CN102172481B - Method for preparing separation membrane with composite structure - Google Patents
Method for preparing separation membrane with composite structure Download PDFInfo
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- CN102172481B CN102172481B CN201110067127.1A CN201110067127A CN102172481B CN 102172481 B CN102172481 B CN 102172481B CN 201110067127 A CN201110067127 A CN 201110067127A CN 102172481 B CN102172481 B CN 102172481B
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- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 238000000926 separation method Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003365 glass fiber Substances 0.000 claims abstract description 30
- 239000002033 PVDF binder Substances 0.000 claims abstract description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 9
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000003075 superhydrophobic effect Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- LABLFKLACYYCPD-UHFFFAOYSA-N 12,12-dimethyltridecyl(fluoro)silane Chemical compound CC(CCCCCCCCCCC[SiH2]F)(C)C LABLFKLACYYCPD-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000012784 inorganic fiber Substances 0.000 abstract 1
- 238000003828 vacuum filtration Methods 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 101700004678 SLIT3 Proteins 0.000 description 1
- 102100027339 Slit homolog 3 protein Human genes 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of membrane separation equipment and relates to a method for preparing a separation membrane with a polyvinylidene fluoride (PVDF) compound and inorganic fibrous membrane composite structure. The method comprises: soaking inorganic glass fibers in trimethyldodecylfluorosilane solution for 2 hours at 60 DEG C to obtain hydrophobic glass fiber membrane; and dissolving the PVDF in a dimethyl sulfoxide or tetrahydrofuran solvent to prepare a solution at a concentration of 0.1 to 1g/mL, allowing the solvent to penetrate the hydrophobic glass fiber membrane by means of vacuum filtration, completely washing the solution on the two sides of the glass fiber membrane with the solvent, drying the glass fiber membrane in a vacuum oven at 100 to 150 DEG C, and completely volatilizing the solvent to obtain the separation membrane with the PVDF compound and inorganic fiber composite structure. In the method, the process is simple, the raw material cost is low, and the separation effect is good; and the method is environment-friendly, low in energy consumption and high in safety.
Description
Technical field:
The invention belongs to the membrane separation plant technical field, relate to the preparation method of a kind of Kynoar (PVDF) compound and inorfil film separation membrane with composite structure, comprise film preparation process conditions and separating water and biological butanol.
Background technology:
Membrane separation technique is emerging comprehensive frontier science, relates to the multiple subjects such as hydrodynamics, calorifics, electricity, mass transfer theory, chemical engineering kinetics, physical chemistry of high polymers, macromolecular material, mechanical engineering.Nineteen fifty W.Juda has manufactured experimently out the diactinic amberplex of high selection, has established electrodialytic practical basis.Nineteen sixty, Loeb and Sourirojin make again first reverse osmosis membrane high-effect, that using value is arranged, and indicate the birth of membrane science and technology subject, and from then on, membrane technology obtains rapidly and all sidedly development.Membrane separation technique has many irreplaceable advantages as a kind of advanced person's isolation technics, and its separating effect and processing cost not only depended in the application in water treatment, and inseparable with its advantage.Membrane separation technique is in separating concentration process, and undergoing phase transition do not have the chemical reaction of phase change yet, thereby do not consume phase-change energy, and power consumption is few; In the film separation process, do not need to add other material from the external world, saved raw material and chemicals; In the film separation process, a kind of material is separated, another kind of (or some), and material then is concentrated, and separates and concentratedly carries out simultaneously, thereby can reclaim those valuable physical resources; High selectivity and membrane aperture according to film vary in size, can be with the material of different-grain diameter separately, and therefore make material obtain purifying and don't change original attribute; Membrane separation process can separate at normal temperatures, thereby does not damage heat is had sensitivity and to heat-labile material, and the separation that is highly suitable for medicine preparation, enzyme preparation, fruit juice etc. is concentrated; The membrane separation process strong adaptability, treatment scale is changeable, and operation and easy to maintenance easily is automated control.There is the history of film research and development in nearly 50 years in China; Ro, NF, UF, MF, electrodialysis, liquid film, membrane reactor etc. are researched and developed successfully in succession during this period; and be widely applied to the energy; electronics; petrochemical industry, heavy industry, light industry; the fields such as food and brewery industry and daily life and environmental protection, particularly outstanding in the application of seawater and brackish water desalination and various water and field of waste water treatment.
At present, general diffusion barrier has numerous species, film two classes that are broadly divided into film and the processing gas of treat liquid, the film of treat liquid comprises again microfiltration membranes, milipore filter, NF membrane, reverse osmosis membrane and amberplex etc., patented technology about profit system diffusion barrier aspect has much at present, for example the patent of CN95113319.5 hydrophilic osmotic evaporating and separating membrane and preparation method thereof is with polyvinyl alcohol and hydrophilic copolymers solution blending, then use chemical cross-linking agent crosslinked, utilize the hydrophily of prepared film to come moisture in the extraction system; Patent CN200410018268.4 discloses a kind of acrylonitrile/maleic acid diffusion barrier hydrophilic modification method, this patent is sloughed a hydrone with adjacent two carboxyls in film surface and is formed acid anhydrides under the dehydrating agent effect, utilize the easy reactivity of acid anhydrides and hydroxyl that the hydrophilic macromolecule polyethylene glycol is grafted to the hydrophily that film is improved on the film surface; Patent 200510013564.X discloses a kind of hydrophilic porous diffusion barrier and preparation method thereof by the polyvinyl alcohol film of the method modifications such as acetalation, esterification and etherificate.The characteristics of existing these films are to utilize the hydrophily of polyvinyl alcohol etc. to realize the purpose of water-oil separating, but existing diffusion barrier ubiquity complex structure, and step of preparation process is many, inferior separating effect, cost is high, is difficult for utilizing the shortcomings such as hydrophilic fuel shedding quality of hydrophobic polymer.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seek to provide a kind of preparation method with hydrophobic PVDF compound and inorfil film nano composite structure diffusion barrier, this diffusion barrier is used for the liquid liquid such as biological butanol and water when separating occasion, lower, effective than traditional fractionation process energy consumption, preparation technology is simple, environmental friendliness, safe and reliable, be easy to apply.
To achieve these goals, has the nano-seam gap structure between the fiber of the inorfil film that the present invention relates to and the fiber, PVDF compounds particle is bonded on the glass fibre that forms the nanometer slit, consist of super-hydrophobic separating interface, hydrone can not pass through the nanometer slit, thereby makes water and separate with the miscible organic solvent of water; First the glass fibre of mineral-type is soaked in weight percent concentration is 5% trimethoxy dodecyl silicon fluoride solution, under 60 ℃ of conditions, soak the glass fibre membrane that obtained hydrophobization in 2 hours; PVDF is dissolved in dimethyl sulfoxide (DMSO) or the tetrahydrofuran solvent, be made into the solution that concentration is 0.1-1g/mL, then make solvent see through the glass fibre membrane of hydrophobization by the mode that filters, again the trimethoxy dodecyl silicon fluoride solution of glass fibre membrane both sides is rinsed well with dimethyl sulfoxide (DMSO) or tetrahydrofuran solvent, to prevent into the PVDF film; Then the glass fibre membrane of preparation is placed in the vacuum drying oven under the 100-150 ℃ of condition dry 10-30 hour, makes the volatilization of dimethyl sulfoxide (DMSO) or tetrahydrofuran solvent totally namely get PVDF compound and inorfil separation membrane with composite structure; During use the profit liquid system of required separation is poured on a side of film, exerting pressure at opposite side to reach the effect of separating profit.
The present invention compared with prior art, its preparation method technique is simple, the required cost of raw material is low, good separating effect, environmental friendliness, energy consumption is low, high safety, and can be according to the butanol concentration that will separate different or desired separation purity or the speed concentration of regulating the PVDF compounds, make suitable diffusion barrier; For requiring the higher fluid of purity, composite membrane that can be by making the different proportion pore size produces a desired effect by the mode of multi-stage separation.
Description of drawings:
Fig. 1 is the structural principle schematic diagram of the inorfil separation membrane with composite structure that the present invention relates to, comprises the nanometer slit 3 between inorfil 1, PVDF compounds 2 and the glass fibre.
Fig. 2 is the scanning electron microscope (SEM) photograph of the inorfil film that the present invention relates to.
Fig. 3 is the scanning electron microscope (SEM) photograph of the separation membrane with composite structure for preparing of the present invention, and the PVDF bead is embedded between the inorfil, reaches the effect of Separation of Organic and water by its surperficial hydrophobic effect.
The specific embodiment:
Also the invention will be further described by reference to the accompanying drawings below by embodiment.
It is in 5% the trimethoxy dodecyl silicon fluoride solution that the present embodiment is immersed in weight percent concentration with an amount of inorganic glass fiber, soaks two hours under 60 ℃ of conditions, can obtain the glass fibre of hydrophobization; PVDF is dissolved in is made into the solution that weight percent concentration is 0.1-1g/mL in dimethyl sulfoxide (DMSO) or the tetrahydrofuran solvent, then make solvent see through the glass fibre membrane of hydrophobization by the mode that filters, the solution of glass fibre membrane both sides is clean with solvent washing, prevent that it from forming the PVDF film; Then the film of preparation is placed in the vacuum drying oven under the 100-150 ℃ of condition dry 10-30 hour, makes solvent evaporates totally namely get the product separation membrane with composite structure.
Embodiment 1:
Soaking glass fibre in weight percent concentration is in 5% the trimethoxy dodecyl silicon fluoride solution 2 hours, again PVDF is dissolved in the dimethyl sulfoxide solvent, be made into the PVDF solution of 0.5mg/mL, make PVDF solution see through glass fibre membrane by the mode that filters, the solution on glass fibre membrane surface is rinsed well with dimethyl sulfoxide (DMSO), be placed on 150 ℃ of lower dry 20h in the vacuum drying oven, prepared separation membrane with composite structure is 0.5-2L/m to the flux of pure water
2H (0.1MPa) is 25.6-120L/m to the flux of pure n-butanol
2H (0.1MPa) has good separating effect to water and the miscible solvent of n-butanol of moisture 10%-70%, and separating degree is more than 99%.
Embodiment 2:
Soaking glass fibre in weight percent concentration is in 5% the trimethoxy dodecyl silicon fluoride solution 2 hours, again PVDF is dissolved in the oxolane, be made into the solution of 1mg/mL, make PVDF solution see through the tunica fibrosa of aluminium oxide by the mode that filters, the solution on film surface is rinsed well with dimethyl sulfoxide (DMSO), 120 ℃ of lower dry 24h in the vacuum drying oven, prepared film is 0.2-1L/m2h (0.1MPa) to the penetrating rate of pure water, penetrating rate to pure normal propyl alcohol is 90-150L/m2h (0.1MPa), penetrating rate to pure n-butanol is 50-140L/m2h (0.1MPa), and the miscible separated from solvent degree of the solvent that the water of moisture 10%-80% and n-butanol are miscible or the water of moisture 10%-50% and n-butanol is more than 98%.
Embodiment 3:
Soaking glass fibre in weight percent concentration is in 5% the trimethoxy dodecyl silicon fluoride solution 2 hours, again PVDF is dissolved in the dimethyl sulfoxide solvent, be made into the PVDF solution of 0.5mg/mL, make PVDF solution see through glass fibre membrane by the mode that filters, the solution on glass fibre membrane surface is rinsed well with dimethyl sulfoxide (DMSO), be placed on 100 ℃ of lower dry 30h in the vacuum drying oven, prepared separation membrane with composite structure is 0.5-2L/m to the flux of pure water
2H (0.1MPa) is 25.6-120L/m to the flux of pure n-butanol
2H (0.1MPa) has good separating effect to water and the miscible solvent of n-butanol of moisture 10%-70%, and separating degree is more than 99%.
Embodiment 4:
The present embodiment uses prepared separation membrane with composite structure to carry out the miscible solution of liquid liquid class when separating, first the miscible liquid system of profit class to be separated is poured on the side of separation membrane with composite structure, apply uniform pressure by machinery or manual type on its another side, the two that can reach during profit is miscible is effectively separated.
Claims (1)
1. the preparation method of a separation membrane with composite structure, it is characterized in that first glass fibre with mineral-type soaks in weight percent concentration is 5% trimethoxy dodecyl silicon fluoride solution, soaks the glass fibre membrane that obtained hydrophobization in 2 hours under 60 ℃ of conditions; PVDF is dissolved in dimethyl sulfoxide (DMSO) or the tetrahydrofuran solvent, be made into the solution that concentration is 0.5mg/mL or 1mg/mL, then the mode by suction filtration makes solvent see through the glass fibre membrane of hydrophobization, again the trimethoxy dodecyl silicon fluoride solution of glass fibre membrane both sides is rinsed well with dimethyl sulfoxide (DMSO) or tetrahydrofuran solvent, to prevent into the PVDF film; Then the glass fibre membrane of preparation is placed in the vacuum drying oven under the 100-150 ℃ of condition dry 10-30 hour, makes the volatilization of dimethyl sulfoxide (DMSO) or tetrahydrofuran solvent totally namely get PVDF compound and inorfil separation membrane with composite structure; During use the liquid system that will separate is poured on a side of film, exerting pressure at opposite side to reach the effect of separation; Has the nano-seam gap structure between the glass fibre of the inorfil film of the diffusion barrier of its preparation, PVDF compounds particle is bonded on the glass fibre that forms the nanometer slit, consist of super-hydrophobic separating interface, hydrone can not pass through the nanometer slit, thereby makes water and separate with the miscible organic solvent of water.
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CN103551053B (en) * | 2013-11-01 | 2015-07-29 | 无锡海特新材料研究院有限公司 | A kind of preparation method of hydrophobic composite membrane |
CN112705052B (en) * | 2020-11-19 | 2022-06-21 | 浙江理工大学 | Glass fiber membrane for oil-water emulsion separation and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1683059A (en) * | 2005-03-03 | 2005-10-19 | 上海一鸣过滤技术有限公司 | Reinforced hollow fiber super filter film and its preparing method |
CN101357303A (en) * | 2008-09-25 | 2009-02-04 | 杭州洁弗膜技术有限公司 | Preparation method of polyvinylidene fluoride hollow fiber composite microporous film with strong interface binding power |
CN101909715A (en) * | 2008-01-16 | 2010-12-08 | 阿斯特罗姆公司 | Coalescence media for separation of water-hydrocarbon emulsions |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN1683059A (en) * | 2005-03-03 | 2005-10-19 | 上海一鸣过滤技术有限公司 | Reinforced hollow fiber super filter film and its preparing method |
CN101909715A (en) * | 2008-01-16 | 2010-12-08 | 阿斯特罗姆公司 | Coalescence media for separation of water-hydrocarbon emulsions |
CN101357303A (en) * | 2008-09-25 | 2009-02-04 | 杭州洁弗膜技术有限公司 | Preparation method of polyvinylidene fluoride hollow fiber composite microporous film with strong interface binding power |
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