CN118477493B - Carbon dioxide trapping base film, preparation method thereof and carbon dioxide trapping film applied to carbon dioxide trapping base film - Google Patents
Carbon dioxide trapping base film, preparation method thereof and carbon dioxide trapping film applied to carbon dioxide trapping base film Download PDFInfo
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- CN118477493B CN118477493B CN202410641132.6A CN202410641132A CN118477493B CN 118477493 B CN118477493 B CN 118477493B CN 202410641132 A CN202410641132 A CN 202410641132A CN 118477493 B CN118477493 B CN 118477493B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 101
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 140
- 239000000843 powder Substances 0.000 claims abstract description 85
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 61
- 239000012528 membrane Substances 0.000 claims abstract description 61
- 239000010457 zeolite Substances 0.000 claims abstract description 61
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003607 modifier Substances 0.000 claims abstract description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 36
- 239000011737 fluorine Substances 0.000 claims abstract description 36
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- AZKVWQKMDGGDSV-BCMRRPTOSA-N Genipin Chemical compound COC(=O)C1=CO[C@@H](O)[C@@H]2C(CO)=CC[C@H]12 AZKVWQKMDGGDSV-BCMRRPTOSA-N 0.000 claims abstract description 10
- AZKVWQKMDGGDSV-UHFFFAOYSA-N genipin Natural products COC(=O)C1=COC(O)C2C(CO)=CCC12 AZKVWQKMDGGDSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- IEARORYJISZKGK-UHFFFAOYSA-N 3-phenylbut-2-enal Chemical compound O=CC=C(C)C1=CC=CC=C1 IEARORYJISZKGK-UHFFFAOYSA-N 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 229920002873 Polyethylenimine Polymers 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- -1 amino zeolite Chemical compound 0.000 claims description 9
- 238000004587 chromatography analysis Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- RRSXICBKOPODSP-UHFFFAOYSA-N 1,4-bis(chloromethoxy)butane Chemical compound ClCOCCCCOCCl RRSXICBKOPODSP-UHFFFAOYSA-N 0.000 claims 2
- 150000003926 acrylamides Chemical class 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 230000035699 permeability Effects 0.000 abstract description 9
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 29
- 239000007789 gas Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000004907 flux Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005576 amination reaction Methods 0.000 description 9
- VKRJVJZWDJDJBX-UHFFFAOYSA-N 1-chloro-4-(chloromethoxy)butane Chemical compound ClCCCCOCCl VKRJVJZWDJDJBX-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- DTGJWZNTRSBQBB-UHFFFAOYSA-N CC(C)c1cccc(C(C)C)c1[N] Chemical compound CC(C)c1cccc(C(C)C)c1[N] DTGJWZNTRSBQBB-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本申请涉及气体分离膜领域，具体公开了一种二氧化碳捕集基膜及其制备方法和应用的二氧化碳捕集膜，其制备方法包括以下步骤：S1、将聚砜经过氨基改性制得氨基化聚砜；S2、将制得的氨基化聚砜、含氟丙烯酰胺改性剂与有机溶剂混合，然后加入沸石粉和超分散剂，超声处理，再加入含有京尼平的交联剂，反应后焙烧，冷却，研磨制得改性聚砜；S3、将改性聚砜与有机溶剂和聚乙二醇混合，形成混合溶液，然后将混合溶液涂覆在无纺布上，冷却制得聚砜基膜；本申请还公开了采用上述方法制得的二氧化碳捕集基膜及其应用的二氧化碳捕集膜，本申请具有提高二氧化碳捕集基膜的选择渗透性能以及高压运行稳定性，适应在二氧化碳捕集环境的特点。The present application relates to the field of gas separation membranes, and specifically discloses a carbon dioxide capture base membrane, a preparation method thereof, and an applied carbon dioxide capture membrane. The preparation method comprises the following steps: S1, modifying polysulfone with amino groups to obtain amino polysulfone; S2, mixing the prepared amino polysulfone, a fluorine-containing acrylamide modifier, and an organic solvent, then adding zeolite powder and a hyperdispersant, ultrasonically treating, and then adding a cross-linking agent containing genipin, calcining after reaction, cooling, and grinding to obtain modified polysulfone; S3, mixing the modified polysulfone with an organic solvent and polyethylene glycol to form a mixed solution, then coating the mixed solution on a non-woven fabric, and cooling to obtain a polysulfone base membrane; the present application also discloses a carbon dioxide capture base membrane prepared by the above method and an applied carbon dioxide capture membrane. The present application has the characteristics of improving the selective permeability and high-pressure operation stability of the carbon dioxide capture base membrane, and adapting to the carbon dioxide capture environment.
Description
Technical Field
The application relates to the technical field of gas separation membranes, in particular to a carbon dioxide trapping base membrane, a preparation method thereof and an applied carbon dioxide trapping membrane.
Background
Global warming has become one of the important environmental problems facing countries around the world, mainly due to the excessive emission of greenhouse gases, especially carbon dioxide. Carbon capture and sequestration refers to a technique that collects carbon dioxide generated from emissions sources such as large power plants, steel plants, chemical plants, etc., and stores it in various ways to avoid its emission into the atmosphere, which is considered to be the most economical and feasible method for reducing greenhouse gas emissions on a large scale in the future, and for mitigating global warming.
Compared with the traditional carbon trapping technology, the membrane separation technology has the advantages of simple operation, low cost, low energy consumption, environmental friendliness and the like, is considered as a second-generation carbon trapping technology, and has wide application prospect. The membrane separation method is suitable for various treatment scales, can be used for a large-scale carbon dioxide separation process and a small-scale dispersed carbon dioxide separation process, and is particularly suitable for occasions with strict occupation requirements on offshore platforms and the like and lack of supporting facilities of oil and gas fields and the like.
The membrane separation method refers to that by means of selective dissolution and permeation between gas and membrane material, one component is quickly dissolved and passes through the membrane under the pushing of pressure difference on two sides of the membrane, so that the mixed gas is separated into two parts of residual gas flow and penetrating gas flow. The function of the base film in the carbon dioxide trapping film is the supporting and conducting function, and the structure and the property of the base film directly influence the separation effect and the selectivity of the film on the gas.
The base film of the carbon dioxide trapping film needs to meet the performance requirements that the base film has good selectivity, namely, the base film needs to have high selectivity on carbon dioxide molecules, namely, the base film can distinguish carbon dioxide and other gas molecules, so that the efficient separation of the carbon dioxide is realized, the base film has high enough permeability, so that the carbon dioxide molecules can quickly pass through the film, the separation efficiency is improved, and the base film has the stability of stable operation under high-pressure operation conditions and can bear various environmental conditions and changes of the operation conditions.
The prior basal membrane for separating carbon dioxide is mainly polysulfone, the pore size distribution of the surface of a polysulfone supporting layer is not uniform, the selective permeability of the polysulfone supporting layer to carbon dioxide is influenced, in addition, the polysulfone supporting layer is used as an organic membrane, the strength is lower, the impact force of gas molecules on a membrane material is enhanced under the high-pressure operation condition, the problem of deformation occurs due to insufficient strength of the basal membrane, and the gas permeation channel is changed, so that the gas flux is influenced, the separation efficiency is reduced, the separation stability of the basal membrane in the operation under the high-pressure condition is influenced, and the carbon dioxide capturing effect is influenced. Therefore, the improvement of the polysulfone support base membrane to improve the permselectivity performance and the high-pressure stability of the polysulfone support base membrane to carbon dioxide is of great significance to the improvement of the carbon dioxide capturing effect of the carbon dioxide capturing membrane.
Disclosure of Invention
In order to improve the selective permeability and high-pressure stability of the carbon dioxide trapping base film and adapt to the carbon dioxide trapping environment, the application provides the carbon dioxide trapping base film, and the preparation method and the application thereof.
In a first aspect, the application provides a preparation method of a carbon dioxide capturing base film, which adopts the following technical scheme that the preparation method of the carbon dioxide capturing base film comprises the following steps:
s1, modifying polysulfone by amino groups to prepare aminated polysulfone;
S2, mixing the prepared aminated polysulfone and fluorine-containing acrylamide modifier with an organic solvent, then adding zeolite powder and hyperdispersant, performing ultrasonic treatment, then adding a cross-linking agent containing genipin, performing high-temperature roasting, cooling, heating and roasting after reaction, cooling, and grinding to obtain modified polysulfone;
S3, mixing the modified polysulfone with an organic solvent and polyethylene glycol to form a mixed solution, coating the mixed solution on non-woven fabrics, and cooling to obtain the polysulfone base membrane.
According to the technical scheme, the amination groups are introduced through amination modification of polysulfone, and then the two are crosslinked with the fluorine-containing acrylamide modifier through the action of the crosslinking agent, so that the fluorine groups are introduced on polysulfone molecular chains, and the fluorine atoms have smaller atomic radius and higher electronegativity, so that the fluorine-containing polymer generally shows excellent hydrophobicity and low surface energy, the fluorine groups are introduced into the polysulfone, the free volume and the porosity of the polysulfone can be increased, more transmission channels and adsorption sites are provided for carbon dioxide molecules, the interaction between the fluorine groups and the carbon dioxide molecules is enhanced, the selectivity of the polysulfone to carbon dioxide is further improved, the selective passing of the base membrane to carbon dioxide is further improved, and the method of crosslinking grafting forms a larger molecular chain, and simultaneously enhances the selective permeability to carbon dioxide, and the strength of the base membrane is also improved, so that the base membrane has better running stability under high-pressure conditions and better supporting and conducting functions.
In addition, before the aminated polysulfone is crosslinked with the fluorine-containing acrylamide modifier, zeolite powder is further dispersed, and the addition of the hyper-dispersant is beneficial to the dispersion of the zeolite powder in the polymer, so that the zeolite powder can be dispersed in a polymer network structure, the selective permeability of the zeolite powder to carbon dioxide can be improved, the supporting strength of a base film can be improved, and the prepared trapping film can be applied in a higher environment, and the environment use scene is widened.
The base membrane of the application finally takes modified polysulfone as a supporting layer, the modified polysulfone supporting layer has better supporting strength and better selective permeability for carbon dioxide, and is beneficial to capturing carbon dioxide, the non-woven fabric is laminated outside the modified polysulfone supporting layer, so that the effect of enhancing and protecting the non-woven fabric is achieved, the non-woven fabric has good ventilation and filtering properties, the separation effect of the capturing membrane on the carbon dioxide is further improved, meanwhile, the non-woven fabric can also prevent the capturing membrane from being physically damaged and chemically corroded in the use process, and the laminated structure ensures that the carbon dioxide capturing membrane has good stability and durability while maintaining high-efficiency separation performance, and can play a better capturing effect in practical application.
Optionally, the zeolite powder in the step S2 is prepared by modifying amino groups, and the specific operation is as follows:
Dissolving polyethylenimine and aminopropyl triethoxysilane in methanol solution, adding zeolite powder, stirring for 5-6h, performing ultrasonic treatment for 10-20min, reflux-heating at 120-130deg.C for 10-12h, cooling to 70-85deg.C, reflux-heating for 20-24h, cooling, filtering, and washing to obtain aminated zeolite powder.
According to the technical scheme, modification of zeolite powder is achieved by adopting an impregnation-grafting combination mode, polyethyleneimine and aminopropyl triethoxysilane are firstly subjected to impregnation and stirring with zeolite powder, then ultrasonic treatment is performed, so that polyethyleneimine is firstly adsorbed on the zeolite powder through Van der Waals force, then amine fixation of zeolite powder is achieved through covalent bonding of aminopropyl triethoxysilane and hydroxyl groups on the zeolite powder at 120-130 ℃, cooling treatment is performed, the desorbed polyethyleneimine is combined on the zeolite powder again, amination modification of the zeolite powder is achieved, aminosilane is adopted during modification, introduction of silane groups and amino groups on the zeolite powder is achieved, and therefore dispersion of the polyethyleneimine in an organic polymer is improved, macromolecular structures can be formed with aminated polysulfone and fluorine-containing acrylamide modifier under the action of a cross-linking agent, the selective passing performance of carbon dioxide is further improved, and the supporting strength of a base film is further improved. In addition, the introduction of silane groups and carbon dioxide molecules form stronger interaction, so that the adsorption of the base film on the carbon dioxide molecules is facilitated, the silane groups can optimize the pore channel structure of the pore structure, the diffusion and the transmission of the carbon dioxide molecules are more suitable, the pore structure distribution of the finally prepared base film is more uniform while the dispersion is more uniform by improving the dispersion of zeolite in an organic matter system, the supporting strength of the base film is improved while the carbon dioxide separation performance is improved, the high-pressure stability of the base film is improved, and the carbon dioxide trapping effect is better.
Optionally, the adding mass ratio of the polyethylenimine to the aminopropyl triethoxysilane is 1 (1.5-2), the adding amount of the zeolite powder is 2-3 times of the adding amount of the polyethylenimine, and the adding mass ratio of the methanol solution is 3-5 times of the adding amount of the polyethylenimine.
Optionally, the fluorine-containing acrylamide modifier in step S2 is prepared by the following method:
In argon atmosphere, adding 3-phenyl-2-butenal and hexafluoroisopropanol into toluene, then adding an aza-carbene catalyst, N-fluoro-bis-benzene sulfonyl imide and potassium carbonate, reacting for 12-24 hours at room temperature, then adding triethylamine, reacting for 18-20 hours at 55-65 ℃, adding dichloromethane for dilution, filtering, washing, concentrating and chromatography to obtain the fluorine-containing acrylamide modifier.
By adopting the technical scheme, the 3-phenyl-2-butenal is used as a substrate to prepare active ester firstly, then triethylamine is added as an aliphatic amine nucleophilic reagent, the amide is prepared through an amine transesterification reaction, and in the process, the introduction of fluorine groups in the final acrylamide is realized by adding N-fluoro-bis-benzenesulfonimide as a fluorinating agent.
Alternatively, the molar ratio of 3-phenyl-2-butenal to hexafluoroisopropanol is 1 (1-1.2), the toluene is added in an amount of 2-3 times by mass as much as the 3-phenyl-2-butenal, the azacarbene catalyst is added in an amount of 0.5-1wt% of 3-phenyl-2-butenal, the N-fluorobisbenzenesulfonimide is added in an amount of 0.5-1wt% of 3-phenyl-2-butenal, the potassium carbonate is added in an amount of 0.3-0.5wt% of 3-phenyl-2-butenal, and the triethylamine is added in an amount of 8-15wt% of 3-phenyl-2-butenal.
Optionally, in the step S2, the post-baking after adding the cross-linking agent adopts two-stage baking, and the specific operation is that firstly, the baking is carried out for 1-2 hours at 130-150 ℃, then the cooling is carried out to 90-100 ℃, the treatment is carried out for 30-40min at the temperature, then the temperature is raised to 150-170 ℃, and the baking treatment is carried out for 3-4 hours.
By adopting the technical scheme, the two-stage roasting treatment mode is adopted after the cross-linking agent is added, so that the establishment of the pore structure of the zeolite powder and the prepared modified polysulfone is facilitated, and the carbon dioxide trapping performance is improved.
Optionally, the specific operation of step S1 is:
dissolving polysulfone powder in dichloromethane, adding 1, 4-dichloro methoxybutane and tin tetrachloride, reacting for 3-4 hours at 55-65 ℃, adding ethanol for precipitation, washing to obtain chloromethylated polysulfone, mixing chloromethylated polysulfone with ethylenediamine, reacting for 20-30 minutes at 25-30 ℃, washing, and drying to obtain aminated polysulfone.
According to the technical scheme, chloromethylation modification of polysulfone is realized under the action of a catalyst tin tetrachloride by taking 1, 4-dichloro methoxyl butane as a potassium chloride reagent, and then the polysulfone is soaked in ethylenediamine, so that nucleophilic substitution is carried out on ethylenediamine which is an aminolysis reagent and chloromethyl on the surface of chloromethylated polysulfone, and the aminated polysulfone is prepared.
Optionally, in step S1, the adding mass ratio of polysulfone powder to dichloromethane is 1:8-10,1,4-dichloromethoxybutane to polysulfone powder is 1 (0.5-0.8), the adding mass ratio of stannic chloride is 1-3wt% of polysulfone powder, and the adding mass ratio of ethylenediamine to chloromethylated polysulfone is 1 (0.6-0.8).
Optionally, in the step S2, the adding mass ratio of the aminated polysulfone to the fluorine-containing acrylamide modifier is 1 (0.1-0.3), the adding amount of the organic solvent is 3-5 times that of the aminated polysulfone, the adding mass ratio of the zeolite powder to the aminated polysulfone is 1 (8-10), the adding amount of the hyperdispersant is 0.3-0.5wt% of the zeolite powder, and the adding amount of the cross-linking agent is 0.3-0.5wt% of the adding amount of the aminated polysulfone;
The adding mass ratio of the modified polysulfone to the organic solvent and to the polyethylene glycol in the step S3 is 1 (2-3) (0.3-0.5), the cross-linking agent is genipin and cerium salt with the mass ratio of 1 (0.4-0.6), and the organic solvent is one or two of N, N-dimethylformamide and N-methylpyrrolidone.
Through adopting the technical scheme, the genipin can crosslink the amino-containing aminated polysulfone and the fluorine-containing acrylamide modifier, and the zeolite after the subsequent amination treatment can also form chemical combination, so that the addition of cerium salt is more beneficial to the formation of chemical combination of an acrylamide compound and a polysulfone molecular chain, and is more beneficial to the improvement of the performance of the finally modified polysulfone base membrane.
In a second aspect, the present application provides a carbon dioxide capturing base film, which adopts the following technical scheme:
A carbon dioxide capture base film made by the method of making.
By adopting the technical scheme, the base film prepared by the application has better carbon dioxide separation performance and higher supporting strength, improves the stability of the base film under high-pressure operation conditions, and has better carbon dioxide capturing effect.
In a third aspect, the present application provides a carbon dioxide capturing film, which adopts the following technical scheme:
a carbon dioxide trapping film comprises a separating layer, an intermediate layer and a base film, wherein the separating layer, the intermediate layer and the base film are sequentially arranged from top to bottom, the intermediate layer is prepared by coating polydimethylsiloxane, and the separating layer is prepared by coating a separating film coating liquid comprising polyvinyl amine.
By adopting the technical scheme, the carbon dioxide trapping film prepared by the application has better carbon dioxide trapping effect, better supporting strength and better stability under high-pressure operation condition, and expands the application scene of the carbon dioxide trapping film on environmental requirements.
In summary, the application has the following beneficial effects:
1. According to the application, an amination group is introduced through amination modification of polysulfone, and then the two are crosslinked with a fluorine-containing acrylamide modifier through the action of a crosslinking agent, so that a fluorine group is introduced on a polysulfone molecular chain, the selective passing property of a base film for carbon dioxide is improved, and a larger molecular chain is formed through a crosslinking grafting method, so that the selective permeability for carbon dioxide is enhanced, the strength of the base film is improved, the stability under high-pressure operation condition is better, and the supporting and conducting effects are better;
2. Before the aminated polysulfone is crosslinked with the fluorine-containing acrylamide modifier, zeolite powder is further dispersed, and the addition of the hyper-dispersant is beneficial to the dispersion of the zeolite powder in the polymer, so that the zeolite powder can be dispersed in a polymer network structure, the selective permeability of the zeolite powder to carbon dioxide can be improved, the supporting strength of a base film can be improved, and the prepared trapping film can be applied in a higher environment, and the environment use prospect is widened;
3. according to the application, modification of zeolite powder is realized by adopting a manner of graft bonding of polyethylenimine dipping-aminopropyl triethoxy silane, and introduction of silane groups and amino groups on the zeolite powder is realized, so that dispersion of the zeolite powder in an organic polymer is improved, a macromolecular structure can be formed with aminated polysulfone and fluorine-containing acrylamide modifier under the action of a cross-linking agent, the selective passing performance of carbon dioxide is further improved, and the supporting strength of a base film is further improved, so that the running stability of the zeolite powder under a high-pressure condition is improved.
Detailed Description
The present application will be described in further detail with reference to the following examples, which are not to be construed as limiting the scope of the application, and the raw materials used in the following examples, unless otherwise specified, are commercially available.
The hyperdispersant in the following examples is selected from the hyperdispersant of the chemical industry trade company of Ruiaceae, tianjin, model RD-9774.
Preparation examples 1 to 4 are preparation examples of fluorine-containing acrylamide modifier
Preparation example 1
A preparation method of a fluorine-containing acrylamide modifier comprises the following steps:
1kg of 3-phenyl-2-butenal is used as a reference, 3-phenyl-2-butenal and hexafluoroisopropanol are mixed according to a molar ratio of 1:1.1 in an argon atmosphere, and then added into toluene, wherein the addition amount of the toluene is 3 times of the addition amount of the 3-phenyl-2-butenal;
then adding 2, 6-diisopropyl phenyl nitrogen heterocyclic carbene catalyst, N-fluoro-bis-benzene sulfonyl imide and potassium carbonate, wherein the addition amount of the 2, 6-diisopropyl phenyl nitrogen heterocyclic carbene catalyst is 0.8wt% of 3-phenyl-2-butenal, the addition amount of the N-fluoro-bis-benzene sulfonyl imide is 0.8wt% of 3-phenyl-2-butenal, the addition amount of the potassium carbonate is 0.4wt% of 3-phenyl-2-butenal, reacting at room temperature for 18h, then adding triethylamine with the addition amount of 12wt% of the addition amount of 3-phenyl-2-butenal, reacting at 60 ℃ for 20h, adding dichloromethane for dilution, filtering, washing an obtained filter cake with dichloromethane, concentrating, and then performing chromatography to obtain the fluorine-containing acrylamide modifier, wherein the eluent in the chromatography adopts petroleum ether and ethyl acetate with the mass ratio of 3:1.
Preparation example 2
A preparation method of a fluorine-containing acrylamide modifier comprises the following steps:
1kg of 3-phenyl-2-butenal is used as a reference, 3-phenyl-2-butenal and hexafluoroisopropanol are mixed according to a molar ratio of 1:1 in an argon atmosphere, and then added into toluene, wherein the addition amount of the toluene is 2 times of the addition amount of the 3-phenyl-2-butenal;
Then adding 2, 6-diisopropyl phenyl nitrogen heterocyclic carbene catalyst, N-fluoro-bis-benzene sulfonyl imide and potassium carbonate, wherein the addition amount of the 2, 6-diisopropyl phenyl nitrogen heterocyclic carbene catalyst is 0.5 weight percent of 3-phenyl-2-butenal, the addition amount of the N-fluoro-bis-benzene sulfonyl imide is 0.5 weight percent of 3-phenyl-2-butenal, the addition amount of the potassium carbonate is 0.3 weight percent of 3-phenyl-2-butenal, reacting for 12h at room temperature, then adding triethylamine with the addition amount of 8wt% of the addition amount of 3-phenyl-2-butenal, reacting for 20h at 55 ℃, adding dichloromethane for dilution, filtering, washing an obtained filter cake with dichloromethane, concentrating, and then performing chromatography to obtain the fluorine-containing acrylamide modifier, wherein the eluent in the chromatography adopts petroleum ether and ethyl acetate with the mass ratio of 3:1.
Preparation example 3
A preparation method of a fluorine-containing acrylamide modifier comprises the following steps:
1kg of 3-phenyl-2-butenal is used as a reference, 3-phenyl-2-butenal and hexafluoroisopropanol are mixed according to a molar ratio of 1:1.2 in an argon atmosphere, and then added into toluene, wherein the addition amount of the toluene is 3 times of the addition amount of the 3-phenyl-2-butenal;
Then adding 2, 6-diisopropyl benzene nitrogen heterocyclic ring carbene catalyst, N-fluoro-bis-benzene sulfonyl imide and potassium carbonate, wherein the addition amount of the 2, 6-diisopropyl benzene nitrogen heterocyclic ring carbene catalyst is 1wt% of 3-phenyl-2-butenal, the addition amount of the N-fluoro-bis-benzene sulfonyl imide is 1wt% of 3-phenyl-2-butenal, the addition amount of the potassium carbonate is 0.5wt% of 3-phenyl-2-butenal, reacting for 24 hours at room temperature, then adding triethylamine, the addition amount of the triethylamine is 15wt% of the addition amount of the 3-phenyl-2-butenal, reacting for 18 hours at 65 ℃, adding dichloromethane for dilution, filtering, washing an obtained filter cake by using dichloromethane, concentrating, and then obtaining a fluorine-containing acrylamide modifier by chromatography, wherein petroleum ether and ethyl acetate with the mass ratio of 3:1 are adopted as eluent in the chromatography.
Preparation example 4
A preparation method of a fluorine-containing acrylamide modifier is carried out according to the method in preparation example 1, except that 3-phenyl-2-butenal in the raw material is replaced with benzaldehyde in equal amount.
Example 1
A method for preparing a carbon dioxide capturing base film, comprising the steps of:
S1, taking the adding amount of polysulfone powder as a reference, dissolving the polysulfone powder in dichloromethane, wherein the adding mass ratio of the polysulfone powder to the dichloromethane is 1:9, then adding 1, 4-dichloro methoxybutane and tin tetrachloride, reacting for 3.5 hours at 60 ℃, then adding ethanol for precipitation, washing to obtain chloromethylated polysulfone, then mixing the chloromethylated polysulfone with ethylenediamine, reacting for 20 minutes at 30 ℃, washing, and drying to obtain aminated polysulfone;
wherein, the adding mass ratio of the 1, 4-dichloro methoxybutane to the polysulfone powder is 1:0.6, the adding mass ratio of the stannic chloride is 2wt% of the polysulfone powder, and the adding mass ratio of the ethylenediamine to the chloromethylated polysulfone is 1:0.7;
s2, mixing the aminated polysulfone prepared in the step S1 and the fluorine-containing acrylamide modifier prepared in the preparation example 1 with an organic solvent, then adding zeolite powder and a hyperdispersant, performing ultrasonic treatment for 25min, adding a cross-linking agent, selecting genipin and cerium salt with the mass ratio of 1:0.5 as the cross-linking agent, reacting for 3h, roasting, cooling, and grinding to obtain modified polysulfone;
wherein the addition mass ratio of the aminated polysulfone to the fluorine-containing acrylamide modifier is 1:0.2, the addition amount of the organic solvent is 4 times that of the aminated polysulfone, the addition mass ratio of the zeolite powder to the aminated polysulfone is 1:9, the addition amount of the hyperdispersant is 0.4wt% of the zeolite powder, and the addition amount of the cross-linking agent is 0.4wt% of the addition amount of the aminated polysulfone;
The roasting after adding the cross-linking agent for reaction adopts two-stage roasting, and the specific operation is that firstly, the roasting is carried out for 1.5 hours at 140 ℃, then the cooling is carried out to 95 ℃, the treatment is carried out for 35 minutes at the temperature, then the temperature is raised to 160 ℃, and the roasting treatment is carried out for 3.5 hours;
S3, mixing the modified polysulfone with an organic solvent and polyethylene glycol according to a mass ratio of 1:2.5:0.4 to form a mixed solution, coating the mixed solution on non-woven fabrics, and cooling to obtain the polysulfone base membrane formed by the non-woven fabrics and the polysulfone support layer.
The organic solvent in the steps S2 and S3 is N, N-dimethylformamide.
Example 2
A method for preparing a carbon dioxide capturing base film, comprising the steps of:
S1, taking the addition amount of polysulfone powder as a reference, dissolving the polysulfone powder in dichloromethane, wherein the addition mass ratio of the polysulfone powder to the dichloromethane is 1:8, then adding 1, 4-dichloro methoxybutane and tin tetrachloride, reacting for 4 hours at 55 ℃, then adding ethanol for precipitation, washing to obtain chloromethylated polysulfone, then mixing the chloromethylated polysulfone with ethylenediamine, reacting for 30 minutes at 25 ℃, washing, and drying to obtain aminated polysulfone;
wherein, the adding mass ratio of the 1, 4-dichloro methoxybutane to the polysulfone powder is 1:0.5, the adding mass ratio of the stannic chloride is 1wt% of the polysulfone powder, and the adding mass ratio of the ethylenediamine to the chloromethylated polysulfone is 1:0.6;
S2, mixing the aminated polysulfone prepared in the step S1 and the fluorine-containing acrylamide modifier prepared in the preparation example 2 with an organic solvent, then adding zeolite powder and a hyperdispersant, carrying out ultrasonic treatment for 20min, adding a cross-linking agent, selecting genipin and cerium salt with the mass ratio of 1:0.4 as the cross-linking agent, reacting for 2h, roasting, cooling, and grinding to obtain modified polysulfone;
Wherein the addition mass ratio of the aminated polysulfone to the fluorine-containing acrylamide modifier is 1:0.1, the addition amount of the organic solvent is 3 times that of the aminated polysulfone, the addition mass ratio of the zeolite powder to the aminated polysulfone is 1:8, the addition amount of the hyperdispersant is 0.3wt% of the zeolite powder, and the addition amount of the cross-linking agent is 0.3wt% of the addition amount of the aminated polysulfone;
The roasting after adding the cross-linking agent for reaction adopts two-stage roasting, and the specific operation is that firstly roasting is carried out for 2 hours at 130 ℃, then cooling is carried out to 90 ℃, the treatment is carried out for 40 minutes at the temperature, then the temperature is raised to 150 ℃, and the roasting treatment is carried out for 4 hours;
S3, mixing the modified polysulfone with an organic solvent and polyethylene glycol according to the mass ratio of 1:2:0.3 to form a mixed solution, coating the mixed solution on non-woven fabrics, and cooling to obtain the polysulfone base membrane formed by the non-woven fabrics layer and the polysulfone support layer.
The organic solvent in the steps S2 and S3 is N, N-dimethylformamide.
Example 3
A method for preparing a carbon dioxide capturing base film, comprising the steps of:
S1, taking the addition amount of polysulfone powder as a reference, dissolving the polysulfone powder in dichloromethane, wherein the addition mass ratio of the polysulfone powder to the dichloromethane is 1:10, then adding 1, 4-dichloro methoxybutane and stannic chloride, reacting for 3 hours at 65 ℃, then adding ethanol for precipitation, washing to obtain chloromethylated polysulfone, then mixing the chloromethylated polysulfone with ethylenediamine, reacting for 20 minutes at 30 ℃, washing, and drying to obtain aminated polysulfone;
Wherein, the adding mass ratio of the 1, 4-dichloro methoxybutane to the polysulfone powder is 1:0.5, the adding mass ratio of the stannic chloride is 3wt% of the polysulfone powder, and the adding mass ratio of the ethylenediamine to the chloromethylated polysulfone is 1:0.8;
s2, mixing the aminated polysulfone prepared in the step S1 and the fluorine-containing acrylamide modifier prepared in the preparation example 3 with an organic solvent, then adding zeolite powder and a hyperdispersant, performing ultrasonic treatment for 30min, adding a cross-linking agent mixed by genipin and cerium salt in a mass ratio of 1:0.6, reacting for 4h, roasting, cooling and grinding to prepare modified polysulfone;
Wherein the addition mass ratio of the aminated polysulfone to the fluorine-containing acrylamide modifier is 1:0.3, the addition amount of the organic solvent is 5 times that of the aminated polysulfone, the addition mass ratio of the zeolite powder to the aminated polysulfone is 1:10, the addition amount of the hyperdispersant is 0.5wt% of the zeolite powder, and the addition amount of the cross-linking agent is 0.5wt% of the addition amount of the aminated polysulfone;
The roasting after the reaction of adding the cross-linking agent adopts two-stage roasting, and the specific operation comprises the steps of firstly roasting for 1h at 150 ℃, then cooling to 90 ℃, treating for 40min at the temperature, then heating to 170 ℃ and roasting for 3h;
S3, mixing the modified polysulfone with an organic solvent and polyethylene glycol according to the mass ratio of 1:3:0.5 to form a mixed solution, coating the mixed solution on non-woven fabrics, and cooling to obtain the polysulfone base membrane formed by the non-woven fabrics layer and the polysulfone support layer.
The organic solvent in the steps S2 and S3 is N, N-dimethylformamide.
Example 4
A method for producing a carbon dioxide capturing base film was carried out in the same manner as in example 1, except that the fluorine-containing acrylamide modifier produced in production example 4 was used as the fluorine-containing acrylamide modifier in step S2.
Example 5
A preparation method of a carbon dioxide trapping base film is carried out according to the method in the embodiment 1, except that the zeolite powder in the step S2 is modified to prepare aminated zeolite powder and then added, and the modification method specifically comprises the following steps:
Mixing polyethylene imine and aminopropyl triethoxysilane according to a mass ratio of 1:1.8, then dissolving in a methanol solution with a mass concentration of 35%, obtaining a mixed solution, adding zeolite powder with an addition amount of 3 times that of the polyethylene imine, stirring for 5.5h, performing ultrasonic treatment for 15min, then refluxing and heating for 11h at 125 ℃, cooling to 80 ℃, refluxing and heating for 22h, cooling, filtering and washing to obtain the amination zeolite powder.
Example 6
A preparation method of a carbon dioxide trapping base film is carried out according to the method in the embodiment 1, except that the zeolite powder in the step S2 is modified to prepare aminated zeolite powder and then added, and the modification method specifically comprises the following steps:
Mixing polyethylene imine and aminopropyl triethoxysilane according to a mass ratio of 1:1.5, dissolving in a methanol solution with a mass concentration of 35%, obtaining a mixed solution, adding zeolite powder with an addition amount of 2 times that of the polyethylene imine, stirring for 5 hours, performing ultrasonic treatment for 10 minutes, then performing reflux heating for 12 hours at 120 ℃, cooling to 70 ℃, performing reflux heating for 24 hours, cooling, filtering, and washing to obtain the amination zeolite powder.
Example 7
A preparation method of a carbon dioxide trapping base film is carried out according to the method in the embodiment 1, except that the zeolite powder in the step S2 is modified to prepare aminated zeolite powder and then added, and the modification method specifically comprises the following steps:
Mixing polyethylene imine and aminopropyl triethoxysilane according to a mass ratio of 1:2, dissolving in a methanol solution with a mass concentration of 35%, obtaining a mixed solution, adding zeolite powder with an addition of 3 times of the polyethylene imine, stirring for 6 hours, performing ultrasonic treatment for 20 minutes, refluxing and heating for 10 hours at 130 ℃, cooling to 85 ℃, refluxing and heating for 20 hours, cooling, filtering and washing to obtain the amino zeolite powder.
Example 8
A method for preparing a carbon dioxide trapping base film was carried out in the same manner as in example 5, except that in the modification of zeolite powder, polyethyleneimine was replaced with aminopropyl triethoxysilane in equal amount.
Example 9
A method for preparing a carbon dioxide trapping base film was carried out in the same manner as in example 5, except that aminopropyl triethoxysilane was replaced with polyethyleneimine in the same amount during modification of zeolite powder.
Comparative example 1
A method for preparing a carbon dioxide capturing base membrane was carried out in the same manner as in example 1, except that polysulfone was not subjected to the modification operations of steps S1 and S2, and the modified polysulfone in step S3 was directly replaced with polysulfone in equal amount.
Comparative example 2
A preparation method of a carbon dioxide trapping base film is carried out according to the method in the embodiment 1, and is characterized in that zeolite powder and hyperdispersant are not added in the step S2, and the preparation method specifically comprises the steps of mixing the aminated polysulfone prepared in the step S1, the fluorine-containing acrylamide modifier prepared in the preparation embodiment 1 and an organic solvent, adding a cross-linking agent, wherein the cross-linking agent is genipin and cerium salt with the mass ratio of 1:0.5, reacting for 3 hours, roasting, cooling and grinding to obtain modified polysulfone.
Comparative example 3
A method for producing a carbon dioxide capturing base film was carried out in the same manner as in example 1, except that the fluorine-containing acrylamide modifier in step S2 was replaced with acrylamide in the same amount.
Comparative example 4
A method for producing a carbon dioxide capturing base membrane was carried out in the same manner as in example 1, except that the aminated polysulfone produced in step S1 was not subjected to the treatment of step S2, and the modified polysulfone in step S3 was replaced with the aminated polysulfone in step S1 in the same amount.
Application example
The carbon dioxide trapping base film is used for preparing the carbon dioxide trapping film, specifically, one side of a polysulfone supporting layer far away from a non-woven fabric layer is coated with polydimethylsiloxane PDMS to form an intermediate layer, then the intermediate layer is coated with a separation coating liquid to form a separation layer, the separation coating liquid comprises polyvinyl amine, sodium polyacrylate, sodium dodecyl sulfate and polyvinyl alcohol in a mass ratio of 1:0.1:0.1:0.2, the separation layer is coated with the polydimethylsiloxane PDMS to form a protective layer, and finally the protective layer, the separation layer, the intermediate layer and the base film are sequentially arranged from top to bottom, wherein the base film comprises a polysulfone supporting layer and a multi-layer structure of the non-woven fabric layer, which are connected with the intermediate layer.
Performance detection
The carbon dioxide capturing base membranes prepared in examples and comparative examples were first tested for running stability by running the prepared base membrane through water at 225psi, counting the decay rate of the water flux for half an hour (specifically, recording the initial flux value of the base membrane at 225psi, then maintaining the pressure for half an hour after running at 225psi, measuring the flux value of the base membrane again, the decay rate= (initial flux value-half an hour flux value)/initial flux value x 100%), and the test results are shown in table 1 below, and the flux stability of the base membrane under high pressure conditions was measured by testing the decay rate of the base membrane for half an hour.
In addition, carbon dioxide capturing films were prepared by the method of the above application examples using the carbon dioxide capturing base films prepared in the examples and comparative examples, and the carbon dioxide separation performance of the capturing films was measured at a test pressure of 0.5MPa and a test temperature of 40 ℃.
Table 1:
table 2:
The permeation rate is CO 2 gas permeation rate, the unit is GPU,1 GPU= -6cm3(STP)cm-2s-1cmHg-1, and the separation factor is the ratio of CO 2 gas permeation rate to N 2、CH4 gas permeation rate.
When the strength of the pore canal of the base membrane is low, the pore canal of the base membrane is collapsed, the half-hour flux of the base membrane is reduced, and the half-hour flux decay rate is high. Referring to the test results of examples 1 and 4, when a benzaldehyde is used as a substrate in the preparation of the fluorine-containing acrylamide modifier, the strength of the finally prepared base film is reduced, the stability is reduced under high-pressure operation conditions, and the separation performance of carbon dioxide is also reduced, and referring to the test results of examples 1 and 5 to 7, it can be seen that zeolite is added after amination modification, thereby facilitating formation of a macromolecular network structure, the strength and separation performance of carbon dioxide are further improved, and the stability is improved under high-pressure operation conditions, and by further combining the test results of examples 5 and 8 and 9, it can be seen that the high-pressure stability and the carbon dioxide separation performance are both reduced when a single aminopropyl triethoxysilane or polyethylenimine is used in the zeolite powder modification process, especially when only polyethylenimine is used, the carbon dioxide separation effect is reduced.
Referring to the test results of example 1 and comparative example 1 again, when the base membrane was directly modified with the unmodified polysulfone, the high pressure stability and carbon dioxide separation performance were significantly reduced compared with those of example 1, and when the test result of comparative example 2 was combined with the modified polysulfone without zeolite powder and hyperdispersant, the high pressure stability was significantly reduced, and when the test result of comparative example 3 was also referred to, and when the fluorine-containing acrylamide modifier was replaced with acrylamide, the base membrane was significantly reduced with respect to carbon dioxide separation performance, and when the polysulfone was combined with comparative example 4, after the polysulfone was not treated with the fluorine-containing acrylamide modifier in step S2, the carbon dioxide separation performance was significantly improved compared with comparative example 1, but still less than the test result of example 1, the high pressure stability was significantly reduced.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
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| CN104801207A (en) * | 2015-01-22 | 2015-07-29 | 天津大学 | Preparation of polyvinylamine/polyaniline mixed matrix membranes used for separation of gas containing carbon dioxide |
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| JP5526067B2 (en) * | 2010-03-29 | 2014-06-18 | 富士フイルム株式会社 | Gas separation membrane, gas separation membrane manufacturing method, gas mixture separation method using them, gas separation membrane module, gas separation device |
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| CN104801207A (en) * | 2015-01-22 | 2015-07-29 | 天津大学 | Preparation of polyvinylamine/polyaniline mixed matrix membranes used for separation of gas containing carbon dioxide |
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