CN104722215A - Preparation method of carbon dioxide separation film based on graphene material - Google Patents
Preparation method of carbon dioxide separation film based on graphene material Download PDFInfo
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- CN104722215A CN104722215A CN201410526519.3A CN201410526519A CN104722215A CN 104722215 A CN104722215 A CN 104722215A CN 201410526519 A CN201410526519 A CN 201410526519A CN 104722215 A CN104722215 A CN 104722215A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000000926 separation method Methods 0.000 title claims abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000013019 agitation Methods 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000007711 solidification Methods 0.000 claims description 10
- 230000008023 solidification Effects 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 230000000640 hydroxylating effect Effects 0.000 claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002861 polymer material Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- -1 shitosan Polymers 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920006018 co-polyamide Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims 1
- 229920002873 Polyethylenimine Polymers 0.000 claims 1
- IYSNYCQLARBERC-UHFFFAOYSA-N methylsulfinylmethane;toluene Chemical compound CS(C)=O.CC1=CC=CC=C1 IYSNYCQLARBERC-UHFFFAOYSA-N 0.000 claims 1
- 229920001601 polyetherimide Polymers 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a carbon dioxide separation film based on a graphene material. The preparation method comprises the following steps: dispersing the graphene material into a polymer and coating on a porous carrier with a polymer to prepare a composite film; and applying the composite film to selective separation of carbon dioxide in mixed gas. The separation film ingeniously utilizes a specific molecule transmission property of the laminar graphene material and breaks through a limitation relation between the permeability and the selectivity in the carbon dioxide separation film, and a good carbon dioxide separation performance is performed. The method process is simple and economical, has a wide application range and is suitable for large-scale preparation.
Description
Technical field:
The present invention relates to a kind of preparation method of the carbon dioxide separation membrane based on grapheme material, prepared film may be used for the separation of carbon dioxide in gas mixture gas.
Background technology:
CO
2a kind of main greenhouse gases.Along with the demand of fossil fuel grows with each passing day, CO
2discharge capacity also sharp increase, the greenhouse effects thereupon produced, global warming issue just day by day serious threat production and the life of the mankind, so, reduce CO
2the most effective approach of global warming is alleviated in discharge.The separation of C O of industrial comparative maturity
2technology mainly contains: solvent absorption, adsorption method of separation, Deep Cooling Method and membrane separation technique.Solvent absorption is to CO
2good separating effect, its shortcoming be consume energy comparatively large, processing cost is higher.Adsorption method of separation utilizes solid absorbent separation of C O
2, its method of operating is simple, adaptable.But it is limited that its shortcoming is adsorption capacity, need a large amount of adsorbents, adsorption-desorption is frequent, and automaticity requires very high.Deep Cooling Method due to energy consumption large, cost is high, is usually applicable to CO in associated gas
2recovery.Compared with above-mentioned traditional separation method, gas membrane Seperation Technology has, non-secondary pollution low without phase transformation, energy consumption and equipment is simple, be easy to the advantages such as operation, is called as the third generation new gas isolation technics of most development and application prospect.In gas membrane Seperation Technology, gas separation membrane serves topmost effect.At present, gas membrane Seperation Technology mainly adopts organic film material, as polysiloxanes, polysulfones, polyacetylene, cellulose, polyamide, polyimides, polyethers etc.Although the pliability that organic film has had, higher separation, excellent processing characteristics, its transmission rates is low, non-refractory, and corrosion resistance is poor.Pure organic polymer films seldom has the restriction that can surmount permeability-selective balance.Inoranic membrane is relating to high temperature, have unique physics, chemical property and have good permeability and selective, but higher manufacturing cost is the restraining factors of its large-scale application in the system of Korrosionsmedium.
Graphene is with the structure of the atomic layer of its uniqueness, and its outstanding electricity, calorifics and mechanical performance, and not only at photoelectric device, sensor, battery material aspect has a wide range of applications, and also there is huge potential value in film field.But the operating condition of Graphene direct formation of film at surface is comparatively harsh, repeatability is poor, and stability is bad, and the grapheme material of self-supporting mechanicalness in actual environment is bad, causes it effectively not apply in actual industrial.
Summary of the invention:
The object of the invention is the preparation method providing a kind of carbon dioxide separation membrane based on grapheme material in order to improve the deficiencies in the prior art, the method is simple.Adopt method grapheme material being scattered in film forming in polymer, have simple to operate, the advantages such as repeatability, good stability are one solution routes effectively.
Technical scheme of the present invention is: a kind of preparation method of the carbon dioxide separation membrane based on grapheme material, and its concrete steps are as follows:
A) grapheme material is joined in solvent, after being disperseed, be configured to the dispersion liquid of 0.1 ~ 3mg/ml;
B) organic polymer material is added in solvent, be configured to the solution that mass percentage concentration is 1 ~ 20%, at 70 DEG C ~ 120 DEG C, add thermal agitation 4 ~ 8 hours, obtain polymer solution set aside for use;
C) by steps A) dispersion liquid join step B) polymer solution in, at 70 DEG C ~ 120 DEG C, add thermal agitation 10 ~ 16 hours, and then standing and defoaming at solution temperature being reduced to 40 DEG C ~ 60 DEG C, obtained coating liquid; Wherein the addition of dispersion liquid is the mass ratio of control grapheme material and organic polymer material is 0.1 ~ 3:100;
D) by step C) in coating liquid be coated on the side of supporter, naturally dry in atmosphere, be then heating and curing, the carbon dioxide separation membrane that solidification obtains based on grapheme material.
Preferably above-mentioned supporter is Kynoar (PVDF), polyether sulfone (PES), PEI (PEI), cellulose acetate (CA), mullite, Al
2o
3or ZrO
2in one or more compound support.The shape of preferred supporter is the one of chip, tubular type or hollow fiber form.The average pore size of preferred above-mentioned supporter is 20nm ~ 2000nm.
Preferably above-mentioned organic polymer material is at least the one in polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose, sodium alginate, shitosan, polyimides, polyether co-polyamide or dimethyl silicone polymer.
Preferably above-mentioned grapheme material is the one in sulfhydrylation Graphene, graphene oxide, hydroxylating Graphene, carboxylated Graphene or amination Graphene.
Preferred above-mentioned solvent is the one in water, ethanol, DMF, DMSO, toluene or dimethylbenzene.
In steps A, grapheme material is joined the mode of disperseing in solvent preferably to stir and ultrasonic disperse; Preferably described solidification temperature is 70 DEG C ~ 120 DEG C, and hardening time is 10 ~ 24 hours.
The present invention preferably carries out pretreatment to supporter, concrete grammar for supporting body surface is polished smooth, ultrasonic cleaning, then with deionized water by its surface washing totally and dry.
Beneficial effect:
The present invention is directed to the deficiency that gas separation membrane material kind is single in the market, use novel grapheme material, and combine the advantage of polymeric film material, the operating condition that compensate for Graphene direct formation of film at surface is comparatively harsh, repeatability is poor, not withstand voltage in actual environment, the shortcomings such as mechanical performance is low, and stability is bad.Meanwhile, by the thickness and the compactness extent that regulate the associated operating steps of the series of parameters of coating liquid and painting membrane process to control diffusion barrier, the gas separating property of Effective Regulation composite membrane, to adapt to different separation requirement.The inventive method technique simple economy, applied widely.
Accompanying drawing illustrates:
Fig. 1 is the transmission electron microscope photo of the composite membrane that example 3 obtains.
Detailed description of the invention:
Embodiment 1
1) taking 0.1g carboxylated Graphene joins in 50ml deionized water, is scattered in completely in water through stirring the ultrasonic carboxylated Graphene that makes.
2) add in 80g ethanol by 4g polyethylene glycol, at 70 DEG C, add thermal agitation 6 hours, solution left standstill is stand-by.
3) by 1) in the aqueous dispersions of carboxylated Graphene add step 2) in polyglycol solution, at 70 DEG C, add thermal agitation 10 hours, then standing and defoaming at solution temperature is reduced to 50 DEG C, obtained coating liquid.
4) by step 3) in coating liquid be coated on the chip Al that average pore size is 20nm
2o
3the side of supporter, dries in atmosphere naturally, and solidification temperature is 80 DEG C, and the time is 24 hours, obtains the gas separation membrane based on grapheme material.
Measure the obtained composite membrane of this example for CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2gas separating property, when temperature is 25 DEG C, when pressure is 0.3MPa, CO
2permeability be 70Barrer, CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2be selectively respectively 82,19 and 9.
Embodiment 2
1) taking 0.15g hydroxylating Graphene joins in 50ml DMF, is scattered in completely in DMF through stirring the ultrasonic carboxylated Graphene that makes.
2) add in 40g toluene by 10g carboxymethyl cellulose, at 80 DEG C, add thermal agitation 5 hours, solution left standstill is stand-by.
3) by 1) in the DMF dispersion liquid of hydroxylating Graphene add step 2) in cmc soln, at 90 DEG C, add thermal agitation 15 hours, then standing and defoaming at solution temperature is reduced to 60 DEG C, obtained coating liquid.
4) by step 3) in coating liquid be coated on the chip ZrO that average pore size is 200nm
2the side of supporter, dries in atmosphere naturally, and solidification temperature is 90 DEG C, and the time is 10 hours, obtains the gas separation membrane based on grapheme material.
Measure the obtained composite membrane of this example for CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2gas separating property, when temperature is 35 DEG C, when pressure is 0.2MPa, CO
2permeability be 82Barrer, CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2be selectively respectively 65,16 and 8.
Embodiment 3
1) taking 0.005g sulfhydrylation Graphene joins in 50ml DMSO, is scattered in completely in DMSO through stirring the ultrasonic sulfhydrylation Graphene that makes.
2) add in 30g dimethylbenzene by 3g sodium alginate, at 110 DEG C, add thermal agitation 4 hours, solution left standstill is stand-by.
3) by 1) in the DMSO dispersion liquid of sulfhydrylation Graphene add step 2) in sodium alginate soln, at 85 DEG C, add thermal agitation 12 hours, then standing and defoaming at solution temperature is reduced to 50 DEG C, obtained coating liquid.
4) by step 3) in coating liquid be coated on the side that average pore size is the tubular type mullite supporter of 1000nm, naturally dry in atmosphere, solidification temperature is 75 DEG C, and the time is 15 hours.Obtain the gas separation membrane based on grapheme material.
Measure the obtained composite membrane of this example for CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2gas separating property, when temperature is 55 DEG C, when pressure is 0.1MPa, CO
2permeability be 55Barrer, CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2be selectively respectively 55,15 and 7.5.Fig. 1 shows the transmission electron microscope photo of the composite membrane prepared by example 3.Can clearly find out from figure, grapheme material presents distinctive layer structure in polymer film, thus effectively improves molecule transmission speed wherein, improves the separating property of the carbon dioxide of composite membrane.
Embodiment 4
1) taking 0.05g amination Graphene enters in 50ml ethanol, is scattered in completely in ethanol through stirring the ultrasonic amination Graphene that makes.
2) add in 25g deionized water by 5g shitosan, at 95 DEG C, add thermal agitation 4 hours, solution left standstill is stand-by.
3) by 1) in the alcohol dispersion liquid of amination Graphene add step 2) in chitosan solution, at 100 DEG C, add thermal agitation 12 hours, then standing and defoaming at solution temperature is reduced to 40 DEG C, obtained coating liquid.
4) by step 3) in coating liquid be coated on the side that average pore size is the hollow fiber form PEI supporter of 500nm, naturally dry in atmosphere, solidification temperature is 100 DEG C, and the time is 20 hours, obtains the gas separation membrane based on grapheme material.
Measure the obtained composite membrane of this example for CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2gas separating property, when temperature is 55 DEG C, when pressure is 0.1MPa, CO
2permeability be 55Barrer, CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2be selectively respectively 55,15 and 7.5.
Embodiment 5
1) taking 0.15g graphene oxide enters in 50ml deionized water, is scattered in completely in deionized water through stirring the ultrasonic graphene oxide that makes.
2) add in 120g toluene by 5g dimethyl silicone polymer, at 90 DEG C, add thermal agitation 8 hours, solution left standstill is stand-by.
3) by 1) in the deionized water dispersion liquid of graphene oxide add step 2) in the dimethyl silicone polymer solution of the inside, at 100 DEG C, add thermal agitation 16 hours, then standing and defoaming at solution temperature is reduced to 40 DEG C, obtained coating liquid.
4) by step 3) in coating liquid be coated on the side that average pore size is the chip PVDF supporter of 1900nm, naturally dry in atmosphere, solidification temperature is 120 DEG C, and the time is 24 hours, obtains the gas separation membrane based on grapheme material.
Measure the obtained composite membrane of this example for CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2gas separating property, when temperature is 25 DEG C, when pressure is 0.2MPa, CO
2permeability be 60Barrer, CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2be selectively respectively 72,17 and 10.
Embodiment 6
1) taking 0.002g hydroxylating Graphene enters in 20ml ethanol, is scattered in completely in ethanol through stirring the ultrasonic hydroxylating graphite that makes.
2) add in 148.5g DMF by 1.5g polyimides, at 90 DEG C, add thermal agitation 6 hours, solution left standstill is stand-by.
3) by 1) in the alcohol dispersion liquid of hydroxylating Graphene add step 2) in the polyimide solution of the inside, at 75 DEG C, add thermal agitation 14 hours, then standing and defoaming at solution temperature is reduced to 50 DEG C, obtained coating liquid.
4) by step 3) in coating liquid be coated on the side that average pore size is the doughnut PES supporter of 1500nm, naturally dry in atmosphere, solidification temperature is 100 DEG C, and the time is 12 hours, obtains the gas separation membrane based on grapheme material.
Measure the obtained composite membrane of this example for CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2gas separating property, when temperature is 25 DEG C, when pressure is 0.3MPa, CO
2permeability be 85Barrer, CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2be selectively respectively 85,21 and 11.
Embodiment 7
1) taking 0.05g carboxylated Graphene enters in 50ml toluene, is scattered in completely in ethanol through stirring the ultrasonic hydroxylating graphite that makes.
2) add in 150g deionization by 3g shitosan, at 70 DEG C, add thermal agitation 5 hours, solution left standstill is stand-by.
3) by 1) in the toluene dispersion liquid of carboxylated Graphene add step 2) in the chitosan solution of the inside, at 90 DEG C, add thermal agitation 10 hours, then standing and defoaming at solution temperature is reduced to 60 DEG C, obtained coating liquid.
4) by step 3) in coating liquid be coated on the chip ZrO that average pore size is 1000nm
2the side of supporter, dries in atmosphere naturally, and solidification temperature is 110 DEG C, and the time is 24 hours, obtains the gas separation membrane based on grapheme material.
Measure the obtained composite membrane of this example for CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2gas separating property, when temperature is 45 DEG C, when pressure is 0.3MPa, CO
2permeability be 105Barrer, CO
2/ N
2, CO
2/ CH
4and CO
2/ H
2be selectively respectively 65,16 and 8.5.
Claims (7)
1., based on the preparation method of the carbon dioxide separation membrane of grapheme material, its concrete steps are as follows:
A) grapheme material is joined in solvent, after dispersion, be configured to the dispersion liquid of 0.1 ~ 3mg/ml;
B) organic polymer material is added in solvent, be configured to the solution that mass percentage concentration is 1 ~ 20%, at 70 DEG C ~ 120 DEG C, add thermal agitation 4 ~ 8 hours, obtain polymer solution set aside for use;
C) by steps A) dispersion liquid join step B) polymer solution in, at 70 DEG C ~ 120 DEG C, add thermal agitation 10 ~ 16 hours, and then standing and defoaming at solution temperature being reduced to 40 DEG C ~ 60 DEG C, obtained coating liquid; Wherein the addition of dispersion liquid is the ratio of control grapheme material and organic polymer material quality is 0.1 ~ 3:100;
D) by step C) in coating liquid be coated on the side of supporter, naturally dry in atmosphere, be then heating and curing, solidify, obtain the carbon dioxide separation membrane based on grapheme material.
2. preparation method according to claim 1, is characterized in that described supporter is at least Kynoar, polyether sulfone, PEI, cellulose acetate, mullite, Al
2o
3or ZrO
2in one.
3. preparation method according to claim 1, is characterized in that the average pore size of described supporter is 20nm ~ 2000nm; The shape of described supporter is the one of chip, tubular type or hollow fiber form.
4. preparation method according to claim 1, is characterized in that described organic polymer material is at least the one in polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose, sodium alginate, shitosan, polyimides, polyether co-polyamide or dimethyl silicone polymer.
5. preparation method according to claim 1, is characterized in that described grapheme material is the one in sulfhydrylation Graphene, graphene oxide, hydroxylating Graphene, carboxylated Graphene or amination Graphene.
6. preparation method according to claim 1, is characterized in that described solvent is the one in water, ethanol, DMF, DMSO toluene or dimethylbenzene.
7. preparation method according to claim 1, it is characterized in that described solidification temperature is 70 DEG C ~ 120 DEG C, hardening time is 10 ~ 24 hours.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413494A (en) * | 2016-01-04 | 2016-03-23 | 福州大学 | High-performance lyophilic PVDF/GO-lysine composite membrane |
| CN105921031A (en) * | 2016-05-15 | 2016-09-07 | 高学理 | Carboxylic oxidized graphene and method for modifying organic release film by means of same |
| CN106310978A (en) * | 2016-10-17 | 2017-01-11 | 江苏新风环保科技有限公司 | Compound air filter membrane based on chitosan and graphene oxide and preparation method of compound air filter membrane |
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| CN108794815A (en) * | 2018-02-12 | 2018-11-13 | 王清扬 | Including the composite material of graphene, preparation method and gas sensor |
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| CN109224782B (en) * | 2018-09-29 | 2021-02-12 | 中国科学院大连化学物理研究所 | Functionalized nano filler composite membrane, preparation method and application |
| CN109269394A (en) * | 2018-10-26 | 2019-01-25 | 钟祥博谦信息科技有限公司 | It is a kind of using PDMS as conductive film of base material and preparation method thereof |
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| CN110394071A (en) * | 2019-07-25 | 2019-11-01 | 辽宁科技大学 | A kind of mixed-matrix gas separation membrane material and preparation method thereof |
| CN113307999A (en) * | 2021-05-27 | 2021-08-27 | 长春工业大学 | Preparation method of amino polyaryletherketone/graphene oxide composite material |
| CN114602336A (en) * | 2022-03-07 | 2022-06-10 | 南京工业大学 | Mixed matrix membrane, steam-induced in-situ synthesis method and application thereof in H2/CO2Use in separations |
| CN114602336B (en) * | 2022-03-07 | 2022-12-20 | 南京工业大学 | Mixed matrix membrane, steam-induced in-situ synthesis method and method for synthesizing mixed matrix membrane in H 2 /CO 2 Use in separations |
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