CN101444703A - Composite film for film bioreactor and method for preparing same - Google Patents
Composite film for film bioreactor and method for preparing same Download PDFInfo
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- CN101444703A CN101444703A CN 200810162858 CN200810162858A CN101444703A CN 101444703 A CN101444703 A CN 101444703A CN 200810162858 CN200810162858 CN 200810162858 CN 200810162858 A CN200810162858 A CN 200810162858A CN 101444703 A CN101444703 A CN 101444703A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M33/00—Means for introduction, transport, positioning, extraction, harvesting, peeling or sampling of biological material in or from the apparatus
- C12M33/14—Means for introduction, transport, positioning, extraction, harvesting, peeling or sampling of biological material in or from the apparatus with filters, sieves or membranes
Abstract
The invention provides a composite film for film bioreactor, mainly comprising a porous material supporting layer and an organic film layer which is attached to the surface of the supporting layer; wherein, the porous material supporting layer is formed by sintering one or more than two polymer materials as follows: polytetrafluor ethylene, polyethylene, polypropylene, polymethylpentenes and polystyrene; the film material of the organic film layer consists of one or more than two polymers as follows: polyether sulfone, polysulphones, polyacrylic acid ester, polybutene, polyamides, PEEK, polycellulose ester, polyacrylonitrile, polyvinyl alcohol, polystyrene, polyphenylene oxide, polyester carbonates, polyurethanes, polyacrylate, polyoxyethylene, and polysiloxanes. The composite film has high supporting strength, good mechanical stability, stable structural shape, convenient cleaning and replacement, and can be applicable to various high-pressure environments, with the surface film not easy to be fallen and damaged.
Description
(1) technical field
The present invention relates to a kind of composite membrane that is used for membrane bioreactor and preparation method thereof.
(2) background technology
Membrane bioreactor (MBR) is to be catalyst with enzyme, microorganism or animal and plant cell, carry out chemical reaction or bio-transformation, relying on ultrafiltration or microfiltering separation film constantly to isolate product simultaneously and hold back catalyst and the device that reacts, is a kind of new and effective technology that is combined with membrane separation technique by course of reaction.Membrane bioreactor can not only can be used for sewage disposal and middle water reuse, can also be used to promote chemistry or biological respinse.Membrane material is the key of membrane Bio-reactor Technology, also is core component.Two kinds of the organic film of film of membrane bioreactor employing at present and inoranic membranes.Organic film mainly contains hollow-fibre membrane, and it is little to have floor space, good purification, and than advantages such as the inoranic membrane cost of investment are low, shortcoming is that film is easy to pollute the cleaned and changed difficulty of film.Inoranic membrane has high temperature high voltage resistant, and anti-chemistry is good, and mechanical strength is good, and shortcoming is to make the process difficulty, and the cost height has limited its application on membrane bioreactor market.What adopt on the present Chinese domestic market all is organic film-bioreactor.A kind of leaf filter that flat sheet membrane directly is compound in supporting layer and forms has been invented by Kubo field company thus, and this filter has characteristics easy to clean, but insufficient strength, and the top layer film comes off easily and breakage, can not adapt to the high pressure working environment.
(3) summary of the invention
The object of the invention provides a kind of easy to clean, high stability, even pore distribution and intensity original text, top layer film difficult drop-off and damaged composite membrane and preparation method thereof.
The technical solution used in the present invention is:
A kind of composite membrane that is used for membrane bioreactor mainly comprises porous material supporting layer and the organic thin film layer that is attached to described support layer surface; Described porous material supporting layer is formed by one of following or wherein two or more macromolecular material sintering: polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polymethylpentene, polystyrene, preferably polyethylene, polypropylene, polytetrafluoroethylene (PTFE), described macromolecular material molecular weight is greater than 10000; The membrane material of described organic thin film layer is one of following or wherein two or more high molecular polymer: polyether sulfone, polysulfones, polyacrylate, polybutene, polyamide, polyether-ether-ketone, poly-cellulose esters, polyacrylonitrile, polyvinyl alcohol, polystyrene, polyphenylene oxide, Merlon, polyurethane, polyacrylate, PEO, polysiloxanes, preferred Kynoar, polyether sulfone, polyether-ketone, polyacrylonitrile and polyvinyl alcohol.Described organic thin film layer in film-forming process, also needs to add additive by being that the preparation liquid that main component is prepared according to a conventional method obtains through curtain coating with above-mentioned high molecular polymer usually.
Described porous material supporting layer thickness is 2～20mm, and porosity is 20～80%, and the aperture is 5～500 μ m.Described organic film layer thickness is 5～5000 μ m.
Preferably, the membrane material of described organic thin film layer is made up of with the quality proportioning of 100:0～30 (be preferably 100: 10～20) high molecular polymer and additive, and described additive is one of following or wherein two or more mixture: polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polybutylcyanoacrylate, polyacrylate-polyurethane, lithium chloride, calcium chloride, lithium nitrate, calcium nitrate, ethanol, ethylene glycol, glycerine, acetone, butanone, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid or water.
The present invention obtains selective membrane by curtain coating on the rigidity porous support layer, this flat composite membrane has compared with traditional organic film a series of advantage is arranged: the support strength height, and mechanical stability is good, and Mechanical Builds is stable, cleaned and changed convenience.Its mechanical performance is determined that by supporting layer its separating effect can apply the top layer film in different apertures mainly by the organic film decision in top layer according to practical application on porous support layer.Rigidity porous material supporting layer has the characteristics of high porosity, and a small amount of preparation liquid is penetrated into and makes formed top layer film closely attached on the supporting layer in the hole, and is incrust.Compare with directly compound flat sheet membrane, have the intensity height, therefore top layer film difficult drop-off and damaged advantage can be used in various elevated pressures environment.
The invention still further relates to the preparation method of described composite membrane, described method comprises:
(1) preparation porous material supporting layer: one or more macromolecular materials are mixed by a certain percentage, under the temperature that is higher than described macromolecular material fusing point, carry out sintering according to a conventional method, obtain described porous material supporting layer;
Concrete, sintering method is as follows: one or more macromolecular materials are mixed by a certain percentage, and mixed proportion is determined according to actual needs, packs into and coats in the mould of releasing agent, puts into the sintering furnace sintering; Sintering temperature should be higher than the fusing point of macromolecular material.
After finishing, takes out sintering mould, cooling, and goods are taken out in die sinking, obtain described porous material supporting layer.Described releasing agent is conventional releasing agent, can be one of following: wax, dimethicone, metallic stearate, polyvinyl alcohol, fluorine-containing oligomer and polyolefin, preferred dimethicone.
(2) high molecular polymer, additive are dissolved in the solvent, standing and defoaming obtains the preparation liquid of high molecular polymer mass content 4～30%, additive mass content 0～9%;
Described additive is one of following or wherein two or more mixture: polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polybutylcyanoacrylate, polyacrylate-polyurethane, lithium chloride, calcium chloride, lithium nitrate, calcium nitrate, ethanol, ethylene glycol, glycerine, acetone, butanone, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid or water;
Described solvent is one of following or wherein two or more mixtures: N ', N-dimethylacetylamide, N ', dinethylformamide, 1-Methyl-2-Pyrrolidone, acetone, ethanol, normal propyl alcohol, n-butanol, pentane, cyclohexane, n-hexane, acetate, ethyl acetate, ether, diox, oxolane, methyl-sulfoxide, benzene,toluene,xylene, water;
(3) preparation liquid is scraped on the porous material supporting layer, caused phase inversion through solution and prepare described composite membrane.
Concrete, described step (3) is as follows: preparation liquid is being scraped on the porous material supporting layer with blade applicator, under 25 ℃ of temperature, relative humidity 64% condition, after in air, leaving standstill 3min, porous material supporting layer behind the knifing tilted to put into 25 ℃ deionized water coagulating bath, take out behind the 2h, natural air drying promptly gets described composite membrane.
Can add particle beams radiation or low temperature plasma irradiation step in the preparation process of high stability composite membrane of the present invention, the effect by reacting gas can strengthen interface interaction.According to the final use of high stability composite membrane, preparation process of the present invention not only can be omitted also can be increased, and can change the order of each preparation process.
Beneficial effect of the present invention is mainly reflected in: composite membrane support strength height of the present invention, and mechanical stability is good, and Mechanical Builds is stable, cleaned and changed convenience, top layer film difficult drop-off and breakage are applicable to various hyperbaric environments.
(4) description of drawings
Fig. 1 is the section electromicroscopic photograph of the compound three-dimensional high stability composite membrane of rigidity porous material support layer material and polyvinylidene fluoride film;
The electromicroscopic photograph of the top layer film of the composite membrane that Fig. 2 makes for the present invention.
(5) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
(1) rigidity porous material supporting layer prepares: the 32g polyethylene is packed into coat in the mould of silicone oil mold release agent, mould specification is 10cm * 10cm * 0.45cm, puts into the sintering furnace sintering.After finishing, do not take out sintering mould, cooling.Open mould, take out goods.
(2) preparation liquid preparation: 152g places the 250mL there-necked flask with N ' N-dimethylacetylamide (DMAc), add Kynoar 40g, polyvinylpyrrolidone 8g, 60 ℃ of heating stirring and dissolving, be configured to the preparation liquid of 20wt% (Kynoar mass content), the sealing and standing deaeration of spending the night obtains preparation liquid.
(3) with blade applicator knifing on above-mentioned rigidity porous material supporting layer.25 ℃ of system film room temperatures, humidity be in relative humidity 64%, in air, leave standstill 3min after, rigidity porous material supporting layer behind the knifing is tilted to put into the deionized water coagulating bath, and coagulation bath temperature is 25 ℃, takes out behind the 2h, natural air drying promptly gets high stability composite membrane of the present invention.
Electronic Speculum picture such as Fig. 1 of the section of the high stability composite membrane that obtains by above-mentioned approach, Electronic Speculum picture such as Fig. 2 of its top layer film.As seen from Figure 1, be made up of supporting layer and two kinds of structures of top layer thin layer with the compound film of high strength that the present invention makes, the top layer thin layer is attached on the supporting layer, and the thickness of its mesexine thin layer is at 50～100 μ m.As seen from Figure 2, the aperture of top layer thin layer is 0.5 μ m, is fit to use various water treatment procedures.According to the characteristics that its three-dimensional stability, easy cleaning, flux easily recover, this composite film material is particularly useful for membrane bioreactor.Because the aperture of rigidity porous material supporting layer is 5～500 μ m, therefore can ignore, and its rigid structure, excellent mechanical intensity are given the three-dimensional stability of NEW TYPE OF COMPOSITE membrane material height with respect to its process resistance of thin layer.
Embodiment 2:
Be applicable to the composite membrane of membrane bioreactor according to the preparation of similarly to Example 1 method, except replacing 20wt% Kynoar preparation liquid with the 17wt% Kynoar as preparation liquid, the additives polyvinyl alcohol quality is the 10wt% of Kynoar quality.
Embodiment 3:
Be applicable to the composite membrane of membrane bioreactor according to the preparation of similarly to Example 1 method, except replacing polyethylene as macromolecular material by polyethylene and polypropylene with mass ratio 80:20 blend, sintering temperature is made as 220 ℃.
Embodiment 4:
Be applicable to the composite membrane of membrane bioreactor according to method preparation similarly to Example 1, except replacing polyethylene as macromolecular material with mass ratio 80:20 blend by polyethylene and polypropylene, sintering temperature is made as 220 ℃, the 17wt% Kynoar replaces 20wt% Kynoar preparation liquid as preparation liquid, and additive glycerine quality is the 10wt% of Kynoar quality.The performance of film is listed in the table 1.
Table 1
| Supporting layer thickness (mm) | Thin layer thickness (μ m) | Supporting layer voidage (%) | Thin layer average pore size (μ m) | Composite membrane water flux (L/m 2·h) | |
| Embodiment 1 | 4.38 | 67 | 37.8 | 0.54 | 42 |
| Embodiment 2 | 4.37 | 52 | 39.2 | 1.02 | 67 |
| Embodiment 3 | 4.41 | 65 | 46.5 | 0.43 | 33 |
| Embodiment 4 | 4.46 | 55 | 44.3 | 0.93 | 50 |
The concrete assay method of table 1 data is as follows:
(1) thickness and average pore size
Supporting layer thickness is measured with feeler, and thin layer thickness and mean outside diameter adopt the light microscope of band scale to measure.
(2) supporting layer porosity
Support layer material is cut into the square block of 1.0cm * 1.0cm, and scales/electronic balance weighing soaked 2 days in silicone oil, took out, and wiped surface adhesion silicone oil, scales/electronic balance weighing rapidly gently.
M
0: square block weight (g) before silicone oil soaks;
M
1: silicone oil soaks back square block weight (g);
P: silicone oil density (0.965g/cm
3);
V: square block volume (cm
3)
(3) composite membrane water flux
The water flux of composite membrane is with under the normal pressure, the running water volume characterization that the unit interval unit are sees through.
Claims (8)
1. a composite membrane that is used for membrane bioreactor is made up of porous material supporting layer and the organic thin film layer that is attached to described support layer surface; Described porous material supporting layer is formed by one of following or wherein two or more macromolecular material sintering: polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polymethylpentene, polystyrene; The membrane material of described organic thin film layer comprises one of following or wherein two or more high molecular polymers: polyether sulfone, polysulfones, polyacrylate, polybutene, polyamide, polyether-ether-ketone, poly-cellulose esters, polyacrylonitrile, polyvinyl alcohol, polystyrene, polyphenylene oxide, Merlon, polyurethane, polyacrylate, PEO, polysiloxanes.
2. composite membrane as claimed in claim 1 is characterized in that described porous material supporting layer thickness is 2～20mm, and porosity is 20～80%, and the aperture is 5～500 μ m.
3. composite membrane as claimed in claim 1 is characterized in that described organic film layer thickness is 5～5000 μ m.
4. composite membrane as claimed in claim 1 is characterized in that described porous material supporting layer is formed by one of following or wherein two or more macromolecular material sintering: polyethylene, polypropylene, polytetrafluoroethylene (PTFE).
5. composite membrane as claimed in claim 1, the membrane material that it is characterized in that described organic thin film layer are one of following or wherein two or more high molecular polymers: Kynoar, polyether sulfone, polyether-ketone, polyacrylonitrile, polyvinyl alcohol.
6. composite membrane as claimed in claim 1, the membrane material that it is characterized in that described organic thin film layer is made up of with the quality proportioning of 100:0～30 high molecular polymer and additive, and described additive is one of following or wherein two or more mixture: polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polybutylcyanoacrylate, polyacrylate-polyurethane, lithium chloride, calcium chloride, lithium nitrate, calcium nitrate, ethanol, ethylene glycol, glycerine, acetone, butanone, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid or water.
7. the preparation method of a composite membrane as claimed in claim 1, described method comprises:
(1) preparation porous material supporting layer: one or more macromolecular materials are mixed by a certain percentage, under the temperature that is higher than described macromolecular material fusing point, carry out sintering, obtain described porous material supporting layer;
(2) high molecular polymer, additive are dissolved in the solvent, standing and defoaming obtains the preparation liquid of high molecular polymer mass content 4～30%, additive mass content 0～9%; Described additive is one of following or wherein two or more mixture: polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polybutylcyanoacrylate, polyacrylate-polyurethane, lithium chloride, calcium chloride, lithium nitrate, calcium nitrate, ethanol, ethylene glycol, glycerine, acetone, butanone, sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid or water; Described solvent is one of following or wherein two or more mixtures: N ', N-dimethylacetylamide, N ', dinethylformamide, 1-Methyl-2-Pyrrolidone, acetone, ethanol, normal propyl alcohol, n-butanol, pentane, cyclohexane, n-hexane, acetate, ethyl acetate, ether, diox, oxolane, methyl-sulfoxide, benzene,toluene,xylene, water;
(3) preparation liquid is scraped on the porous material supporting layer, caused phase inversion through solution and prepare described composite membrane.
8. method as claimed in claim 6, it is characterized in that described step (3) is as follows: preparation liquid is being scraped on the porous material supporting layer with blade applicator, under 25 ℃ of temperature, relative humidity 64% condition, after in air, leaving standstill 3min, porous material supporting layer behind the knifing tilted to put into 25 ℃ deionized water coagulating bath, take out behind the 2h, natural air drying promptly gets described composite membrane.
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| CN 200810162858 CN101444703B (en) | 2008-12-05 | 2008-12-05 | Composite film for film bioreactor and method for preparing same |
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| CN 200810162858 CN101444703B (en) | 2008-12-05 | 2008-12-05 | Composite film for film bioreactor and method for preparing same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670243B (en) * | 2009-09-30 | 2011-11-09 | 浙江工业大学 | Preparation method of polyethylene hollow fiber membrane with aperture in gradient distribution |
| CN102886213A (en) * | 2011-07-22 | 2013-01-23 | 三星电子株式会社 | Separation membrane, method of manufacturing the separation membrane, and water processing device comprising the separation membrane |
| CN103421262A (en) * | 2013-08-22 | 2013-12-04 | 成都英德生物医药设备有限公司 | High-molecular polymer composite suitable for bioreactor and method for manufacturing high-molecular polymer composite |
| CN104411389A (en) * | 2012-06-26 | 2015-03-11 | 富士胶片制造欧洲有限公司 | Gas separation membrane with intermixed layers |
| CN110280138A (en) * | 2019-07-23 | 2019-09-27 | 费特膜(北京)科技有限公司 | A kind of disc tube reverse osmosis (dt-ro) film packet element |
| CN110430936A (en) * | 2017-03-24 | 2019-11-08 | 三菱制纸株式会社 | Semi-transparent film support |
| CN110713253A (en) * | 2019-10-11 | 2020-01-21 | 湖南叶之能科技有限公司 | Bioreactor membrane and preparation process |
| WO2020087761A1 (en) * | 2018-10-31 | 2020-05-07 | 中国石油大学(华东) | Polyurethanee/polyvinylidene fluoride composite film for extracting organic sulfide from naphtha and preparation method therefor |
| CN114832794A (en) * | 2022-04-29 | 2022-08-02 | 国网河北省电力有限公司电力科学研究院 | Novel adsorption filtering material and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI317363B (en) * | 2005-05-31 | 2009-11-21 | Univ Chung Yuan Christian | Composite membranes containing polytetrafluoroethylene and method for forming the same |
| CN1978036A (en) * | 2005-12-06 | 2007-06-13 | 浙江工商大学 | Method for preparing polyuinyl alcohol/polyamide |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670243B (en) * | 2009-09-30 | 2011-11-09 | 浙江工业大学 | Preparation method of polyethylene hollow fiber membrane with aperture in gradient distribution |
| CN102886213A (en) * | 2011-07-22 | 2013-01-23 | 三星电子株式会社 | Separation membrane, method of manufacturing the separation membrane, and water processing device comprising the separation membrane |
| CN104411389A (en) * | 2012-06-26 | 2015-03-11 | 富士胶片制造欧洲有限公司 | Gas separation membrane with intermixed layers |
| CN104411389B (en) * | 2012-06-26 | 2017-04-12 | 富士胶片制造欧洲有限公司 | Gas separation membrane with intermixed layers |
| CN103421262A (en) * | 2013-08-22 | 2013-12-04 | 成都英德生物医药设备有限公司 | High-molecular polymer composite suitable for bioreactor and method for manufacturing high-molecular polymer composite |
| CN103421262B (en) * | 2013-08-22 | 2015-09-09 | 成都英德生物医药设备有限公司 | A kind of polymer composite material being applicable to bio-reactor and preparation method thereof |
| CN110430936A (en) * | 2017-03-24 | 2019-11-08 | 三菱制纸株式会社 | Semi-transparent film support |
| WO2020087761A1 (en) * | 2018-10-31 | 2020-05-07 | 中国石油大学(华东) | Polyurethanee/polyvinylidene fluoride composite film for extracting organic sulfide from naphtha and preparation method therefor |
| CN110280138A (en) * | 2019-07-23 | 2019-09-27 | 费特膜(北京)科技有限公司 | A kind of disc tube reverse osmosis (dt-ro) film packet element |
| CN110713253A (en) * | 2019-10-11 | 2020-01-21 | 湖南叶之能科技有限公司 | Bioreactor membrane and preparation process |
| CN114832794A (en) * | 2022-04-29 | 2022-08-02 | 国网河北省电力有限公司电力科学研究院 | Novel adsorption filtering material and preparation method and application thereof |
| CN114832794B (en) * | 2022-04-29 | 2023-09-05 | 国网河北省电力有限公司电力科学研究院 | Adsorption filter material and preparation method and application thereof |
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