CN103706263B - High flux carbon dioxide separation cellulose ether derivatives composite membrane and preparation method thereof - Google Patents
High flux carbon dioxide separation cellulose ether derivatives composite membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 102
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 87
- 150000002170 ethers Chemical class 0.000 title claims abstract description 75
- 229920003086 cellulose ether Polymers 0.000 title claims abstract description 72
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000000926 separation method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 14
- 230000004907 flux Effects 0.000 title claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000004807 desolvation Methods 0.000 claims abstract description 8
- 238000007711 solidification Methods 0.000 claims abstract description 8
- 230000008023 solidification Effects 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 20
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 20
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000001856 Ethyl cellulose Substances 0.000 claims description 15
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 15
- 229920001249 ethyl cellulose Polymers 0.000 claims description 15
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 15
- 229920000609 methyl cellulose Polymers 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004697 Polyetherimide Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229920001601 polyetherimide Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000012510 hollow fiber Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001761 ethyl methyl cellulose Substances 0.000 claims description 2
- 235000010944 ethyl methyl cellulose Nutrition 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
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- 239000004642 Polyimide Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000009792 diffusion process Methods 0.000 abstract description 6
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- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 82
- 210000004379 membrane Anatomy 0.000 description 69
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- 230000008595 infiltration Effects 0.000 description 35
- 229940071676 hydroxypropylcellulose Drugs 0.000 description 19
- 229910000831 Steel Inorganic materials 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000001923 methylcellulose Substances 0.000 description 12
- 235000010981 methylcellulose Nutrition 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 239000012465 retentate Substances 0.000 description 11
- 235000012489 doughnuts Nutrition 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
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- 229920003091 Methocel™ Polymers 0.000 description 6
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- 238000013019 agitation Methods 0.000 description 5
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- 238000007761 roller coating Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
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- 210000000433 stratum disjunctum Anatomy 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000012530 fluid Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of high flux carbon dioxide separation cellulose ether derivatives composite membrane and preparation method thereof, belongs to gas separation field.Cellulose ether derivatives coating solution is coated in high polymer stephanoporate support membrane surface by this composite membrane, forms the composite membrane of the cellulose ether derivatives selection compacted zone with 2～20 μm.Its preparation method is: mixed with good solvent by cellulose ether derivatives, 25～80 DEG C of stirrings, deaerations and remove solid impurity, is configured to the cellulose ether derivatives coating solution that content is 2～12wt.%；Cellulose ether derivatives coating solution is coated in high polymer stephanoporate support membrane surface, desolvation, forms cellulose ether derivatives after dry solidification and select compacted zone.The composite membrane of the present invention, has high CO concurrently2Selectivity and permeability, be better than tradition CO2Separate film, and stability is higher than current faciliated diffusion film；Raw material sources is extensive, cheap, nontoxic pollution-free.
Description
Technical field
The present invention relates to one and from industrial gases, separate carbon dioxide (CO based on selectively penetrating mechanism2) high-performance fiber element ether
Analog derivative composite membrane, and the preparation method of this film, belong to gas separation field.This composite gas separation utilizes fiber
The affinity interaction of ether-oxygen bond functional group in element ether derivative, preferentially through CO2, and propped up at high polymer stephanoporate by the inventive method
The surface of support film is prepared ultra-thin flawless cellulose ether derivatives and is selected compacted zone, it is achieved that CO2Infiltration high flux and high selection
Property.
Background technology
From gas, carbon dioxide removal is the separation process that the fields such as oil, chemical industry, the energy and environment generally exist.Natural gas,
CO in manufactured gas2The calorific value of fuel can be reduced, containing a large amount of CO in the flue gas of burning and exhausting2, its discharge is to cause greenhouse
The main cause of effect, therefore, is badly in need of efficient isolation technics and removes CO cost-effectively from these systems2, reduce CO2's
Discharge.
Membrane Gas Separation Processes is a kind of isolation technics without phase-changeable gas with transmembrane pressure as motive force, has that energy consumption is low, technique is simple
The advantages such as list.High selectivity is the key that high-efficiency and low-cost industrial gases separate with the gas separation membrane of Thief zone speed.Business at present
The CO of industry2Separate film generally with glassy polymers or rubbery feel polymer for fine and close selective separating.Glassy state CO2Separate film
Selectivity is higher, but infiltration rate is on the low side, such as, the polyetherimde films of the preparations such as calendar year 2001 Shieh and Chung, CO2/CH4
Selectivity is up to 62, but CO2Infiltration rate only has 7.44GPU(10-6cm3.cm-2.s-1.cmHg-1)；Hillock in 2007 and
The polyimide film of the preparation such as Koros, CO2/CH4Selectivity reaches 45, CO2Infiltration rate only has 10GPU.Rubbery state CO2
The infiltration rate separating film is higher, but selectivity is on the low side, such as, and poly dimethyl prepared by Scholes and Stevens in 2010 etc.
Silicone film, CO2Infiltration rate reach 780GPU, but CO2/N2Selectivity only has 11；Calendar year 2001 Orme and Harrup
Deng the poly phosphazene film of preparation, CO2Infiltration rate reaches 75GPU, but CO2/N2Selectivity only has 20.Select suitable high score
Sub-material, uses suitable masking means, research and development to have Thief zone speed and high score concurrently from selective CO2Separate film, be realize low
Cost removing CO2Problem demanding prompt solution.
In recent years, faciliated diffusion membrance separation CO2Research get more and more: based on ether-oxygen bond functional group to CO2The separation of affinity interaction
Film, typical material has Polyethylene Glycol, ether-amide block copolymer, polyethyleneglycol diacrylate；Based on anionic functional group with
CO2Forming the separation film of Lewis Acids and Bases effect, typical material has ionic liquid, poly ion liquid, quaternized material；Based on
Amine functional group is to CO2The separation film of chemical absorbing, typical material have ethanolamine, polyvinylamine, amine grafting functional fluidized polymer,
Chitosan.Although these macromolecular materials containing specific functional groups can realize CO simultaneously2Thief zone speed and high selectivity,
But these materials are in deficiencies such as filming performance, material price, membrane stabilities, strongly limit faciliated diffusion CO2Separate film industrialization.
Cellulose is the natural macromolecular material being widely present in a kind of nature, is a kind of macromolecular polysaccharide being made up of glucose.
Prepare gas separation membrane with cellulose and cellulose derivative for raw material, be construct membrane technology industry based on Renewable resource important
Approach.But, there is hydrogen bond action between the alcoholic extract hydroxyl group functional group of cellulose, insoluble in most of solvents, it is difficult to prepare gas and divide
From film.Chemical modification (aoxidize, be esterified, be etherified, graft copolymerization) can be greatly improved cellulose dissolving energy in organic solvent
Power, thus improve machine-shaping property, such as, cellulose and acetic anhydride at 20 century 70s just react the cellulose acetate generated
For preparing gas separation membrane, it it is one of most important several industrialization membrane material.
Cellulose ether derivatives, such as ethyl cellulose, methyl is generated with halogenated hydrocarbon or reacting ethylene oxide after cellulose alkalization
Cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose.Under room temperature, cellulose ether derivatives chloroform, toluene, methanol,
In ethanol, acetone, butanone, oxolane, ethyl acetate, pyridine equal solvent, dissolubility is higher, can prepare macromolecular solution and prepare
Gas separation membrane.Late 1980s, ethyl cellulose is just used for preparing gas separation membrane.Younger sisters Chen Shan in 1988 etc. are by molten
Liquid casting is prepared for ethyl cellulose homogeneous membrane, but stratum disjunctum is thicker, and gas permeability is relatively low.The patent of Pinnau application in 1989
(US Patent No:4871378) describe a kind of with ethyl cellulose porous asymmetric film as basement membrane, with poly-4-methyl-1-pentene
Alkene is the composite membrane selecting cortex, separates for oxygen nitrogen.1994, Liu Guixiang et al., with non-woven fabrics as supporting layer, passed through inversion of phases
Method is prepared for the anisotropic membrane of ethyl cellulose, separates for oxygen nitrogen, but is limited by technique, and cortex is defective, and separation selectivity is relatively
Low.
One important feature of cellulose ether derivatives is characterised by (can having in 1 glucose ring group containing a large amount of ether-oxygen bond functional groups
5 ether oxygens key functional groups), for CO2Faciliated diffusion provides the carrier of abundance.Obviously, cellulose ether derivatives is that one has concurrently
CO2Faciliated diffusion and good filming, and natural macromolecule modification material cheap and easy to get.Cellulose ether derivatives is utilized to prepare
High performance gas separation film, is that low-cost separation traps CO2Effective way.Prepare ultra-thin flawless cellulose ether derivatives
Selective separating, is to produce high flux, high selectivity CO2Separate the key of film.
The structure of cellulose ether derivatives
Summary of the invention
It is an object of the invention to provide a kind of high flux carbon dioxide separation cellulose ether derivatives composite membrane and preparation method thereof.
This composite membrane has cellulose ether derivatives and selects compacted zone and high polymer stephanoporate support membrane；Will by the way of solution applies
Cellulose ether derivatives coating solution is coated in high polymer stephanoporate support membrane surface, is compounded to form the cellulose ether with 2～20 μm
Analog derivative selects the composite membrane of compacted zone.This cellulose ether derivatives composite membrane, utilizes the affinity interaction of ether-oxygen bond functional group
Improving carbon dioxide selectivity, its ultra-thin flawless selection compacted zone provides high gas permeation rate simultaneously.
For achieving the above object, the technical scheme preparing cellulose ether derivatives composite membrane that the present invention provides is: use solution to be coated with
The method of applying selects to cause at the ultra-thin flawless cellulose ether derivatives that surface recombination thickness is 2～20 μm of high polymer stephanoporate support membrane
Close layer, realizes high selectivity by ether-oxygen bond functional group faciliated diffusion and zero defect structure, achieves Thief zone by superthin structure and leads to
Amount.
The preparation method of the high flux carbon dioxide separation cellulose ether derivatives composite membrane of the present invention, its step is as follows:
(1) preparation of cellulose ether derivatives coating solution: mixed with its good solvent by cellulose ether derivatives, at 25～80 DEG C
Stirring, deaeration also remove solid impurity, are configured to the cellulose ether derivatives coating solution that content is 2～12wt.%；Configuration fiber
Operation temperature during element ether derivative solution determines according to the boiling point of cellulose ether derivatives good solvent, than selected cellulose
Ether derivative good solvent boiling point is low 20～45 DEG C, and too high temperature causes solvent saturated vapour pressure higher, and too low temperature causes fibre
Dimension element ether derivative dissolution velocity is the slowest.
(2) preparation of cellulose ether derivatives composite membrane: cellulose ether derivatives coating solution is coated in high polymer stephanoporate and props up
Support film surface, desolvation under the conditions of 20～50 DEG C, form the cellulose ether derivatives that thickness is 2～20 μm after dry solidification
Compacted zone, high polymer stephanoporate support membrane and cellulose ether derivatives is selected to select the integral structure of compacted zone to be cellulose ethers
Derivant composite membrane；After film, solvent evaporating temperature determines according to the boiling point of cellulose ether derivatives good solvent, than the fiber selected
Element ether derivative good solvent boiling point is low 25～50 DEG C, and too high temperature causes solvent evaporation excessive velocities, it is difficult to formed flawless
Selective separating, too low temperature causes solution viscosity big, it is difficult to prepare the cellulose ether derivatives separation skin of ultra-thin (2～20 μm)
Layer.
The cellulose ether derivatives that the present invention uses is ethyl cellulose, methylcellulose, hydroxyethyl cellulose or hydroxy propyl cellulose
One or more mixing of element, its average degree of polymerization is 500～3000, average substitution degree is 1.2～2.3.
The cellulose ether derivatives good solvent that the present invention uses is chloroform, toluene, methanol, ethanol, acetone, butanone, tetrahydrochysene furan
Mutter, ethyl acetate, pyridine one or more mixing.
The surface porosity factor material of the high molecular polymer porous support membrane that the present invention uses is polypropylene, Polyetherimide, polyamides Asia
Amine, polysulfones, poly (aryl ether sulfone ketone), polyether sulfone, Merlon, Kynoar, polyacrylonitrile etc., be not limited to above-mentioned material.
The surface porosity factor of the high molecular polymer porous support membrane that the present invention uses is 60～80%, average pore size 10～200nm；Table
Face porosity is too high, and the mechanical strength of composite membrane is low, it is difficult to commercial Application, and surface porosity factor is too low, and composite membrane gas permeability is poor；
Aperture is excessive, and cellulose ether derivatives solution penetrates in fenestra, it is difficult to preparing ultra-thin selective separating, gas permeation rate is low, hole
Footpath is too small, and cellulose ether derivatives cortex is poor with porous support layer associativity, is easily peeled off, poor stability.
The high polymer stephanoporate support membrane of the multi-form that the present invention uses is hollow fiber form, flat or tubular type.
The mode being coated on porous support layer by solution in the present invention can be dip-coating, roller coating, scratch and spray.
The present invention prepares the cellulose ether derivatives composite membrane prepared by the present invention in the present invention, can be used for gas separation process,
From industrial gases, especially separate CO2(natural gas, crude synthesis gas, flue gas, biogas, refinery exhaust etc.).
Beneficial effects of the present invention:
1) present invention selects cellulose ether derivatives to prepare CO2Separating film, this is that a class natural macromolecular material is cellulose modified
Product, wide material sources, cheap, nontoxic pollution-free；May be dissolved in multi-solvents, convenient processing film forming.
2) present invention selects cellulose ether derivatives to prepare CO2Separate film, be coated with membrane process and can select ethanol, acetone, acetic acid second
Esters etc. are nontoxic, non-environmental-pollution solvent, can build green masking route.
3) present invention selects cellulose ether derivatives as selective separating, contains and promotes CO in a large number2The ether-oxygen bond functional group of infiltration,
The composite membrane of preparation has higher CO2Separation selectivity.
4) solution of cellulose ether derivatives is coated on suitable porous support layer preparation CO by the present invention2Composite membrane for separation, system
Standby process is simple, and film-formation result is good, zero defect selective separating thickness little (2～20 μm), and gas permeation rate is fast, and composite membrane machinery is strong
Degree height, resistance to pressure is good.
5) the cellulose ether derivatives composite membrane selectivity of the present invention is high, fast (high osmosis film: the CO of infiltration rate2Infiltration rate
More than 120GPU, CO2/CH4Selectivity is not less than 20；High selective membrane: CO2/CH4Selectivity is more than 60, CO2Infiltration speed
Rate is not less than 15GPU), exceed the CO prepared at present with rubbery state/glassy polymers2Separate the performance of film.
6) the cellulose ether derivatives composite membrane of the present invention is used to carry out CO2Removing, CO2Removing degree and concentrating degree high,
Valuable gases utilization rate is high, membrane separation device scale down, and separation costs reduces.
Accompanying drawing explanation
Fig. 1 is the experimental provision of the separating property of test cellulose ether derivatives composite membrane.
Fig. 2 is the composite membrane microstructure of polyacrylonitrile flat porous support layer blade coating cellulose ether derivatives.
Fig. 3 is the composite membrane microstructure of Polypropylene plates porous support layer roller coating cellulose ether derivatives.
Fig. 4 is the composite membrane microstructure of polyvinylidene fluoride flat porous support layer blade coating cellulose ether derivatives.
Fig. 5 is the composite membrane microstructure of Polyetherimide doughnut porous support layer dip-coating cellulose ether derivatives.
Fig. 6 is the composite membrane microstructure of Polyetherimide doughnut porous support layer spray fiber element ether derivative.
In figure: R is the organo-functional groups such as ethyl, methyl, ethoxy or hydroxypropyl；H is hydrogen atom；O is oxygen atom；a1、
a2It it is gaseous mixture steel cylinder；B is preheating/surge tank；C is hollow fiber film assembly；D is plate film assembly, e1～e3It it is Pressure gauge；
f1～f5It it is sampling valve；g1～g4It it is effusion meter.
Detailed description of the invention
In embodiment described later, use the gas fractionation unit shown in Fig. 1, utilize cellulose ether derivatives composite membrane from
CO2/N2、CO2/CH4Deng separation CO in gaseous mixture2.The hollow fiber film assembly of test, loads 10 hollow fiber film threads,
Silk external diameter 800 μm, length 25cm, effective length 20cm after filling, the effective infiltrating area of assembly is 50.24cm2.Test is used
Plate film assembly, film diameter 5cm, effective diameter 4cm after filling, effective infiltrating area 12.56cm of assembly2。
The gas permeability and separation performance of membrane module is drawn by below equation.
F unstripped gas；R oozes residual air；P permeates gas；I component i(CO2；N2；CH4).
Q volume flow cm3/s；Y mole fraction；P pressure cmHg；Δ p transmembrane pressure cmHg；A area cm2。
J infiltration rate cm3/cm2/cmHg/s；αCO2>iCO in process of osmosis2Selectivity to i.
Containing CO2Gas is from steel cylinder (a1<CO2/N2>, simulated flue gas；a2<CO2/CH4>, simulate raw gas) it is decompressed to survey
Pressure testing power (0.1～2.0MPag) exports, and temperature is controlled at 25～60 DEG C in preheating/surge tank (b).Unstripped gas enters film
After assembly, first assembly feed side is purged, 20 minutes time；Residual air is oozed by the Valve controlling of regulation retentate side after having purged
Flow, with the ratio of regulation infiltration gas and unstripped gas；After stablizing 30 minutes, pass through e1～e3Measure unstripped gas and the pressure of infiltration gas
Power, the pressure oozing residual air is approximately equal to feed pressure；By sampling valve f1～f5Gather gaseous sample, carry out gas chromatographic analysis；Logical
Inflow-rate of water turbine meter g1～g4Measuring and ooze residual air and the flow of infiltration gas, the flow of unstripped gas is sum of the two, and its unit is cm3/s.Above-mentioned
Sampling and data acquisition all repeat three times.Finally, by the flow, pressure and the composition data that obtain, the gas calculating film oozes
Separating property thoroughly.Gas permeation rate unit is GPU(10-6cm3.cm-2.s-1.cmHg-1).
Hollow fiber film assembly (c) is tested: gaseous mixture enters the tube side (filametntary inner chamber) of assembly from membrane module entrance；CO2
Penetrate through membrance separation layer, enter the shell side of assembly, from the outlet output of infiltration gas；N2Or CH4Tunicle stratum disjunctum retains, along
Filametntary direction is at tube side flow, from oozing residual air outlet output.
Plate film assembly (d) is tested: gaseous mixture enters the feed reservoir of assembly from membrane module entrance；CO2Penetrate through membrance separation layer,
Enter the osmotic cell of assembly, from the outlet output of infiltration gas；N2Or CH4Tunicle stratum disjunctum retains, along membrane plane direction at raw material
Pond effluent moves, from oozing residual air outlet output.
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Solution is prepared: accurately weighed by electronic balance 92g ethanol (analytical pure) and 8g methylcellulose powder (analytical pure,
Average substitution degree 1.85, average degree of polymerization 2000)；Ethanol and methylcellulose are mixed in ground conical flask, seals bottleneck,
Under the conditions of 40 DEG C, magnetic agitation dissolves 24h one-tenth homogeneous phase solution；Use 100 mesh filter-cloth filtering solution, then (maskings under room temperature condition
Room temperature controls at 25 DEG C) stand 24h deaeration, obtain the methylcellulose/ethanol coating solution of 8wt.%, stand-by.
Porous support layer pretreatment: (surface porosity factor about 68%, average pore size is about for the asymmetric porous support layer of homemade polyacrylonitrile
73nm) in thermostatic drying chamber, (50 DEG C) are dried 8h, are cooled to room temperature 25 DEG C；Dried supporting layer is fixed on flat board,
Horizontal positioned is stand-by.
Blade coating film forming: the methocel solution configured is watered in right amount on the porous support layer being fixed on flat board；By smooth
Methocel solution is scratched on porous support layer by straight Glass rod equably；The copper wire being tied with a diameter of 100 μm on Glass rod comes
Control the thickness of blade coating solution.
Dry solidification: blow and coat the related fixed flat planar of supporting layer of methocel solution and put into that to heat up in advance be the constant temperature of 40 DEG C together
In drying baker, at 40 DEG C of dry 12h desolvations, Methyl cellulose element coating is made to be fully cured film forming；The flat composite membrane that will make
Taking off from fixed flat planar, the diaphragm being cut into a diameter of 5cm dresses up plate film assembly, stand-by.
Performance test 1: raw material is from steel cylinder a1<CO2/N2>, CO2Content be 15mol%, by temperature in preheating/surge tank
Control at 45 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1；0.2；0.4；0.8；1.5；2.0MPag)；
By regulation effusion meter inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by infiltration gas with former
The ratio of material gas controls to be about 0.15.
Performance test 2: raw material is from steel cylinder a2<CO2/CH4>, CO2Content be 8mol%, by temperature in preheating/surge tank
Control at 45 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1/0.2/0.5/1.0/2.0MPag)；Flowed by regulation
Gauge inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by the ratio of infiltration gas with unstripped gas
Control is about 0.10.
The separating property of table 1 polyacrylonitrile flat porous support layer blade coating Compound methylcellulose films.
Data from table 1 understand, in test pressure limit, and the CO of polyacrylonitrile/Compound methylcellulose films2/N2Selectivity can
Reach 42.0, CO2/CH4Selectivity can reach 67, CO2Infiltration rate can reach 25.5GPU.Before guarantee is higher optionally
Put, the CO that the infiltration rate of this composite membrane is higher higher than other selectivitys2Separate film.
Embodiment 2
Solution is prepared: accurately weighed 96g ethyl acetate (analytical pure) by electronic balance and 4g hydroxypropyl cellulose powder (divides
Analyse pure, average substitution degree 1.70, average degree of polymerization 1500)；Ethyl acetate and hydroxypropyl cellulose are mixed in ground conical flask,
Sealing bottleneck, under the conditions of 60 DEG C, magnetic agitation dissolves 12h one-tenth homogeneous phase solution；Use 100 mesh filter-cloth filtering solution, then room
Under the conditions of temperature, (masking room temperature controls at 25 DEG C) stands 24h deaeration, obtains the hydroxypropyl cellulose/ethyl acetate film of 4wt.%
Solution, stand-by.
Porous support layer pretreatment: the asymmetric porous support layer of polypropylene (surface porosity factor about 78%, the average pore size about 185 of purchase
Nm) soak and remove oiliness pollutant in acetone, be transferred in deionized water remove acetone and other hydrophilic substances, after natural air drying
In thermostatic drying chamber, (50 DEG C) are dried 8h, are cooled to room temperature 25 DEG C；Dried supporting layer is cut into suitable dimension, Gu
It is scheduled on the roller of roll-on device, places stand-by.
Roller coating film forming: the hydroxypropyl cellulose solution configured is added the material fluid bath of roll-on device, secures the roller portion of supporting layer
Sub-dip enters in coating solution (edge immerses about 1cm), rotates (2 circles/minute) according to setting speed, removes material fluid bath after two circles,
It is rotated further roller substantially to evaporate to solvent.
Dry solidification: take off the polypropylene support layer scribbling hydroxypropyl cellulose from roller, putting into the constant temperature that intensification in advance is 50 DEG C
In drying baker, at 50 DEG C of dry 8h desolvations, hydroxy propyl cellulose element coating is made to be fully cured film forming；The plate compounding that will make
Film is cut into the diaphragm of a diameter of 5cm and dresses up plate film assembly, stand-by.
The separating property of table 2 Polypropylene plates porous support layer roller coating hydroxypropyl cellulose composite membrane.
Performance test 1: raw material is from steel cylinder a1<CO2/N2>, CO2Content be 15mol%, by temperature in preheating/surge tank
Control at 25 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1；0.2；0.4；0.8；1.5；2.0MPag)；
By regulation effusion meter inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by infiltration gas with former
The ratio of material gas controls to be about 0.15.
Performance test 2: raw material is from steel cylinder a2<CO2/CH4>, CO2Content be 8mol%, by temperature in preheating/surge tank
Control at 25 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1/0.2/0.5/1.0/2.0MPag)；Flowed by regulation
Gauge inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by the ratio of infiltration gas with unstripped gas
Control is about 0.10.
Data from table 2 understand, in test pressure limit, and the CO of polypropylene/hydroxypropyl cellulose composite membrane2Infiltration rate can
Reach 105.4, CO2/N2Selectivity can reach 29.4, CO2/CH4Selectivity can reach 15.6.Before ensureing relatively Thief zone speed
Putting, this composite membrane selectivity is better than the CO that other infiltration rates are higher2Separate film.
Embodiment 3
Solution is prepared: accurately weighed 88g oxolane (analytical pure) by electronic balance and 12g ethyl cellulose powder (is analyzed
Pure, average substitution degree 2.25, average degree of polymerization 1200)；Oxolane and ethyl cellulose are mixed in ground conical flask, seals
Bottleneck, under the conditions of 30 DEG C, magnetic agitation dissolves 24h one-tenth homogeneous phase solution；Use the filter-cloth filtering solution of 100 mesh, then room temperature
Under the conditions of (masking room temperature controls at 25 DEG C) stand 24h deaeration, the ethyl cellulose/oxolane film obtaining 12wt.% is molten
Liquid, stand-by.
Porous support layer pretreatment: the asymmetric porous support layer of homemade Kynoar (surface porosity factor about 60%, average pore size
About 25nm) (50 DEG C) dry 8h in thermostatic drying chamber, it is cooled to room temperature 25 DEG C；Dried supporting layer is fixed on flat
On plate, horizontal positioned is stand-by.
Blade coating film forming: the ethyl cellulose solution configured is watered in right amount on the porous support layer being fixed on flat board；By smooth
Ethyl cellulose solution is scratched on porous support layer by straight Glass rod equably；The copper wire being tied with a diameter of 100 μm on Glass rod comes
Control the thickness of blade coating solution.
Dry solidification: blow and coat the related fixed flat planar of supporting layer of ethyl cellulose solution and put into that to heat up in advance be the constant temperature of 35 DEG C together
In drying baker, then heat to 50 DEG C at 35 DEG C of dry 6h and be dried 6 hours desolvations, make ethyl cellulose element coating the most solid
Chemical conversion film；Being taken off from fixed flat planar by the flat composite membrane made, the diaphragm being cut into a diameter of 5cm dresses up plate film assembly,
Stand-by.
Performance test 1: raw material is from steel cylinder a1<CO2/N2>, CO2Content be 15mol%, by temperature in preheating/surge tank
Control at 25 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1；0.2；0.4；0.8；1.5；2.0MPag)；
By regulation effusion meter inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by infiltration gas with former
The ratio of material gas controls to be about 0.15.
Performance test 2: raw material is from steel cylinder a2<CO2/CH4>, CO2Content be 8mol%, by temperature in preheating/surge tank
Control at 25 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1/0.2/0.5/1.0/2.0MPag)；Flowed by regulation
Gauge inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by the ratio of infiltration gas with unstripped gas
Control is about 0.10.
Data from table 3 understand, in test pressure limit, and the CO of polypropylene/hydroxypropyl cellulose composite membrane2Infiltration rate can
Reach 47.7, CO2/N2Selectivity can reach 30.1, CO2/CH4Selectivity can reach 16.3.Before ensureing relatively Thief zone speed
Putting, this composite membrane selectivity is better than the CO that other infiltration rates are higher2Separate film.
The separating property of table 3 polyvinylidene fluoride flat porous support layer blade coating ethyl cellulose composite membrane.
Embodiment 4
Solution is prepared: accurately weighed by electronic balance 92g pyridine (analytical pure) and 8g methylcellulose powder (analytical pure,
Average substitution degree 1.85, average degree of polymerization 2000)；Pyridine and methylcellulose are mixed in ground conical flask, seals bottleneck,
Under the conditions of 60 DEG C, magnetic agitation dissolves 4h one-tenth homogeneous phase solution；Use the filter-cloth filtering solution of 100 mesh, then (system under room temperature condition
Film room temperature controls at 25 DEG C) stand 24h deaeration, obtain the methylcellulose/pyridine coating solution of 8wt.%, stand-by.
Porous support layer pretreatment: homemade Polyetherimide doughnut porous support layer (surface porosity factor about 72%, average hole
Footpath about 45nm) (50 DEG C) dry 8h in thermostatic drying chamber, it is cooled to room temperature 25 DEG C；By dried doughnut porous
Supporting layer is cut into appropriate length (30cm), stand-by.
Dip-coating film forming: the methocel solution configured is added in dip tank；The doughnut porous support layer that will be of convenient length
Stage casing immerse in methocel solution and keep 30 seconds, after taking-up, filametntary two ends are fixed on traversing carriage.
Dry solidification: scrape and coat the related support of supporting layer of methocel solution and put into that to heat up in advance be the freeze-day with constant temperature of 55 DEG C together
In case, at 65 DEG C of dry 12h desolvations, Methyl cellulose element coating is made to be fully cured film forming；The doughnut made is combined
Film takes off from support, is cut into the silk of 25cm length according to painting diaphragm area, is assembled into membrane module stand-by.
Performance test 1: raw material is from steel cylinder a1<CO2/N2>, CO2Content be 15mol%, by temperature in preheating/surge tank
Control at 45 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1；0.2；0.4；0.8；1.5；2.0MPag)；
By regulation effusion meter inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by infiltration gas with former
The ratio of material gas controls to be about 0.15.
The separating property of table 4 Polyetherimide doughnut porous support layer dip-coating Compound methylcellulose films.
Performance test 2: raw material is from steel cylinder a2<CO2/CH4>, CO2Content be 8mol%, by temperature in preheating/surge tank
Control at 45 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1/0.2/0.5/1.0/2.0MPag)；Flowed by regulation
Gauge inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by the ratio of infiltration gas with unstripped gas
Control is about 0.10.
Data from table 4 understand, in test pressure limit, and the CO of Polyetherimide/Compound methylcellulose films2/N2Selectivity
Can reach 39.7, CO2/CH4Selectivity can reach 64.2, CO2Infiltration rate can reach 26.8GPU.Ensureing higher selectivity
On the premise of, the CO that the infiltration rate of this composite membrane is higher higher than other selectivitys2Separate film.
Embodiment 5
Solution is prepared: accurately weighed by electronic balance 97g acetone (analytical pure) and 3g hydroxypropyl cellulose powder (analytical pure,
Average substitution degree 1.70, average degree of polymerization 1200)；Acetone and hydroxypropyl cellulose are mixed in ground conical flask, seal bottleneck,
Under the conditions of 30 DEG C, magnetic agitation dissolves 24h one-tenth homogeneous phase solution；Use the filter-cloth filtering solution of 100 mesh, then under room temperature condition
(masking room temperature controls at 25 DEG C) stands 24h deaeration, obtains the hydroxypropyl cellulose/acetone coating solution of 8wt.%, stand-by.
Porous support layer pretreatment: homemade Polyetherimide doughnut porous support layer (surface porosity factor about 72%, average hole
Footpath about 45nm) (50 DEG C) dry 8h in thermostatic drying chamber, it is cooled to room temperature 25 DEG C；By dried doughnut porous
Supporting layer is cut into appropriate length (30cm)；Filametntary two ends are fixed on traversing carriage, between each cellosilk, avoid phase mutual connection
Touch, stand-by.
Spraying film forming: the hydroxypropyl cellulose solution configured is added in the material liquid tank of atomizing lance, be sprayed on by nitrogen atomization
On the cellosilk fixed；Spraying 5 seconds, intermittently 1 minute, spray four times every time.
Dry solidification: be coated with the related support of supporting layer of hydroxypropyl cellulose solution and put into that to heat up in advance be that the constant temperature of 30 DEG C is done together
In dry case, then heat to 50 DEG C at 30 DEG C of dry 6h and be dried 6 hours desolvations, make hydroxy propyl cellulose element coating the most solid
Chemical conversion film；The hollow fiber composite membrane made is taken off from support, is cut into the silk of 25cm length according to painting diaphragm area, is assembled into
Membrane module is stand-by.
The separating property of table 5 Polyetherimide doughnut porous support layer spraying hydroxypropyl cellulose composite membrane.
Performance test 1: raw material is from steel cylinder a1<CO2/N2>, CO2Content be 15mol%, by temperature in preheating/surge tank
Control at 45 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1；0.2；0.4；0.8；1.5；2.0MPag)；
By regulation effusion meter inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by infiltration gas with former
The ratio of material gas controls to be about 0.15.
Performance test 2: raw material is from steel cylinder a2<CO2/CH4>, CO2Content be 8mol%, by temperature in preheating/surge tank
Control at 45 DEG C；Unstripped gas enters the pressure of membrane module and is divided into 5 grades (0.1/0.2/0.5/1.0/2.0MPag)；Flowed by regulation
Gauge inlet valve, the Stress control of infiltration gas is atmospheric pressure；By regulating the valve of retentate side, by the ratio of infiltration gas with unstripped gas
Control is about 0.10.
Data from table 5 understand, in test pressure limit, and the CO of polypropylene/hydroxypropyl cellulose composite membrane2Infiltration rate can
Reach 131.2, CO2/N2Selectivity can reach 28.2, CO2/CH4Selectivity can reach 15.0.Before ensureing relatively Thief zone speed
Putting, this composite membrane selectivity is better than the CO that other infiltration rates are higher2Separate film.
Claims (6)
1. a high flux carbon dioxide separation cellulose ether derivatives composite membrane, it is characterised in that this composite membrane has cellulose ether derivatives and selects compacted zone and high polymer stephanoporate support membrane；By the way of solution applies, cellulose ether derivatives coating solution is coated in high polymer stephanoporate support membrane surface, is compounded to form and has 2 ~ 20μThe cellulose ether derivatives of m selects the composite membrane of compacted zone；
Described cellulose ether derivatives is one or more mixing of ethyl cellulose, methylcellulose, hydroxyethyl cellulose or hydroxypropyl cellulose, and its average degree of polymerization is 500 ~ 3000, average substitution degree is 1.2 ~ 2.3；The surface porosity factor of high polymer stephanoporate support membrane is 60 ~ 80%, average pore size 10 ~ 200nm.
High flux carbon dioxide separation cellulose ether derivatives composite membrane the most according to claim 1, it is characterized in that, the material of described high polymer stephanoporate support membrane is polypropylene, Polyetherimide, polyimides, polysulfones, poly (aryl ether sulfone ketone), polyether sulfone, Merlon, Kynoar or polyacrylonitrile.
3. according to the preparation method of the high flux carbon dioxide separation cellulose ether derivatives composite membrane described in claim 1 or 2, it is characterised in that:
(1) preparation of cellulose ether derivatives coating solution: mixed with good solvent by cellulose ether derivatives, 25 ~ 80 DEG C of stirrings, deaerations and remove solid impurity, is configured to the cellulose ether derivatives coating solution that content is 2 ~ 12 wt.%；
(2) preparation of cellulose ether derivatives composite membrane: cellulose ether derivatives coating solution is coated in high polymer stephanoporate support membrane surface, desolvation under the conditions of 20 ~ 50 DEG C, forming thickness after dry solidification is 2 ~ 20μThe cellulose ether derivatives of m selects compacted zone, high polymer stephanoporate support membrane and cellulose ether derivatives to select the integral structure of compacted zone to be cellulose ether derivatives composite membrane.
The preparation method of high flux carbon dioxide separation cellulose ether derivatives composite membrane the most according to claim 3, it is characterized in that, described good solvent is one or more mixing of chloroform, toluene, methanol, ethanol, acetone, butanone, oxolane, ethyl acetate, pyridine.
The preparation method of high flux carbon dioxide separation cellulose ether derivatives composite membrane the most according to claim 3, it is characterised in that described high polymer stephanoporate support membrane is hollow fiber form, flat or tubular type.
The preparation method of high flux carbon dioxide separation cellulose ether derivatives composite membrane the most according to claim 4, it is characterised in that described high polymer stephanoporate support membrane is hollow fiber form, flat or tubular type.
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| CN88102873A (en) * | 1987-04-08 | 1988-11-30 | 联合碳化公司 | Be used for the composite membrane that enhance fluid is separated |
| CN1043949A (en) * | 1987-11-05 | 1990-07-18 | 联合碳化公司 | Poly-(methyl methacrylate) mixture composite membrane and the preparation method and the purposes of modification |
| US6472016B1 (en) * | 1998-12-04 | 2002-10-29 | Societe Des Ceramiques Techniques | Membrane comprising a porous carrier and a layer of a molecular sieve and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN88102873A (en) * | 1987-04-08 | 1988-11-30 | 联合碳化公司 | Be used for the composite membrane that enhance fluid is separated |
| CN1043949A (en) * | 1987-11-05 | 1990-07-18 | 联合碳化公司 | Poly-(methyl methacrylate) mixture composite membrane and the preparation method and the purposes of modification |
| US6472016B1 (en) * | 1998-12-04 | 2002-10-29 | Societe Des Ceramiques Techniques | Membrane comprising a porous carrier and a layer of a molecular sieve and its preparation |
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