CN101229487A - PDMS/PVDF complex film for separating organic steam and preparation method thereof - Google Patents
PDMS/PVDF complex film for separating organic steam and preparation method thereof Download PDFInfo
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- CN101229487A CN101229487A CNA200710176855XA CN200710176855A CN101229487A CN 101229487 A CN101229487 A CN 101229487A CN A200710176855X A CNA200710176855X A CN A200710176855XA CN 200710176855 A CN200710176855 A CN 200710176855A CN 101229487 A CN101229487 A CN 101229487A
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 52
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 52
- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 37
- 235000013870 dimethyl polysiloxane Nutrition 0.000 title claims abstract description 37
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 title claims abstract description 37
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 210000004379 membrane Anatomy 0.000 claims abstract description 65
- 239000012528 membrane Substances 0.000 claims abstract description 65
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 19
- 239000004945 silicone rubber Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 19
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 19
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 13
- -1 Dimethyl siloxane Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000000280 densification Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 230000009969 flowable effect Effects 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 2
- 239000008096 xylene Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 20
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000004907 flux Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920005573 silicon-containing polymer Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Abstract
The invention discloses a PDMS/PVDF composite membrane for separating organic vapor which pertains to the technical field of vapor permeation membrane separation and a preparation method thereof. The steps to prepare the composite membrane are that: polyvinylidene fluoride is firstly dissolved in a solvent to prepare a basement membrane and the basement membrane is dried, treated by a surfactant and reserved. Silicone rubber is dissolved in normal heptane to be prepared into a uniform membrane casting solution; then the filtered and defoamed membrane casting solution is coated on the treated basement membrane and PDMS/PVDF composite membrane is obtained after being cured at different temperatures. The PDMS separation layer prepared by the invention is uniformly distributed, compact and sound, and is closely combined with the PVDF. The obtained PDMS/PVDF composite membrane by preparation is applied to separating dimethylmethane/N2 system, the total flux reaches 615*10<6>cm<3>(STP)/(cm<2>s cmHg) and the separation factor is larger than 20.
Description
Technical field
The invention belongs to the vapor permeable membrane separation technology field.Be particularly related to PDMS/PVDF composite membrane of a kind of separating organic steam and preparation method thereof.
Background technology
In the storage and transportation of petrochemical industry, organic synthesis and oil gas, usually there is a large amount of organic matters to be discharged in the air, not only cause organic waste, and cause environmental pollution.Under the more and more important situation of environmental protection and energy savings, from environmental protection with reclaim resource, the recovery of organic steam is just become necessary.
The method traditional to the recovery of organic steam has active carbon adsorption, compression condensation method, dark condensation method etc.Absorption method is an organic steam partition method the earliest, adopts adsorption cleaning waste gas such as active carbon, uses the steam desorption and regeneration then.Advantage is recyclable solvent, does not need heating when purifying cryogenic gas.But need preliminary treatment to remove dust and wet goods impurity, be applicable to that light concentration gas separates.In addition, in adsorption process, heat of adsorption causes the organic vapor blast easily, and security is relatively poor.Condensation method can reclaim organic matter in the liquid mode, but is mainly used in the organic recovery of higher boiling, high concentration, then needs cryogenic separation for lower boiling organic matter, has increased energy consumption greatly.
Membrane separation technique is a kind of novel chemical separation technology, and the organic steam infiltration is a kind of of membrane separation technique.With respect to traditional organic steam recovery method, this invention use membrane separation technique have separative efficiency height, small investment, operating cost low, be easy to scale, be convenient to remarkable advantage such as control.
The core of organic steam infiltration is the selection of membrane material.From the condensed state structure of membrane material, polymer is divided into two kinds of glassy state and rubbery states usually, selects according to practical application.For the fixed gas of little molecule penetrated preferably (as H
2, N
2, O
2, He etc.) separation, often adopt the polymer of glassy state, as in gas industry, adopt CAM to remove or reclaim CO
2Employing polyimide film in the concise factory carries out H
2Separate.For condensated gas/can not coagulate the separation and the recovery of gas, with respect to the little molecule that can not coagulate, the big molecule penetrated preferably polymer film that hope can be coagulated.The vitrification point of rubbery feel polymer is low, and strand is curls shape, is in the vibration that does not stop and the motion of continuing, and does not stop moving passage continuously thereby can form one in inside, makes component diffusion velocity in film accelerate.A large amount of rubbery feel polymer films that studies show that preferentially permeate bigger molecule, are applicable to that organic steam/condensable gas separates.
In rubbery feel polymer, the most frequently used membrane material is a silicon rubber.The dimethyl silicone polymer macromolecular chain is very soft, and its viscosity activation energy is little; In addition, the helical structure of siloxanes makes that interaction force is little between the silica chain, molal volume is big, surface tension is little.These 2 all help not stopping moving passage continuously one of the inner formation of silicon rubber, thereby promote the mass transport process of component in film, make dimethyl silicone polymer have very strong permeability.Therefore, the dimethyl silicone polymer film gas separate and water in remove and use very extensively in the organic infiltration evaporation process, but it is also rarely found to be used for the research that organic steam permeates.US4553983 has introduced the separation of employing composite silicone rubber membrane and has reclaimed ethanol, methyl alcohol, perchloroethylene and trichloroethanes etc., the infiltration coefficient of organic steam is greater than 3000Barrer, desirable separation factor is greater than 50, but in their system, the concentration of organic steam is less than 20000ppm.Companies such as Germany GKSS company, MTR company and day eastern electrician are used for casing-head gas with the dimethyl silicone polymer composite membrane and reclaim, the occasions such as recovery of monomer in the production processes of polyalcohol such as polypropylene, though industrialization, but the counterdie of the composite membrane that they adopt is a PEI, materials such as polysulfones; And, there is not detailed research membrane structure, operating conditions etc. are to the influence of separation and recyclability.
The film form that adopts in the film separation process has three kinds usually, i.e. symmetric membrane, anisotropic membrane and composite membrane.Separating layer and supporting layer all are to adopt a kind of membrane material preparation in symmetric membrane and the anisotropic membrane.Symmetric membrane on whole film thickness, have same density and film thicker, so the permeation flux of film is lower.And anisotropic membrane exists the cortex and a porous support layer of thin densification, compare with symmetric membrane, owing to the thickness that has reduced separating layer has increased the permeation flux of film, but be difficult to prepare flawless cortex, thereby reduced the separation factor of separation system.Separating layer is different with the material that supporting layer is adopted in the composite membrane, has one usually the thin layer separating layer of selection separating property and the supporting layer of a porous are arranged, and supporting layer provides enough mechanical strengths of composite membrane and chemical stability etc.
Summary of the invention
The purpose of this invention is to provide PDMS/PVDF composite membrane of a kind of separating organic steam and preparation method thereof.
The PDMS/PVDF composite membrane of described separating organic steam is characterized in that: the organic steam composite membrane is evenly to apply the PDMS separating layer of one deck densification and get on the PVDF of porous counterdie; Obtain the zero defect compacted zone, and the composite membrane combination is firmly, it contains:
Kynoar (PVDF) counterdie, mass fraction is 14～22;
Dimethyl siloxane rubber (PDMS) glued membrane, mass fraction is 20～50; Be coated on the described Kynoar counterdie.
The preparation process of the PDMS/PVDF composite membrane of described separating organic steam is as follows:
Step 1: the preparation of counterdie
The Kynoar of above-mentioned mass ratio is dissolved among the solvent I fully, behind 70 ℃ of following mechanical agitation 24b, obtain the casting film solution of clear, behind filtration and vacuum deaerator, adopt scraper that coating solution is scraped on the polyester non-woven fabric, blade thickness is 140-250 μ m, makes Kynoar porous counterdie in 15-25 ℃ water behind the gel.
Step 2: the preparation of silicone rubber membrane liquid
The dimethyl siloxane rubber of above-mentioned mass ratio is dissolved in the solvent II, mixes the back and add crosslinking agent, its consumption is 8% of a solution gross weight; Add catalyst then, consumption is 2% of a solution gross weight, and magnetic agitation is the back standing and defoaming evenly.
Step 3: basement membrane is handled
The gamma-amino propyl trimethoxy silicane is dissolved in the absolute ethyl alcohol, configures gamma-amino propyl trimethoxy silicane surfactant solution, the PVDF basement membrane is soaked 10-60min in this solution by the 10%-30% volume by volume concentration, standby after 50 ℃ of oven dry;
Step 4: the silicone rubber membrane liquid of gained in the step 2 is coated on the PVDF basement membrane that step 3 handled, solidified 24～96 hours, promptly get described PDMS/PVDF composite membrane after doing.
Used solvent I is N in the described step 1, the N-dimethylacetylamide, triethyl phosphate or vinylpyridine alkane ketone.
Described dimethyl silicone rubber is a flowable state, and its viscosity is between 5000Pa.s～50000Pa.s.
Used solvent II is any one in n-hexane, normal heptane, normal octane, benzene, toluene and the dimethylbenzene in the described step 2.
Crosslinking agent is an ethyl orthosilicate, vinyltrimethoxy silane, phenyl triethoxysilane, any one in the γ-An Jibingjisanyiyangjiguiwan.
Advantage of the present invention is the organic steam infiltration composite membrane of preparation, and production cost is low, and is simple in structure, and the PDMS compacted zone is evenly distributed on the PVDF counterdie, and zero defect and the two are in conjunction with tight.PVDF that is adopted and PDMS material all are commercializations, cheap and easy to get.The PDMS/PVDF composite membrane for preparing is used for propane/N
2The separation of system, when the propane mass ratio is 10%, operating temperature is 298K, and pressure differential is 0.3MPa, and when gas flow rate was 300ml/min, total flux reached 615 * 10
6Cm
3(STP)/(cm
2S cmHg), separation factor is greater than 20.
The specific embodiment
The invention provides PDMS/PVDF composite membrane of a kind of separating organic steam and preparation method thereof.The PDMS/PVDF composite membrane of described separating organic steam is evenly to apply the PDMS separating layer of one deck densification and get on the PVDF of porous counterdie; Obtain the zero defect compacted zone, and composite membrane is in conjunction with firm.
Following embodiment is done more detailed description to the present invention, but described embodiment is not construed as limiting the invention.
Embodiment 1
The Kynoar of mass fraction 15 is dissolved in N fully, in the N-dimethylacetylamide, behind 70 ℃ of following mechanical agitation 24h, obtain the casting film solution of clear, behind filtration and vacuum deaerator, adopt scraper that coating solution is scraped on the polyester non-woven fabric, blade thickness is 150 μ m, makes Kynoar porous counterdie in 20 ℃ water behind the gel.Configure gamma-amino propyl trimethoxy silicane surfactant solution by 20% volume by volume concentration, the PVDF counterdie is soaked 10-60min in this solution, standby after 50 ℃ of oven dry.The mass ratio of dimethyl silicone rubber according to mass fraction 30 is dissolved in the normal heptane solvent, mixes the back and add the crosslinking agent ethyl orthosilicate, mass percent is 8% of a dimethyl silicone rubber solution gross weight; Add dibutyl tin laurate then and make catalyst, consumption is 2% of a dimethyl silicone rubber solution gross weight, and magnetic agitation is the back standing and defoaming evenly.Silicone rubber membrane liquid is coated on the PVDF counterdie of handling, and promptly gets described PDMS/PVDF composite membrane after the curing 24.
Embodiment 2
With the Kynoar of mass fraction 20 be dissolved in fully triethyl phosphate or vinylpyridine in the alkane ketone, behind 70 ℃ of following mechanical agitation 24h, obtain the casting film solution of clear respectively, behind filtration and vacuum deaerator, adopt scraper respectively two kinds of coating solutions to be scraped on the polyester non-woven fabric, blade thickness is 150 μ m, makes Kynoar porous counterdie in 20 ℃ water behind the gel.Configure gamma-amino propyl trimethoxy silicane-ethanol surfactant solution by 30% volume by volume concentration, the PVDF counterdie is soaked 10-60min in this solution, standby after 50 ℃ of oven dry.Dimethyl silicone rubber is dissolved in the n-hexane solvent according to 30% mass ratio, mixes the back and add the crosslinking agent vinyltrimethoxy silane, mass percent is 8% of a dimethyl silicone rubber solution gross weight; Add dibutyl tin laurate then and make catalyst, consumption is 2% of a dimethyl silicone rubber solution gross weight, and magnetic agitation is the back standing and defoaming evenly.Silicone rubber membrane liquid is coated to respectively on above-mentioned two kinds of PVDF counterdies of handling, promptly gets described PDMS/PVDF composite membrane after the curing 24.
Following examples see Table 1, table 2 and table 3.
The preparation condition of table 1 embodiment PDMS/PVDF composite membrane
| Embodiment number | 1 | 2 | 3 | 4 | ||
| Film liquid is formed | Basement membrane | PVDF (％) | PVDF(15) | PVDF(15) | PVDF(18) | PVDF(20) |
| Solvent (%) | N, N-dimethylacetylamide (85) | N, N-dimethylacetylamide (85) | Triethyl phosphate (82) | N-methyl pyrrole alkane ketone (80) | ||
| Separating layer | PDMS (％) | PDMS5000(30) | PDMS50000(30) | PDMS10000(30) | PDMS10000 (30) | |
| Solvent (%) | Normal heptane (68) | Normal heptane (68) | Normal heptane (68) | Normal heptane (68) | ||
| Crosslinking agent (%) | Ethyl orthosilicate (8) | Ethyl orthosilicate (8) | Ethyl orthosilicate (8) | Ethyl orthosilicate (8) | ||
| Catalyst (%) | Dibutyl tin laurate (4) | Dibutyl tin laurate (4) | Dibutyl tin laurate (4) | Dibutyl tin laurate (4) | ||
| The PDMS dissolution conditions | Temperature (℃) | 25 | 20 | 25 | 18 | |
| Time (h) | 3 | 4 | 3 | 4 | ||
| Film preparation technology | Basement membrane | Coagulation bath is formed | Water | Water | Water | Water |
| The coagulation bath temperature (℃) | 21 | 21 | 21 | 21 | ||
| Separating layer | Solidification temperature (℃) | 50 | 80 | 25 | 25 | |
| Hardening time | 48 | 48 | 48 | 48 | ||
The preparation condition of table 2 embodiment PDMS/PVDF composite membrane
| Embodiment number | 5 | 6 | 7 | 8 | ||
| Film liquid is formed | Basement membrane | PVDF (％) | PVDF(18) | PVDF(20) | PVDF(18) | PVDF(18) |
| Solvent (%) | N, N-dimethylacetylamide (88) | N, N-dimethylacetylamide (80) | Triethyl phosphate (82) | N-methyl pyrrole alkane ketone (88) | ||
| Separating layer | PDMS (％) | PDMS5000(30) | PDMS50000(30) | PDMS10000(30) | PDMS10000 (30) | |
| Solvent (%) | Normal heptane (68) | Normal heptane (68) | Normal heptane (68) | Normal heptane (68) | ||
| Crosslinking agent (%) | Ethyl orthosilicate (8) | Ethyl orthosilicate (8) | Ethyl orthosilicate (8) | Ethyl orthosilicate (8) | ||
| Catalyst (%) | Dibutyl tin laurate (4) | Dibutyl tin laurate (4) | Dibutyl tin laurate (4) | Dibutyl tin laurate (4) | ||
| The PDMS dissolution conditions | Temperature (℃) | 25 | 20 | 25 | 18 | |
| Time (h) | 3 | 4 | 3 | 4 | ||
| Film preparation technology | Basement membrane | Coagulation bath is formed | Water | Water | Water | Water |
| The coagulation bath temperature (℃) | 21 | 21 | 21 | 21 | ||
| Separating layer | The assimilation temperature (℃) | 50 | 80 | 100 | 120 | |
| Assimilation time | 24 | 36 | 24 | 12 | ||
The separating property of the PDMS/PVDF composite membrane of table 3 embodiment preparation
| Embodiment number | Test condition | Infiltration total flux * 10 6cm 3(STP)/(cm 2scmHg) | Separation factor | |
| Temperature (K) | Pressure differential (MPa) | |||
| 1 | 298 | 0.3 | 681.4 | 14.2 |
| 2 | 298 | 0.3 | 615.3 | 20.6 |
| 3 | 298 | 0.3 | 420.3 | 8.1 |
| 4 | 298 | 0.3 | 439.4 | 17.4 |
| 5 | 298 | 0.3 | 590.7 | 11.7 |
| 6 | 298 | 0.3 | 491.8 | 15.3 |
| 1 | 298 | 0.5 | 623.4 | 18.1 |
| 1 | 328 | 0.3 | 380.5 | 10.5 |
Annotate: the mass fraction of propane is 10% in 1 material mixed gas, N
2Mass fraction be 90%.
Gas flow rate is 300-500ml/min in 2 test process.
Claims (6)
1. the PDMS/PVDF composite membrane of a separating organic steam is characterized in that, this composite membrane is the PDMS separating layer that evenly applies one deck densification on the PVDF of porous counterdie, and the composite membrane combination is firmly, and it contains:
Kynoar PVDF counterdie, mass fraction are 14～22;
Dimethyl siloxane rubber PDMS glued membrane, mass fraction is 20～50; Be coated on the described Kynoar counterdie.
2. according to the PDMS/PVDF composite membrane of the described separating organic steam of claim 1, it is characterized in that: described dimethyl silicone rubber is a flowable state, and its viscosity is between 5000Pa.s～50000Pa.s.
3. the preparation method of the PDMS/PVDF composite membrane of a separating organic steam is characterized in that, the preparation process of composite membrane is as follows:
Step 1: the preparation of counterdie
The Kynoar of above-mentioned mass ratio is dissolved among the solvent I fully, behind 70 ℃ of following mechanical agitation 24h, obtain the casting film solution of clear, behind filtration and vacuum deaerator, adopt scraper that coating solution is scraped on the polyester non-woven fabric, blade thickness is 140-250 μ m, makes Kynoar porous counterdie in 15-25 ℃ water behind the gel;
Step 2: the preparation of silicone rubber membrane liquid
The dimethyl silicone rubber of above-mentioned mass ratio is dissolved in the solvent II fully, mixes the back and add crosslinking agent, its consumption is 8% of a solution gross weight; Add dibutyl tin laurate then and make catalyst, consumption is 2% of a solution gross weight, and magnetic agitation is the back standing and defoaming evenly;
Step 3: counterdie is handled
The gamma-amino propyl trimethoxy silicane is dissolved in the absolute ethyl alcohol, configures gamma-amino propyl trimethoxy silicane surfactant solution, the PVDF basement membrane is soaked 10-60min in this solution by the 10%-30% volume by volume concentration, standby after 50 ℃ of oven dry;
Step 4: the silicone rubber membrane liquid of gained in the step 2 is coated on the PVDF basement membrane that step 3 handled, solidified 24～96 hours, promptly get described PDMS/PVDF composite membrane after doing.
4. according to the preparation method of the PDMS/PVDF composite membrane of the described separating organic steam of claim 3, it is characterized in that: used solvent I is N in the described step 1, the N-dimethylacetylamide, triethyl phosphate or vinylpyridine alkane ketone.
5. according to the preparation method of the PDMS/PVDF composite membrane of the described separating organic steam of claim 3, it is characterized in that: used solvent II is any one in n-hexane, normal heptane, normal octane, the benzene,toluene,xylene in the described step 2.
6. according to the preparation method of the PDMS/PVDF composite membrane of the described separating organic steam of claim 3, it is characterized in that: crosslinking agent is an ethyl orthosilicate, vinyltrimethoxy silane, phenyl triethoxysilane, any one in the γ-An Jibingjisanyiyangjiguiwan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710176855XA CN100569350C (en) | 2007-11-06 | 2007-11-06 | PDMS/PVDF composite membrane of separating organic steam and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710176855XA CN100569350C (en) | 2007-11-06 | 2007-11-06 | PDMS/PVDF composite membrane of separating organic steam and preparation method thereof |
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| CN107297148A (en) * | 2016-04-15 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of preparation method of high-performance organic gas composite membrane for separation |
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| CN108295669A (en) * | 2018-03-05 | 2018-07-20 | 北京清源洁华膜技术有限公司 | A kind of composite membrane and preparation method thereof of separation VOCs |
| CN110713645A (en) * | 2018-07-12 | 2020-01-21 | 中国科学院化学研究所 | Polymer-based two-dimensional topological material and preparation method and application thereof |
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