CN102614787A - Method for preparing hydrophilic macromolecule microporous composite membrane - Google Patents
Method for preparing hydrophilic macromolecule microporous composite membrane Download PDFInfo
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- CN102614787A CN102614787A CN2012100869963A CN201210086996A CN102614787A CN 102614787 A CN102614787 A CN 102614787A CN 2012100869963 A CN2012100869963 A CN 2012100869963A CN 201210086996 A CN201210086996 A CN 201210086996A CN 102614787 A CN102614787 A CN 102614787A
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- membrane
- polyvinyl formal
- aqueous solution
- microporous
- hydrophilic macromolecule
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Abstract
A method for preparing a hydrophilic macromolecule microporous composite membrane is characterized by comprising the steps: (1) adding polyvinyl formal into 5-30% by mass of hydrochloric acid or sulfuric acid aqueous solution to be heated to the temperature of 40-100 DEG C and dissolved, performing standing and defoaming, wherein the adding amount of the polyvinyl formal is 8-20% by mass of polyvinyl formal in feed liquid; and (2) performing blade coating to coat the feed liquid on polyester non-woven fabrics, submerging the polyester non-woven fabrics in an alkaline aqueous solution with the temperature of 20-50 DEG C, and forming the microporous membrane through phase separation and solidification. In the preparation process, an organic solvent is not used so that the method is environment-friendly and safe. Hydrophilic functional group-OH in a polyvinyl alcohol structure is utilized, and the problem that polyvinyl alcohol is difficultly and directly prepared into the microporous membrane is solved. The composite membrane prepared by means of the method is made of a hydrophilic membrane material which has high membrane flow under the lower pressure and good fouling resistant performance and is used as a flat membrane material, and can remarkably improve processing capability and efficiency of a membrane bioreactor.
Description
Technical field
The invention belongs to the membrane separation technique field, relate to a kind of hydrophilic macromolecule microporous compound film and preparation method thereof.
Background technology
Membrane bioreactor (MBR) is a kind of new and effective sewage disposal technology, is representing the developing direction of following water technology.The key of membrane bioreactor is a membrane material, and the film pollution can cause the reduction of its disposal ability and efficient.In general, the hydrophily of membrane material is strong more, and its anti-fouling performance is good more.The hydrophily of improving membrane material is to the hydrophobic polymer film, and like PVDF, PE etc., the anti-fouling performance difference is not able to and for it method, and method commonly used is blend or surface modification, and its effect can only be limited.The hydrophilic film material of seeking superior performance is expected to fundamentally solve the pollution problem of membrane material.In addition, the hydrophily of membrane material is good more, and its flux under low pressure is high more, so pollution has double meaning with the reduction film to improving membrane flux to develop the membrane material with superior hydrophilicity.
Summary of the invention
Technical problem to be solved by this invention is to seek a kind of substitute products of dull and stereotyped MBR membrane material, to solve problems such as film anti-fouling performances such as existing dull and stereotyped PVDF, PE are poor, membrane flux is low.
Technical scheme of the present invention realizes in the following manner.
(1) polyvinyl formal being joined mass percent is in 5～30% the hydrochloric acid or aqueous sulfuric acid; Be heated to 40～100 ℃ and make its dissolving; Standing and defoaming, wherein the polyvinyl formal addition is: the mass percent concentration of polyvinyl formal is 8～20% in the feed liquid.
(2) with above-mentioned feed liquid blade coating on polyester non-woven fabric, be immersed in then in 20～50 ℃ the alkaline aqueous solution, be frozen into microporous barrier through being separated.
Described alkaline aqueous solution is the aqueous solution of NaOH or potassium hydroxide, and pH is between 8～11.
This hydrophilic macromolecule microporous compound film is used to make the flat sheet membrane of membrane bioreactor.
The hydrophilic macromolecule that the present invention adopts is the acetalation modifier of polyvinyl alcohol, and its acetalizing degree is 30～70%, in the molecular structure is contain a large amount of hydrophilic functional group-OH, and water insoluble, resistance to water improves greatly.Importantly acetalizing degree is that 30～70% polyvinyl alcohol modification thing can be dissolved in certain density hydrochloric acid or the aqueous sulfuric acid, after this acid feed liquid is met water, because the change of pH, is separated and solidifies.
Inventive point of the present invention is to process casting solution with acidic aqueous solution dissolve polyvinyl alcohol formal, and utilizes the variation of pH value in the system to cause the difference of solubility to create phase separation, and the mechanism that is separated thus prepares microporous barrier.In its preparation process not with an organic solvent, Environmental Safety; Both utilized the hydrophilic functional group-OH on the polyvinyl alcohol structures, solved a difficult problem that is difficult to directly process perforated membrane again with polyvinyl alcohol.
Good effect of the present invention is: utilize the polyvinyl formal that contains hydrophilic functional group-OH to process flat plate porous film; It belongs to the high new membrane material of hydrophily, the microporous compound film that the inventive method makes, and its aperture is controlled in 0.1～0.5 μ m; Under low pressure has higher membrane flux; And the hydrophily of material itself has been given its superior stain resistance, as the flat sheet membrane material, can significantly improve the disposal ability and the efficient of membrane bioreactor.
Description of drawings
Accompanying drawing 1 is the stereoscan photograph in the cross section of embodiment 1 made hydrophilic macromolecule microporous compound film.
Accompanying drawing 2 is the stereoscan photograph on the surface of embodiment 1 made hydrophilic macromolecule microporous compound film.
Accompanying drawing 3 is the stereoscan photograph in the cross section of embodiment 2 made hydrophilic macromolecule microporous compound films.
Accompanying drawing 4 is the stereoscan photograph on the surface of embodiment 2 made hydrophilic macromolecule microporous compound films.
The specific embodiment
The present invention will be described further through following examples.
Embodiment 1.
1, the preparation of casting solution: 100g polyvinyl formal (acetalizing degree is 56%) is joined in 520g 15% aqueous hydrochloric acid solution, be heated to 80 ℃ and make its dissolving, standing and defoaming.
2, knifing: with scraper with the casting solution blade coating on polyester non-woven fabric.
3, solidify: above-mentioned casting solution is immersed in 40 ℃, the sodium hydrate aqueous solution of pH=9, is frozen into microporous barrier through being separated.
Sample is made structure and morphology observation with ESEM after drying, the result is shown in accompanying drawing 1, accompanying drawing 2, the about 20 μ m of top layer thickness, and average membrane pore size is 0.2 μ m.
Under 1.5 meter water column pressure, recording its clear water flux is 28m
3/ m
2D.
Embodiment 2.
1, the preparation of casting solution: 100g polyvinyl formal (acetalizing degree is 60%) is joined in 520g 16% aqueous hydrochloric acid solution, be heated to 80 ℃ and make its dissolving, standing and defoaming.
2, knifing: with scraper with the casting solution blade coating on polyester non-woven fabric.
3, solidify: above-mentioned casting solution is immersed in 25 ℃, the sodium hydrate aqueous solution of pH=10, is frozen into microporous barrier through being separated.
Sample is made structure and morphology observation with ESEM after drying, the result is shown in accompanying drawing 3, accompanying drawing 4, the about 10 μ m of top layer thickness, and average membrane pore size is 0.45 μ m.
Under 1.5 meter water column pressure, recording its clear water flux is 36m
3/ m
2D.
Embodiment 3.
1, the preparation of casting solution: 100g polyvinyl formal (acetalizing degree is 60%) is joined in 700g 12% aqueous sulfuric acid, be heated to 85 ℃ and make its dissolving, standing and defoaming.
2, knifing: with scraper with the casting solution blade coating on polyester non-woven fabric.
3, solidify: above-mentioned casting solution is immersed in 45 ℃, the potassium hydroxide aqueous solution of pH=10.5, is frozen into microporous barrier through being separated.
Under 1.5 meter water column pressure, recording its clear water flux is 32m
3/ m
2D.
Embodiment 4.
1, the preparation of casting solution: 100g polyvinyl formal (acetalizing degree is 52%) is joined in 450g 15% aqueous sulfuric acid, be heated to 90 ℃ and make its dissolving, standing and defoaming.
2, knifing: with scraper with the casting solution blade coating on polyester non-woven fabric.
3, solidify: above-mentioned casting solution is immersed in 40 ℃, the sodium hydrate aqueous solution of pH=9.5, is frozen into microporous barrier through being separated.
Under 1.5 meter water column pressure, recording its clear water flux is 20m
3/ m
2D.
Claims (2)
1. the preparation method of a hydrophilic macromolecule microporous compound film is characterized in that following these steps to:
(1) polyvinyl formal being joined mass percent is in 5～30% the hydrochloric acid or aqueous sulfuric acid; Be heated to 40～100 ℃ and make its dissolving; Standing and defoaming, wherein the polyvinyl formal addition is: the mass percent concentration of polyvinyl formal is 8～20% in the feed liquid;
(2) with above-mentioned feed liquid blade coating on polyester non-woven fabric, be immersed in then in 20～50 ℃ the alkaline aqueous solution, be frozen into microporous barrier through being separated.
2. the preparation method of hydrophilic macromolecule microporous compound film according to claim 1 is characterized in that described alkaline aqueous solution is the aqueous solution of NaOH or potassium hydroxide, and pH is between 8～11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100869963A CN102614787A (en) | 2012-03-29 | 2012-03-29 | Method for preparing hydrophilic macromolecule microporous composite membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100869963A CN102614787A (en) | 2012-03-29 | 2012-03-29 | Method for preparing hydrophilic macromolecule microporous composite membrane |
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| CN102614787A true CN102614787A (en) | 2012-08-01 |
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| CN2012100869963A Pending CN102614787A (en) | 2012-03-29 | 2012-03-29 | Method for preparing hydrophilic macromolecule microporous composite membrane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921312A (en) * | 2012-11-01 | 2013-02-13 | 北京市射线应用研究中心 | Polyvinyl formal filtering membrane and preparation method thereof |
| CN103480283A (en) * | 2013-09-05 | 2014-01-01 | 西安建筑科技大学 | Preparation method of hydrophilic ethylene/vinyl alcohol copolymer composite flat plate ultrafiltration membrane |
| CN105088789A (en) * | 2015-09-22 | 2015-11-25 | 浙江新达经编有限公司 | High-strength and anti-corrosion fabric and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5384880A (en) * | 1976-12-30 | 1978-07-26 | Masanori Kanematsu | Manufacture of polyvinyl formal membrane |
| CN1868573A (en) * | 2005-05-27 | 2006-11-29 | 天津膜天膜工程技术有限公司 | Hydrophilic porous diffusion barrier and its prepn. method |
| CN1973971A (en) * | 2006-12-01 | 2007-06-06 | 北京工业大学 | Prepn process of soiling resistant modified PVA film |
| CN102151496A (en) * | 2011-01-20 | 2011-08-17 | 成都市青白江区富发膜过滤器材有限公司 | Method for preparing polyvinyl formal (PVF) micro-filtration membrane |
-
2012
- 2012-03-29 CN CN2012100869963A patent/CN102614787A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5384880A (en) * | 1976-12-30 | 1978-07-26 | Masanori Kanematsu | Manufacture of polyvinyl formal membrane |
| CN1868573A (en) * | 2005-05-27 | 2006-11-29 | 天津膜天膜工程技术有限公司 | Hydrophilic porous diffusion barrier and its prepn. method |
| CN1973971A (en) * | 2006-12-01 | 2007-06-06 | 北京工业大学 | Prepn process of soiling resistant modified PVA film |
| CN102151496A (en) * | 2011-01-20 | 2011-08-17 | 成都市青白江区富发膜过滤器材有限公司 | Method for preparing polyvinyl formal (PVF) micro-filtration membrane |
Non-Patent Citations (2)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 20090915 周翀 "化学方法对相转化膜结构和性能的影响" 1-2 , 第09期 * |
| 周翀: ""化学方法对相转化膜结构和性能的影响"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921312A (en) * | 2012-11-01 | 2013-02-13 | 北京市射线应用研究中心 | Polyvinyl formal filtering membrane and preparation method thereof |
| CN102921312B (en) * | 2012-11-01 | 2014-08-20 | 北京市射线应用研究中心 | Polyvinyl formal filtering membrane and preparation method thereof |
| CN103480283A (en) * | 2013-09-05 | 2014-01-01 | 西安建筑科技大学 | Preparation method of hydrophilic ethylene/vinyl alcohol copolymer composite flat plate ultrafiltration membrane |
| CN103480283B (en) * | 2013-09-05 | 2015-07-15 | 西安建筑科技大学 | Preparation method of hydrophilic ethylene/vinyl alcohol copolymer composite flat plate ultrafiltration membrane |
| CN105088789A (en) * | 2015-09-22 | 2015-11-25 | 浙江新达经编有限公司 | High-strength and anti-corrosion fabric and preparation method thereof |
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Application publication date: 20120801 |