AU2021104398A4 - A Preparation Method For A Mixed Matrix Membrane Utilized To Screen Gas Molecule Pairs Precisely - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 11
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 27
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 25
- 239000002608 ionic liquid Substances 0.000 claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 17
- -1 polydimethylsiloxane Polymers 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000013251 zeolitic imidazolate framework-71 Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229920002614 Polyether block amide Polymers 0.000 claims description 5
- INDFXCHYORWHLQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-3-methylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F INDFXCHYORWHLQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 5
- 239000004697 Polyetherimide Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000012924 metal-organic framework composite Substances 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000013165 zeolitic imidazolate framework-100 Substances 0.000 claims description 4
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 claims description 4
- 239000013164 zeolitic imidazolate framework-95 Substances 0.000 claims description 4
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 8
- 238000012216 screening Methods 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 10
- 230000035699 permeability Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
- B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
- B01D71/643—Polyether-imides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention discloses a preparation method for a mixed matrix membrane
utilized to screen gas molecule pairs precisely, which belongs to the technical field of
membrane separation. Specifically, the activated MOF particles are dispersed in an
ionic liquid solution, and then the low-boiling point solvent in the solution is fully
volatilized, and thus a MOF/ionic liquid composite can be obtained. In addition, a
solvent would be selected to wash off the ionic liquid on the surface of the composite,
and thus obtain a composite with different ionic liquid content in an analogous core
shell structure, which would be mixed into a polymer solution and cast into a
membrane later. This method can modify the pore size of the MOF to a certain range
from the point of orderly regulating the size of the porous channel of filler by utilizing
stuffing in order, and make the precise screening be applicable to gas molecule pairs
with different sizes, which provides an innovative and feasible idea for separation
process of other gas pairs with similar physical and chemical properties but in
different sizes.
Drawings of Descriptions
100
80
ZIF-8
----- [Bmim][PF6] (a),ZIF-8 ~60
---- [Bmim][PF]
40
20
0 --- -
0 100 200 300 400 500 600 700
Temperature /C
Figure 1
100
80
ZIF-8
[60 Bmim][PF 1(a@ZIF-8
[Bmim][PF I
S40
20
0
0 100 200 300 400 500 600 700
Temperature /C
Figure 2
A I"%
Description
Drawings of Descriptions 100
80
ZIF-8 - - - [Bmim][PF6] (a),ZIF-8 ~60 ---- [Bmim][PF]
40
20
0 --- - 0 100 200 300 400 500 600 700 Temperature /C
Figure 1
100
80
ZIF-8 Bmim][PF 1(a@ZIF-8
[60
[Bmim][PF I
S40
20
0 0 100 200 300 400 500 600 700 Temperature /C
Figure 2
Descriptions
A Preparation Method for a Mixed Matrix Membrane Utilized to Screen Gas Molecule Pairs Precisely
Technical Field
[0001] The present invention belongs to the technical field of membrane separation, particularly relates to a preparation method for a mixed matrix membrane utilized to precisely screen gas molecule pairs with different sizes.
Background Technology
[0002] Since excessive high concentration of CO2 in the atmosphere would exacerbate the global warming, thus, CO2 capturing has become one of thorny issues need to be addressed for human society in the 21st century. Furthermore, as a common associated gas of natural gas, coal field gas, and biogas, etc., if theCO 2 cannot be removed in advance, it will corrode pipeline during transportation and reduce the calorific value of fuel, so that influence the efficiency of energy supply. Traditionally, the separation of CO2 mainly uses methods of pressure swing adsorption, chemical absorption and low-temperature distillation, etc. Nowadays, a new type of separation technology which can be used for CO 2 capturing is emerged, i.e., gas membrane separation technology. Compared with traditional separation methods, gas membrane separation method has the advantages of without phase change, and with mild process conditions, at low operating cost, and occupying small footprint, which has been developed rapidly in recent years. Wherein, membrane material is the key element of membrane separation technology. Furthermore, under the condition that the traditional polymer membrane materials are used forCO 2 separation, there are problems such as low separation performance, serious plasticization, and being incapable of bearing high temperature and high pressure, etc., would be occurred, which may restrict the industrial development of CO 2 membrane separation. Therefore, researching membrane materials which can meet both separation requirements and mechanical performance requirements becomes the key element of this field.
[0003] Mixed matrix membrane (MixedMatrixMembrane) is a new material which integrates the strong separation performance of inorganic membranes with the mechanical properties and the cost advantages of polymer membranes to meet the requirements of the membrane separation industry in future. The selection of inorganic fillers is the t key point to prepare high-performance mixed matrix membranes. Meanwhile, metal-organic frameworks (MOFs) manifest better interfacial compatibility in membrane materials due to their inherent nature of being partially organic. Furthermore, due to porous channels of MOFs are composed of metal ions and organic ligands, the types of MOFs are constantly would be updated based upon the functional diversity of organic ligands, and thus results in tens of thousands of types of MOFs at present. However, due to the pore size of MOFs is generally larger than the kinetic size of gas molecular, and cannot be located between the two gases to be separated ideally, so that resulting in failure of exerting screening effect of the filler fully. Although the pore structure can be modified by methods such as metal ion substitution and ligand modification, it also cannot meet actual requirements due to the high difficulty in operation.
Summary of the Present Invention
[0004] Based on the problems in the prior art, the present invention is proposed for the purpose of preparing a mixed matrix membrane utilized to precisely screen gas molecule pairs with different sizes.
[0005] The technical scheme of the present invention is:
[0006] 1. A preparation method for a mixed matrix membrane utilized to screen gas molecule pairs precisely, characterized in that the steps of which are as follows:
[0007] The ionic liquid (RTILs) at the room temperature with different sizes and
different physical and chemical properties is selected, and then dispersed in solvent A with the filler MOF powder activated in oven and at the temperature of 150°C, after that, the RTILs/MOF composite can be obtained by means of the natural volatilization of solvent A, meanwhile, the solvent B would be selected to wash off all dissociative ion liquid remained the surface of the composite, and thus the RTILs/MOF composites with different ionic liquid content can be obtained, which shall be denoted as IL@MOF, after that, mix it into the polymer solution and cast into a membrane.
[0008] The mass ratio of the said RTILs and MOF is 0.5-5;
[0009] The said ionic liquid at the room temperature is1-Ethyl-3-methylimidazolium hexafluorophosphate [Emim][PF6], 1-Butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF6], 1-Hexyl-3- methylimidazolium hexafluorophosphate [Hmim][PF6], 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [Bmim][Tf2N] or 1-Ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [Emim][Tf2N].
[0010] The saidMOF is a MOF with a cage-pore structure, such as ZIF-71, ZIF-67, ZIF-7, ZIF-8, ZIF -90, ZIF-95 or ZIF-100.
[0011] The said solvent A can be acetone, chloroform, ethyl ether or dichloromethane.
[0012] The said solvent B can be N, N-dimethylformamide, N, N dimethylacetamide or dimethyl sulfoxide.
[0013] The said polymer is polyether block amide 1657(Pebaxl657), polyimide, polyetherimide, polyether sulfone or polydimethylsiloxane
[0014] The application amount of the said polymer shall be determined according to the formula:
[0015]
Loading capacity of filler (wt%) X100%. m py-e
[0016] The beneficial effects of the present invention are: the range of ionic liquid content of the ionic liquid @MOFs composite prepared by the present invention can be between 3% and 20%, meanwhile, under the test conditions of at the temperature of 25C, and at the pressure of 0.3MPa, the permeability coefficient
of CO 2 of the present invention has been increased by 92.1%compared with the
pure Pebax membrane, after being mixed into Pebax1657 to prepare a mixed matrix membrane, which reaches up to 115 Barrer, and the selectivity of C /N 2 2
separation has been increased by 54.5%, which reaches up to 85, and exceeds the upper limit of C0 2/N2Roberson in 2008.
Brief Description of the Drawings
[0017] Figure 1 is the thermo-gravimetric curve of Embodiment 1, ZIF-8,
[Bmim][PF6]@ZIF-8 complex, and [Bmim][PF 6].
[0018] Figure 2 is the thermo-gravimetric curve of Embodiment 2, ZIF-8,
[Bmim][PF 6]@ZIF-8 complex, and [Bmim][PF].
[0019] Figure 3 is the thermo-gravimetric curve of Embodiment 3, ZIF-8,
[Bmim][Tf2N]@ZIF-8 complex, and [Bmim][Tf2N].
[0020] Figure 4 is the thermo-gravimetric curve of Embodiment 4, ZIF-71,
[Emim][Tf2N]@ZIF-71 complex, and [Emim][Tf2N].
Detailed Description of the Presently Preferred Embodiments
[0021] The text below will further describe the specific embodiment of the present invention in conjunction with the drawings and technical scheme.
[0022] Embodiment 1
[0023] The ionic liquid of1-Butyl-3-methylimidazolium hexafluorophosphate
[Bmim][PF] was selected, and 0.07g of [Bmim][PF] was added to 20mL of acetone, then, stirred it at low speed (<250r/min) for 1 hour to make the
[Bmim][PF6] be distributed in acetone evenly. After adding 0.2g of activated ZIF 8 powder, the product should be subjected to water bath ultrasonic process to make the ZIF-8 be fully dispersed in the [Bmim][PF]/acetone solution, and then guaranteed the acetone be volatilized naturally by stirring, and thus the
[Bmim][PF]/ZIF-8 composite could be obtained, which should be subjected to thermal treatment in an oven at the temperature of 105°C overnight to make the ionic liquid enter the ZIF-8 pores as much as possible. After that, the washing collection of N, N-dimethylformamide should be repeated for three times, and be operated for ten minutes each time, and thus it could guarantee that the
[Bmim][PF] remained on the surface of ZIF-8 has been thoroughly washed off, wherein, the composite after washing should be denoted as [Bmim][PF]@ZIF-8, which would be put into an oven at the temperature of 150°C later to make the N,N-dimethylformamide be volatilized fully. After the material was cooled down, a certain mass of product would be weighed, which should be mixed into 3wt% of Pebax1657 solution, and then cast into a membrane. After that, the prepared membrane material should be put into a vacuum oven at the temperature of 50°C for 24 hours for annealing treatment, and then could be used to test.
[0024] The thermogravimetric test result indicated that the [Bmim][PF] contained in the [Bmim][PF 6 ]@ZIF-8 composite material prepared in this embodiment accounted for 8.07%. In addition, under the test conditions of at the temperature of
°C, and at the pressure of 0.3MPa, as well as the amount of filler reached 25%, the
permeability coefficient of CO2 of the present invention has been increased by 92.1%
compared with the pure Pebax 1657 membrane, which reached up to 115 Barrer, and the selectivity of C0 2/N 2 separation has been increased by 54.5%, which reached up to 85.
[0025] Embodiment 2
[0026] The ionic liquid of 1-Butyl-3-methylimidazolium hexafluorophosphate
[Bmim][PF ]6 was selected, and 0.3g of [Bmim][PF] was added to 20mL of chloroform, then, stirred it at low speed (<250r/min) for 1 hour to make the
[Bmim][PF] be distributed in acetone evenly. After adding 0.2g of activated ZIF-8 powder, the product should be subjected to water bath ultrasonic process to make the ZIF-8 be fully dispersed in the [Bmim][PF]/chloroform solution, and then guaranteed the chloroform be volatilized naturally by stirring, and thus the
[Bmim][PF]/ZIF-8 composite could be obtained, which should be subjected to thermal treatment in an oven at the temperature of 105°C overnight to make the ionic liquid enter the ZIF-8 porous channels as much as possible. After that, the washing-collection of dimethyl sulfoxide should be repeated for three times, and be operated for ten minutes each time, and thus it could guarantee that the [Bmim][PF6 ] remained on the surface of ZIF-8 has been thoroughly washed off, wherein, the composite after washing should be denoted as [Bmim][PF]@ZIF-8, which would be put into an oven at the temperature of 150°C later to make the dimethyl sulfoxide be volatilized fully. After the material was cooled down, a certain mass of product would be weighed, which should be mixed into 3wt% of Pebax1657 solution, and then cast into a membrane. After that, the prepared membrane material should be put into a vacuum oven at the temperature of 50°C for 24 hours for annealing treatment, and then could be used to test.
[0027] The thermogravimetric test result indicated that the [Bmim][PF] contained in the [Bmim][PF 6 ]@ZIF-8 composite material prepared in this embodiment accounted for 12.05%. In addition, under the test conditions of at the temperature of °C, and at the pressure of 0.3MPa, as well as the amount of filler reached 10%, the permeability coefficient of CO2 of the present invention has been increased by 71.6%compared with the pure Pebax 1657 membrane, which reached up to 101
Barrer, and the selectivity of C0 2/N 2 separation has been increased by 62.9%, which reached up to 90.
[0028] Embodiment 3
[0029] The ionic liquid of 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [Bmim][Tf2N] was selected, and 0.7g of
[Bmim][Tf2N] was added to 20mL of acetone, then, stirred it at low speed (<250r/min) for 1 hour to make the [Bmim][Tf2N] be distributed in acetone evenly. After adding 0.2g of activated ZIF-8 powder, the product should be subjected to water bath ultrasonic process to make the ZIF-8 be fully dispersed in the
[Bmim][Tf2N]/acetone solution, and then guaranteed the acetone be volatilized naturally by stirring, and thus the [Bmim][Tf2N]/ZIF-8 composite could be obtained, which should be subjected to thermal treatment in an oven at the temperature of 105°C overnight to make the ionic liquid enter the ZIF-8 porous channels as much as possible. After that, the washing-collection of N, N-dimethylformamide should be repeated for three times, and be operated for ten minutes each time, and thus it could guarantee that the [Bmim][Tf2N] remained on the surface of ZIF-8 has been thoroughly washed off, wherein, the composite after washing should be denoted as
[Bmim][Tf2N]@ZIF-8, which would be put into an oven at the temperature of 150°C later to make the N,N-dimethylformamide be volatilized fully. After the material was cooled down, a certain mass of product would be weighed, which should be mixed into 3wt% of polyetherimide solution, and then cast into a membrane. After that, the prepared membrane material should be put into a vacuum oven at the temperature of °C for 24 hours for annealing treatment, and then could be used to test.
[0030] The test result indicated that the [Bmim][Tf2N] contained in the
[Bmim][Tf 2N]@ZIF-8 composite material prepared in this embodiment accounted for 8%. In addition, under the test conditions of at the temperature of 25°C, and at the pressure of 0.3MPa, as well as the amount of filler reached 15%, the permeability coefficient of CO2 of the present invention has been increased by 155% compared with the pure polyimide membrane, which reached up to 28.7 Barrer, and the selectivity of C0 2 /N 2 separation has been increased by 42%, which reached up to 24.5.
[0031] Embodiment 4
[0032] The ionic liquid of 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [Emim][Tf2N] was selected, and 0.5g of
[Emim][Tf2N] was added to 20mL of chloroform, then, stirred it at low speed (<250r/min) for 1 hour to make the [Emim][Tf2N] be distributed in chloroform evenly. After adding 0.2g of activated ZIF-71 powder, the product should be subjected to water bath ultrasonic process to make the ZIF-71 be fully dispersed in the [Emim][Tf2N]/chloroform solution, and then guaranteed the chloroform be volatilized naturally by stirring, and thus the [Emim][Tf2N]/ZIF-71 composite could be obtained, which should be subjected to thermal treatment in an oven at the temperature of 105°C overnight to make the ionic liquid enter the ZIF-71 porous channels as much as possible. After that, the washing-collection of N, N dimethylformamide should be repeated for three times, and be operated for ten minutes each time, and thus it could guarantee that the [Emim][Tf2N] remained on the surface of ZIF-71 has been thoroughly washed off, wherein, the composite after washing should be denoted as [Emim][Tf2N]@ZIF-71, which would be put into an oven at the temperature of 150°C later to make the N,N-dimethylformamide be volatilized fully. After the material was cooled down, a certain mass of product would be weighed, which should be mixed into 3wt% of polyetherimide solution, and then cast into a membrane. After that, the prepared membrane material should be put into a vacuum oven at the temperature of 50°C for 24 hours for annealing treatment, and then could be used to test.
[0033] The test result indicated that the [Emim][Tf 2N] contained in the
[Emim][Tf2N]@ZIF-71 composite material prepared in this embodiment accounted for 18.4%. In addition, under the test conditions of at the temperature of 25°C, and at the pressure of 0.3MPa, as well as the amount of filler reached 10%, the permeability coefficient of CO2 of the present invention has been increased by 64% compared with the pure polyimide membrane, which reached up to 30.5 Barrer, and the selectivity of CO2/N 2 separation has been increased by 59%, which reached up to 20.6.
Claims (10)
- Claims 1. A preparation method for a mixed matrix membrane utilized to screen gas molecule pairs precisely, characterized in that the steps of which are as follows: The ionic liquid RTILs at the room temperature with different sizes and different physical and chemical properties is selected, and then dispersed in solvent A with activated filler MOF at the temperature of 150°C, after that, the solvent A is utilized to volatilize naturally, and thus the RTILs/MOF composite can be obtained, meanwhile, the solvent B would be selected to wash off all dissociative ion liquid remained the surface of the composite, and thus the RTILs/MOF composites with different ionic liquid content can be obtained, which shall be denoted as IL@MOF, after that, mix it into the polymer solution and cast into a membrane.
- 2. The said preparation method according to claim 1, characterized in that the mass ratio of the said RTILs and MOF is 0.5-5.
- 3. The said preparation method according to claim 1 or 2, characterized in that the said polymer can be polyether block amide 1657, polyimide, polyetherimide, polyether sulfone or polydimethylsiloxane; wherein, the application amount of the said polymer shall be determined according to the formula:Loading capacity of filer (wt%) m x100%.
- 4. The said preparation method according to claim 1 or 2, characterized in that the said ionic liquid at the room temperature is 1-Ethyl-3-methylimidazolium hexafluorophosphate [Emim][PF 6], 1-Butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF 6], 1-Hexyl-3- methylimidazolium hexafluorophosphate [Hmim][PF 6], 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [Bmim][Tf 2N] or 1-Ethyl-3 methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [Emim][Tf 2N].
- 5 The said preparation method according to claim 3, characterized in that the said ionic liquid at the room temperature is 1-Ethyl-3-methylimidazolium hexafluorophosphate [Emim][PF 6], 1-Butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF 6], 1-Hexyl-3- methylimidazolium hexafluorophosphate [Hmim][PF 6], 1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [Bmim][Tf 2N] or 1-Ethyl-3 methylimidazolium bis[(trifluoromethyl)sulfonyl]imide [Emim][Tf 2N].
- 6 The said preparation method according to claim 1, 2 or 5, characterized in that the said MOF is a MOF with a cage-pore structure, such as ZIF-71, ZIF-67, ZIF-7, ZIF-8, ZIF -90, ZIF-95 or ZIF-100.
- 7 The said preparation method according to claim 3, characterized in that the said MOF is a MOF with a cage-pore structure, such as ZIF-71, ZIF-67, ZIF-7, ZIF-8, ZIF -90, ZIF-95 or ZIF-100.
- 8 The said preparation method according to claim 4, characterized in that the said MOF is a MOF with a cage-pore structure, such as ZIF-71, ZIF-67, ZIF-7, ZIF-8, ZIF -90, ZIF-95 or ZIF-100.
- 9 The said preparation method according to claim 1, 2, 5, 7 or 8, characterized in that the said solvent A can be acetone, chloroform, ethyl ether or dichloromethane; In addition, the said solvent B can be N, N-dimethylformamide, N, N dimethylacetamide or dimethyl sulfoxide.
- 10 The said preparation method according to claim 6, characterized in that the said solvent A can be acetone, chloroform, ethyl ether or dichloromethane; In addition, the said solvent B can be N, N-dimethylformamide, N, N dimethylacetamide or dimethyl sulfoxide.
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| CN113813801A (en) * | 2021-09-28 | 2021-12-21 | 浙江工商大学 | Mixed matrix ultrafiltration membrane doped with ZIFs @ polyion liquid compound and preparation method thereof |
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| CN116351265A (en) * | 2022-01-17 | 2023-06-30 | 中国科学院过程工程研究所 | Preparation and application of high-performance mixed matrix gas separation membrane based on ionic liquid coordination |
| CN116351265B (en) * | 2022-01-17 | 2024-06-07 | 中国科学院过程工程研究所 | Preparation and application of high-performance mixed matrix gas separation membrane based on ionic liquid coordination |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113813801A (en) * | 2021-09-28 | 2021-12-21 | 浙江工商大学 | Mixed matrix ultrafiltration membrane doped with ZIFs @ polyion liquid compound and preparation method thereof |
| CN113813801B (en) * | 2021-09-28 | 2023-06-06 | 浙江工商大学 | Mixed matrix ultrafiltration membrane doped with ZIFs@polyionic liquid compound and preparation method thereof |
| CN114225707A (en) * | 2021-11-26 | 2022-03-25 | 浙江工业大学 | Hydrophobic modified hollow fiber membrane and preparation method and application thereof |
| CN116351265A (en) * | 2022-01-17 | 2023-06-30 | 中国科学院过程工程研究所 | Preparation and application of high-performance mixed matrix gas separation membrane based on ionic liquid coordination |
| CN116351265B (en) * | 2022-01-17 | 2024-06-07 | 中国科学院过程工程研究所 | Preparation and application of high-performance mixed matrix gas separation membrane based on ionic liquid coordination |
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