CN102188916A - Method for controlling thickness of active layer of polyamide composite membrane - Google Patents
Method for controlling thickness of active layer of polyamide composite membrane Download PDFInfo
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- CN102188916A CN102188916A CN2010101152215A CN201010115221A CN102188916A CN 102188916 A CN102188916 A CN 102188916A CN 2010101152215 A CN2010101152215 A CN 2010101152215A CN 201010115221 A CN201010115221 A CN 201010115221A CN 102188916 A CN102188916 A CN 102188916A
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Abstract
The invention belongs to a method for controlling the thickness of an active layer of a polyamide composite membrane. After a porous support base membrane is immersed into a polyamine aqueous solution and before the porous support base membrane is compounded with a polyacyl chloride solution to form a film, a polymer dilute solution or alkali or salt dilute solution is used for treating the base membrane, and a thin film formed on the surface of the base membrane after the dilute solution is completely removed in a spraying way can inhibit subsequent interfacial polymerization of amine and acyl chloride, thus the thickness of the polyacyl chloride active layer is controlled. The method comprises the following stages of: soaking the porous support base membrane into an additive-containing phenylenediamine or piperazine monomer aqueous solution in a certain concentration for a period of time, removing excessive amine on the surface by adopting a rolling method, and soaking and treating with a polymer dilute solution, or alkali or salt dilute solution or solution of a mixture of the polymer dilute solution and alkali or salt dilute solution. The polymer comprises polymers of hydrophilic organic acid, organic amine and organic alcohol or a nonpolar hydrophobic polymer solution. The treated base membrane is vertically placed to remove the excessive solution on the surface of the membrane, after the excessive solution is removed in the spraying way until the membrane is half-dry in the air, the membrane is immersed in the polyacyl chloride solution to cause the phenylenediamine or piperazine monomer immersed into the base membrane and the polyacyl chloride monomer to carry out interfacial polymerization so as to form the membrane, and fully washing is carried out before and after heat treatment, thus water flux of the obtained membrane is multiplied.
Description
Technical field
The invention belongs to a kind of method of controlling polyamide composite film active layer thickness.After will supporting counterdie and being immersed in polyamine solution, use polymer, or alkali, the weak solution immersion treatment of salt is drenched and is done after the surface forms skim, should support counterdie and continue to be immersed in the polynary solution of acid chloride and form polyamide composite film.
Background technology
Nanofiltration and reverse osmosis membrane are because of the separating property to the brilliance of organic molecule and inorganic ion, and safety, environmental friendliness, advantage such as easy to operate and become one of key technology of water treatment.Its application comprises the seawater and the bitter degree of saltinessization, water softening, and middle water reclaims, Industrial Wastewater Treatment, wide spectrums such as ultra-pure water preparation.Wherein composite membrane can be with the rejection of film because of it, water flux, performance optimization such as stability and become current with fastest developing speed, use maximum film kinds, surpassing 90% nanofiltration and reverse osmosis membrane in the market is composite membrane.Composite membrane is meant very thin, the different materials fine and close, that the special separation function is arranged of compound one deck on the support counterdie of porous.Compare with integrated film, the surface compact layer thickness of composite membrane is thinner, thereby makes film have the high solute separation rate and the transmission rates of water simultaneously, and optimizable physical chemistry structure, can satisfy various Selective Separation demand.The current composite membrane that is widely used in the water treatment field is mainly taked the mode of interfacial polymerization, polyamide film is compound to micropore supports the counterdie surface.Common technical process has detailed introduction at the United States Patent (USP) 4277344 of initiative.The micropore counterdie that at first polysulfones is coated on the polyester non-woven fabric and forms, be immersed in the diamines or the polyamines aqueous solution, drench by wind then, methods such as roll-in are removed the unnecessary amine aqueous solution in film surface, be immersed in again in organic non-polar solution of polynary acyl chlorides and acyl chlorides generation interface polymerization reaction, thereby form the fine and close ultra-thin active layer with separation function on the surface, after the film forming, fully washing and suitable heat cure are handled and can be increased film properties.Water flux as an important parameter of film properties, except depending on chemical constitution and form, outside the appearance structure, more depends on film thickness, especially the thickness of active layer.Under the prerequisite that does not influence rejection and stability, active layer is got over Bao Yuehao.Thickness circle of current commercial nanofiltration and reverse osmosis composite membrane is in several nanometers to the hundreds of nanometer, and by the structure of polyamines, concentration and additive structure and concentration determine usually.Because many ammonia and polynary acyl chloride reaction activity are very high, speed is very fast, thereby the difficult acquisition of the aramid layer of thinner densification, thereby has limited the further raising of water flux.
Summary of the invention
The purpose of this invention is to provide the method for control polyamide active layer thickness in a kind of recombination process, thereby improve the water flux of film.
After will supporting counterdie and in polyamine solution, soaking into certain hour, do or the unnecessary amine aqueous solution in roll-in method removal surface with drenching, then this counterdie is dipped into a kind of weak solution or alkali of polymer, take out behind the certain hour in the weak solution of salt or the mixture of above material, vertical placement counterdie is excluded surperficial redundant solution and drenches in air to half-dried, make the counterdie surface form one deck ultrathin membrane, this support counterdie is continued to be immersed in certain hour in the solution of acid chloride to be made amine in the counterdie carry out polymerisation with acyl chlorides to become composite membrane, through the heat treatment and the washing of necessity, form last composite membrane then.The effect of the ultrathin membrane on counterdie surface is that amine molecule is limited between counterdie and this ultrathin membrane, thus with the acyl chlorides polymerization process in, restriction amine or acyl chlorides are at the interface diffusion velocity, the thickness of formed like this polyamide active layer is with controlled.This film can partly or entirely be dissolved in subsequently the employed solvent of recombination process, as the alkane in the solution of acid chloride, or the acid in the washing process afterwards, in aqueous slkali and the pure water, also this ultrathin membrane finally can be retained in the structure of composite membrane, and become the part of composite membrane.
The specific embodiment
Embodiment provided by the invention is as follows:
Comparative Examples: the polysulfones counterdie of the about 200A of average pore size was immersed in 2.0% the m-phenylene diamine (MPD) aqueous solution 2 minutes, was immersed in after half-dried with squeegee roll-in film surface in 0.2% the pyromellitic trimethylsilyl chloride hexane solution 90 seconds.Put into 90 ℃ oven 10 minutes after the taking-up.The following condition test of composite membrane performance of gained: the concentration of aqueous solution of NaCl: 1500ppm; Test pressure: 1.5MPa; Probe temperature: 25 ℃.The rejection 98.9% of gained test result: NaCl, water flux are 0.77M
3/ M
2.d.
Embodiment 1-12, other condition is identical with Comparative Examples, rolling process and and the acyl chloride reaction film-forming process between, with the solution immersion treatment certain hour of various variable concentrations and kind, as polyvinyl alcohol, polyacrylic acid, polymethyl methacrylate, polyethylene, polybutadiene, egg is clear, NaCl solution, and the mixed solution of NaCl/ polyvinyl alcohol, vertically place counterdie surperficial redundant solution is excluded and in air, drench to the surface half-dried, then with the pyromellitic trimethylsilyl chloride polymerization film formation.Test condition is identical with Comparative Examples, and gained the results are shown in table 1.
Table 1
| Embodiment | The Polymer Solution treatment conditions | Hold back (%) | Water flux (M 3/M 2.D) |
| Comparative Examples | Do not have | 98.9 | 0.77 |
| Embodiment 1 | 0.01% polyvinyl alcohol/water solution, 10 seconds | 98.3 | 0.87 |
| Embodiment 2 | 0.05% polyvinyl alcohol/water solution, 30 seconds | 95.4 | 0.99 |
| Embodiment 3 | 0.01% polyacrylic acid/the aqueous solution, 5 seconds | 98.0 | 0.98 |
| Embodiment 4 | 0.05% polyacrylic acid/the aqueous solution, 30 seconds | 93.8 | 1.65 |
| Embodiment 5 | 0.01% polymethyl methacrylate/aqueous isopropanol 5 seconds | 98.7 | 0.89 |
| Embodiment 6 | 0.01% polymethyl methacrylate/aqueous isopropanol 30 seconds | 98.1 | 0.94 |
| Embodiment 7 | 0.01% polyethylene/chloroformic solution 10 seconds | 98.8 | 1.01 |
| Embodiment 8 | 0.05% polyethylene/chloroformic solution 30 seconds | 98.5 | 1.11 |
| Embodiment 9 | 0.1% polybutadiene/toluene solution 30 seconds | 98.5 | 1.45 |
| Embodiment 10 | 0.1% egg is clear/aqueous solution 30 seconds | 99.1 | 0.99 |
| Embodiment 11 | The 1.0%NaCl/ aqueous solution 30 seconds | 99.0 | 1.02 |
| Embodiment 12 | 1.0%NaCl/0.01% polyvinyl alcohol/water solution 20 seconds | 99.5 | 1.14 |
Claims (10)
1. a method of making composite membrane comprises that polyamine and polynary acyl chlorides support the counterdie surface in porous and carry out the interface polymerization reaction film forming, forms polyamide work of separation ergosphere.The feature of method is, after porous supported counterdie and be immersed in amine aqueous solution, before acyl chlorides polymerisation film forming, use polymer solution, aqueous slkali, salting liquid, or the solution immersion treatment of its mixture, the vertical counterdie of placing after handling is excluded surperficial redundant solution and drenches to half-dried in air, makes the surface attachment thin film, and then contacts with polynary solution of acid chloride and to carry out interface polymerization reaction and become composite membrane.
2. as right 1 described method, after porous supported counterdie and be immersed in amine aqueous solution, before acyl chlorides polymerisation film forming, the solution of the employed polymer of immersion treatment comprises hydrophily, hydrophobicity, amphipathic polymer, and natural polymers, or the solution of its copolymer and blend.
3. right 2 described hydrophilic polymers comprise and comprise hydroxyl, carboxyl, amido, amide groups in the repetitive, ether, the polymer of groups such as aldehyde radical and salt thereof also comprise water insoluble but contain polar group such as sulfuryl, ketone group, ester group, acid halide group, sulfonic group, the polymer of siloxy.
4. right 2 described hydrophobic polymers comprise hydrocarbon polymer.
5. right 2 described natural polymerses comprise protein, starch, natural glue.
6. right 2 described copolymers comprise that the polymer side chain that will comprise hydrophilic radical is grafted to the graft copolymer on the hydrophobic polymer main chain, and the polymer side chain that maybe will comprise hydrophobic grouping is grafted to the graft copolymer on the hydrophilic polymer main chain.
7. be 0.001%-5% as right 1 described polymer solution concentration scope, salt, the alkaline concentration scope is 0.1-10%.
8. the oligomer that comprises linear and ring-type as right 1 described polymer.
9. comprise inorganic and organic base solution as right 1 described aqueous slkali, salting liquid comprises inorganic and organic slat solution.
As the described weak solution of right 1 drench do the formed film in back can partly or entirely be dissolved in subsequently solution of acid chloride or composite membrane-forming after in the employed cleaning solution, or do not dissolve fully and be retained in the structure of composite membrane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012188A (en) * | 2018-09-09 | 2018-12-18 | 郑州成济堂生物科技有限公司 | A kind of preparation method of high-flux composite nanofiltration membrane |
| CN110394069A (en) * | 2018-04-25 | 2019-11-01 | 华中科技大学 | Using the polyamide composite film of inorganic additives preparation, its preparation and application |
| CN111185105A (en) * | 2020-01-14 | 2020-05-22 | 同济大学 | High-performance polyamide composite separation membrane based on biopolymer-contaminated basement membrane and preparation method thereof |
| CN114146572A (en) * | 2021-12-07 | 2022-03-08 | 天津大学 | Preparation method of amide chain segment embedded covalent organic framework composite membrane and filter membrane thereof |
-
2010
- 2010-03-01 CN CN2010101152215A patent/CN102188916A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110394069A (en) * | 2018-04-25 | 2019-11-01 | 华中科技大学 | Using the polyamide composite film of inorganic additives preparation, its preparation and application |
| CN109012188A (en) * | 2018-09-09 | 2018-12-18 | 郑州成济堂生物科技有限公司 | A kind of preparation method of high-flux composite nanofiltration membrane |
| CN111185105A (en) * | 2020-01-14 | 2020-05-22 | 同济大学 | High-performance polyamide composite separation membrane based on biopolymer-contaminated basement membrane and preparation method thereof |
| CN114146572A (en) * | 2021-12-07 | 2022-03-08 | 天津大学 | Preparation method of amide chain segment embedded covalent organic framework composite membrane and filter membrane thereof |
| CN114146572B (en) * | 2021-12-07 | 2023-06-30 | 天津大学 | Preparation method of amide chain segment embedded covalent organic framework composite membrane and filter membrane thereof |
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Application publication date: 20110921 |