CN112156659A - M-gate metal organic framework membrane and preparation method and application thereof - Google Patents
M-gate metal organic framework membrane and preparation method and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 21
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012920 MOF membrane Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000498 ball milling Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 20
- 239000013110 organic ligand Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 229940074391 gallic acid Drugs 0.000 claims description 10
- 235000004515 gallic acid Nutrition 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 7
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 5
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
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- 238000000576 coating method Methods 0.000 description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 1
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Images
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
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
Abstract
The invention relates to an M-gate metal organic framework membrane and a preparation method and application thereof. The method is characterized in that: the M-gallolite MOF membrane consists of an M-gallolite crystal layer and a support body, wherein the thickness of the M-gallolite crystal layer is in a range of 3-20 mu M. The method comprises the following specific steps: A. preparing M-ballast liquid crystal; B. uniformly dispersing the seed crystal liquid on a support body to prepare uniform seed crystals; C. and carrying out hydrothermal synthesis or counter-diffusion hydrothermal synthesis on the support body modified with the seed crystal through a reaction kettle to obtain the M-gate metal-organic framework membrane. And applied to the separation of ethylene/ethane gas, and single-component and mixed gas performance tests show that the prepared M-gate membrane has good ethylene permeability and ethylene/ethane separation selectivity.
Description
Technical Field
The invention belongs to the technical field of gas separation membranes, and particularly relates to an M-gate metal organic framework membrane, and a preparation method and application thereof.
Background
Olefin/alkane separation is an extremely energy-consuming process in petrochemical production. The low-carbon hydrocarbon is obtained by catalytic cracking. However, the product of the process is a mixture of olefin and alkane, and the product must be separated and purified to carry out production synthesis. Ethylene as synthetic fiberThe basic chemical raw materials of rubber and plastics are one of the chemical products with the largest yield in the world. Ethylene/ethane (C)2H4/C2H6) The separation is currently carried out by cryogenic distillation, but because of the ethylene (C)2H4) And ethane (C)2H6) Similar physicochemical properties, this separation process is very energy intensive. Alternative low energy separation techniques such as membranes, adsorption and the like have thus been important research areas. Wherein, the membrane separation technology has the advantages of low energy consumption, high efficiency, high filling density, simple operation and the like, and is shown in the specification C2H4/C2H6The separation aspect has great application potential. The biggest limitation of current membrane separation technology is the lack of good C2H4/C2H6Separation of the Selective sum C2H4A permeable membrane material. The organic polymer membranes developed at present have the disadvantage of low selectivity, and the organic membranes have the contradiction between selectivity and permeability. Metal-organic frameworks (MOFs) are being developed vigorously as a new organic-inorganic hybrid material, and have the characteristics of large specific surface area, adjustable pore channels, rich topological structure and the like. The diversity and the modifiability of the MOFs enable scientific researchers to select proper MOFs structures according to a target separation system so as to realize efficient separation of the target system. The MOFs membrane has great application potential in the field of gas separation.
Disclosure of Invention
The invention aims to provide an M-gate metal organic framework membrane, a preparation method of the M-gate metal organic framework membrane and application of the M-gate metal organic framework membrane to C2H4/C2H6Separation of (4).
The technical scheme of the invention is as follows: an M-gate metal organic framework membrane is characterized in that: the M-galateMOF membrane consists of an M-galatee crystal layer and a support, wherein the M-galatee crystal layer is uniformly distributed on the support and is tightly combined with the support, and the thickness of the M-galatee crystal layer ranges from 3 mu M to 20 mu M.
Preferably, the support is alumina or an organic porous support; wherein the organic support is more preferably nylon (PA), Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF).
Preferably, the M-gate is at least one of Mg-gate, Ni-gate or Co-gate.
The invention also provides a method for preparing the M-gate metal organic framework membrane, which comprises the following specific steps: A. preparing M-ballast liquid crystal; B. uniformly dispersing the seed crystal liquid on a support body to prepare uniform seed crystals; C. and carrying out hydrothermal synthesis or counter-diffusion hydrothermal synthesis on the support body modified with the seed crystal through a reaction kettle to obtain the M-gate metal-organic framework membrane.
Preferably, the step of preparing the M-gate crystal liquid in the step A comprises the following steps: first, M-gallate crystals (reference: 10.1002/anie.201808716(DOI)) were synthesized; then putting the synthesized M-gate crystal into a ball milling tank and using ethanol as a solvent, wherein the mass ratio of the M-gate crystal to the ethanol is as follows: 1, (10-20) performing ball milling for 10-60 min to obtain M-gate ethanol dispersion liquid; the resulting M-gate ethanol dispersion was diluted with ethanol to 50 to 100 times the original volume, and the diluted dispersion was used as a seed crystal solution.
Preferably, the step B of uniformly dispersing the liquid crystal on the support to prepare uniform seed crystals is to obtain uniformly dispersed seed crystals on the support by spin coating, soaking or suction filtration.
Preferably, the reaction kettle in the step C is hydrothermally synthesized into: weighing metal salt and organic ligand according to the molar ratio of the metal salt to the organic ligand being 1 (1-4), adding deionized water, stirring and dissolving to obtain a precursor solution; adjusting the pH value of the precursor solution to 7.5-9, then pouring the MOF precursor solution into a reaction kettle and ensuring that a support body is immersed in the precursor solution, and reacting in an oven for 12-48h at the reaction temperature of 80-120 ℃; taking out the MOF membrane after the reaction is finished, cleaning the MOF membrane by using deionized water, and then placing the MOF membrane in an oven for drying; wherein the metal salt is: magnesium chloride hexahydrate, cobalt chloride hexahydrate or nickel chloride hexahydrate, and the organic ligand is gallic acid.
Preferably, the counter-diffusion hydrothermal synthesis in step C: respectively preparing a metal salt aqueous solution and a ligand aqueous solution which are equal in volume, wherein the molar ratio of metal salt to ligand is 1 (1-4), and adjusting the pH value of the organic ligand aqueous solution to 7.5-9; clamping the support body in a counter diffusion device, adding a metal salt solution into one side of the counter diffusion device, and adding a ligand aqueous solution for adjusting the pH value into the other side of the counter diffusion device, so as to ensure that the support body is completely immersed by the metal salt solution and the ligand solution; then reacting for 12-24h in an oven at 70-90 ℃; taking out the M-gate membrane after the reaction is finished, washing the M-gate membrane by deionized water, and then putting the membrane in an oven for drying; the metal salt is: magnesium chloride hexahydrate, cobalt chloride hexahydrate or nickel chloride hexahydrate, and the organic ligand is gallic acid.
Preferably, the substances for adjusting the pH value of the solution are all potassium hydroxide, sodium hydroxide, triethylamine or ethylenediamine.
The invention also provides application of the M-gate metal organic framework membrane in ethylene/ethane separation in the field of gas separation. Application of the prepared M-gap MOF Membrane to C2H4/C2H6And (5) gas separation. The gas testing pressure range is 0.1MPa-0.5 MPa.
Has the advantages that:
(1) the selected M-gate material pair has excellent adsorption selectivity. The pore size of M-gate can allow C2H4Preferential permeation of gas and effective prevention of C2H6The transport of molecules;
(2) pure M-ballast membranes of the invention for C2H4/C2H6Separation of the System, C, which is superior to conventional Polymer materials2H4Permeability and C2H4/C2H6And (4) selectivity.
Drawings
FIG. 1 is the XRD pattern of a Ni-gate pure film prepared on an alumina support in example 1.
FIG. 2 is SEM images of (a) cross section and (b) surface of Ni-gate pure membrane prepared on alumina support in example 1.
FIG. 3 is SEM images of (a) cross section and (b) surface of Ni-gate pure membrane supported by nylon in example 2. FIG. 4 is a (a) cross-section and (c) surface view of a PVDF support Ni/Co-gate membrane of example 5; section (b) and surface (d) of PTFE support Ni/Co-gate membrane.
Detailed Description
The present invention is further described with reference to the following examples, but the scope of the present invention is not limited to the examples. The following examples are process references for the synthesis of M-gate crystals: 10.1002/anie.201808716 (DOI). Wherein the unit of permeability is Barrer.
Barrer＝10-10cm3(STP)·cm·cm-2·s-1·cmHg-1
Example 1
(1) The reference synthesizes Ni-gate crystals. 2g of the obtained crystals are added into a ball milling tank, 20g of ethanol is added, and ball milling is carried out at the rotating speed of 400rpm for 20 minutes, and then ball milling liquid is taken out. 1mL of ball milling liquid is diluted to 100mL and used as liquid crystal.
(2) And (3) placing the alumina porous support body on a spin coater, uniformly coating the seed crystal liquid on the support body in a spin coating mode, placing the support body in a 60 ℃ oven for 2h, and taking out. The spin coating parameters were: the rotation speed is 1500rpm, the time is 30s, and the number of spin-coating times is 10.
(3) 0.238g (1mmol) of nickel chloride hexahydrate and 0.34g (2mmol) of gallic acid were weighed into a 100mL beaker, and 30mL of deionized water was added. And (3) dropwise adding triethylamine under the stirring condition when the metal salt and the organic ligand are completely dissolved, and adjusting the pH value of the solution to 8.5. The prepared solution was added to a 50mL reaction vessel, and the alumina support with the seed crystal was immersed therein. And (3) placing the reaction kettle in an oven, heating at 120 ℃ for 12h, and taking out to obtain the Ni-gate pure membrane. After 3 washes with deionized water, it was dried in an oven at 60 ℃ for 12 h. From XRD of FIG. 1, it can be seen that the characteristic peaks of Ni-gate membrane are consistent with the characteristic peaks of Ni-gate crystal and support, indicating that Ni-gate membrane is successfully prepared on support. The SEM representation of FIG. 2 shows that the Ni-gate crystal film is about 5 μm thick and the crystal film layer is tightly bonded to the support.
(4) Ni-ballast pure membranes were used for ethylene and ethane gas performance tests and the results show: at 0.15MPa, the ethylene permeability is 256Barrer, the ethane permeability is 34Barrer, and the ideal selectivity is 7.52.
Example 2
(1) The reference synthesizes Ni-gate crystals. And adding 1g of the obtained crystals into a ball milling tank, adding 20g of ethanol, carrying out ball milling at the rotating speed of 400rpm for 60 minutes, and taking out ball milling liquid. 1mL of ball milling liquid is diluted to 80mL to be used as liquid crystal.
(2) 10ml of the liquid crystal is taken out and filtered on an organic support PTFE with the diameter of 47mm and the aperture of 100nm, the liquid crystal is taken out after being dried for 2h at the temperature of 60 ℃, and the support is fixed in a counter diffusion device.
(3) 0.475g (2mmol) of nickel chloride hexahydrate was dissolved in 80mL of deionized water to prepare a metal salt solution. 0.64g (4mmol) of gallic acid is dissolved in 80mL of deionized water, and triethylamine is added dropwise to adjust the pH of the solution to 8, thus obtaining a ligand solution. And adding a metal salt solution to one side of the liquid crystal layer in the diffusion glass device, adding a ligand solution to the other side, and completely immersing the support body by the solutions on the two sides. Growing for 12h at 80 ℃ to obtain the Ni-gate pure film. Washed by deionized water and dried for 2h at 60 ℃. The Ni-gate membrane was found to be tightly bound to the support by SEM characterization of FIG. 3, and the Ni-gate was well intergrown with a membrane thickness of 5.5 μm.
(4) The Ni-gate pure film is subjected to gas separation test, the ethylene permeability is 237Barrer and the ethane permeability is 32Barrer under 0.3Mpa, C2H4/C2H6The ideal selectivity is about 7.41.
Example 3
(1) Co-gate crystals were synthesized with reference to the reference. 2g of the obtained crystals are added into a ball milling tank, 20g of ethanol is added, ball milling is carried out at the rotating speed of 400rpm for 30min, and then ball milling liquid is taken out. 1mL of ball milling liquid is diluted to 100mL and used as liquid crystal.
(2) And (3) placing the alumina porous support body on a spin coater, uniformly coating the seed crystal liquid on the alumina support body in a spin coating mode, placing the support body in a 60 ℃ oven, drying for 2h, and taking out. The spin coating parameters were: the rotation speed is 1500rpm, the time is 30s, and the number of spin-coating times is 10.
(3) 0.238g (1mmol) of cobalt chloride hexahydrate and 0.51g (3mmol) of gallic acid were weighed into a 150mL beaker, and 100mL of deionized water was added. After the metal salt and organic ligand were completely dissolved, 0.5M KOH solution was added dropwise with stirring to adjust the pH to 7.8. 25ml of the above solution was taken out and placed in a 50ml reaction vessel, and the support with the seed crystal was immersed therein. And (3) placing the reaction kettle in an oven, heating at 80 ℃ for 24h, and taking out to obtain the Co-gate membrane. After washing with deionized water for 3 times, the mixture was dried in an oven at 60 ℃ for 12 hours to give a film thickness of 9.8. mu.m.
(4) Co-ballast pure membranes were used for ethylene and ethane gas performance testing and the results show: at 0.3MPa, C2H4Has a permeability of 214Barrer, C2H6Has a permeability of 27Barrer and an ideal selectivity of 7.9. C on Co-gate membranes2H4/C2H6And (5) testing the performance of the mixed gas with the same volume. At 0.5MPa, C2H4Permeability of 203Barrer, C2H6Has a permeability of 30Barrer, C2H4/C2H6The selectivity was 6.8.
Example 4
(1) The reference synthesizes Mg-gate crystals. And adding 1g of the obtained crystals into a ball milling tank, adding 20g of ethanol, carrying out ball milling at the rotating speed of 400rpm for 60min, and taking out ball milling liquid. 1mL of ball milling liquid is diluted to 50mL to be used as liquid crystal.
(2) 10ml of seed crystal liquid is taken and filtered in Al2O3And (3) placing the support body on a 60 ℃ oven for 2h, and taking out.
(3) 0.407g (2mmol) of magnesium chloride hexahydrate and 0.34g (2mmol) of gallic acid were weighed into a 50mL polytetrafluoroethylene reaction kettle, and 20mL of deionized water was added to dissolve them, and then ethylenediamine was added dropwise to adjust the pH of the solution to 9. And placing the support in a reaction kettle, heating the support in an oven at 120 ℃ for 48h, and taking out the support to obtain the Mg-gate pure membrane. After washing with deionized water 3 times, the mixture was dried in an oven at 60 ℃ for 12 hours to give a film thickness of 18 μm.
(4) Use of Mg-gate film for C2H4And C2H6Gas performance test, the result shows: at 0.5MPa, C2H4Has a permeability of 224Barrer, C2H6Has a permeability of 44Barrer and an ideal selectivity of 5.1. C2H4/C2H6The performance test result of the equal-volume gas mixture shows that: at 0.5MPa, C2H4Has a permeability of 205Barrer, C2H6Has a permeability of 47Barrer, C2H4/C2H6The selectivity was 4.36.
Example 5
(1) Co-gate and Ni-gate crystals were synthesized with reference to the references. And respectively taking 1g of powder of the two crystals, adding the powder into a ball milling tank, adding 20g of ethanol, carrying out ball milling at the rotating speed of 400rpm for 60min, and taking out ball milling liquid. 1mL of the ball milling solution is diluted to 100mL to prepare a Co-gate and Ni-gate mixed crystal liquid.
(2) And respectively soaking PVDF and PTFE support bodies with the diameter of 25mm in the liquid crystal for 10min, and then taking out. The support body is placed in an oven at 60 ℃ for 2h and then taken out.
(3) 0.238g (1mmol) of cobalt chloride hexahydrate, 0.238g (1mmol) of nickel chloride hexahydrate and dissolved in 160ml of deionized water were weighed out. 0.68g (4mmol) of gallic acid was weighed into a 250mL beaker and dissolved by sonication with 160mL of deionized water. When the organic ligand is completely dissolved, ethylenediamine is added dropwise under stirring to adjust the pH value to 8. And respectively placing the pretreated PVDF and PTFE support bodies in two diffusion devices, and respectively adding a metal salt solution and an organic ligand solution into two sides to ensure that the support bodies are completely immersed by the solutions on the two sides. And (3) placing the reaction kettle in an oven, heating at 70 ℃ for 24h, and taking out to obtain the Co/Ni-gate pure film. After 3 washes with deionized water, it was dried in an oven at 60 ℃ for 12 h. It is found from fig. 4 that: the thickness of the membrane on the PVDF support was 5.5 μm and the thickness of the membrane on the PTFE support was 17.7. mu.m.
(4) Co/Ni-gate pure membranes were used for ethylene and ethane gas performance tests and the results show: PVDF support Co/Ni-gate membrane: at 0.2MPa, C2H4Has a permeability of 237Barrer, C2H6Has a permeability of 28Barrer and an ideal selectivity of 8.46. C on Co/Ni-gate film2H4/C2H6And (5) testing the performance of the mixed gas with the same volume. At 0.2MPa, C2H4Permeability of 213Barrer, C2H6Has a permeability of 30Barrer, C2H4/C2H6The selectivity was 7.1. (vii) PTFE support Co/Ni-gate membrane: at 0.2MPa, C2H4Has a permeability of 145Barrer, C2H6Has a permeability of 23Barrer and an ideal selectivity of 6.30. C on Co/Ni-gate film2H4/C2H6And (5) testing the performance of the mixed gas with the same volume. At 0.2MPa, C2H4Permeability of 123Barrer, C2H6Has a permeability of 25Barrer, C2H4/C2H6The selectivity was 4.92.
Example 6
(1) The reference synthesizes Co-gate crystals. 2g of the obtained crystals are added into a ball milling tank, 20g of ethanol is added, ball milling is carried out at the rotating speed of 400rpm for 20min, and then ball milling liquid is taken out. 1mL of ball milling liquid is diluted to 50mL to be used as liquid crystal.
(2) 10ml of seed crystal liquid is taken out and filtered on a PA supporting body, and the supporting body is placed in an oven at 60 ℃ for 2 hours and then taken out.
(3) 0.238g (1mmol) of cobalt chloride hexahydrate was weighed out and dissolved in 80ml of deionized water. 0.68g (4mmol) of gallic acid was weighed into a 150mL beaker and dissolved by sonication by adding 80mL of deionized water. And (3) dropwise adding triethylamine to adjust the pH value to 7.6 under stirring when the organic ligand is completely dissolved. And (3) placing the pretreated PA support body in a counter diffusion device, and respectively adding the prepared metal salt solution and the organic ligand solution at two sides to ensure that the solutions at two sides completely immerse the support body. And (3) placing the reaction kettle in an oven, heating at 90 ℃ for 12h, and taking out to obtain the Co-gate pure membrane. After 3 washes with deionized water, it was dried in an oven at 60 ℃ for 12 h. The film thickness was 3.9. mu.m.
(4) The Co-ballast membrane was used for ethylene and ethane gas performance testing and the results show: at 0.1MPa, C2H4Has a permeability of 312Barrer, C2H6Has a permeability of 34Barrer and an ideal selectivity of 9.18. C on Co-gate membranes2H4/C2H6And (5) testing the performance of the mixed gas with the same volume. At 0.1MPa, C2H4Permeability of 301Barrer, C2H6Has a permeability of 36Barrer, C2H4/C2H6The selectivity was 8.36.
Claims (10)
1. An M-gate metal organic framework membrane is characterized in that: the M-gate metal organic framework membrane consists of an M-gate crystal layer and a support body, wherein the thickness range of the M-gate crystal layer is 3-20 mu M.
2. The M-gate metal organic framework membrane of claim 1, wherein: the support body is alumina or an organic porous support body; wherein the organic porous support is nylon, polytetrafluoroethylene or polyvinylidene fluoride.
3. The M-gate metal organic framework membrane of claim 1, wherein: the M-gate is at least one of Mg-gate, Ni-gate or Co-gate.
4. A method for preparing the M-gate metal organic framework membrane of claim 1, comprising the following steps: A. preparing M-ballast liquid crystal; B. uniformly dispersing the seed crystal liquid on a support body to prepare uniform seed crystals; C. and carrying out hydrothermal synthesis or counter-diffusion hydrothermal synthesis on the support body modified with the seed crystal through a reaction kettle to obtain the M-gate metal-organic framework membrane.
5. The method of claim 4, wherein the step of preparing the M-gate seed crystal liquid in step A comprises: firstly, synthesizing M-gate crystal; then putting the synthesized M-gate crystal into a ball milling tank and using ethanol as a solvent, wherein the mass ratio of the M-gate crystal to the ethanol is as follows: 1, (10-20) ball-milling to obtain M-gate ethanol dispersion liquid; diluting the obtained M-gate ethanol dispersion liquid with ethanol to 50-100 times of the original volume, and taking the diluted dispersion liquid as a liquid crystal.
6. The method of claim 4, wherein the step B of uniformly dispersing the liquid crystal on the support to prepare uniform seed crystals is to obtain uniformly dispersed seed crystals on the support by spin coating, soaking or suction filtration.
7. The method of claim 4, wherein the reaction kettle in the step C is hydrothermally synthesized into: weighing metal salt and organic ligand according to the molar ratio of the metal salt to the organic ligand being 1 (1-4), adding deionized water, stirring and dissolving to obtain a precursor solution; adjusting the pH value of the precursor liquid to 7.5-9, then pouring the MOF precursor liquid into a reaction kettle, ensuring that a support body is immersed in the precursor liquid, and reacting in an oven at 80-120 ℃ for 12-48 h; taking out the MOF membrane after the reaction is finished, cleaning the MOF membrane by using deionized water, and then placing the MOF membrane in an oven for drying; wherein the metal salt is: magnesium chloride hexahydrate, cobalt chloride hexahydrate or nickel chloride hexahydrate, and the organic ligand is gallic acid.
8. The method of claim 4, wherein the counter-diffusion hydrothermal synthesis in step C comprises: respectively preparing a metal salt aqueous solution and a ligand aqueous solution which are equal in volume, wherein the molar ratio of metal salt to ligand is 1 (1-4), and adjusting the pH value of the organic ligand aqueous solution to 7.5-9; clamping the support body in a counter diffusion device, adding a metal salt solution into one side of the counter diffusion device, and adding a ligand aqueous solution for adjusting the pH value into the other side of the counter diffusion device, so as to ensure that the support body is completely immersed by the metal salt solution and the ligand solution; then reacting for 12-24h in an oven at 70-90 ℃; taking out the M-gate membrane after the reaction is finished, washing the M-gate membrane by deionized water, and then putting the membrane in an oven for drying; the metal salt is: magnesium chloride hexahydrate, cobalt chloride hexahydrate or nickel chloride hexahydrate, and the organic ligand is gallic acid.
9. The method of claim 7 or 8, wherein: the substances for adjusting the pH value of the solution are potassium hydroxide, sodium hydroxide, triethylamine or ethylenediamine.
10. Use of an M-gate metal organic framework membrane as defined in claim 1 for ethylene/ethane separation in the field of gas separation.
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