is 50.4% to the rejection of sodium chloride, shows the different separating powers to monovalent salt and divalent salts.Nano-titania particle by the chloride modification can well be dispersed in organic phase, forms uniform decentralized photo, helps to form uniform membrane structure with water in interface polymerization reaction.Effect in the present invention and benefit are: with the nano-TiO of chlorobenzoyl chloride group
2Form amido link with the piperazine reaction in interface polymerization reaction, form rock-steady structure, can improve the mechanical strength of NF membrane, improve the film pure water flux, the existence of nano particle simultaneously can strengthen the contamination resistance of NF membrane.
Claims (2)
1. the preparation method of a NF membrane, its feature comprises the following steps:
(1) configuration quality concentration is 0.1% ~ 0.3% pyromellitic trimethylsilyl chloride organic phase solution, and wherein solvent is IsoparG oil; Then add benzoyl chlorination nano-TiO
2, ultrasonic dispersion 1 hour is made into and contains benzoyl chlorination nano-TiO
2Mass concentration is 0.005% ~ 0.2% unit for uniform suspension;
(2) the polysulfones support membrane being put into mass concentration is that 0.1% ~ 0.5% the piperazine aqueous solution soaked 30 ~ 180 seconds, wherein contains mass concentration and be 0.01% ~ 0.2% polyvinyl alcohol and mass concentration and be 0.01% dodecyl sodium sulfate; Wherein the molecular weight of polyvinyl alcohol is 60000 ~ 70000;
Unnecessary solution is removed in the polysulfones support membrane rubber rollers roll extrusion of (3) soaking through piperazine solution;
(4) after solution was done, the organic phase solution of completing with firm ultrasonic dispersion contacted 10 ~ 120 seconds;
(5) film that said process is made is put into the vacuum drying oven of 80 ~ 100 ℃ and was kept 10 ~ 15 minutes, dry getting final product.
2. the preparation method of a kind of NF membrane according to claim 1 is characterized in that described benzoyl chlorination modified nano-titanium dioxide is with two kinds of groups: phenyl ring and chlorobenzoyl chloride group.
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Cited By (9)
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| CN103877872A (en) * | 2014-03-28 | 2014-06-25 | 杭州水处理技术研究开发中心有限公司 | Preparation method of nano material modified poly piperazine amide nanofiltration membrane |
| CN104275094A (en) * | 2013-07-08 | 2015-01-14 | 南京理工大学 | Chitosan quaternary ammonium HTCC/polyethersulfone composite nanofiltration membrane and preparation |
| CN104607070A (en) * | 2015-02-09 | 2015-05-13 | 杭州水处理技术研究开发中心有限公司 | Preparation method of charged nanofiltration membrane |
| CN104785124A (en) * | 2015-03-30 | 2015-07-22 | 北京工业大学 | Charged TiO2/polyelectrolyte composite nanofiltration membrane as well as preparation method and application thereof |
| CN106823867A (en) * | 2017-03-06 | 2017-06-13 | 北京理工大学 | Using the method for polyalcohols/ester blend hydrophilic modification hydrophobic type polymeric membrane for separation |
| CN108607368A (en) * | 2018-05-07 | 2018-10-02 | 浙江工业大学 | A kind of polytetrafluoroethylene (PTFE) ultrafiltration membrane hydrophilic modification method |
| CN110975622A (en) * | 2019-12-25 | 2020-04-10 | 恩泰环保科技（常州）有限公司 | Novel charged nanofiltration membrane and preparation method thereof |
| CN110975620A (en) * | 2019-12-25 | 2020-04-10 | 恩泰环保科技（常州）有限公司 | Nanofiltration membrane based on weak base buffer system and preparation method thereof |
| CN111001317A (en) * | 2019-12-05 | 2020-04-14 | 浙江工业大学 | Novel high-flux high-selectivity composite nanofiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104275094A (en) * | 2013-07-08 | 2015-01-14 | 南京理工大学 | Chitosan quaternary ammonium HTCC/polyethersulfone composite nanofiltration membrane and preparation |
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| CN104785124A (en) * | 2015-03-30 | 2015-07-22 | 北京工业大学 | Charged TiO2/polyelectrolyte composite nanofiltration membrane as well as preparation method and application thereof |
| CN106823867A (en) * | 2017-03-06 | 2017-06-13 | 北京理工大学 | Using the method for polyalcohols/ester blend hydrophilic modification hydrophobic type polymeric membrane for separation |
| CN108607368A (en) * | 2018-05-07 | 2018-10-02 | 浙江工业大学 | A kind of polytetrafluoroethylene (PTFE) ultrafiltration membrane hydrophilic modification method |
| CN111001317A (en) * | 2019-12-05 | 2020-04-14 | 浙江工业大学 | Novel high-flux high-selectivity composite nanofiltration membrane and preparation method thereof |
| CN111001317B (en) * | 2019-12-05 | 2022-02-11 | 浙江工业大学 | High-flux high-selectivity composite nanofiltration membrane and preparation method thereof |
| CN110975622A (en) * | 2019-12-25 | 2020-04-10 | 恩泰环保科技（常州）有限公司 | Novel charged nanofiltration membrane and preparation method thereof |
| CN110975620A (en) * | 2019-12-25 | 2020-04-10 | 恩泰环保科技（常州）有限公司 | Nanofiltration membrane based on weak base buffer system and preparation method thereof |
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Application publication date: 20130522 |