CN1100594C - Method for prepn. of permeation vaporization compound membrane - Google Patents
Method for prepn. of permeation vaporization compound membrane Download PDFInfo
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- CN1100594C CN1100594C CN98123190A CN98123190A CN1100594C CN 1100594 C CN1100594 C CN 1100594C CN 98123190 A CN98123190 A CN 98123190A CN 98123190 A CN98123190 A CN 98123190A CN 1100594 C CN1100594 C CN 1100594C
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- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title claims abstract description 12
- 230000008016 vaporization Effects 0.000 title claims abstract description 12
- 238000009834 vaporization Methods 0.000 title abstract 3
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000004094 surface-active agent Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011282 treatment Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 210000004379 membrane Anatomy 0.000 claims description 57
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 41
- 210000002469 basement membrane Anatomy 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 14
- 238000001764 infiltration Methods 0.000 claims description 13
- 230000008595 infiltration Effects 0.000 claims description 13
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000002309 gasification Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 238000007766 curtain coating Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- 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 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 5
- QVHXWWMPFSSZIM-UHFFFAOYSA-N [Cl-].C(CCCCCCCCCCC)[NH+](C1=C(C(=CC=C1)C)C)C1=C(C(=CC=C1)C)C Chemical compound [Cl-].C(CCCCCCCCCCC)[NH+](C1=C(C(=CC=C1)C)C)C1=C(C(=CC=C1)C)C QVHXWWMPFSSZIM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920004933 Terylene® Polymers 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 125000001931 aliphatic group Chemical group 0.000 claims 2
- 229950007687 macrogol ester Drugs 0.000 claims 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 description 32
- 239000010410 layer Substances 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 230000004907 flux Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011158 industrial composite Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a method for the preparation of a permeation and vaporization compound membrane. In the method, PAN is dissolved in a solvent to prepare a basal membrane, PVA is dissolved in water to prepare seaprting-layer membrane liquid for standby, the separating-layer membrane liquid is added with a surface active agent, the prepared separating-layer membrane liquid containing the surface active agent is then coated on the basal membrane, the compound membrane is finally carried out with post treatment, and then the product of the present invention is prepared. The experimental result indicates that the method of the present invention can greatly improve wettability between PVA membrane liquid and the PAN basal membrane when used for preparing a permeation and vaporization compound membrane so that separating layers are uniformly laid on the basal membrane and are firmly combined.
Description
The present invention relates to a kind of method for preparing osmosis vaporizing compound membrane, belong to the infiltrating and vaporizing membrane separation technology field.
The osmosis vaporizing compound membrane that processability is good is the key of infiltration evaporation membrane separation technique, also is the core of whole membrane technology secret.Osmosis vaporizing compound membrane is to go up the separating layer that covers one deck densification by the basement membrane of porous (supporting layer) to form.The separating layer of composite membrane is the homogeneous membrane of atresia, plays centrifugation in the infiltration evaporation process; Basement membrane is generally asymmetrical porous milipore filter, and separating layer is played a supportive role.Separating layer and basement membrane are generally made with different materials.Composite membrane is mainly decided by the thickness of separating layer the permeation flux of separated component, and the selectivity of film is also relevant with the thickness of separating layer.So in order to improve flux and selectivity, the thickness of separating layer is should guarantee to approach as much as possible under the condition that evenly covers on the support membrane.According to composite membrane preparation method difference, the thickness of separating layer can be from 0.1 μ m to several μ m.
The process for preparing composite membrane with rubbing method is: the Polymer Solution that the separating layer material is mixed with debita spissitudo, after filtration, deaeration, with coating, spraying or impregnating method it is covered on the basement membrane equably, after super-dry, crosslinking Treatment, makes composite membrane.With rubbing method prepare the key of composite membrane and difficult point be how to make fine and close separating layer thin and evenly, no leak source, and with the basement membrane strong bonded.Infiltrating and vaporizing membrane is by its basic separating property and application, can be divided into three types of preferential water permeable membrane, preferential saturating organic matter film and organic matter diffusion barriers.The separating layer of preferential water permeable membrane is to be that the high polymer of good hydrophilic property is made with containing hydrophilic radical.Involved in the present invention is a kind of preparation of excellent water permeable membrane, and wherein basement membrane is polyacrylonitrile (PAN) porous milipore filter, separating layer polyvinyl alcohol (PVA).
The PVA material has very strong hydrophily.And interact owing to the strong cyano group of interchain in the big molecule of polyacrylonitrile, make the PAN strand present the spiral space structure of irregular (tortuous and reverse), thereby make the minority that only is distributed in the film surface that really can attract hydrone among the PAN not form the free cyano group of cyanogen dipole pairing key and dipolar nature hydrogen bond, so the PAN membrane surface has demonstrated hydrophobicity.This just makes can be higher than the surface energy of PAN basement membrane by the surface of the prepared macromolecule aqueous solution of water wetted materials such as PVA.Because the surface on polyacrylonitrile basement membrane surface can be low, has incompatibility, is difficult to wetting and bonding.When with rubbing method PVA film liquid (aqueous solution) being coated with on the PAN basement membrane, PVA film liquid can not wetting well PAN membrane surface, and the PVA parting material can't be spread on the basement membrane equably, causes the composite membrane separating layer inhomogeneous show-through pitting to occur
Owing to occur uneven leak source on the composite membrane separating layer, the selectivity of film is reduced greatly, serious even lost separating effect.Practice shows, this is a technical barrier of the overslaugh industrial membrane for preparing the large tracts of land favorable reproducibility.
The objective of the invention is to design a kind of method for preparing osmosis vaporizing compound membrane, improve the wetability between PVA separating layer membrane liquid and the PAN basement membrane, make separating layer can spread over membrane surface equably, thereby solve the key technology of industrial composite membrane preparation.
The method for preparing osmosis vaporizing compound membrane that the present invention proposes comprises the following steps:
(1) basement membrane preparation: polyacrylonitrile (PAN) is dissolved in dimethylacetylamide or the solvent dimethylformamide, be mixed with that to contain PAN be 14～17% (wt) preparation liquid, after filtration, deaeration, curtain coating is on polyester non-woven fabric or terylene woven cloth, curtain coating thickness is 150～180 μ m, makes PAN porous basement membrane in 0～8 ℃ water behind the gel.
(2) preparation of separating layer membrane liquid: PVA is dissolved in the water is mixed with the film liquid of 5～8% (wt), through filtration, standby after the deaeration.
(3) in separating layer membrane liquid, add surfactant, by a certain percentage surfactant is added (2) and go on foot in the separating layer membrane liquid for preparing, make the separating layer membrane liquid that contains surfactant.
(4) preparation of composite membrane: the separating layer membrane liquid that contains surfactant that will prepare is coated on the basement membrane, coating thickness 30～50 μ m.Be made composite membrane behind the airing.
(5) processing of composite membrane can be any in the following method:
(a) heat treatment: 120～150 ℃ of treatment temperatures in 0.5～1 hour processing time, are the integrated gasification combined film of infiltration of the present invention.
(b) formal is handled: aldehyde concentration is 2～6% (wt) in the formalin, and treatment temperature is 30～80 ℃, and the processing time is 1～2 hour, is the integrated gasification combined film of infiltration of the present invention.
(c) glutaraldehyde cross-linking: the concentration of aldehyde is 0.1～2% (wt) in the glutaraldehyde water solution, and treatment temperature is 25～40 ℃, and processing time 5～60min is the integrated gasification combined film of infiltration of the present invention.
(d) the maleic acid esterification is crosslinked: the PVA unit of pressing every mol adds the maleic acid of 0.02～0.05mol, under 120～150 ℃ temperature, reacts 0.5～1 hour, is the integrated gasification combined film of infiltration of the present invention.
In (3) step of the present invention used surfactant be dodecyl dixylyl ammonium chloride (hereinafter to be referred as a), any in the stearyl dimethyl benzyl ammonium chloride (hereinafter to be referred as b), castor oil polyoxyethylene ether (hereinafter to be referred as d), AEO (hereinafter to be referred as e), AEO potassium phosphate (hereinafter to be referred as f), fatty acid polyethylene glycol ester (hereinafter to be referred as i), the ratio C of added surfactant, by formula
Calculate, in the formula, W
1For joining the weight of the surfactant in the film liquid, W
2Be the weight of separating layer material in the film liquid, the C value of different surfactants is as follows: dodecyl dixylyl ammonium chloride is 3～7% (wt); Stearyl dimethyl benzyl ammonium chloride is 2～6% (wt); Castor oil polyoxyethylene ether is 1.4-11.2% (wt), and AEO is 1～11% (wt); The AEO potassium phosphate is 5～10% (wt); Fatty acid polyethylene glycol ester is 4～8% (wt).
Surfactant is a kind of can being adsorbed on the boundary, thereby can reduce surface energy (surface tension or interfacial tension) between phase and phase greatly, changes the material of system boundary state.Surfactant molecule can be regarded as the hydrocarbonylation thing molecule with one or several polar substituent, and its molecular structure is the both sexes structure.When surfactant molecule is done directed absorption on the phase interface, will reduce the free energy of boundary.The rule similar according to polarity, when the PVA film liquid that contains surfactant was coated with on the PAN basement membrane, an end hydrophilic in the surfactant molecule was towards the PVA molecule, and a hydrophobic end is towards the PAN basement membrane.The lipophile (hydrophobicity) that this just improves PVA film liquid has reduced its surface free energy, also just makes the critical surface tension of the surface tension of PVA film liquid less than ripple coating PAN basement membrane, thereby obtains good spreading wetting and adhesiving effect.In addition, after in advance the PAN basement membrane being handled with surfactant, the surfactant molecule orientation vertically is adsorbed in the PAN membrane surface, and a hydrophilic end is outside, the hydrophily and the surface free energy of basement membrane are improved greatly, thereby improved the wettability of membrane surface.
PVA film liquid is in the wetability and the spreadability of PAN membrane surface, and is relevant with physical and chemical performance, molecular size, molecular structure and the surfactant concentrations of surfactant.In addition, surfactant concentrations not only influences the thickness (monolayer or bilayer) of surfactant molecular layer on the PAN surface, and adsorption layer molecularly oriented and arrange tightness degree also influences the separating property of composite membrane simultaneously.Therefore, surfactant concentrations should be selected to suit, and concentration is too low, can not reach the wetting of application and sprawl degree; Yet concentration is too high, can bring adverse effect to the separating property of film.
The present invention makes homogeneous membrane (atresia) with the PAN material, several surfactants such as (a) and (b), (d), (e), (f), (i) are mixed with various solution in different concentration, be used to handle the PAN homogeneous membrane, after treating airing, water adopts and drips the contact angle that the bubble method is measured film as liquid medium.The result shows that through the PAN homogeneous membrane that surfactant was handled, contact angle all reduces greatly.The contact angle that experiment records the PAN film of handling without surfactant is 59 °, and is the PAN film that the aqueous solution of the surfactant (a) of 0.2～3% (wt) was handled with concentration, and contact angle is 0 °; Concentration is that the contact angle of film was 0～3 ° after (b) of 0.4～2.5% (wt) handled; Concentration is that the contact angle of film was 0～5 ° after (d) of 0.3～5% (wt) handled; Concentration is that the contact angle of film was 0～11 ° after (e) of 0.6～1% (wt) handled; Concentration is that the contact angle of film was 0～9 ° after (f) of 0.5～5% (wt) handled; Concentration is that the contact of film was 0～7 ° after (i) of 0.5～6% (wt) handled.This explanation can improve greatly through the surface of the PAN basement membrane that surfactant was handled.
Introduce embodiments of the invention below:
Example one, adopting molecular weight is 78000, alcoholysis degree is that 98% PVA is a parting material, it is 15% (wt) film liquid that PAN is mixed with concentration, curtain coating is on polyester non-woven fabric after filtration, the deaeration, and curtain coating thickness is 180 μ m, and gel is made PAN porous basement membrane in 8 ℃ water.Compound concentration is the PVA aqueous solution 100g of 8% (wt), the dodecyl benzyl dimethyl ammonium chloride (a) of adding 0.408 or 0.248 stearyl dimethyl benzyl ammonium chloride (b) in film liquid, at this moment, (a) ratio in PVA film liquid is C=5% (wt), (b) the ratio C=3% in film liquid (wt).To contain (a) or PVA film liquid (b) is evenly coated on the PAN basement membrane, coating thickness is 40 μ m.At room temperature the PVA/PAN composite membrane behind the airing behind heat treatment 1h under 120 ℃ the temperature, is measured the Pervaporation Separation of film to ethanol water.Concentration of alcohol is 95% (wt) in feed liquid, and when feeding temperature was 70 ℃, the permeation flux of film was 380g/m
2H, piece-rate system is about 350.
Example two, adopt molecular weight 78000, alcoholysis degree be 99% PVA as parting material, the preparation method of basement membrane is with example one.Preparation contains the aqueous solution 100g that PVA is 8% (wt), adds 0.508 castor oil polyoxyethylene ether (d) in film liquid, at this moment (d) ratio C=6.25% (wt) in film liquid.The PVA film liquid that will contain (d) is evenly coated on the PAN basement membrane, and coating thickness is 40 μ m.The PVA/PAN composite membrane of at room temperature making behind the airing after the glutaraldehyde water solution of 0.2% (wt) is handled, is that the ethanol water of 95% (wt) carries out infiltration evaporation and separates to concentration of alcohol, when feed temperature is 70 ℃, and permeation flux 120g/m
2About h, separation is 600.
Example three, adopting average degree of polymerization is 1750, and alcoholysis degree is that 99% PVA makes parting material, and the basement membrane preparation method is with example one.Preparation 100ml contains the PVA aqueous solution of 7% (wt), in this aqueous solution, add the maleic acid of 0.025mol by the PVA of every mol monomer after, add the AEO (e) of 0.7g again, (e) ratio in film liquid is 10% (wt) at this moment.PVA film liquid is evenly coated on the basement membrane, and coating thickness is 50 μ m, behind the airing, 120 ℃ of following heat treatments 1 hour, makes maleic acid crosslinked PVA/PAN composite membrane.Film separates the infiltration evaporation of ethanol water, and concentration of alcohol is 95% (wt) in feed liquid, and when feeding temperature was 70 ℃, the permeation flux of film was 120g/m
2H, separation are 1350.
The parting material that example four is used is with example three, and the basement membrane preparation method is with example one.Preparation contains the aqueous solution 100g that PVA is 8% (wt), in film liquid, add 0.6g AEO potassium phosphate (f), at this moment, (f) the ratio c=7.5% in PVA film liquid, the film liquid that will contain (f) is evenly coated on the PAN basement membrane, and coating thickness is 40 μ m.At room temperature behind the airing, film is dipped in the formalin of 3% (wt), under 60 ℃ of temperature, handles 1h.Measure the Pervaporation Separation of film to aqueous acetone solution, when feed temperature is 52 ℃, when ketone content was 96% (wt) in the charging, permeation flux was 240g/m
2H, separation are 500.
The parting material that example five is used is with example three, and the basement membrane preparation method is with example one.Preparation contains the aqueous solution 100g of 8% (wt), adds 0.49g fatty acid polyethylene glycol ester (i) in film liquid, at this moment, (i) the ratio c=5% in PVA film liquid, the film liquid that will contain (i) is evenly coated on the PAN basement membrane, and coating thickness is 40 μ m.At room temperature behind the airing, by the condition of example four composite membrane is carried out formal and handle.The film of preparing is used for the separation of normal propyl alcohol aqueous systems, and normal propyl alcohol concentration is 63% (wt) in charging, and when temperature was 61.5 ℃, permeation flux was 862g/m
2H, separation are tending towards infinitely great (detecting less than normal propyl alcohol in infiltration).
Claims (1)
1, a kind of method for preparing osmosis vaporizing compound membrane is characterized in that this method comprises the following steps:
(1) basement membrane preparation: polyacrylonitrile (PAN) is dissolved in dimethylacetylamide or the solvent dimethylformamide, be mixed with that to contain PAN be 14～17% (wt) preparation liquid, after filtration, deaeration, curtain coating is on polyester non-woven fabric or terylene woven cloth, curtain coating thickness is 150～180 μ m, makes PAN porous basement membrane in 0～8 ℃ water behind the gel;
(2) preparation of separating layer membrane liquid: PVA is dissolved in the water is mixed with the film liquid of 5～8% (wt), through filtration, standby after the deaeration;
(3) in separating layer membrane liquid, add surfactant, surfactant is any in dodecyl dixylyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, castor oil polyoxyethylene ether, AEO, AEO potassium phosphate, the aliphatic acid Macrogol Ester, the ratio C of added surfactant, by formula
Calculate, in the formula, W
1For joining the weight of the surfactant in the film liquid, W
2Be the weight of separating layer material in the film liquid, the C value of different surfactants is as follows: dodecyl dixylyl ammonium chloride is 3～7% (wt); Stearyl dimethyl benzyl ammonium chloride is 2～6% (wt); Castor oil polyoxyethylene ether is 1.4-11.2% (wt), and AEO is 1～11% (wt); The AEO potassium phosphate is 5～10% (wt); The aliphatic acid Macrogol Ester is 4～8% (wt), by a certain percentage surfactant is added (2) and goes on foot in the separating layer membrane liquid for preparing, and makes the separating layer membrane liquid that contains surfactant;
(4) preparation of composite membrane: the separating layer membrane liquid that contains surfactant that will prepare is coated on the basement membrane, and coating thickness 30～50 μ m are made composite membrane behind the airing;
(5) processing of composite membrane, any in the following method:
(a) heat treatment: 120～150 ℃ of treatment temperatures in 0.5～1 hour processing time, are the integrated gasification combined film of infiltration of the present invention;
(b) formal is handled: aldehyde concentration is 2～6% (wt) in the formalin, and treatment temperature is 30～80 ℃, and the processing time is 1～2 hour, is the integrated gasification combined film of infiltration of the present invention;
(c) glutaraldehyde cross-linking: the concentration of aldehyde is 0.1～2% (wt) in the glutaraldehyde water solution, and treatment temperature is 25～40 ℃, and processing time 5～60min is the integrated gasification combined film of infiltration of the present invention;
(d) the maleic acid esterification is crosslinked: the PVA unit of pressing every mol adds the maleic acid of 0.02～0.05mol, under 120～150 ℃ temperature, reacts 0.5～1 hour, is the integrated gasification combined film of infiltration of the present invention.
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| CN98123190A CN1100594C (en) | 1998-12-11 | 1998-12-11 | Method for prepn. of permeation vaporization compound membrane |
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| CN98123190A CN1100594C (en) | 1998-12-11 | 1998-12-11 | Method for prepn. of permeation vaporization compound membrane |
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| CN1100594C true CN1100594C (en) | 2003-02-05 |
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| CN98123190A Expired - Fee Related CN1100594C (en) | 1998-12-11 | 1998-12-11 | Method for prepn. of permeation vaporization compound membrane |
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| CN100395008C (en) * | 2006-03-31 | 2008-06-18 | 华南理工大学 | A hydrophilic-hydrophobic bipolar composite membrane and method for preparing same |
| EE05604B1 (en) * | 2009-12-21 | 2012-12-17 | Osa�hing Bioconsult | Filter material for the separation of h drophilic substances from the environment of various h drophobic liquids or gases and a process for the production of this material |
| CN105169959B (en) * | 2015-07-20 | 2017-05-24 | 北京工业大学 | Method for rapid and environmentally-friendly production of compact separation membrane |
| CN110917890A (en) * | 2019-11-08 | 2020-03-27 | 北京中环膜材料科技有限公司 | Hydrophilic agent, modified ethylene-chlorotrifluoroethylene membrane and preparation method thereof |
| CN117753210B (en) * | 2023-12-28 | 2024-09-10 | 安徽泽升科技股份有限公司 | Acetonitrile recovery method of acetonitrile-containing waste solvent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4527999A (en) * | 1984-03-23 | 1985-07-09 | Abcor, Inc. | Separation membrane and method of preparing and using same |
| JPH04176330A (en) * | 1990-11-09 | 1992-06-24 | Kuraray Co Ltd | Production of charge type separation membrane |
-
1998
- 1998-12-11 CN CN98123190A patent/CN1100594C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4527999A (en) * | 1984-03-23 | 1985-07-09 | Abcor, Inc. | Separation membrane and method of preparing and using same |
| JPH04176330A (en) * | 1990-11-09 | 1992-06-24 | Kuraray Co Ltd | Production of charge type separation membrane |
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| CN1221649A (en) | 1999-07-07 |
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