CN1895761A - Organic steam-separated blend composite film and its production - Google Patents
Organic steam-separated blend composite film and its production Download PDFInfo
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- CN1895761A CN1895761A CN 200610012264 CN200610012264A CN1895761A CN 1895761 A CN1895761 A CN 1895761A CN 200610012264 CN200610012264 CN 200610012264 CN 200610012264 A CN200610012264 A CN 200610012264A CN 1895761 A CN1895761 A CN 1895761A
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- silicon rubber
- organic steam
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 5
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 37
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 14
- -1 dimethyl siloxane Chemical class 0.000 claims abstract description 12
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 210000004379 membrane Anatomy 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 210000002469 basement membrane Anatomy 0.000 claims description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- JGHTXIKECBJCFI-UHFFFAOYSA-N trifluoro(propyl)silane Chemical compound CCC[Si](F)(F)F JGHTXIKECBJCFI-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 239000000463 material Substances 0.000 claims description 11
- 239000004945 silicone rubber Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 230000009969 flowable effect Effects 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 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 229920001281 polyalkylene Polymers 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 3
- MWBHZZNXYOSZDS-UHFFFAOYSA-N 3,3,3-trifluoropropylsilicon Chemical compound FC(F)(F)CC[Si] MWBHZZNXYOSZDS-UHFFFAOYSA-N 0.000 abstract 1
- 239000004697 Polyetherimide Substances 0.000 abstract 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 229920001601 polyetherimide Polymers 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 230000004907 flux Effects 0.000 description 9
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005573 silicon-containing polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229940062057 nitrogen 80 % Drugs 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- YRMJGYDMKMGBSB-UHFFFAOYSA-N propane;prop-1-ene Chemical compound CCC.CCC.CC=C YRMJGYDMKMGBSB-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A composite mixture membrane for separating organic vapor is prepared through dissolving polyetherimide in solvent, preparing basic film, dissolving dimethyl siloxane or trifluoropropyl silicon rubber in solvent, sequentially adding ethyl n-silicate, tin dibutylbilaurate and silane, stirring, coating the mixture solution on said basic film, and heat treating.
Description
Technical field:
The present invention relates to a kind of blend composite film that is used for the organic steam separation and preparation method thereof, belong to the vapor permeable membrane separation technology field.
Background technology:
In the discharging gas of petrochemical industry many organic compounds are arranged, its toxicity is very big, and part has been listed in carcinogenic substance, as vinyl chloride, benzene, polycyclic aromatic hydrocarbon lamp.Organic steam is inflammable and explosive, has increased insecurity to manufacturing enterprise.2005, China produced more than 640 ten thousand tons of polyvinyl chloride, more than 530 ten thousand tons of polyethylene, more than 500 ten thousand tons of polypropylene, more than 1,600 ten thousand tons of liquefied petroleum gas, natural gas 490 billion cubic meters per year.The vapor permeable membrane technology is used for the MONOMER RECOVERY of polyethylene, polypropylene, polyvinyl chloride production, C3 in the gas production and above and acid gas removal, advantages such as liquefied gas recovery in liquefied gas is produced are obvious especially, and the existing many cover steam infiltration commercial plants of China are in operation at present.But it is pointed out that its core technology is mainly from German GKSS company.
At present, the processing method to organic steam has two classes: destroy method and non-destroy method.Firing method belongs to destroy method, and it changes into CO with organic steam through burning
2And water.Non-destroy method has three kinds of condensation method, absorption method and membrane separation processes.Membrane separation technique is a novel chemical separation technology, and the steam infiltration is a kind of of membrane separation technique.With respect to traditional separation method, this invention is used that membrane separation technique has small investment, operating cost is low, separative efficiency is high, is easy to scale, expandability is good, be convenient to remarkable advantage such as control.
2005, more than 1,000 ten thousand tons of China's ethene, third rare output.Alkene is the flagship product of petrochemical industry, and the petrochemical industry that is separated in of olefin/paraffin occupies critical role.Because the two boiling-point difference is very little, adopts that traditional deep cooling or absorption method separating energy consumption are big, the investment height.Adopt steam permeability and separation technology to substitute original cold separation technology, energy-conservation remarkable especially.For the separation of hydrocarbon-containifirst gas, the polymer membrane of glassy state or rubbery state all shows good selection performance.But the flux of glassy state is too low, and this has just limited its scope of application.Rubbery feel polymer has good through performance to hydrocarbon gas, and this makes it be used for large-scale industrial production economical and technical all more feasible.
The core that organic steam separates is the selection of membrane material, from the condensed state structure of membrane material, for improving the permeation flux of film, should adopt the rubbery state film as far as possible.Because the vitrification point of rubbery feel polymer is low, 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.Silicon oxygen bond bond energy height in the silicon rubber, bond length is long, bond angle is big.Dimethyl silicone polymer as main chain has two methyl shieldings, and this makes macromolecular chain 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.This high flux advantage of dimethyl silicone rubber makes aspects such as its organic matter in water is deviate from, gas separation obtain widely using, but it is also rare to be used for the research that organic steam separates.Fluorosioloxane rubber has obtained extensive studies and application owing to have performances such as good oil resistant, anti-solvent in petrochemical industry, automobile industry, because the influence of trifluoro propyl on the side chain, cause the permeability of fluorosioloxane rubber relatively low, because the influence of fluorine atom on the side chain, make it have certain polarity, to polar substances to be separated, show bigger selectivity.For this reason, further improve the prescription of dimethyl silicone rubber and fluorosioloxane rubber as required, it is very necessary to develop new organic steam separation membrane material.
The organic steam diffusion barrier is the dissolving Selective Control, and the solubility of organic steam in film is big, and permeation flux is big; The solubility of little molecule fixed gas in film is little, and permeation flux is little.Organic steam has been realized separating with little molecule fixed gas like this.
Key technology of the present invention is the good organic steam composite membrane for separation of processability.Composite membrane is to get by applying the separating layer of one deck densification on the basement membrane of porous.The key of preparation composite membrane is how to make fine and close separating layer thin and spread over membrane surface equably, and combines securely with basement membrane.Based on this, the present invention has at first solved silicon rubber and kept excellent chemical stability under the infiltration of organic steam condensation water, can not produce plasticizing, excessive swelling and the problem that comes off.
Summary of the invention
Blend composite film that provides at above-mentioned technical problem a kind of organic steam separation and preparation method thereof is provided.This film can be when keeping the original separating property of silicone rubber membrane material, and permeation flux increases considerably, to overcome the low shortcoming of membrane material self flux.By adjusting the mixed proportion of silicon rubber, it is main inventive point of the present invention that permeation flux can be improved to some extent.So-called permeation flux improves, and is meant the comparison between the composite membrane for preparing with the usual method that does not add dimethyl silicone rubber in the composite membrane of method gained of the present invention and the casting solution.
Invent described blend composite film, it is characterized in that it contains:
The polyacrylonitrile basement membrane, the quality percentage composition of polyacrylonitrile is 15%-25% in the film liquid;
The PEI basement membrane, the quality percentage composition of PEI is 15%-25% in the film liquid;
The silicon rubber blend film, it is coated on the described basement membrane; Described silicon rubber blend film is that dimethyl polysiloxane PDMS or the trifluoro propyl silicon rubber of 10%-40% is formed by mass percent.
Described method contains following steps successively:
Step 1: basement membrane preparation
PEI is dissolved in N by the mass percent of 15%-23%, in N-dimethylacetylamide or the N-methyl pyrrolidone, be configured to preparation liquid, after filtration, after the deaeration, hydrostomia is on polyester non-woven fabric, hydrostomia thickness is 120 μ m～180 μ m, makes PEI porous basement membrane in 15-25 ℃ water behind the gel;
Step 2: configuration separating layer blend film liquid
Is mass percent that dimethyl siloxane silicon rubber or the trifluoro propyl silicon rubber ratio on demand of 15%-30% is dissolved in the normal heptane solvent, adds the crosslinking agent ethyl orthosilicate again, and mass percent is 10%; Add the 6ml-8ml dibutyl tin laurate then and make catalyst, be configured to separating layer blend film liquid;
Step 3: preparation contains the separating layer blend film liquid of surfactant
γ-the mercaptopropyl trimethoxysilane that adds mass percent and be 1%-6% in the separating layer blend film liquid that step 2 makes is made coupling agent, makes the separating layer blend film liquid that contains surfactant, after filtration, standby after the deaeration;
Step 4: blend film preparation
The uniform hydrostomia of separating layer blend film liquid that contains surfactant of gained in the step 3 on the PEI basement membrane that step 1 makes, was solidified 5～24 hours, promptly get described blend composite film after doing;
Described dimethyl silicone rubber is a flowable state, and its viscosity is between 5000Pa.s～50000Pa.s.
Described trifluoro propyl silicon rubber is flowable state, and viscosity is between 5000Pa.s～20000Pa.s.
Used solvent is any one in n-hexane, normal heptane, normal octane, cyclohexane, the benzene,toluene,xylene in the described step 2.
Surfactant solution in the described step 3 is the hybrid films liquid with the γ that contains 1%-6%-mercaptopropyl trimethoxysilane configuration.
The organic steam of the present invention's preparation separates blend composite film, and simple in structure, production cost is low.Polysiloxanes is to be the multiple polymers of skeleton with the silicon oxygen bond, is maximum, the most widely used classes of quantity in all silicon-containing compounds, and dimethyl silicone polymer accounts for more than 90% of the total consumption of siloxanes.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment 1
PEI is dissolved in N, in N-dimethylacetamide solvent or the N-methyl pyrrolidone, being mixed with concentration is the film liquid of 15-25%, and hydrostomia is on polyester non-woven fabric after filtration, the deaeration, hydrostomia thickness is 150 μ m, and gel is made PEI porous basement membrane in 15 ℃ water.Dimethyl siloxane silicon rubber or trifluoro propyl silicon rubber are dissolved in the normal heptane, and stirring is fully dissolved it.Add ethyl orthosilicate, dibutyl tin laurate and γ-mercaptopropyl trimethoxysilane again, continue stirring reaction a period of time, after filtration, the deaeration, film liquid is coated on the PEI basement membrane of handling, then under infrared lamp, solidify certain hour, promptly get composite membrane after doing.
Following examples see Table 1 and table 2 and table 3.
The preparation condition of table 1 example film
| Embodiment number | 1 | 2 | 3 | 4 | |||
| Film liquid is formed | Basement membrane | Membrane material (%) | PEI [15] | PEI [18] | PEI [20] | PEI [23] | |
| Solvent (%) | N-methyl pyrrolidone [70] | N-methyl pyrrolidone [68] | N-methyl pyrrolidone [65] | N-methyl pyrrolidone [62] | |||
| Separating layer | Membrane material (%) | Dimethyl silicone rubber (viscosity 10000Pa.s) [15] | Dimethyl silicone rubber (viscosity 10000Pa.s) [20] | Dimethyl silicone rubber (viscosity 10000Pa.s) [25] | Dimethyl silicone rubber (viscosity 10000Pa.s) [30] | ||
| Solvent (%) | Normal heptane [75] | Normal heptane [70] | Normal heptane [65] | Normal heptane [60] | |||
| Crosslinking agent (%) | Ethyl orthosilicate [10] | Ethyl orthosilicate [10] | Ethyl orthosilicate [10] | Ethyl orthosilicate [10] | |||
| Catalyst (mL) | Dibutyl tin laurate [8] | Dibutyl tin laurate [7] | Dibutyl tin laurate [6] | Dibutyl tin laurate [8] | |||
| Coupling agent (mL) | γ-mercaptopropyl trimethoxysilane [6] | γ-mercaptopropyl trimethoxysilane [7] | γ-mercaptopropyl trimethoxysilane [8] | γ-mercaptopropyl trimethoxysilane [8] | |||
| Dissolution conditions | Temperature (℃) | 25 | 25 | 25 | 25 | ||
| Time (min) | 120 | 180 | 210 | 240 | |||
| Film preparation technology | Basement membrane | Coagulation bath | Temperature (℃) | 15 | 15 | 15 | 15 |
| Form | Water | Water | Water | Water | |||
| Separating layer | One-step solidification | Temperature (℃) | 60 | 70 | 80 | 90 | |
| Time (h) | 5 | 6 | 7 | 8 | |||
Annotate: 1.[] the concrete numerical value of interior expression.
The preparation condition of table 2 example film
| Embodiment number | 5 | 6 | 7 | 8 | |||
| Film liquid is formed | Basement membrane | Membrane material (%) | PEI [15] | PEI [18] | PEI [20] | PEI [23] | |
| Solvent (%) | N-N-dimethylacetylamide [70] | N-N-dimethylacetylamide [68] | N-N-dimethylacetylamide [65] | N-N-dimethylacetylamide [62] | |||
| Separating layer | Membrane material (%) | Trifluoro propyl silicon rubber (viscosity 20000Pa.s) [15] | Trifluoro propyl silicon rubber (viscosity 20000Pa.s) [20] | Trifluoro propyl silicon rubber (viscosity 20000Pa.s) [25] | Trifluoro propyl silicon rubber (viscosity 20000Pa.s) [30] | ||
| Solvent (%) | Normal heptane [75] | Normal heptane [70] | Normal heptane [65] | Normal heptane [60] | |||
| Crosslinking agent (%) | Ethyl orthosilicate [10] | Ethyl orthosilicate [10] | Ethyl orthosilicate [10] | Ethyl orthosilicate [10] | |||
| Catalyst (mL) | Dibutyl tin laurate [8] | Dibutyl tin laurate [7] | Dibutyl tin laurate [6] | Dibutyl tin laurate [8] | |||
| Coupling agent (mL) | γ-mercaptopropyl trimethoxysilane [6] | γ-mercaptopropyl trimethoxysilane [7] | γ-mercaptopropyl trimethoxysilane [8] | γ-mercaptopropyl trimethoxysilane [8] | |||
| Dissolution conditions | Temperature (℃) | 25 | 25 | 25 | 25 | ||
| Time (min) | 120 | 180 | 210 | 240 | |||
| Film preparation technology | Basement membrane | Coagulation bath | Temperature (℃) | 15 | 15 | 15 | 15 |
| Form | Water | Water | Water | Water | |||
| Separating layer | One-step solidification | Temperature (℃) | 60 | 70 | 80 | 90 | |
| Time (h) | 9 | 10 | 11 | 12 | |||
Annotate: 1.[] the concrete numerical value of interior expression.
The film properties tabulation of table 3 example film
| No. | Infiltration coefficient P * 10 10(cm 3(STP)·cm)/(cm 2·s·cmHg) | Selectivity α=P Propylene/P Propane | |
| Propylene | Propane | ||
| 1 | 51 | 15 | 3.4 |
| 2 | 41.9 | 13.1 | 3.2 |
| 3 | 25.8 | 8.9 | 2.9 |
| 4 | 15.2 | 5.8 | 2.6 |
Annotate: 1. propylene accounts for 55% in the raw material, propane 45% (volume content), experimental temperature: room temperature, gas flow rate: 10-15ml/min, pressure reduction: 300-400kPa
The film properties tabulation of table 4 example film 3
| Temperature (K) | Infiltration coefficient P * 10 10(cm 3(STP)·cm)/(cm 2·s·cmHg) | Selectivity α=P Propylene/P Propane | |
| Propylene | Nitrogen | ||
| 293 | 7510 | 185 | 40.6 |
| 313 | 6120 | 265 | 23.1 |
Annotate: 1. propylene accounts for 20% in the raw material, nitrogen 80% (volume content), gas flow rate: 10-15ml/min, pressure reduction: 300-400kPa.
Claims (9)
1. the blend composite film that separates of an organic steam is characterized in that it contains:
Polyalkylene polyether acid imide basement membrane, membrane material are PEI, and mass percent all is 15%-23%, and solvent is N, N-dimethylacetylamide or N-methyl pyrrolidone;
The silicon rubber blend film is coated on the described PEI basement membrane; In this silicon rubber blend film, membrane material is dimethyl siloxane silicon rubber or trifluoro propyl silicon rubber, and mass percent all is 15%-30%, and crosslinking agent all is an ethyl orthosilicate, and mass percent is 10%, and solvent all is a normal heptane.
2. the preparation method of the separatory blend composite film of organic steam is characterized in that, contains following steps successively:
Step 1: basement membrane preparation
PEI is dissolved in N by the mass percent of 15%-23%, in N-dimethylacetylamide or the N-methyl pyrrolidone, be configured to preparation liquid, after filtration, after the deaeration, hydrostomia is on polyester non-woven fabric, hydrostomia thickness is 120 μ m～180 μ m, makes PEI porous basement membrane in 15-25 ℃ water behind the gel;
Step 2: configuration separating layer blend film liquid
Is mass percent that dimethyl siloxane silicon rubber or the trifluoro propyl silicon rubber ratio on demand of 15%-30% is dissolved in the normal heptane solvent, adds the crosslinking agent ethyl orthosilicate again, and mass percent is 10%; Add the 6ml-8ml dibutyl tin laurate then and make catalyst, be configured to separating layer blend film liquid;
Step 3: preparation contains the separating layer blend film liquid of surfactant
γ-the mercaptopropyl trimethoxysilane that adds mass percent and be 1%-6% in the separating layer blend film liquid that step 2 makes is made coupling agent, makes the separating layer blend film liquid that contains surfactant, after filtration, standby after the deaeration;
Step 4: blend film preparation
The uniform hydrostomia of separating layer blend film liquid that contains surfactant of gained in the step 3 on the PEI basement membrane that step 1 makes, was solidified 5～24 hours, promptly get described blend composite film after doing.
3. a kind of organic steam according to claim 1 separates the preparation method of blend composite film, and it is characterized in that: described dimethyl silicone rubber is a flowable state, and its viscosity is between 5000Pa.s～50000Pa.s.
4. a kind of organic steam according to claim 2 separates the preparation method of blend composite film, and it is characterized in that: used dimethyl silicone rubber is a flowable state in the step 2, and its viscosity is between 5000Pa.s～50000Pa.s.
5. a kind of organic steam according to claim 1 separates the preparation method of blend composite film, and it is characterized in that: described trifluoro propyl silicon rubber is flowable state, and its viscosity is between 5000Pa.s～50000Pa.s.
6. a kind of organic steam according to claim 2 separates the preparation method of blend composite film, and it is characterized in that: used trifluoro propyl silicon rubber is flowable state in the step 2, and its viscosity is between 5000Pa.s～50000Pa.s.
7. a kind of organic steam according to claim 1 separates the preparation method of blend composite film, and it is characterized in that: the solvent in the film liquid of described silicon rubber blend film is any one in n-hexane, normal heptane, normal octane, cyclohexane, the benzene,toluene,xylene.
8. the preparation method of the blend composite film that a kind of organic steam according to claim 2 separates, it is characterized in that: the used solvent of the described separating layer blend film of step 2 liquid is any one in n-hexane, normal heptane, normal octane, cyclohexane, the benzene,toluene,xylene.
9. the preparation method of the blend composite film that a kind of organic steam according to claim 2 separates is characterized in that: the surfactant solution in the step 3 is the hybrid films liquid that contains the γ that mass percent is 1%-6%-mercaptopropyl trimethoxysilane configuration.
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| CN101590375A (en) * | 2008-05-27 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Be used for composite membrane of removing organic sulfide from liquefied gas thing and preparation method thereof |
| CN101591580A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of desulfuration method of environmental-friendly liquefied petroleum gas |
| CN101254416B (en) * | 2007-12-07 | 2010-05-19 | 厦门大学 | Preparation of gelatine- aminosilane- -anode alumina compound film with affinity |
| CN102327747A (en) * | 2011-08-01 | 2012-01-25 | 大连理工大学 | Fluorine-containing polysiloxane rubber state composite gas separation membrane, preparation method and application thereof |
| CN111054224A (en) * | 2020-01-17 | 2020-04-24 | 南京大学 | Preparation method of high-molecular composite membrane for gas separation |
| CN114432893A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Fluorine-containing pervaporation membrane and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101254416B (en) * | 2007-12-07 | 2010-05-19 | 厦门大学 | Preparation of gelatine- aminosilane- -anode alumina compound film with affinity |
| CN101590375A (en) * | 2008-05-27 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Be used for composite membrane of removing organic sulfide from liquefied gas thing and preparation method thereof |
| CN101590375B (en) * | 2008-05-27 | 2013-04-17 | 北京三聚环保新材料股份有限公司 | Composite membrane for removing organic sulfide from liquefied gas and preparation method thereof |
| CN101591580A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of desulfuration method of environmental-friendly liquefied petroleum gas |
| CN101591580B (en) * | 2008-05-29 | 2013-06-26 | 北京三聚环保新材料股份有限公司 | Desulfuration method of environmental-friendly liquefied petroleum gas |
| CN102327747A (en) * | 2011-08-01 | 2012-01-25 | 大连理工大学 | Fluorine-containing polysiloxane rubber state composite gas separation membrane, preparation method and application thereof |
| CN111054224A (en) * | 2020-01-17 | 2020-04-24 | 南京大学 | Preparation method of high-molecular composite membrane for gas separation |
| CN111054224B (en) * | 2020-01-17 | 2021-06-22 | 南京大学 | Preparation method of high-molecular composite membrane for gas separation |
| CN114432893A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Fluorine-containing pervaporation membrane and preparation method thereof |
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