CN104841288B - One kind is used for CO2/N2Detached microgel composite membrane of gas and preparation method thereof - Google Patents
One kind is used for CO2/N2Detached microgel composite membrane of gas and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of be used for CO2/N2Detached microgel composite membrane of gas and preparation method thereof, with N-isopropylacrylamide (NIPAM) as monomer, N, N methylene-bisacrylamides are crosslinking agent, ammonium persulfate is initiator, prepares PNIPAM PNIPAM microgels (particle diameter is in 600～800nm) under normal temperature with hyperhydrated ability using surfactant- free emulsion polymerization.Adopt polysulfones Flat Membrane for filter layer, suction filtration is carried out to microgel dispersion, make PNIPAM microgels uniformly be compounded in membrane surface, form the composite film material with Molecular Sieving Properties.Test shows that composite membrane is to CO2Permeability and separation is functional, for CO2/N2Pure gas, CO2Infiltration rate is (60～180) cm3(STP)/cm2S cmHg, ideal separation factor 20～70.For 20vol%CO2/ 80vol%N2Mixed gas, CO2Infiltration rate is in 70～180cm3(STP)/cm2S cmHg, mixed gas separation are 15～60.The membrane separating process Nonpoisonous, non-environmental-pollution, process is simple can be applicable to gas separation field.
Description
Technical field
The invention belongs to separation material field, more particularly to a kind of for CO2/N2Gas separation material and preparation method thereof.
Background technology
Greenhouse gases CO2A large amount of discharges caused by global warming become one of main Environmental Problems now,
During economic development, it is to realize energy-saving and emission-reduction, eco-friendly GDP growth pattern, realizes the zero growth rate of carbon emission
Even how negative growth, control CO2Discharge, reasonably trapping, reclaim CO2Gas, to realize its recycling, is the whole world
The Tough questions for facing.
Gas membrane Seperation Technology has small investment, and operating cost is low, and equipment is simply light easy to operate, and environmental friendliness etc. is excellent
Gesture, is widely used in the CO of the separation of refuse landfill aerogenesis, natural gas refining, power plant flue gas and industrial process waste gas2Point
From fields such as enrichments.It is solution coating (dip-coating) method for composite gas separation most common method is prepared, dip coating is letter
The method that single practical preparation has thin and compact cortex composite membrane.In research in recent years, the gas point that thus prepared by method
Very big lifting has been obtained from compound film properties.
Cationic polymer polymethylacrylic acid-N, N- dimethylaminoethyls (PDMAEMA) are coated in poly- by Feng et al.
Sulfone milipore filter basement membrane cortical surface, and make crosslinking agent with to benzyl dichloride (XDC), in the solid-state separating layer of PDMAEMA/PS composite membranes
And the interface between liquid cross-linking reagent solution carries out cross-linking reaction, define with stable molecule structure and can be with CO2Gas
There is the quaternized crosslinked polymer coated film of invertible dissolution diffusion.【Poly (N, N-dimethylaminoethyl
methacrylate)/polysulfone composite membranes for gas separations.Journal of
Membrane Science, 2006,279：76-85】In CO2When feeding gas partial pressure is 0.41MPa, CO2Infiltration rate be 30 ×
10-6cm3(STP)/cm2S cmHg, CO2/N2Gas selectivity is 53.
Ji et al. is by radical polymerization and interface-cross-linked synthesis one kind simultaneous with alkaline quaternary amines and ether epoxide
Polymethylacrylic acid-the N of group, N- dimethylaminoethyls-polyethylene glycol monomethyl ether acrylate (PDMAEMA-PEGMEA) copolymerization
Thing, the functional layer as composite gas separation are coated in the polysulfones material hollow-fibre membrane surface of loose structure.【Impacts
of coating condition on composite membrane performance for CO2
Separation.Separation and Purification Technology, 2010,71：160-167】When copolymer
Ethanol solution concentration is 2wt%, and when repeating 6 coating operations, composite membrane is to obtain most at 0.3MPa in feed gas pressure
Best performance, CO2Infiltration rate is 25 × 10-6cm3(STP)/cm2S cmHg, CO2/N2、CO2/CH4And CO2/H2Segregative line
Number is respectively 45,20 and 4.1.
Wang et al. proposes to prepare the CO in separation flue gas first2Anti-oxidant composite gas separation general
Read.【An antioxidative composite membrane with the carboxylate group as a fixed
carrier for CO2Separation from flue gas.Energy＆Environmental Science, 2011,4：
3955-3959】PAA (AAS) with different ratio with acrylamide (AAm) mixture as monomer, using radical polymerization
Conjunction has been synthesized can be with CO2There is the base copolymer P (AAS-co-AAm) containing carboxylate radical that dissolving diffusion interacts,
With the polymer as gas separating. functional layer, polysulfones basement membrane is supporting layer, is prepared for the faciliated diffusion film only containing carboxylate radical carrier
PAAS/PS and P (AAS-co-AAm)/PS.By a series of gas permeation rates, separation property test is selected to show the carboxylate radical
Fixed carrier composite membrane stable performance, is difficult oxidized, and CO2Infiltration rate up to 180 × 10-6cm3(STP)/cm2·s·
cmHg.
CO2In Deng transmittance process of the sour gas in film, gas permeation rate and selection separating property and gas are multiple
The dissolving diffusion rate that closes in film has relation.In film, the presence of Free water can greatly strengthen CO2Affine energy with composite membrane
Power, CO2Combined in the form of Weak Acid Ion with water, reversible reaction is occurred with functional layer gelatin polymer in film, so as in pressure reduction
In the presence of be delivered to opposite side from the side of film.Intelligent temperature sensing material PNIPAM microgels possess excellent hydration at normal temperatures
Ability, for nanoscale gel particle, water-swellable multiplying power is loaded to PS membrane membrane surface and is conducive to carrying up to decades of times
High gas separation membrane is to CO2Deng the dissolving diffusion of sour gas, separating power is selected so as to improve which.
Content of the invention
It is an object of the invention to provide a kind of with PNIPAM PNIPAM micro-gel particles as functional layer
Composite membrane and preparation method thereof, the composite membrane with mechanical performance, pressure functional, to CO2Gas has excellent separation property
Can be a kind of novel gas separation membrane material of structure with selected area update strategy performance.
Present invention microgel composite membrane and its preparation technology are as follows：
Prepared by 1.PNIPAM microgels
1.1 with temperature sensing material N-isopropylacrylamide (NIPAM) as monomer, and N-isopropylacrylamide monomer is through 4: 6 hexamethylenes
Use after being vacuum dried at 40 DEG C after alkane/toluene Mixed Solvent recrystallization purification.N, N- methylene-bisacrylamide is crosslinking agent.
Ammonium persulfate is initiator, and monomer is 14: 1～15: 1 with crosslinking agent quality ratio, with deionized water as solvent, consumption be monomer with
50～80 times of crosslinking agent gross mass.3～5wt% of the initiator amount for monomer gross mass, being made into mass percent concentration is
The initiator solution of 1wt%.
1.2 synthesize PNIPAM microgel emulsions using surfactant- free emulsion polymerization.By the monomer of said ratio, crosslinking agent point
Do not add in the deionized water of letting nitrogen in and deoxidizing, be dissolved to colourless transparent solution, be added to and turn equipped with reflux condensing tube, magnetic force
In the 250ml there-necked flasks of son, thermometer and nitrogen inlet, after stirring one hour, 70 DEG C are warming up to, after constant temperature 30min, are added
Initiator solution, after a few minutes, system is changed into light blue from colourless, then to milky.After 3h, reaction terminates, and is cooled to room
Temperature, products therefrom are the translucent microgel dispersions of PNIPAM.25 DEG C, particle size range is 300～800nm.
Above-mentioned products therefrom deionized water is cleaned three times by 1.3, by centrifugation after cleaning every time, by gel and water
Solution is separated, to remove unreacted monomer, crosslinking agent or small molecule.Finally by PNIPAM microgel dispersions in deionized water
In.
2. prepared by flat board basement membrane
2.1 prepare casting solution, and casting solution consists of membrane material polysulfones, pore-foaming agent PVP K30, and solvent is
DMA.Membrane material mass fraction is 14%～20%, and pore-foaming agent mass fraction is 0～6%.
2.2 add above-mentioned casting solution component in 500ml there-necked flasks according to a certain ratio, mechanical agitation heating at 70 DEG C
12-24h forms homogeneous mixed liquor, and at 50 DEG C, de-bubbled 12-24h is standby.
2.3 are poured on casting solution on clean smooth glass plate, with stainless steel metal rod by its uniform striking film forming.In glass
Plate is scraped the film for making and places about 30s in air, then immerses glass plate in deionized water, is frozen into asymmetric many
Hole plate film, saves backup under room temperature under distillation water environment.
3. micro-gel particles thin-film composite membrane
3.1 compound membrane process.Polysulfones Flat Membrane obtained above is cut into the circle that diameter is suitable for, in absolute ethyl alcohol
Middle immersion 12 hours is improving basement membrane hydrophily；Take and prepare PNIPAM microgel dispersions, diaphragm is placed for filter layer
In Buchner funnel, microgel dispersion 25ml～100ml under negative pressure, is filtered, make PNIPAM gels be evenly distributed on PS membrane
Surface, forms microgel functional layer.
The 3.2 micro-gel particles thin-film composite membranes for obtaining said process are 20-30 DEG C in temperature, and humidity is 80%-
Save backup in 100% climatic chamber.
The method have the characteristics that uniform for temperature sensing material PNIPAM micro-gel particles suction filtration is coated on polysulphone super-filter membrane base
Film surface, obtains for CO2/N2Detached composite gas separation.PNIPAM gel particle Film laminateds prepared by the present invention
Film is to CO2/N2Have2Infiltration rate, it is easy to operate, simple structure.For CO2
And N2Pure gas, when feed gas pressure is 0.1MPa-1MPa, ideal separation factor α CO2/N2=40～55, CO2Maximum infiltration speed
Rate is up to 126 × 10-6cm3(STP)/cm2S cmHg, for 20vol%CO2/ 80vol%N2Mixed gas, in feeding gas
When pressure is 0.1MPa-1MPa, maximum separation factor alpha CO2/N2Up to 47, CO2Maximum infiltration rate is up to 140 × 10-6cm3
(STP)/cm2·s·cmHg.
Advantage for present invention：
1., under room temperature normal temperature, the PNIPAM micro-gel particles with temperature-sensing property are in below 33 DEG C of critical solution temperature,
Can high degree of hydration swelling, swelling ratio is coated on PS membrane surface up to 20～50 times, enhances the water-retaining property on film surface
Energy.
2. the high degree of hydration of composite film surface PNIPAM micro-gel particles is conducive to CO2The dissolving diffusion of gas, height water
The micro-gel particles of conjunction are used as CO2The transmission channel of gas and carrier promote composite membrane to CO2/N2The permeability and separation of gas
Energy.
Specific embodiment：
The present invention is further discussed below with reference to embodiment, but the present invention should not be limited by the examples；
Embodiment 1：
By 1.4g N-isopropylacrylamides (NIPAM) monomer (using front through 4: 6 hexamethylenes/toluene Mixed Solvent recrystallization
After purification at 40 DEG C be vacuum dried after), 0.1gN, N- methylene-bisacrylamides add 120ml deionized waters in, immigration is equipped with
In the 250ml there-necked flasks of condenser pipe, thermometer and nitrogen inlet, heat up after letting nitrogen in and deoxidizing 30min under 100rpm stirring at low speed
To 70 DEG C, constant temperature 30min, after adding 1wt% ammonium persulfate aqueous solutions 5ml reaction 3h, is cooled to room temperature, and products therefrom is
The translucent microgel dispersions of PNIPAM.Above-mentioned products therefrom deionized water is cleaned three times, by centrifugation after cleaning every time
Gel is separated by mode with the aqueous solution, to remove unreacted monomer, crosslinking agent or small molecule.Finally by PNIPAM microgels point
Dissipate in deionized water.
The polysulfones casting solution that mass percentage concentration is 14%, pore-foaming agent concentration are prepared as solvent with DMA
For 3%, at 70 DEG C, fully melting forms homogeneous casting solution.Casting solution is poured on clean smooth glass plate after deaeration completely, is used
Stainless steel metal rod is by its uniform striking film forming.The film for making is scraped in glass plate about 30s is placed in air, then by glass plate
In immersion deionized water, asymmetric porous flat plate film is frozen into, is saved backup under distillation water environment under room temperature.
Flat Membrane is cut into circle, is soaked 12 hours in absolute ethyl alcohol, is laid in Buchner funnel, takes PNIPAM microgels
Dispersion liquid 50ml, with diaphragm as filter layer, filters the microgel dispersion under negative pressure, make gel be evenly distributed on PS membrane table
Face, forms PNIPAM microgel functional layers, obtains the composite membrane with PNIPAM micro-gel particles as functional layer.
Use CO2, N2Pure gas carries out performance test respectively to composite membrane, when admission pressure is 0.1MPa-1MPa, CO2Infiltration
Speed (85～126) × 10-6cm3(STP)/cm2S cmHg, between ideal separation factor 40～55.For 20vol%CO2/
80vol%N2Mixed gas, when feed gas pressure is 0.1MPa～1MPa, CO2Infiltration rate (85～140) × 10-6cm3
(STP)/cm2S cmHg, mixed gas separation 30～50.
Embodiment 2：
By 1.5g N-isopropylacrylamides (NIPAM) (using front through 4: 6 hexamethylenes/toluene Mixed Solvent recrystallization purification
After being vacuum dried at 40 DEG C afterwards), 0.1gN, N- methylene-bisacrylamides are put into 80ml deionized waters simultaneously and stir, immigration
In 250ml there-necked flasks equipped with condenser pipe, thermometer and nitrogen inlet, letting nitrogen in and deoxidizing 30min under 100rpm stirring at low speed rises
To 70 DEG C, constant temperature 30min, after adding 6ml ammonium persulfate aqueous solutions reaction 3h, is cooled to room temperature to temperature, and products therefrom is PNIPAM
Translucent microgel dispersion.Above-mentioned products therefrom deionized water is cleaned three times, will by centrifugation after cleaning every time
Gel is separated with the aqueous solution, to remove unreacted monomer, crosslinking agent or small molecule, finally by microgel dispersion in deionized water
In.At 25 DEG C, microgel particle diameter is 600nm or so.
The polysulfones casting solution that mass percentage concentration is 17%, pore-foaming agent concentration are prepared as solvent with DMA
For 6%, at 70 DEG C, fully melting forms homogeneous casting solution.Casting solution is poured on clean smooth glass plate after deaeration completely, is used
Stainless steel metal rod is by its uniform striking film forming.The film for making is scraped in glass plate about 30s is placed in air, then by glass plate
In immersion deionized water, asymmetric porous flat plate film is frozen into, is saved backup under distillation water environment under room temperature.
Flat Membrane is cut into circle, is soaked 12 hours in absolute ethyl alcohol, is laid in Buchner funnel, takes microgel dispersion
100ml, with diaphragm as filter layer, filters the microgel dispersion under negative pressure, make gel be evenly distributed on PS membrane surface, is formed
PNIPAM microgel functional layers, obtain the composite membrane with PNIPAM micro-gel particles as functional layer.
Use CO2, N2Gas carries out performance test respectively to composite membrane, when feed gas pressure is 0.1MPa～1MPa, CO2Ooze
Saturating speed (65～105) × 10-6cm3(STP)/cm2·s·cmHg.Ideal separation factor 45～70.For 20vol%CO2/
80vol%N2Mixed gas, when feed gas pressure is 0.1MPa～1MPa, CO2Infiltration rate (70～100) × 10-6cm3
(STP)/cm2S cmHg, mixed gas separation 30～60.
Embodiment 3：
By 1.5g N-isopropylacrylamides (NIPAM) (using front through 4: 6 hexamethylenes/toluene Mixed Solvent recrystallization purification
After being vacuum dried at 40 DEG C afterwards), 0.1gN, N- methylene-bisacrylamides are put into 100ml deionized waters simultaneously and stir, shifting
Enter in the 250ml there-necked flasks equipped with condenser pipe, thermometer and nitrogen inlet, letting nitrogen in and deoxidizing 30min under 100rpm stirring at low speed,
70 DEG C are warming up to, constant temperature 30min, after adding 7.5ml ammonium persulfate aqueous solutions reaction 3h, is cooled to room temperature, and products therefrom is
The translucent microgel dispersions of PNIPAM.Above-mentioned products therefrom deionized water is cleaned three times, by centrifugation after cleaning every time
Gel is separated by mode with the aqueous solution, to remove unreacted monomer, crosslinking agent or small molecule, finally by microgel dispersion in going
In ionized water.At 25 DEG C, micro-gel particles particle diameter is 800nm or so.
The polysulfones casting solution that mass percentage concentration is 17% is prepared, pore-foaming agent concentration is 3%, and DMA is
Solvent, at 70 DEG C, fully melting forms homogeneous casting solution.Casting solution is poured on clean smooth glass plate after deaeration completely, with not
Rust steel metal rod is by its uniform striking film forming.The film for making being scraped in glass plate about 30s being placed in air, then glass plate is soaked
Enter in deionized water, be frozen into asymmetric porous flat plate film, save backup under distillation water environment under room temperature.
Flat Membrane is cut into circle, is soaked 12 hours in absolute ethyl alcohol, is laid in Buchner funnel, takes microgel dispersion
25ml, with diaphragm as filter layer, filters the microgel dispersion under negative pressure, make gel be evenly distributed on PS membrane surface, is formed
PNIPAM microgel functional layers, obtain the composite membrane with PNIPAM micro-gel particles as functional layer.
Use CO2, N2Pure gas carries out performance test respectively to composite membrane, when feed gas pressure is 0.1MPa～1MPa, CO2
Infiltration rate (95～180) × 10-6cm3(STP)/cm2·s·cmHg.Ideal separation factor 20～30.For 20vol%CO2/
80vol%N2Mixed gas, when feed gas pressure is 0.1MPa～1MPa, CO2Infiltration rate (130～180) × 10-6cm3
(STP)/cm2S cmHg, mixed gas separation 15～35.
It should be noted last that, above specific embodiment only in order to technical scheme to be described and unrestricted,
Although being described in detail to the present invention with reference to example, it will be understood by those within the art that, can be to the present invention
Technical scheme modify or equivalent, without deviating from the spirit and scope of technical solution of the present invention, which all should be covered
In the middle of scope of the presently claimed invention.
Claims (5)
1. a kind of for CO2/N2The preparation method of the detached microgel composite membrane of gas, it is characterised in that preparation process is as follows：
1) with temperature sensing material N-isopropylacrylamide (NIPAM) as monomer, using front through 4: 6 hexamethylenes/toluene Mixed Solvent weight
Use after being vacuum dried at 40 DEG C after crystallization and purification；N, N- methylene-bisacrylamide is crosslinking agent, monomer and crosslinking agent quality
Than for 14: 1～15: 1；With deionized water as solvent, consumption is 50～80 times of monomer and crosslinking agent gross mass；Mass percent
Ammonium persulfate solution for 1% is initiator, and initiator amount is the 3～5% of monomer gross mass；
2) monomer of said ratio, crosslinking agent are separately added in the deionized water of letting nitrogen in and deoxidizing, are dissolved to water white transparency
Solution, is added in the 250ml there-necked flasks equipped with reflux condensing tube, magnetic rotor, thermometer and nitrogen inlet, and stirring one is little
Shi Hou, is warming up to 70 DEG C, after constant temperature 30min, adds the ammonium persulfate aqueous solution that mass percent is 1%；After 3h, reaction terminates,
Room temperature is cooled to, products therefrom is translucent PNIPAM (PNIPAM) microgel dispersion；25 DEG C, gained micro-
Microgel particle size range in gel dispersion liquid is 300-800nm；By above-mentioned products therefrom deionized water clean three times, every time
By centrifugation after cleaning, gel is separated with the aqueous solution, to remove unreacted monomer, crosslinking agent or small molecule, finally
By PNIPAM microgel dispersions in deionized water；
3) polysulfones flat board basement membrane is prepared：Prepare casting solution, polysulfones is membrane material, pore-foaming agent is PVP K30, solvent
For DMA, polysulfones mass fraction is 14%～20%, and pore-foaming agent PVP K30 mass fraction is
0～6%；Above-mentioned casting solution component is added in 500ml there-necked flasks according to a certain ratio, mechanical agitation heating 12-24h at 70 DEG C
Homogeneous mixed liquor is formed, de-bubbled 12-24h is standby at 50 DEG C；
4) casting solution is poured on clean smooth glass plate, with stainless steel metal rod by its uniform striking film forming；Scrape in glass plate
The film for making places 30s in air, then immerses glass plate in deionized water, is frozen into asymmetric porous flat plate film, room
Save backup under distillation water environment under temperature；It is some that the polysulfones basement membrane for obtaining is cut into the appropriate circular film of diameter, in anhydrous second
Abundant soaked overnight in alcohol；
5) polysulfones Flat Membrane obtained above is cut into the circle that diameter is suitable for, 12 hours are soaked in absolute ethyl alcohol to change
Kind basement membrane hydrophily；Take and prepare PNIPAM microgel dispersions, diaphragm is positioned in Buchner funnel for filter layer, negative pressure
Lower filtration microgel dispersion 25ml～100ml, makes PNIPAM gels be evenly distributed on PS membrane surface, forms microgel work(
Ergosphere, obtains the composite membrane with PNIPAM micro-gel particles as functional layer.
2. the one kind according to claims 1 is used for CO2/N2The preparation method of the detached microgel composite membrane of gas, its are special
Levy and be that it is with temperature sensing material N-isopropylacrylamide as monomer, using front through 4: 6 hexamethylenes/toluene to prepare PNIPAM microgels
Use after being vacuum dried at 40 DEG C after mixed solvent recrystallization purification；N, N- methylene-bisacrylamide be crosslinking agent, monomer with
Crosslinking agent quality ratio is 14: 1～15: 1；With deionized water as solvent, consumption is 50～80 times of monomer and crosslinking agent gross mass；
It is initiator that mass percent is 1% ammonium persulfate solution, and initiator amount is the 3～5% of monomer gross mass.
3. the one kind according to claims 1 is used for CO2/N2The preparation method of the detached microgel composite membrane of gas, its are special
Levy when being 25 DEG C of the PNIPAM microgels that prepare, particle size range is 300～800nm.
4. the one kind according to claims 1 is used for CO2/N2The preparation method of the detached microgel composite membrane of gas, its are special
Levy be polysulfones Flat Membrane carry out microgel compound before, 12 hours will be soaked in absolute ethyl alcohol in advance to reach hydrophilic changing
The purpose of property.
5. the one kind according to claims 1 is used for CO2/N2The preparation method of the detached microgel composite membrane of gas, its are special
Levy and be with polysulfones Flat Membrane as filter membrane, with PNIPAM microgel dispersions as the suction filtration recombination process that filtrate is carried out in, micro- solidifying
Glue dispersion liquid is in 25ml～100ml scopes.
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| CN106040015A (en) * | 2016-06-29 | 2016-10-26 | 浙江大学 | High-throughput multilayer composite nano-filtration membrane and preparation method thereof |
| CN106110899B (en) * | 2016-07-08 | 2019-04-09 | 浙江工业大学 | Method for preparing carbon dioxide responsive membrane |
| US11052354B2 (en) * | 2016-12-20 | 2021-07-06 | Monash University | Reverse osmosis membrane and method of use |
| CN108097070B (en) * | 2017-12-19 | 2020-05-01 | 太原理工大学 | Zeolite imidazole ester doped polyether block amide gas separation membrane and preparation method and application thereof |
| CN109908765B (en) * | 2019-03-14 | 2021-12-03 | 闽江学院 | L-tartaric acid modified self-made microporous polymer membrane and preparation method thereof |
| CN111992037A (en) * | 2019-05-27 | 2020-11-27 | 宝山钢铁股份有限公司 | Forward osmosis hydrogel draw solution, preparation method and application thereof |
| CN112755808B (en) * | 2019-10-21 | 2022-12-09 | 中国石油化工股份有限公司 | Gel composite membrane for gas separation by hydrate method and preparation method thereof |
| KR20220053100A (en) * | 2020-10-21 | 2022-04-29 | 포항공과대학교 산학협력단 | Super-hydrophilic surface treatment method of filtration media, filter having super-hydrophilic surface for oil-water separation and method of fabricating the same |
| CN112244010A (en) * | 2020-10-26 | 2021-01-22 | 中国农业科学院农业环境与可持续发展研究所 | Temperature response type nanogel, preparation method thereof and preparation method of temperature response type pesticide drug-loading system containing nanogel |
| CN113785754B (en) * | 2021-09-07 | 2023-04-07 | 广东百林生态科技股份有限公司 | Preparation method and application of light three-dimensional greening water-retaining matrix |
| CN115212737B (en) * | 2022-07-15 | 2024-06-04 | 中国科学院烟台海岸带研究所 | Separation membrane for separating oxygen from air |
| CN115925101B (en) * | 2022-11-20 | 2024-08-23 | 沃顿科技股份有限公司 | High-efficient antipollution MBR membrane module |
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| JPS63270525A (en) * | 1987-04-30 | 1988-11-08 | Toray Ind Inc | Composite membrane for gas separation |
| JP2003038942A (en) * | 2001-07-31 | 2003-02-12 | Dainippon Ink & Chem Inc | Separation membrane |
| CN101910314A (en) * | 2007-11-05 | 2010-12-08 | Co2Crc技术股份有限公司 | Gas separation membranes and processes for the manufacture thereof |
| CN101638485B (en) * | 2009-07-17 | 2011-06-01 | 淮阴师范学院 | Method for synthesizing temperature sensitive degradation PNIPAM/CMCS microgel in nuclear shell structure |
| CN104490844A (en) * | 2014-12-02 | 2015-04-08 | 天津工业大学 | Core-shell-type microgel and preparation method thereof |
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