CN115337795B - ZTIF-1/cellulose acetate blend membrane and preparation method and application thereof - Google Patents
ZTIF-1/cellulose acetate blend membrane and preparation method and application thereof Download PDFInfo
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- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 107
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 229920006254 polymer film Polymers 0.000 claims abstract description 10
- 238000009489 vacuum treatment Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 229920005994 diacetyl cellulose Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000006872 improvement Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229920001747 Cellulose diacetate Polymers 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- -1 organic acid ester Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 3
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000004941 mixed matrix membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/50—Control of the membrane preparation process
-
- 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)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application provides a preparation method of a ZTIF-1/cellulose acetate blend membrane for gas separation, which comprises the following steps: heating and dissolving the dried cellulose acetate particles in a first solvent to prepare a cellulose acetate solution; preparing ZTIF-1 dispersion by dispersing ZTIF-1 in a second solvent in advance; cooling the cellulose acetate solution to room temperature, and adding the ZTIF-1 dispersion liquid under continuous stirring to form a blend membrane solution; after defoaming by vacuum treatment, the blend film solution is uniformly coated on a clean horizontal glass plate in an oven, and the solvent is evaporated to shape a pure polymer film; then placing the shaped pure polymer film under vacuum condition, heat treating at 100deg.C and 1110 deg.C, soaking in deionized water for a certain time, and separating the film from the glass plate by using water tension; and finally, drying the film to obtain the ZTIF-1/cellulose acetate blend film for gas separation. The application also relates to the ZTIF-1/cellulose acetate blend membrane obtained by the method and application thereof.
Description
Technical Field
The application relates to the technical field of gas separation and purification, in particular to an N for separation 2 、CO 2 、CH 4 、O 2 ZTIF-1/cellulose acetate blend membrane of any component, and preparation method and application thereof.
Background
Currently, cellulose Acetate (CA) is the earliest commercially produced and evolving organic acid ester of cellulose among cellulose derivativesHas the advantages of low price, wide sources, environmental protection and the like. Cellulose acetate to carbon dioxide (CO) 2 ) The gas has higher solubility, can be prepared into film forming materials and is applied to the field of gas separation. Conventional gas separation membrane materials include cellulose acetate, polyimide, polysulfone ether, fluoropolymers, and the like. Compared with other gas separation membranes, cellulose acetate gas separation membranes have the advantages of high cost effectiveness, easiness in processing, biodegradability and the like, but have relatively low gas permeability, and the gas separation performance is often improved by blending or crosslinking with other components.
Disclosure of Invention
The application provides a method for separating N 2 、CO 2 、CH 4 、O 2 The ZTIF-1/cellulose acetate blend membrane of any component and the preparation method and the application thereof can effectively solve the problems.
The application is realized in the following way:
the application provides a preparation method of a ZTIF-1/cellulose acetate blend membrane for gas separation, which comprises the following steps:
step one, heating and dissolving the dried cellulose acetate particles in a first solvent to prepare a cellulose acetate solution; preparing ZTIF-1 dispersion by dispersing ZTIF-1 in a second solvent in advance;
step two, cooling the cellulose acetate solution to room temperature, and adding the ZTIF-1 dispersion liquid under continuous stirring to form a blend membrane solution;
step three, after defoaming by vacuum treatment, the blend film solution is uniformly coated on a clean horizontal glass plate in an oven, and the solvent is evaporated to shape the pure polymer film; then placing the shaped pure polymer film under vacuum condition, heat-treating at 100-140 deg.C, then soaking in deionized water for a certain time, utilizing water tension to make the film be separated from glass plate; and finally, drying the film to obtain the ZTIF-1/cellulose acetate blend film for gas separation.
Furthermore, the application further provides a ZTIF-1/cellulose acetate blend membrane prepared by the method.
Furthermore, the application further provides an application of the ZTIF-1/cellulose acetate blend membrane prepared by the method in gas separation.
The application has the beneficial effects that:
1) The ZTIF-1/cellulose acetate blend membrane for gas separation provided by the application is mainly prepared from cellulose acetate, has wide raw material sources, low price, environmental friendliness and high economic benefit, and is easy to degrade;
2) The ZTIF-1/cellulose acetate blend membrane for gas separation can effectively improve the permeability of a cellulose acetate film to carbon dioxide gas, and further improve the gas separation effect through high selective affinity to the carbon dioxide gas;
3) In the ZTIF-1/cellulose acetate blend membrane for gas separation, ZTIF-1 particles have better compatibility with a cellulose acetate matrix, and the tensile strength and modulus of the membrane can be enhanced through interaction with a cellulose acetate molecular chain. Specifically, the molecular chain of the cellulose acetate used for blending contains acetyl, hydroxyl and other groups, and the ZTIF-1 particle used for blending contains azole compound ligands, and is rich in a plurality of nitrogen-hydrogen bonds, carbon-nitrogen bonds, nitrogen-nitrogen double bonds and carbon-carbon double bonds; after the cellulose acetate and the ZTIF-1 particles are blended into a film, the azole compound in the ZTIF-1 particles is easy to generate hydrogen bond action with hydroxyl on the cellulose acetate, so that the compatibility of the ZTIF-1 particles and a cellulose acetate matrix is enhanced; after the ZTIF-1 particles are doped with the cellulose acetate matrix, the structure of the original high molecular polymer molecular chain can be expanded, the flexibility and free volume of the cellulose acetate molecular chain are increased, a channel for gas transportation in a film is provided, and the mechanical property of the film is enhanced. In the ZTIF-1/cellulose acetate blend membrane, tetrazole ligand in the used ZTIF-1 particles contains noncoordinating nitrogen atoms, and has stronger selective adsorption capacity on carbon dioxide.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
The SOD topology of ZTIF-1 is shown in the left diagram in FIG. 1, and the CO with ZTIF-1 is shown in the right diagram 2 Affinity schematic;
FIG. 2 is a synthesis equation for the selected ZTIF-1 particles;
FIG. 3 is an X-ray diffraction pattern of ZTIF-1 particles, sample 1# and sample 4# of example 6 of the present application;
FIG. 4 is a chart showing Fourier infrared test spectra of ZTIF-1 particles, sample # 1, sample # 3, sample # 4 and sample # 5 in example 7 of the present application;
FIG. 5 is a partial magnified view of Fourier infrared test spectra of ZTIF-1 particles, sample 1# and sample 4# of example 7 of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application. Thus, the following detailed description of the embodiments of the application, as presented in the figures, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, based on the embodiments of the application, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the application.
In the description of the present application, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The embodiment of the application provides a preparation method of a ZTIF-1/cellulose acetate blend membrane for gas separation, which comprises the following steps:
step one, heating and dissolving the dried cellulose acetate particles in a first solvent to prepare a cellulose acetate solution; preparing ZTIF-1 dispersion by dispersing ZTIF-1 in a second solvent in advance;
step two, cooling the cellulose acetate solution to room temperature, and adding the ZTIF-1 dispersion liquid under continuous stirring to form a blend membrane solution;
step three, after defoaming by vacuum treatment, the blend film solution is uniformly coated on a clean horizontal glass plate in an oven, and the solvent is evaporated to shape the pure polymer film; then placing the shaped pure polymer film under vacuum condition, heat-treating at 100-140 deg.C, then soaking in deionized water for a certain time, utilizing water tension to make the film be separated from glass plate; and finally, drying the film to obtain the ZTIF-1/cellulose acetate blend film for gas separation.
In the first step, the first solvent and the second solvent are selected from one or more solvents such as Tetrahydrofuran (THF), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-butyl acetate, and the like.
As a further improvement, the content of cellulose acetate particles in the cellulose acetate solution is 3-10wt%, the stirring temperature is controlled at 50-80 ℃, and the stirring time is controlled at 6-24 hours. The polymer content is related to the viscosity of the polymer solution prepared: if the content is too low, the viscosity of the polymer solution is low, the fluidity is strong when the film is coated, and the film thickness is too low; if the content is too high, agglomeration easily occurs in the process of evaporating the solvent, so that the surface of the film is rough, the film is thicker, and the gas separation performance is poor. Experiments prove that the thickness of the subsequent film forming can be ensured to be in a proper range by controlling the concentration of the cellulose acetate solution, and the film forming has enough flatness. The content of the cellulose acetate particles is 3 to 10 weight percent, and the film thickness can be controlled within the range of 5 to 100 mu m. Preferably, the cellulose acetate particle content is 5 to 8wt% and the film thickness can be controlled to be about 20 to 50. Mu.m. Further, the polymer can be better and faster dissolved in the solvent through temperature control, and when the temperature is too low, the dissolution of the polymer is slow, so that the dissolution treatment time can be delayed; the subsequent treatment needs to be carried out at normal temperature, so that the cost is increased and the heat energy is wasted due to the fact that the temperature is too high.
The general formula of the cellulose acetate is preferably (I):
in formula (I), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Selected from any one of hydrogen and acetyl. More preferably, R in formula (I) 1 、R 2 、R 3 At least two of them are acetyl; r in formula (I) 4 、R 5 、R 6 At least two of them are acetyl groups. In one embodiment, R 1 、R 2 R is R 4 、R 5 All are acetyl groups, so that the acetyl content of the cellulose acetate can reach 39.8 weight percent, and the hydroxyl content is 3.5 weight percent. Common cellulose acetate materials can be classified into cellulose diacetate and cellulose triacetate according to the degree of acetylation, and cellulose diacetate with the degree of acetylation of 2.4 is selected in the work. The acetyl in the polymer structure has a certain selective adsorption effect on carbon dioxide, so that the higher substitution degree of the acetyl is beneficial to improving the gas separation performance; the ZTIFs material used in the work has a certain hydrogen bond with hydroxyl carried by cellulose acetate, and a sufficient amount of hydroxyl in a polymer molecular chain needs to be ensured to enhance the compatibility of the mixed matrix film, so that the cellulose diacetate is selected instead of the cellulose acetate to have higher degree of acetylationIs a cellulose triacetate of (a).
As a further improvement, the content of ZTIF-1 particles in the ZTIF-1 dispersion is 0.1wt% to 10wt%. Since the selected ZTIF-1 particles are insoluble in the selected solvent, the selection of a lower level allows for efficient suspension of the particles in the dispersion medium, facilitating further addition of the polymer solution for subsequent agitation. If the content is too low, a large amount of dispersing medium needs to be added, so that the waste of raw materials and time is caused; if the content is too high, ZTIF-1 particles will be largely settled in the dispersion medium and will not be uniformly dispersed. More preferably, the ZTIF-1 particles are present in an amount of 1wt% to 3wt%. In one embodiment, the ZTIF-1 particles are present in an amount of about 2 wt%. The ZTIF-1 is Zn (2-ethylimidazole) x (5-methyltetrazole) 2-x The general formula is (II):
preferably, R in formula (II) 1 、R 2 、R 3 、R 4 Independently selected from any one of 2-ethylimidazole and 5-methyltetrazole. The tetrazole ligand in the ZTIF-1 particle of (II) contains an uncomplexed nitrogen atom, so that the selective adsorption capacity of carbon dioxide is stronger. Furthermore, the azole compound is easy to generate hydrogen bond action with hydroxyl on cellulose acetate, so that the compatibility of ZTIF-1 particles and cellulose acetate matrixes is enhanced. In addition, the ZTIF-1 particles can prop open the structure of the original high molecular polymer molecular chain after being doped with the cellulose acetate matrix, so that the flexibility and free volume of the cellulose acetate molecular chain are increased, a channel for gas transportation in a film is provided, and the mechanical property of the film is enhanced.
In the second step, as a further improvement, in the blend membrane solution, ZTIF-1 particles account for 0-20wt% of the total mass of the solid components in the feeding process, and the stirring time for preparing the blend membrane solution is controlled to be 6-12 hours. The main purpose of the ZTIF-1 doping into the CA matrix is to fully utilize the characteristic of selective adsorption of carbon dioxide, and improve the gas separation performance of the mixed matrix membrane. At low ratios, gas permeation performance and gas separation performance show positive correlation with increasing ZTIF-1 particle loading; and after the load reaches a certain threshold, excessive ZTIF-1 particles are agglomerated in the membrane, the membrane material starts to have larger pore diameter, and the gas separation performance and the mechanical strength of the membrane are reduced. Thus, it is preferred that the ZTIF-1 particles account for 1wt% to 5wt% of the total mass of the solid components at the time of feeding. In one embodiment, ZTIF-1 particles comprise about 2.5wt% of the total mass of the solid components at the time of feeding.
In the third step, as a further improvement, the evaporating solvent adopts a temperature programming mode, and the temperature is raised by 20 ℃ every 1 or 2 hours; the upper limit temperature of the evaporating solvent is 100-140 ℃, the lower limit temperature of the evaporating solvent is 40-80 ℃, and the duration of the evaporating solvent is controlled between 6-24 hours.
As a further improvement, the shaped pure polymer film is subjected to heat treatment at a temperature of 100-140 ℃ under vacuum for 2-12 hours. Too low a temperature can not completely remove the solvent, the film formation carries solvent molecules, the performance is unstable and accurate test is difficult; if the treatment temperature is too high, heat energy is wasted, and the morphology of the film is destroyed.
Specific examples: (the starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified).
The analysis method in the embodiment of the application is as follows:
the material was subjected to X-ray diffraction analysis using a MiniFlex-II type X-ray diffractometer.
Fourier infrared testing of the material was performed using a VERTEX70 tester.
And testing the gas permeability by using a BSG-11A gas permeability tester by adopting a differential pressure method.
Tensile testing was performed using an Instron 1211 type electronic tensile machine.
In the examples ZTIF-1 starting material was obtained:
the zeolitic imidazol-tetrazole-type framework material (ZTIF-1) used in the examples below may be either ready-made or prepared as follows, the synthesis equation of which is shown in fig. 2:
zinc acetate dihydrate (0.5 mmol,0.110 g), 2-ethylimidazole (0.5 mmol,0.048 g) and 5-methyltetrazole (0.5 mmol,0.042 g) were dissolved in a mixed solvent of N, N-dimethylformamide (2 mL) and methanol (2 mL), heated at 120℃for 3 days in a 20mL closed reaction flask, and cooled to room temperature. The yellow polyhedral crystals obtained in the above operation are washed with ethanol, dried at room temperature and the ZTIF-1 product is obtained.
Test example 1 preparation of pure cellulose acetate film
Placing 0.5g of cellulose acetate granules dried in vacuum and 10mLN, N-dimethylformamide into a 25mL single-neck flask, stirring for 12 hours at 65 ℃, cooling to room temperature, defoaming by adopting vacuum treatment, uniformly coating on a clean horizontal glass plate in an oven, starting solvent evaporation from 60 ℃, heating to 20 ℃ every 2 hours, and continuing constant-temperature heating for 6 hours after the treatment temperature is raised to 120 ℃ to ensure film shaping on the glass plate; and (3) placing the shaped pure cellulose acetate film in a vacuum drying oven for heat treatment at 120 ℃ for 6 hours, cooling to room temperature, immersing the film in deionized water for 10 minutes, gently removing the film by a clean scraper, evaporating residual deionized water, and storing in a dryer to obtain the pure cellulose acetate film, which is marked as sample No. 1.
Example 2 preparation of ZTIF-1/cellulose acetate blend film
0.4875g of the vacuum-dried cellulose acetate pellets and 9mLN, N-dimethylformamide were placed in a 25mL single-neck flask and stirred at 65℃for 12 hours; taking 0.0125g of ZTIF-1 particles dried in vacuum and 1mLN, putting N-dimethylformamide into a 5mL beaker, uniformly stirring, adding all the materials into a cellulose acetate solution, and continuously stirring for 12 hours; after defoaming by vacuum treatment, uniformly coating on a clean horizontal glass plate in an oven, starting to evaporate solvent from 60 ℃, heating to 20 ℃ every 2 hours, and continuously heating at constant temperature for 6 hours after the treatment temperature is raised to 120 ℃ to ensure that the film on the glass plate is shaped; and (3) placing the shaped pure cellulose acetate film in a vacuum drying oven for heat treatment at 120 ℃ for 6 hours, cooling to room temperature, immersing the film in deionized water for 10 minutes, gently tearing off the film by a clean scraper, evaporating residual deionized water, and storing in a dryer to obtain a 2.5% ZTIF-1 doped cellulose acetate blend film, which is marked as sample No. 2.
Example 3 preparation of ZTIF-1/cellulose acetate blend film
0.475g of the cellulose acetate granules dried in vacuum and 9mLN, N-dimethylformamide are placed in a 25mL single-neck flask and stirred for 12 hours at 65 ℃; taking 0.025g of ZTIF-1 particles dried in vacuum and 1mLN, putting N-dimethylformamide into a 5mL beaker, uniformly stirring, adding all the materials into a cellulose acetate solution, and continuously stirring for 12 hours; after defoaming by vacuum treatment, uniformly coating on a clean horizontal glass plate in an oven, starting to evaporate solvent from 60 ℃, heating to 20 ℃ every 2 hours, and continuously heating at constant temperature for 6 hours after the treatment temperature is raised to 120 ℃ to ensure that the film on the glass plate is shaped; and (3) placing the shaped pure cellulose acetate film in a vacuum drying oven for heat treatment at 120 ℃ for 6 hours, cooling to room temperature, immersing the film in deionized water for 10 minutes, gently tearing off the film by a clean scraper, evaporating residual deionized water, and storing in a dryer to obtain a 5% ZTIF-1 doped cellulose acetate blend film, which is marked as sample No. 3.
Example 4 preparation of ZTIF-1/cellulose acetate blend film
0.4625g of the cellulose acetate granules dried in vacuo and 9mLN, N-dimethylformamide were placed in a 25mL single-neck flask and stirred at 65℃for 12 hours; taking 0.0375g of ZTIF-1 particles dried in vacuum and 1mLN, putting N-dimethylformamide into a 5mL beaker, uniformly stirring, adding all the materials into a cellulose acetate solution, and continuously stirring for 12 hours; after defoaming by vacuum treatment, uniformly coating on a clean horizontal glass plate in an oven, starting to evaporate solvent from 60 ℃, heating to 20 ℃ every 2 hours, and continuously heating at constant temperature for 6 hours after the treatment temperature is raised to 120 ℃ to ensure that the film on the glass plate is shaped; and (3) placing the shaped pure cellulose acetate film in a vacuum drying oven for heat treatment at 120 ℃ for 6 hours, cooling to room temperature, immersing the film in deionized water for 10 minutes, gently tearing off the film by a clean scraper, evaporating residual deionized water, and storing in a dryer to obtain a 7.5% ZTIF-1 doped cellulose acetate blend film, which is marked as sample No. 4.
Example 5 preparation of ZTIF-1/cellulose acetate blend film
0.45g of the cellulose acetate granules dried in vacuo and 9mLN, N-dimethylformamide were placed in a 25mL single-neck flask and stirred at 65℃for 12 hours; taking 0.05g of ZTIF-1 particles dried in vacuum and 1mLN, putting N-dimethylformamide into a 5mL beaker, uniformly stirring, adding all the materials into a cellulose acetate solution, and continuously stirring for 12 hours; after defoaming by vacuum treatment, uniformly coating on a clean horizontal glass plate in an oven, starting to evaporate solvent from 60 ℃, heating to 20 ℃ every 2 hours, and continuously heating at constant temperature for 6 hours after the treatment temperature is raised to 120 ℃ to ensure that the film on the glass plate is shaped; and (3) placing the shaped pure cellulose acetate film in a vacuum drying oven for heat treatment at 120 ℃ for 6 hours, cooling to room temperature, immersing the film in deionized water for 10 minutes, gently tearing off the film by a clean scraper, evaporating residual deionized water, and storing in a dryer to obtain a 10% ZTIF-1 doped cellulose acetate blend film, which is marked as sample No. 5.
Example 6X-ray diffraction characterization of samples
X-ray diffraction analysis was performed on representative ZTIF-1 particles, sample No. 1, sample No. 4, and the results are shown in FIG. 3. As can be seen from fig. 3, ZTIF-1 has strong crystallization peaks at planes where 2θ is 7.4 °, 8.3 °, 10.4 °, 12.7 ° and 16.7 °, and these crystallization peaks are also reflected on the blend film after the incorporation of the cellulose acetate film material, which demonstrates successful blending of ZTIF-1 particles with the cellulose acetate polymer. In addition, by comparing the patterns of the sample 1# and the sample 4#, the loading of the ZTIF-1 can easily be known to further widen the special wide diffraction peak of the cellulose diacetate, so that the incorporation of the ZTIF-1 particles can open up the piled molecular chains, the disorder of the arrangement of the molecular chains is increased, and the free volume is further increased.
Fourier infrared test characterization of example 7 samples
Fourier infrared test analysis was performed on representative ZTIF-1 particles, sample 1#, sample 3#, sample 4#, sample 5# and the results are shown in fig. 4. As can be seen from FIG. 4, as the ZTIF-1 loading increases, 3469cm of the stretching vibration is attributed to the hydroxyl group -1 Characteristic peaks at the positions gradually decrease, which indicates ZTIF-1 and vinegarThe presence of certain hydrogen bonding between the acid celluloses weakens the infrared peak intensity attributed to the stretching vibration of the hydroxyl groups. In addition, FIG. 5 shows ZTIF-1, sample # 4 at 2000cm -1 ～500cm -1 The spectrum of the local amplification in the range is not only the superposition of partial ZTIF-1 characteristic peak and cellulose acetate original characteristic peak which is difficult to distinguish, but also the infrared spectrum of the blend film sample No. 4 basically keeps the original characteristic peak of cellulose acetate and is 1670cm at the same time -1 ,1450cm -1 、955cm -1 、767cm -1 746cm -1 Characteristic peaks respectively attributed to ZTIF-1 appear, and successful loading of ZTIF-1 particles is jointly demonstrated with the X-ray diffraction analysis in example 6.
Example 8 gas separation Performance test
Gas separation performance was tested on representative samples # 1, # 3, and # 4, and the selected samples tested for N using a differential pressure method under gas separation operating conditions of 35℃and 1.05MPa 2 、CO 2 、CH 4 The results of the gas permeation performance of (2) are shown in Table 1.
TABLE 1 gas permeation properties of samples # 1, # 3, # 4
As can be seen from Table 1, the prepared ZTIF-1/cellulose acetate blend membrane (sample No. 3 and sample No. 4) has obviously improved permeability to carbon dioxide and CO compared with the pure cellulose acetate membrane (sample No. 1) 2 /CH 4 CO 2 /N 2 The selectivity of (2) can be doubled.
Example 9 mechanical Property test
The mechanical properties of samples # 1, # 3, # 4, and # 5 were tested and the tensile properties are shown in Table 2. As can be seen from Table 2, the incorporation of ZTIF-1 enhances the tensile strength and modulus of the cellulose acetate film.
TABLE 2 tensile Property test of samples # 1, # 3, # 4, # 5
| Sample numbering | Tensile strength (MPa) | Modulus (GPa) | Elongation at break (%) |
| 1# | 14.27 | 35.18 | 1.2 |
| 3# | 18.91 | 60.66 | 1.6 |
| 4# | 23.86 | 62.05 | 2.9 |
| 5# | 21.54 | 60.66 | 1.8 |
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, and various modifications and variations may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. A method for preparing a ZTIF-1/cellulose acetate blend membrane for gas separation, comprising the steps of:
step one, heating and dissolving the dried cellulose acetate particles in a first solvent to prepare a cellulose acetate solution; the ZTIF-1 is dispersed in a second solvent in advance to prepare ZTIF-1 dispersion liquid, and the cellulose acetate is diacetyl cellulose;
step two, cooling the cellulose acetate solution to room temperature, and adding the ZTIF-1 dispersion liquid under continuous stirring to form a blend membrane solution;
step three, after defoaming by vacuum treatment, the blend film solution is uniformly coated on a clean horizontal glass plate in an oven, and the solvent is evaporated to shape the pure polymer film; then placing the shaped pure polymer film under vacuum condition, heat-treating at 100-140 deg.C, then soaking in deionized water for a certain time, utilizing water tension to make the film be separated from glass plate; finally, drying the film to obtain a ZTIF-1/cellulose acetate blend film for gas separation;
in the cellulose acetate solution, the content of cellulose acetate particles is 3-10wt%, the stirring temperature is controlled at 50-80 ℃, and the stirring time is controlled at 6-24 hours;
in the blend membrane solution, ZTIF-1 particles account for 1 to 20 weight percent of the total mass of solid components in the feeding process, and the stirring time for preparing the blend membrane solution is controlled to be 6 to 12 hours.
2. The method for preparing ZTIF-1/cellulose acetate blend membrane for gas separation according to claim 1, wherein: the first solvent and the second solvent are selected from one or more of Tetrahydrofuran (THF), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and N-butyl acetate.
3. The method for preparing ZTIF-1/cellulose acetate blend membrane for gas separation according to claim 1, wherein: in the ZTIF-1 dispersion liquid, the content of ZTIF-1 particles is 0.1wt percent to 10wt percent.
4. The method for preparing ZTIF-1/cellulose acetate blend membrane for gas separation according to claim 1, wherein: the evaporating solvent adopts a temperature programming mode, and the temperature is raised by 20 ℃ every 1 or 2 hours; the upper limit temperature of the evaporating solvent is 100-140 ℃, the lower limit temperature of the evaporating solvent is 40-80 ℃, and the duration of the evaporating solvent is controlled between 6-24 hours.
5. The method for preparing ZTIF-1/cellulose acetate blend membrane for gas separation according to claim 1, wherein: and (3) placing the shaped pure polymer film under vacuum condition, and heat-treating at 100-140 ℃ for 2-12 hours.
6. The method for preparing ZTIF-1/cellulose acetate blend membrane for gas separation according to claim 1, wherein: the general formula of the cellulose acetate is as follows:
in formula (I), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Selected from any one of hydrogen and acetyl.
7. A ZTIF-1/cellulose acetate blend membrane, characterized in that: the ZTIF-1/cellulose acetate blend membrane is obtained according to the method for preparing a ZTIF-1/cellulose acetate blend membrane for gas separation according to any one of claims 1 to 6.
8. An application of a ZTIF-1/cellulose acetate blend membrane in gas separation, which is characterized in that: the ZTIF-1/acetate fiberThe plain blend membrane is obtained by the method for producing ZTIF-1/cellulose acetate blend membrane for gas separation according to any one of claims 1 to 6, and ZTIF-1/cellulose acetate blend membrane is used for N 2 、CO 2 、CH 4 、O 2 Separation of a mixed gas composed of any one component and a plurality of components.
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