CN109316977B - A kind of MOF/MOP/metal hydroxide ceramic composite membrane and preparation method - Google Patents
A kind of MOF/MOP/metal hydroxide ceramic composite membrane and preparation method Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000000919 ceramic Substances 0.000 title claims abstract description 35
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 30
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001338 self-assembly Methods 0.000 claims abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002135 nanosheet Substances 0.000 claims description 10
- 238000005373 pervaporation Methods 0.000 claims description 10
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 229910018661 Ni(OH) Inorganic materials 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 12
- 239000003446 ligand Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000005406 washing Methods 0.000 description 16
- 238000002791 soaking Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- 230000004907 flux Effects 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- -1 Co (OH)2 Chemical class 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种MOF/MOP/金属氢氧化物陶瓷复合膜及制备方法，属于膜分离领域。本发明利用陶瓷管作为基底，利用动态自组装成膜法在金属氢氧化物纳米阵列中填充了一定量的MOP颗粒，并加入配体后利用金属氢氧化物诱导制备了同源金属的MOF颗粒弥补了缺陷，进一步的增强了复合膜的稳定性。本发明制备工艺简单，材料成本低廉，对于芳烃/烷烃体系有一定的分离效果，对于MOP‑MOF基复合膜有一定的指导意义。A MOF/MOP/metal hydroxide ceramic composite membrane and a preparation method thereof belong to the field of membrane separation. In the invention, ceramic tubes are used as substrates, a certain amount of MOP particles are filled in the metal hydroxide nano-array by the dynamic self-assembly film-forming method, and the MOF particles of homologous metals are prepared by induction of metal hydroxide after adding ligands. It makes up for the defects and further enhances the stability of the composite membrane. The invention has simple preparation process and low material cost, has a certain separation effect for the aromatic hydrocarbon/alkane system, and has certain guiding significance for the MOP-MOF-based composite membrane.
Description
Technical Field
The invention relates to a pervaporation separation membrane and a preparation technology thereof, belonging to the field of membrane separation.
Background
According to the dissolution-diffusion mechanism, pervaporation is widely applied to systems which are difficult to separate by traditional separation methods, such as compounds with similar boiling points, azeotrope, thermodynamically unstable compounds and the like, as an efficient and mature membrane technology. The realization of membrane processes with high performance and high stability is a central issue in the field of separation membranes. Therefore, it is important to select a suitable membrane material, which is advantageous in improving both the selectivity to aromatic molecules and the stability.
Typical representatives of 2D lamellar materials are metal hydroxides, such as Co (OH)2、Ni(OH)2、Mg(OH)2Etc. having a vertical array structure. The MOP is a one-dimensional nano material assembled by independent molecules, and the advantages of rich benzene rings, unsaturated metal sites, stability, solubility and the like are beneficial to improving the performance, can effectively avoid the agglomeration phenomenon, and ensure high loading performance and uniform dispersibility. In addition Cu in MOP molecule2+D-pi conjugation and pi-pi conjugation formed by the d-orbit and the pi-orbit in the benzene ring structure and the pi-orbit on the aromatic hydrocarbon molecule further improve the adsorption selectivity of the composite membrane on the aromatic hydrocarbon molecule. This outer membrane flux assurance benefits from the high porosity of the MOP. The MOF is a crystalline porous material which is formed by metal ions or metal clusters and organic ligands through a self-assembly process and has a periodic infinite network structure, large specific surface area, adjustable pore diameter and poresHigh efficiency, functional pore channel, controllable particle size and the like, and has attracted wide attention in the field of separation membranes. The stability of the composite membrane is enhanced through the coordination and connection effect of the metal source of the metal hydroxide and the MOF ligand. According to the invention, MOP particles are fixed by utilizing the limited space of the metal hydroxide, the defective MOP/hydroxide composite membrane is prepared through dynamic self-assembly, and the stability of the MOP/hydroxide composite membrane is improved through the coordination of the MOF ligand and the metal source.
Disclosure of Invention
The invention aims to provide an MOF/MOP/hydroxide ceramic composite membrane for pervaporation separation of an aromatic hydrocarbon/alkane system and a preparation method thereof.
A preparation method of an MOF/MOP/metal hydroxide ceramic composite membrane is characterized by comprising the following steps:
(1) soaking the cleaned ceramic substrate in a dopamine hydrochloride solution for pretreatment for 1-60 min, taking out, washing and soaking for multiple times by using deionized water until free polydopamine on the surface is completely washed away, and finally, carrying out vacuum drying in an oven;
(2) preparing a precursor solution A required by the metal hydroxide in the product, wherein the solute of the precursor solution A comprises soluble metal salt and hexamethylenetetramine;
(3) placing the treated ceramic substrate into the precursor solution A prepared in the step (2), and placing the ceramic substrate into a drying oven for reaction and in-situ growth; after a period of reaction, taking the film out of the reaction kettle, repeatedly washing the film with deionized water, and putting the film into an oven for vacuum drying to obtain the metal hydroxide nanosheet array film;
(4) dissolving MOP in a solvent, stirring to prepare MOP membrane casting solution, and filling MOP in a metal hydroxide nanosheet array by a dynamic self-assembly membrane method to prepare a metal hydroxide/MOP composite membrane;
(5) preparing an organic ligand precursor solution B required for preparing the MOF, wherein the precursor solution B adopts a solvent B;
(6) placing the prepared metal hydroxide/MOP composite membrane into the organic ligand precursor solution B prepared in the step (5), and placing the organic ligand precursor solution B into an oven for reaction and growth; and (3) after a period of reaction, taking the membrane out of the reaction kettle, repeatedly washing the membrane by using the solvent adopted in the step (5), and putting the membrane into an oven for vacuum drying to obtain the MOP membrane prepared by the MOF particle stable metal hydroxide nano array in an auxiliary manner, namely the MOF/MOP/metal hydroxide ceramic composite membrane.
The metal hydroxide in the invention is of a nanosheet layered structure, forms a vertical array structure with a substrate, and is divided into Co (OH)2And Ni (OH)2And the like. The concentration of the metal salt in the precursor solution A is 0.02 mol/L-0.06 mol/L, and the molar concentration of the metal salt and the hexamethylenetetramine is 3:1-1: 3.
The molecule-based MOP is selected from tBu-MOP, SO3One or more of-MOP and OH-MOP.
The ceramic substrate material is Al2O3、TiO2、ZrO2Or SiO2The oxide has three forms of flat plate, tube and hollow fiber, and the ceramic tube base has pore size of 10 nm to 1 micron.
The reaction temperature of the in-situ growth in the step (3) is 80-120 ℃, and the reaction time is 1-24 h.
The concentration of the casting solution in the step (4) of the invention is 1.7 g/L-5.5 g/L, and the time of dynamic self-assembly is 5 min-10 min.
In the step (5), the concentration of the organic ligand is 0.02-0.05 mol/L, and MOP is stable in the solvent B.
The MOF growth reaction temperature in the step (6) of the invention is 100-135 ℃, and the reaction temperature is 1-48 h.
The composite membrane of the invention is used for the pervaporation separation of an aromatic hydrocarbon/alkane system.
The technical principle of the invention is as follows: the ceramic substrate is immersed into the dopamine hydrochloride solution to enhance the binding force between the membrane and the substrate. And then, soaking the ceramic substrate in a precursor solution of metal hydroxide, placing the ceramic substrate in a reaction kettle, growing the ceramic substrate in an oven, taking out the ceramic substrate, washing the ceramic substrate with a large amount of deionized water, and drying the ceramic substrate in vacuum. Then filling MOP particles in the nano-arrays by a dynamic self-assembly membrane method, and finally performing a hydrothermal reaction to enable organic ligands required for preparing the MOF material to perform a coordination reaction with a metal source in the metal hydroxide to form MOF particles so as to enhance the stability of the composite membrane. The composite membrane utilizes the confined space of the metal hydroxide nanosheets to fill MOP particles, and the performance and stability of the membrane are enhanced by the combination of MOP as a molecular-based porous material and the stability of MOF.
Drawings
FIG. 1 is a scanning electron microscope characterization of the surface and cross-section of a ceramic substrate.
FIG. 2 inventive example 1Co (OH)2And (4) performing scanning electron microscope characterization on the surface and the section of the film.
FIG. 3 example 1tBu-MOP/Co (OH) according to the invention2And (4) characterization of the surface and the section of the composite film by a scanning electron microscope.
FIG. 4 example 1 of the present invention MOF/tBu-MOP/Co (OH)2And (4) characterization of the surface and the section of the composite film by a scanning electron microscope.
Detailed Description
The aromatic hydrocarbon/alkane pervaporation separation performance of the MOF/MOP/hydroxide composite membrane of the present invention will be further described in detail with reference to examples. However, the present invention is not limited to the following examples.
Example 1
The preparation method of the composite membrane comprises the following steps:
(1) pretreating the ceramic substrate: 50mmol of tris (hydroxymethyl) aminomethane, 2g of dopamine hydrochloride and 5mmol of CuSO are weighed4And 19.6mmol H2O2Dissolving in 1000mL deionized water, soaking the substrate in the prepared solution for 10min, washing with a large amount of deionized water, repeatedly soaking until no color is lost, and vacuum drying in an oven at 50 ℃.
(2) The preparation concentration is 0.2mol/L Co (NO3)2·6(H2O) and 0.2mol/L hexamethylenetetramine solution, and performing ultrasonic stirring to be uniform after mixing; placing the ceramic substrate in a precursor solution, reacting for 6h in an oven at 90 ℃, taking out, washing with deionized water, soaking and vacuum-dryingAir-drying to obtain Co (OH)2And (3) a membrane.
(3) 330mg tBu-MOP was weighed out and dissolved in 120mL of N-methylpyrrolidone, and the vacuum degree was made 0.095MPa by a negative pressure pumping method, and Co (OH) was allowed to stand after 10 minutes2The nano-sheets are filled with a certain amount of tBu-MOP particles.
(4) 0.39g of benzimidazole was weighed out and dissolved in 60ml of N-dimethylformamide, and the resulting solution was stirred with ultrasound to dissolve the benzimidazole completely. The solution was transferred to a reaction kettle and tBu-MOP/Co (OH)2The membrane was placed in a ligand solution and reacted in an oven at 135 ℃ for 24 h. And (3) taking out, washing the film by using DMF, activating the film by using DMF and dichloromethane, and finally drying the film in a drying oven at 120 ℃ in vacuum to obtain the MOF/MOP/hydroxide composite film.
The prepared composite membrane is subjected to pervaporation performance test, the test system is a toluene/n-heptane (1:1) mixture, and the temperature of a feeding liquid is 40 ℃.
The toluene permeability of the composite membrane was measured as follows: the flux was 269 g/(m)2h) The separation factor was 2.3.
Example 2
The preparation method of the composite membrane comprises the following steps:
(1) pretreating the ceramic substrate: 50mmol of tris (hydroxymethyl) aminomethane, 2g of dopamine hydrochloride and 5mmol of CuSO are weighed4And 19.6mmol H2O2Dissolving in 1000mL deionized water, soaking the substrate in the prepared solution for 10min, washing with a large amount of deionized water, repeatedly soaking until no color is lost, and vacuum drying in an oven at 50 ℃.
(2) The preparation concentration is 0.2mol/L Co (NO3)2·6(H2O) and 0.2mol/L hexamethylenetetramine solution, and performing ultrasonic stirring to be uniform after mixing; placing the ceramic substrate in a precursor solution, reacting for 9h in an oven at 90 ℃, taking out, washing and soaking by deionized water, and drying in vacuum to obtain Co (OH)2And (3) a membrane.
(3) 330mg tBu-MOP was weighed out and dissolved in 120mL of N-methylpyrrolidone, and the vacuum degree was made 0.095MPa by a negative pressure pumping method, and Co (OH) was allowed to stand after 10 minutes2The nano sheets are filled with a certain amount of tBu-MOP particles。
(4) 0.39g of benzimidazole was weighed out and dissolved in 60ml of N-dimethylformamide, and the resulting solution was stirred with ultrasound to dissolve the benzimidazole completely. The solution was transferred to a reaction kettle and tBu-MOP/Co (OH)2The membrane was placed in a ligand solution and reacted in an oven at 135 ℃ for 24 h. And (3) taking out, washing the film by using DMF, activating the film by using DMF and dichloromethane, and finally drying the film in a drying oven at 120 ℃ in vacuum to obtain the MOF/MOP/hydroxide composite film.
The prepared composite membrane is subjected to pervaporation performance test, the test system is a toluene/n-heptane (1:1) mixture, and the temperature of a feeding liquid is 40 ℃.
The toluene permeability of the composite membrane was measured as follows: the flux was 346 g/(m)2h) The separation factor was 2.9.
Example 3
The preparation method of the composite membrane comprises the following steps:
(1) pretreating the ceramic substrate: 50mmol of tris (hydroxymethyl) aminomethane, 2g of dopamine hydrochloride and 5mmol of CuSO are weighed4And 19.6mmol H2O2Dissolving in 1000mL deionized water, soaking the substrate in the prepared solution for 10min, washing with a large amount of deionized water, repeatedly soaking until no color is lost, and vacuum drying in an oven at 50 ℃.
(2) The preparation concentration is 0.2mol/L Co (NO3)2·6(H2O) and 0.2mol/L hexamethylenetetramine solution, and performing ultrasonic stirring to be uniform after mixing; placing the ceramic substrate in a precursor solution, reacting for 12h in an oven at 90 ℃, taking out, washing and soaking by deionized water, and drying in vacuum to obtain Co (OH)2And (3) a membrane.
(3) 330mg tBu-MOP was weighed out and dissolved in 120mL of N-methylpyrrolidone, and the vacuum degree was made 0.095MPa by a negative pressure pumping method, and Co (OH) was allowed to stand after 10 minutes2The nano-sheets are filled with a certain amount of tBu-MOP particles.
(4) 0.39g of benzimidazole was weighed out and dissolved in 60ml of N-dimethylformamide, and the resulting solution was stirred with ultrasound to dissolve the benzimidazole completely. The solution was transferred to a reaction kettle and tBu-MOP/Co (OH)2The membrane was placed in a ligand solution and reacted in an oven at 135 ℃ for 24 h. Taking outAnd then washing the film by DMF, activating the film by DMF and dichloromethane, and finally drying the film in a drying oven at 120 ℃ in vacuum to obtain the MOF/MOP/hydroxide composite film.
The prepared composite membrane is subjected to pervaporation performance test, the test system is a toluene/n-heptane (1:1) mixture, and the temperature of a feeding liquid is 40 ℃.
The toluene permeability of the composite membrane was measured as follows: the flux was 382 g/(m)2h) The separation factor was 3.4.
Example 4
The preparation method of the composite membrane comprises the following steps:
(1) pretreating the ceramic substrate: 50mmol of tris (hydroxymethyl) aminomethane, 2g of dopamine hydrochloride and 5mmol of CuSO are weighed4And 19.6mmol H2O2Dissolving in 1000mL deionized water, soaking the substrate in the prepared solution for 10min, washing with a large amount of deionized water, repeatedly soaking until no color is lost, and vacuum drying in an oven at 50 ℃.
(2) The preparation concentration is 0.2mol/L Co (NO3)2·6(H2O) and 0.2mol/L hexamethylenetetramine solution, and performing ultrasonic stirring to be uniform after mixing; placing the ceramic substrate in a precursor solution, reacting for 9h in an oven at 90 ℃, taking out, washing and soaking by deionized water, and drying in vacuum to obtain Co (OH)2And (3) a membrane.
(3) 330mg tBu-MOP was weighed out and dissolved in 120mL of N-methylpyrrolidone, and the vacuum degree was made 0.095MPa by the method of negative pressure pumping, and Co (OH) was allowed to stand after 5 minutes2The nano-sheets are filled with a certain amount of tBu-MOP particles.
(4) 0.39g of benzimidazole was weighed out and dissolved in 60ml of N-dimethylformamide, and the resulting solution was stirred with ultrasound to dissolve the benzimidazole completely. The solution was transferred to a reaction kettle and tBu-MOP/Co (OH)2The membrane was placed in a ligand solution and reacted in an oven at 135 ℃ for 24 h. And (3) taking out, washing the film by using DMF, activating the film by using DMF and dichloromethane, and finally drying the film in a drying oven at 120 ℃ in vacuum to obtain the MOF/MOP/hydroxide composite film.
The prepared composite membrane is subjected to pervaporation performance test, the test system is a toluene/n-heptane (1:1) mixture, and the temperature of a feeding liquid is 40 ℃.
The toluene permeability of the composite membrane was measured as follows: the flux was 254 g/(m)2h) The separation factor was 2.1.
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| CN104415670B (en) * | 2013-08-23 | 2017-02-22 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework membrane and preparation method and application thereof |
| AU2016289276B2 (en) * | 2015-07-08 | 2020-11-05 | Commonwealth Scientific And Industrial Research Organisation | Composition and system for gas storage |
| CN105233702B (en) * | 2015-10-17 | 2017-06-13 | 大连理工大学 | A kind of utilization cobalt nano-array layer conversion forms the preparation method of the films of metal organic framework ZIF 67 |
| CN108579468B (en) * | 2018-04-18 | 2020-08-21 | 北京工业大学 | MOP/hydroxide ceramic composite membrane, preparation method and application |
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