CN107899437A - A kind of high-performance water-oil separationg film based on interfacial polymerization and preparation method thereof - Google Patents
A kind of high-performance water-oil separationg film based on interfacial polymerization and preparation method thereof Download PDFInfo
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- CN107899437A CN107899437A CN201711163997.2A CN201711163997A CN107899437A CN 107899437 A CN107899437 A CN 107899437A CN 201711163997 A CN201711163997 A CN 201711163997A CN 107899437 A CN107899437 A CN 107899437A
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- 238000012695 Interfacial polymerization Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims abstract description 13
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002346 layers by function Substances 0.000 claims abstract description 7
- 229920006159 sulfonated polyamide Polymers 0.000 claims abstract description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 60
- 238000000108 ultra-filtration Methods 0.000 claims description 15
- 238000007654 immersion Methods 0.000 claims description 11
- 229920006393 polyether sulfone Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 241000255964 Pieridae Species 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- JSHJJLQJRLNBBA-UHFFFAOYSA-N 2-amino-3-chlorophenol Chemical compound NC1=C(O)C=CC=C1Cl JSHJJLQJRLNBBA-UHFFFAOYSA-N 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 2
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 abstract description 7
- 230000004907 flux Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000010148 water-pollination Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 1
- 229920002647 polyamide Polymers 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 64
- 235000019198 oils Nutrition 0.000 description 32
- 238000001035 drying Methods 0.000 description 18
- 235000019484 Rapeseed oil Nutrition 0.000 description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
- 239000004519 grease Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- RXCMFQDTWCCLBL-UHFFFAOYSA-N 4-amino-3-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(N)=C(O)C=C(S(O)(=O)=O)C2=C1 RXCMFQDTWCCLBL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- -1 o-phthaloyl chloride Chemical compound 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a kind of high-performance water-oil separationg film based on interfacial polymerization, belong to separation membrane material technical field.The film is made of nonwoven layer, porous support layer and sulfonated polyamide functional layer, by selecting the activated monomer with sulfonic acid group to be used as water phase, acyl chlorides monomer, using the method for interfacial polymerization, substantial amounts of sulfonic acid group is introduced into polyamide and obtains hydrophilic and oleophobic ultrathin functional layer as oil phase.The seperation film has the characteristics of standby NF membrane and hydrophily water-oil separationg film concurrently, possesses high osmosis and high separability, at the same time can separate small-molecular emulsifier and oil from oil hydrosol, while also possess higher flux under low pressure.The method for separating and preparing is simple, is easy to industrialization continuity production.
Description
Technical field
The invention belongs to separation membrane material technical field, and in particular to a kind of high-performance grease point based on interfacial polymerization
From film and preparation method thereof.
Background technology
The a large amount of oily waste waters produced by industries such as oil, chemical industry, steel, food processings are a kind of important pollution sources,
The COD (COD) of oily waste water is very high, if directly being discharged without effective processing, can cause serious environmental pollution with
Ecological disruption.Compared using embrane method processing oily waste water with conventional method, it is not necessary to add any other reagent, equipment and operation
Mode is all very simple, has very big economic advantages.Composite separating film as one of most important developing direction in membrane science, it
It is made of nonwoven layer, porous support layer and Core Feature layer.Core Feature layer is prepared by interfacial polymerization more, preparation process letter
Single, quick, polymerisation can be completed at normal temperatures and pressures, be that one kind is easy to industrialized preparation method.
Have the substantial amounts of patent report preparation method of hydrophily water-oil separationg film, such as Application No. at present
The patents such as CN201310224027.4, CN201310487811.4, CN201410692535.X.Although separation process is simple, can
The separation of grease is realized by gravity.But preparation process is complicated, the polymer being related to is more, is unfavorable for industrialized continuous raw
Production.Secondly separative efficiency is not high, does not have good separating capacity especially for the stabilization oil hydrosol with emulsifying agent.As specially
Sharp application number CN201410692535.X carries out alkali process to commodity Vingon, its surface is produced double bond, then basis
Sulfydryl-epoxy and sulfydryl-alkene addition reaction form one layer of hydrogel in commodity film surface, reach super hydrophilic property, the film
There is good separating capacity to grease dispersion liquid.
But in actual application process, the component of oily waste water is sufficiently complex.Particularly some special constructions have breast
The introducing of the impurity of change effect can cause oily waste water to become the aqueous emulsion of stable dispersion, this causes the processing of such oily waste water
Become more difficult.Common commodity NF membrane can have this kind of small-molecular emulsifier good separating capacity, but its function
Rotating fields hydrophily is poor, bad as water-oil separationg film permeance property.How its sieve performance to small molecule same is kept
When, the hydrophily of functional layer is greatly improved, is to put forward high performance key point.
The content of the invention
It is an object of the invention to solve the defect of prior art and provide a kind of high-performance grease based on interfacial polymerization
Seperation film and preparation method thereof, suitable for the quick separating of the oil hydrosol of small-molecular emulsifier.
The present invention is achieved by the following technical solutions：
A kind of high-performance water-oil separationg film based on interfacial polymerization, by nonwoven layer, porous ultra-filtration membrane supporting layer and
Sulfonated polyamide functional layer forms.
The porous ultra-filtration membrane supporting layer is：Polysulfones, polyether sulfone, polyacrylonitrile, Kynoar or polyvinyl chloride.
The sulfonated polyamide functional layer is by the activated monomer with sulfonic acid group as water phase, and acyl chlorides monomer is as oil
Phase, is prepared using the method for interfacial polymerization.
The activated monomer with sulfonic acid group is：2,2'- disulfonic acids benzidine, 4- amino -2'- nitro hexichol
Amine -4'- sulfonic acid, 5- amino -2- (4- methoxybenzenes amido) benzene sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid sodium, catechol -3,
5- sodium disulfonates, 1- amino-8-naphthol -4- sulfonic acid, Ortho-Aminophenol -4- sulfonic acid, 6- nitros-Ortho-Aminophenol -4- sulphurs and 4-
Any one or a few mixture in chloro- Ortho-Aminophenol -6- sulfonic acid.
The acyl chlorides monomer is：Pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, o-phthaloyl chloride, m-phthaloyl chloride
With one or more of mixtures in four acyl chlorides of biphenyl.
Second object of the present invention is to provide a kind of preparation side of the high-performance water-oil separationg film based on interfacial polymerization
Method, comprises the following steps：
(1) oil, the preparation of water phase：Aqueous phase monomers are soluble in water, PH=8~11 are adjusted using PH conditioning agents, stirring is equal
Water phase is obtained after even；Acyl chlorides monomer is dissolved in organic solvent and obtains oil phase；
(2) more porous ultrafiltration membranes are immersed in the water phase of step (1) preparation, the concentration of aqueous phase monomers is 0.1~10wt%, leaching
1s~1h is steeped, is air-dried after taking-up, up to filter membrane A；
(3) to be reacted in the oil phase for obtaining filter membrane A immersion steps (1), the concentration of oil phase monomer is 0.01~10wt%,
Reaction time is 1s~10h, and reaction temperature is 5~40 DEG C, up to filter membrane B；
(4) filter membrane B is obtained into high-performance water-oil separationg film after 40~90 DEG C of hot water clean.
Water phase PH conditioning agents described in step (1) for sodium hydroxide, potassium hydroxide, sodium acid carbonate, sodium carbonate, potassium carbonate and
Any one or a few mixture in triethylamine.
The solvent of acyl chlorides monomer described in step (1) is any one in n-hexane, hexamethylene, normal heptane or normal octane
Or several mixture.
Water-oil separationg film obtained by the present invention, in 0.5Mpa, the feed water rapeseed oil containing 1000ppm or castor oil,
0.1% dodecyl sodium sulfate, temperature are to be tested at 25 DEG C, and separative efficiency is more than 98%, and water flux is in more than 15GFD.
Compared with prior art, beneficial effects of the present invention
1st, the film is provided simultaneously with the characteristics of nanofiltration and super hydrophilic film, has to grease particular with the grease of emulsifying agent stronger
Separative efficiency, can at the same time by oil and small-molecular emulsifier be separated from the water.
2nd, the film is prepared by interfacial polymerization, can directly use existing reverse osmosis or nanofiltration product film production
Equipment, it is not necessary to be modified to equipment, be easy to industrialization continuity production.
Brief description of the drawings
Fig. 1 is the water-oil separationg film surface atom power phenogram obtained by embodiment 1.
Fig. 2 is the water-oil separating film surface Electronic Speculum phenogram obtained by embodiment 1.
Fig. 3 is the water-oil separationg film section Electronic Speculum phenogram obtained by embodiment 1.
Fig. 4 is the water-oil separationg film surface IR Characterization figure obtained by embodiment 1,2,3.
Fig. 5 is the raw water of the water fat liquor through the water-oil separationg film obtained by embodiment 1 and the contrast photo of production water.
Embodiment
Limited with reference to specific embodiment technical scheme is further, but claimed
Scope is not only limited to made description.
Embodiment 1：
The preparation of water-oil separationg film 1：
(1) preparation of water phase：2,2'- disulfonic acid benzidine 10g are weighed in the beaker of 1L, 990g water are added, with three second
Amine adjusts PH=9, and the aqueous phase solution that concentration is 1wt% is obtained after stirring evenly.
(2) preparation of oil phase：1g pyromellitic trimethylsilyl chlorides are weighed in 1L beakers, 999g hexamethylenes are added, after stirring evenly
Obtain the oil phase that concentration is 0.1%.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 3min, after taking out drying, immerses in oil phase and react
1min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
Embodiment 2：
The preparation of water-oil separationg film 2：
(1) preparation of water phase：With embodiment 1.
(2) preparation of oil phase：With embodiment 1.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 3min, after taking out drying, immerses in oil phase and react
3min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
Embodiment 3：
The preparation of water-oil separationg film 3：
(1) preparation of water phase：With embodiment 1.
(2) preparation of oil phase：With embodiment 1.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 3min, after taking out drying, immerses in oil phase and react
10min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
Embodiment 4：
The preparation of water-oil separationg film 4：
(1) preparation of water phase：2,2'- disulfonic acid benzidine 20g are weighed in the beaker of 1L, 980g water are added, with three second
Amine adjusts PH=9, and the aqueous phase solution that concentration is 2wt% is obtained after stirring evenly.
(2) preparation of oil phase：With embodiment 1.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 3min, after taking out drying, immerses in oil phase and react
1min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
Embodiment 5：
The preparation of water-oil separationg film 5：
(1) preparation of water phase：2,2'- disulfonic acid benzidine 30g are weighed in the beaker of 1L, 970g water are added, with three second
Amine adjusts PH=9, and the aqueous phase solution that concentration is 3wt% is obtained after stirring evenly.
(2) preparation of oil phase：With embodiment 1.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 3min, after taking out drying, immerses in oil phase and react
1min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
Embodiment 6：
The preparation of water-oil separationg film 6：
(1) preparation of water phase：With embodiment 1.
(2) preparation of oil phase：2g pyromellitic trimethylsilyl chlorides are weighed in 1L beakers, 998g hexamethylenes are added, after stirring evenly
Obtain the oil phase that concentration is 0.2%.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 3min, after taking out drying, immerses in oil phase and react
1min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
Embodiment 7：
The preparation of water-oil separationg film 7：
(1) preparation of water phase：With embodiment 1.
(2) preparation of oil phase：3g pyromellitic trimethylsilyl chlorides are weighed in 1L beakers, 997g hexamethylenes are added, after stirring evenly
Obtain the oil phase that concentration is 0.3%.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 3min, after taking out drying, immerses in oil phase and react
1min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
Embodiment 8：
The preparation of water-oil separationg film 8：
(1) preparation of water phase：With embodiment 1.
(2) preparation of oil phase：With embodiment 1.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 5min, after taking out drying, immerses in oil phase and react
1min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
Embodiment 9：
The preparation of water-oil separationg film 9：
(1) preparation of water phase：With embodiment 1.
(2) preparation of oil phase：With embodiment 1.
(3) poly (ether-sulfone) ultrafiltration membrane of 10 × 10cm is immersed into water phase 10min, after taking out drying, immerses in oil phase and react
1min.Diaphragm is put into 70 DEG C of hot water after immersion 1min after drying and is taken out, obtains high-performance water-oil separationg film.
Film is taken to use dead-end filtration device to test, pressure 0.5Mpa, the rapeseed oil containing 1000ppm, 0.1% in feedwater
Dodecyl sodium sulfate, acquired results such as table 1.
The performance indicator of 1 water-oil separationg film of table
From a kind of table as can be seen that high-performance water-oil separationg film of the present invention using dodecyl sodium sulfate to being used as emulsifying agent
The grease stable emulsion of rapeseed oil has good separating capacity, under 0.5Mpa flux in 30GFD or so, rejection up to 98% with
On, wherein there is obvious influence in the reaction time in oil phase to the performance of the film, with the increase in reaction time, can effectively carry
High rejection, but flux has certain loss.Secondly rejection can also be improved by improving the concentration of water phase, but flux reduces.Oil
Phase concentration and water are in contact influence unobvious of the change to the film properties of time.Therefore compound film preparation provided by the present invention
Method is simple, performance is prominent, reaction condition is gentle and easily controllable.
Claims (8)
1. a kind of high-performance water-oil separationg film based on interfacial polymerization, it is characterised in that by nonwoven layer, more porous ultrafiltration membrane branch
Support layer and sulfonated polyamide functional layer composition.
2. high-performance water-oil separationg film according to claim 1, it is characterised in that the porous ultra-filtration membrane supporting layer
For：Polysulfones, polyether sulfone, polyacrylonitrile, Kynoar or polyvinyl chloride.
3. high-performance water-oil separationg film according to claim 1, it is characterised in that the sulfonated polyamide functional layer by
Activated monomer with sulfonic acid group is prepared as water phase, acyl chlorides monomer as oil phase using the method for interfacial polymerization.
4. high-performance water-oil separationg film according to claim 3, it is characterised in that the aqueous phase monomers are double for 2,2'-
Sulfonic acid benzidine, 4- amino -2'- nitrodiphenylamine -4'- sulfonic acid, 5- amino -2- (4- methoxybenzenes amido) benzene sulfonic acid, 1- ammonia
Base-beta naphthal -4- sodium sulfonates, catechol -3,5- sodium disulfonates, 1- amino-8-naphthol -4- sulfonic acid, Ortho-Aminophenol -4- sulphurs
Any one or a few mixture in acid, 6- nitros-Ortho-Aminophenol -4- sulphurs and the chloro- Ortho-Aminophenol -6- sulfonic acid of 4-.
5. high-performance water-oil separationg film according to claim 3, it is characterised in that the acyl chlorides monomer is equal benzene front three
One or more of mixtures in acyl chlorides, paraphthaloyl chloride, four acyl chlorides of o-phthaloyl chloride, m-phthaloyl chloride and biphenyl.
6. according to the preparation method of Claims 1 to 5 any one of them high-performance water-oil separationg film, it is characterised in that main
Comprise the following steps：
(1) oil, the preparation of water phase：Aqueous phase monomers are soluble in water, PH=8~11 are adjusted using PH conditioning agents, after stirring evenly
Obtain water phase；Acyl chlorides monomer is dissolved in organic solvent and obtains oil phase；
(2) more porous ultrafiltration membranes are immersed in the water phase of step (1) preparation, the concentration of aqueous phase monomers is 0.1~10wt%, soaks 1s
~1h, air-dries after taking-up, up to filter membrane A；
(3) reacted in the oil phase for obtaining filter membrane A immersion steps (1), the concentration of oil phase monomer is 0.01~10wt%, reaction
Time is 1s~10h, and reaction temperature is 5~40 DEG C, up to filter membrane B；
(4) filter membrane B is obtained into high-performance water-oil separationg film after 40~90 DEG C of hot water clean.
7. the preparation method of the high-performance water-oil separationg film according to right 6, water phase PH conditioning agents are in the step (1)
Any one or a few mixture in sodium hydroxide, potassium hydroxide, sodium acid carbonate, sodium carbonate, potassium carbonate and triethylamine.
8. the preparation method of the high-performance water-oil separationg film according to right 6, the solvent of acyl chlorides monomer in the step (1)
For any one or a few the mixture in n-hexane, hexamethylene, normal heptane or normal octane.
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