CN114515515A - Super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof - Google Patents
Super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof Download PDFInfo
- Publication number
- CN114515515A CN114515515A CN202210089394.7A CN202210089394A CN114515515A CN 114515515 A CN114515515 A CN 114515515A CN 202210089394 A CN202210089394 A CN 202210089394A CN 114515515 A CN114515515 A CN 114515515A
- Authority
- CN
- China
- Prior art keywords
- hollow
- super
- hollow fiber
- mofs
- fiber composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- 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
- B01D61/364—Membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
Abstract
The invention discloses a super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof in alcohol/water rectification. The preparation method comprises the following steps of etching MOFs by adopting polyphenol to form hollow MOFs, enabling the hollow MOFs to have rich reaction sites, carrying out super-hydrophobic modification on the hollow MOFs to obtain super-hydrophobic hollow MOFs, introducing the super-hydrophobic hollow MOFs into Polydimethylsiloxane (PDMS) coating liquid, coating the inner side of a hollow fiber membrane component to obtain a super-hydrophobic hollow MOFs modified hollow fiber composite membrane, and carrying out alcohol/water rectification by taking the super-hydrophobic hollow MOFs as regular packing. The invention has the advantages that the prepared super-hydrophobic hollow MOFs modified hollow fiber composite membrane greatly reduces the mass transfer resistance under the condition of reducing membrane wetting, and has good market application prospect.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to a super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof in alcohol/water rectification.
Background
With the increasing shortage of non-renewable energy sources such as coal, oil, natural gas and the like, the economic development of the world faces a severe test. Fuel alcohols (ethanol, isopropanol, etc.) have gradually become the focus of research as renewable energy sources. Most industries require high purity fuel alcohols and they are prone to azeotrope formation with water. However, in alcohol/water separation applications, conventional azeotropic distillation, extractive distillation, and the like have high energy consumption and low separation efficiency. In view of this, researchers propose that the hollow fiber membrane is used as regular filler for alcohol/water rectification, compared with the traditional rectification, the hollow fiber membrane has the advantages of large contact surface, indirect contact of gas phase and liquid phase, and avoidance of phenomena such as flooding, channeling and the like which seriously affect the rectification performance.
The current research shows that the rectification performance of the membrane can be effectively improved by improving the hydrophobicity of the membrane. However, the hydrophobic polymer coating commonly used at present is PDMS, but the structure is compact, so that the resistance of material exchange in the membrane rectification process is greatly increased; meanwhile, the water contact angle of PDMS is 100 degrees, and a large lifting space is provided.
In order to solve the problems of poor hydrophobicity and low microporosity of the conventional hollow fiber membrane, the invention provides a method for improving the microporosity and the hydrophobicity of the hollow fiber membrane by adopting a hydrophobic hollow MOFs material. The improvement of the micro-porosity of the membrane can effectively reduce the resistance of the hollow fiber membrane in the rectification process and increase the total mass transfer coefficient, thereby improving the rectification separation efficiency of the hollow fiber membrane.
Disclosure of Invention
In order to overcome the defects of low microporosity, poor hydrophobicity and the like in the conventional hollow fiber membrane, the invention provides a super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof in alcohol/water rectification, wherein the super-hydrophobic hollow MOFs modified hollow fiber composite membrane has higher rectification efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a super-hydrophobic hollow MOFs modified hollow fiber composite membrane, which is prepared by the following method:
(1) preparation of super-hydrophobic hollow MOF: uniformly dispersing an MOF material in water to obtain 5-20 mg/mL (preferably 10mg/mL) MOF dispersion liquid, adding 1-5 mg/mL (preferably 3mg/mL) polyphenol solution, stirring for 2-8 min (preferably 5min), centrifuging, sequentially washing the obtained precipitate with methanol and hexane A, then suspending the precipitate in hexane B, adding a silane coupling agent, stirring and reacting at 50-100 ℃ for 6-48 h (preferably 80 ℃ for 24h), and performing post-treatment on the obtained reaction liquid to obtain the super-hydrophobic hollow MOF; the solvent of the polyphenol solution is one or a mixture of water, methanol and ethanol; the mass ratio of polyphenol contained in the MOF material and the polyphenol solution to the silane coupling agent is 10: 1-5: 1-60 (preferably 10:3: 30); hexane A, B was hexane, A, B was used only to distinguish the different stages of hexane, and nothing else was intended.
(2) The super-hydrophobic hollow MOF modified hollow fiber composite membrane comprises the following components: uniformly dispersing the super-hydrophobic hollow MOF obtained in the step (1) in 1-20 wt% (preferably 10 wt%) of Polydimethylsiloxane (PDMS) solution, adding a catalyst and a cross-linking agent, and reacting at room temperature for 10 min-2 h (preferably 20min) to obtain a coating solution; injecting the coating liquid into the inner cavity of the hollow fiber membrane, soaking for 1-10 min (preferably 5min), pouring out the rest coating liquid, blowing by nitrogen to evaporate the solvent, and ventilating and drying to obtain the super-hydrophobic hollow MOFs modified hollow fiber composite membrane; the mass ratio of the super-hydrophobic hollow MOF to polydimethylsiloxane, the catalyst and the cross-linking agent in the polydimethylsiloxane solution is 1-20: 20: 1-10: 5-20 (preferably 2:20:5: 10); the catalyst is dibutyltin dilaurate; the cross-linking agent is vinyl trimethoxy silane, tetraethyl orthosilicate and phenyl triethoxysilane (preferably tetraethyl orthosilicate).
Preferably, the MOF material in step (1) is ZIF-8, ZIF-7 or ZIF-67 (preferably ZIF-67).
Further, the MOF material in step (1) is synthesized by solvothermal means. The preparation method specifically comprises the following steps:
and (3) uniformly mixing the metal salt solution and the organic ligand solution under stirring, standing at room temperature for 12-48 h for reaction, centrifuging, washing the obtained precipitate, and drying to obtain the MOF material.
Further, the metal salt solution contains one or a mixture of more than two of zinc chloride, zinc nitrate, zinc acetate, cobalt chloride, cobalt nitrate and cobalt acetate.
Further, the organic ligand contained in the organic ligand solution is one or a mixture of two of 2-methylimidazole and benzimidazole.
Further, the volume of hexane B in step (1) is 20-100mL/g (preferably 100mL/g) based on the mass of the MOF material.
Further, the post-treatment in the step (1) is as follows: and centrifuging the reaction solution, washing the obtained precipitate with hexane, and drying to obtain the super-hydrophobic hollow MOF material.
Further, the polyphenol contained in the polyphenol solution in the step (1) is one or a mixture of more than two of catechol, resorcinol, tea polyphenol and tannic acid (preferably tea polyphenol).
Further, in the step (1), the silane coupling agent is at least one or a mixture of two or more of vinyltrimethoxysilane, chlorosilane, n-propyltrimethoxysilane, n-octyltrimethoxysilane and n-dodecyltrimethoxysilane (preferably n-dodecyltrimethoxysilane).
Further, the hollow fiber membrane in the step (2) is made of Polysulfone (PS), Polyethersulfone (PES), polyvinylidene fluoride (PVDF), or polyacrylonitrile (preferably polysulfone).
Further, the solvent of the Polydimethylsiloxane (PDMS) solution in the step (2) is one or a mixture of two or more of hexane, heptane, and cyclohexane (preferably heptane).
In the step (2), in order to facilitate subsequent tests, 8 hollow fiber membranes are placed into a quartz glass liner tube, two ends of the tube are fixed by epoxy resin to form a membrane component, and then coating liquid is injected to obtain the super-hydrophobic hollow MOF modified hollow fiber composite membrane component which is directly used for alcohol/water rectification.
The invention also provides an application of the super-hydrophobic hollow MOFs modified hollow fiber composite membrane in alcohol-water solution rectification.
Preferably, the alcohol-water solution comprises isopropanol as the alcohol.
The invention discovers a super-hydrophobic hollow MOFs modified hollow fiber composite membrane, the modification method can well improve the hydrophobicity and the microporosity of the hollow fiber membrane, and compared with the prior art, the invention has the beneficial effects that:
(1) on one hand, the polyphenol enables MOFs to become a hollow structure, so that the MOFs forms a structure with a microporous structure shell layer and a mesoporous structure cavity; on the other hand, reaction sites are provided for further hydrophobic functionalization, and the microporosity of the hollow fiber membrane is effectively improved, so that the mass transfer resistance of the membrane is effectively reduced;
(2) the introduction of the super-hydrophobic modified MOFs further improves the hydrophobicity of the hollow fiber membrane, effectively relieves the wetting behavior of the membrane and indirectly strengthens the mass transfer behavior of the membrane.
(3) The invention discovers a super-hydrophobic hollow MOFs modified hollow fiber composite membrane, the modification method can well prepare the hydrophobic porous composite membrane, and the hydrophobic porous hollow fiber composite membrane has good alcohol/water rectification performance and can be applied to concentrating volatile fuel alcohol such as ethanol, isopropanol and the like.
Drawings
FIG. 1 is a schematic diagram of the preparation of a super-hydrophobic hollow MOFs material.
FIG. 2(a) TEM image of the superhydrophobic hollow MOFs of example 3 and (b) water contact angle of the superhydrophobic hollow MOFs of example 3.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples, and various modifications and implementations are intended to be included within the technical scope of the present invention without departing from the content and scope of the present invention.
The volume of PDMS in heptane indicated below is the volume of heptane, the heptane density is 0.68g/mL, and the mass of PDMS in 5mL of heptane is 0.3824g, with a mass fraction of 10 wt%.
Example 1:
(1) preparation of ZIF-8: respectively preparing 100mL of ZnCl2Then uniformly mixing the methanol solution (1mol/L) and the methanol solution of 2-methylimidazole (2mol/L) under the condition of stirring, standing at room temperature for reaction for 24 hours, centrifuging, washing with methanol and drying to obtain the ZIF-8 material.
(2) Preparing a super-hydrophobic hollow ZIF-8: dispersing a ZIF-8 material in 30mL of water in an ultrasonic stirring manner to obtain a ZIF-8 dispersion liquid of 10mg/mL, then adding 30mL of a tea polyphenol water solution of 3mg/mL, stirring for 5min, then centrifuging, sequentially washing with methanol and hexane, then dispersing the ZIF-8 dispersion liquid in 30mL of hexane again, adding 1mL (0.89g) of n-dodecyl trimethoxy silane, stirring and reacting at 80 ℃ for 24h, centrifuging, washing with hexane, and drying to obtain the super-hydrophobic hollow ZIF-8 material.
(3) The super-hydrophobic hollow ZIF-8 modified hollow fiber composite membrane and the component thereof are as follows: PS polymer hollow fibers are used as a support membrane (molecular weight cut-off of 6 ten thousand, Tianjin membrane Tianmen engineering Co.). 0.038g of the super-hydrophobic hollow ZIF-8 prepared in the step (2) is dispersed in 5mL of a heptane solution (10 wt%) of PDMS by means of stirring and ultrasonic, and 0.0956g of catalyst dibutyltin dilaurate and 0.1912g of cross-linking agent tetraethyl orthosilicate (the mass ratio of PDMS: catalyst: cross-linking agent is 20:5:10) are added and stirred at room temperature for reaction for 20min to obtain a coating liquid. And then fixing the hollow fiber membrane module on an iron support, injecting the prepared coating liquid into the membrane module, soaking the membrane module in the hollow fiber membrane for 5min, pouring out the membrane-making liquid, blowing by using nitrogen to evaporate the solvent, and then placing the membrane module on a clean workbench for ventilation and drying to obtain the super-hydrophobic hollow ZIF-8 modified hollow fiber composite membrane and the module.
The prepared super-hydrophobic hollow ZIF-8 modified hollow fiber composite membrane isopropanol/water rectification method is applied to the following steps:
the membrane rectification experiment was carried out under total reflux with a separation system of 20 v/v% isopropanol/water solution (5.5 mol/mol%) and a heating power of 90W. The results showed that the rectified product had a molar isopropanol concentration of 66.5 mol/mol% and a mass transfer unit Height (HTU) of 3.4 cm.
Example 2:
(1) preparation of ZIF-7: respectively preparing 100mL of ZnCl2Then uniformly mixing the methanol solution (1mol/L) and the methanol solution of benzimidazole (2mol/L) under the condition of stirring, standing at room temperature for reaction for 24 hours, centrifuging, washing with methanol and drying to obtain the ZIF-7 material.
(2) Preparing a super-hydrophobic hollow ZIF-7: dispersing a ZIF-7 material in water by an ultrasonic stirring mode to obtain a ZIF-7 dispersion liquid of 10mg/mL, then adding 30mL of a tea polyphenol water solution of 3mg/mL, stirring for 5min, then centrifuging, sequentially washing with methanol and hexane, then dispersing the ZIF-7 dispersion liquid in 30mL of hexane again, adding 1mL (0.89g) of n-dodecyl trimethoxy silane, stirring and reacting at 80 ℃ for 24h, centrifuging, washing with hexane, and drying to obtain the super-hydrophobic hollow ZIF-7 material.
(3) The super-hydrophobic hollow ZIF-7 modified hollow fiber composite membrane and the component thereof are as follows: PS polymer hollow fibers are used as a support membrane (molecular weight cut-off of 6 ten thousand, Tianjin membrane Tianmen engineering Co.). 0.038g of the super-hydrophobic hollow ZIF-7 prepared in the step (2) is dispersed in 5mL of a heptane solution (10 wt%) of PDMS by means of stirring and ultrasonic, and 0.0956g of catalyst dibutyltin dilaurate and 0.1912g of cross-linking agent tetraethyl orthosilicate (the mass ratio of PDMS: catalyst: cross-linking agent is 20:5:10) are added and stirred at room temperature for reaction for 20min to obtain a coating liquid. And then fixing the hollow fiber membrane module on an iron support, injecting the prepared coating liquid into the membrane module, soaking the membrane module in the hollow fiber membrane for 5min, pouring out the membrane-making liquid, then blowing the membrane-making liquid by using nitrogen to evaporate the solvent, and then placing the membrane module on a clean workbench for ventilation and drying to obtain the super-hydrophobic hollow ZIF-7 modified hollow fiber composite membrane and the module.
The prepared super-hydrophobic hollow ZIF-7 modified hollow fiber composite membrane isopropanol/water rectification method is applied as follows:
the membrane rectification experiment was carried out under total reflux with a separation system of 20 v/v% isopropanol/water solution (molar concentration 5.5%) and a heating power of 90W. The results showed that the rectified product had an isopropanol molar concentration of 65.8 mol/mol% and a mass transfer unit Height (HTU) of 3.8 cm. Example 3:
(1) preparation of ZIF-67: 100mL of CoCl was prepared separately2Then uniformly mixing the methanol solution (1mol/L) and the methanol solution of 2-methylimidazole (2mol/L) under the condition of stirring, standing at room temperature for reaction for 24 hours, centrifuging, washing with methanol and drying to obtain the ZIF-67 material.
(2) Preparing a super-hydrophobic hollow ZIF-67: dispersing a ZIF-67 material in water by an ultrasonic stirring mode to obtain a ZIF-67 dispersion liquid of 10mg/mL, then adding 30mL of a tea polyphenol aqueous solution of 3mg/mL, stirring for 5min, then centrifuging, sequentially washing with methanol and hexane, then dispersing the ZIF-67 dispersion liquid in 30mL of hexane again, adding 1mL (0.89g) of n-dodecyl trimethoxy silane, stirring and reacting at 80 ℃ for 24h, centrifuging, washing with hexane, and drying to obtain the super-hydrophobic hollow ZIF-67 material.
(3) The super-hydrophobic hollow ZIF-67 modified hollow fiber composite membrane and the component thereof are as follows: PS polymer hollow fibers are used as a support membrane (molecular weight cut-off of 6 ten thousand, Tianjin membrane Tianmen engineering Co.). 0.038g of the super-hydrophobic hollow ZIF-67 prepared in the step (2) is dispersed in 5mL of a heptane solution (10 wt%) of PDMS by means of stirring and ultrasonic, and 0.0956g of catalyst dibutyltin dilaurate and 0.1912g of cross-linking agent tetraethyl orthosilicate (the mass ratio of PDMS: catalyst: cross-linking agent is 20:5:10) are added and stirred at room temperature for reaction for 20min to obtain a coating liquid. And then fixing the hollow fiber membrane module on an iron support, injecting the prepared coating liquid into the membrane module, soaking the membrane module in the hollow fiber membrane for 5min, pouring out the membrane preparation liquid, then blowing by using nitrogen to evaporate the solvent, and then placing the membrane module on a clean workbench for ventilation and drying to obtain the super-hydrophobic hollow ZIF-67 modified hollow fiber composite membrane and the module.
The prepared super-hydrophobic hollow ZIF-67 modified hollow fiber composite membrane isopropanol/water rectification method is applied as follows:
the membrane rectification experiment was carried out under total reflux with a separation system of 20 v/v% isopropanol/water solution (molar concentration 5.5%) and a heating power of 90W. The results showed that the rectified product had a molar isopropanol concentration of 66.7 mol/mol% and a mass transfer unit Height (HTU) of 3.2 cm.
Comparative example 1:
hollow fiber composite membranes and modules: PS polymer hollow fibers are used as a support membrane (molecular weight cut-off of 6 ten thousand, Tianjin membrane Tianmen engineering Co.). 5mL of a PDMS heptane solution (10 wt%), 0.0956g of dibutyltin dilaurate as a catalyst and 0.1912g of tetraethyl orthosilicate as a crosslinking agent (the mass ratio of PDMS: catalyst: crosslinking agent is 20:5:10) were added, and the mixture was stirred and reacted at room temperature for 20min to obtain a coating solution. And then fixing the hollow fiber membrane module on an iron support, injecting the prepared coating liquid into the membrane module, soaking the membrane module in the hollow fiber membrane for 5min, pouring out the membrane-making liquid, blowing by using nitrogen to evaporate the solvent, and then placing the membrane module on a clean workbench for ventilation and drying to obtain the hollow fiber composite membrane and the hollow fiber module.
The prepared hollow fiber composite membrane isopropanol/water rectification method is applied to the following steps:
the membrane distillation experiment was carried out under total reflux with a separation system of 20 v/v% isopropanol/water solution (molar concentration 5.5%) and a heating power of 90W. The results showed that the rectified product had an isopropanol molar concentration of 60.1 mol/mol% and a mass transfer unit Height (HTU) of 9.2 cm.
Comparative example 2:
(1) preparation of ZIF-8: respectively preparing 100mL of ZnCl2Then uniformly mixing the methanol solution (1mol/L) and the methanol solution of 2-methylimidazole (2mol/L) under the condition of stirring, standing at room temperature for reaction for 24 hours, centrifuging, washing with methanol and drying to obtain the ZIF-8 material.
(2) ZIF-8 modified hollow fiber composite membrane and module: PS polymer hollow fibers are used as a support membrane (molecular weight cut-off of 6 ten thousand, Tianjin membrane Tianmen engineering Co.). 0.038g of ZIF-8 prepared in the step (1) is dispersed in 5mL of a heptane solution (10 wt%) of PDMS by means of stirring and ultrasound, 0.0956g of catalyst dibutyltin dilaurate and 0.1912g of cross-linking agent tetraethyl orthosilicate (mass ratio of PDMS: catalyst: cross-linking agent is 20:5:10) are added, and stirring and reaction are carried out for 20min at room temperature to obtain a coating liquid. And then fixing the hollow fiber membrane module on an iron support, injecting the prepared coating liquid into the membrane module, soaking the membrane module in the hollow fiber membrane for 5min, pouring out the membrane-making liquid, blowing by using nitrogen to evaporate the solvent, and then placing the membrane module on a clean workbench for ventilation and drying to obtain the ZIF-8 modified hollow fiber composite membrane and the ZIF-8 modified hollow fiber membrane module.
The prepared ZIF-8 modified hollow fiber composite membrane isopropanol/water rectification method is applied as follows:
the membrane rectification experiment was carried out under total reflux with a separation system of 20 v/v% isopropanol/water solution (molar concentration 5.5%) and a heating power of 90W. The results showed that the rectified product had a molar isopropanol concentration of 63.4 mol/mol% and a mass transfer unit Height (HTU) of 5.9 cm.
Claims (10)
1. A super-hydrophobic hollow MOFs modified hollow fiber composite membrane is characterized by being prepared by the following method:
(1) preparation of the superhydrophobic hollow MOF: uniformly dispersing an MOF material in water to obtain 5-20 mg/mL MOF dispersion liquid, adding 1-5 mg/mL polyphenol solution, stirring for 2-8 min, centrifuging, sequentially cleaning the obtained precipitate with methanol and hexane A, then suspending the precipitate in hexane B, adding a silane coupling agent, stirring and reacting for 6-48 h at 50-100 ℃, and performing post-treatment on the obtained reaction liquid to obtain the super-hydrophobic hollow MOF; the solvent of the polyphenol solution is one or two of water, methanol and ethanol; the mass ratio of polyphenol contained in the MOF material and the polyphenol solution to the silane coupling agent is 10: 1-5: 1-60;
(2) the super-hydrophobic hollow MOF modified hollow fiber composite membrane comprises the following components: uniformly dispersing the super-hydrophobic hollow MOF in the step (1) in 1-20 wt% of polydimethylsiloxane solution, adding a catalyst and a cross-linking agent, and reacting at room temperature for 10 min-2 h to obtain a coating solution; injecting the coating liquid into the inner cavity of the hollow fiber membrane, soaking for 1-10 min, pouring out the rest coating liquid, blowing by nitrogen to evaporate the solvent, and ventilating and drying to obtain the super-hydrophobic hollow MOFs modified hollow fiber composite membrane; the mass ratio of the super-hydrophobic hollow MOF to polydimethylsiloxane, the catalyst and the cross-linking agent in the polydimethylsiloxane solution is 1-20: 20: 1-10: 5-20; the catalyst is dibutyltin dilaurate; the cross-linking agent is vinyl trimethoxy silane, tetraethyl orthosilicate and phenyl triethoxysilane.
2. The superhydrophobic hollow MOFs modified hollow fiber composite membrane of claim 1, wherein: in the step (1), the MOF material is ZIF-8, ZIF-7 or ZIF-67.
3. The superhydrophobic hollow MOFs-modified hollow fiber composite membrane of claim 1, wherein: the volume of hexane B in step (1) is 20-100mL/g based on the mass of the MOF material.
4. The superhydrophobic hollow MOFs-modified hollow fiber composite membrane according to claim 1, wherein the post-treatment of step (1) is: and centrifuging the reaction liquid, washing and drying the obtained precipitate by using hexane to obtain the super-hydrophobic hollow MOF material.
5. The superhydrophobic hollow MOFs-modified hollow fiber composite membrane of claim 1, wherein: the polyphenol contained in the polyphenol solution in the step (1) is one or a mixture of more than two of catechol, resorcinol, tea polyphenol and tannic acid.
6. The superhydrophobic hollow MOFs-modified hollow fiber composite membrane of claim 1, wherein: the silane coupling agent in the step (1) is at least one or a mixture of more than two of vinyl trimethoxy silane, chlorosilane, n-propyl trimethoxy silane, n-octyl trimethoxy silane and n-dodecyl trimethoxy silane.
7. The superhydrophobic hollow MOFs-modified hollow fiber composite membrane of claim 1, wherein: the hollow fiber membrane in the step (2) is made of polysulfone, polyethersulfone, polyvinylidene fluoride or polyacrylonitrile.
8. The superhydrophobic hollow MOFs-modified hollow fiber composite membrane of claim 1, wherein: the solvent of the polydimethylsiloxane solution in the step (2) is one or a mixture of more than two of hexane, heptane and cyclohexane.
9. Use of the superhydrophobic hollow MOFs-modified hollow fiber composite membrane of claim 1 in rectification of alcohol-water solutions.
10. The use of claim 9, wherein: the alcohol-water solution contains isopropanol as alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210089394.7A CN114515515B (en) | 2022-01-25 | 2022-01-25 | Super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210089394.7A CN114515515B (en) | 2022-01-25 | 2022-01-25 | Super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114515515A true CN114515515A (en) | 2022-05-20 |
| CN114515515B CN114515515B (en) | 2023-06-23 |
Family
ID=81597335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210089394.7A Active CN114515515B (en) | 2022-01-25 | 2022-01-25 | Super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114515515B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816814A (en) * | 2014-03-06 | 2014-05-28 | 北京工业大学 | Porous granule MCM-41-ZIF-8/PDMS pervaporation hybrid membrane, preparation and application |
| WO2017124101A2 (en) * | 2016-01-15 | 2017-07-20 | The Broad Institute Inc. | Semi-permeable arrays for analyzing biological systems and methods of using same |
| CN109224861A (en) * | 2017-07-10 | 2019-01-18 | 浙江工业大学 | A kind of modified nanofiltration/reverse osmosis membrane of metal organic framework and its application |
| CN112778772A (en) * | 2020-12-31 | 2021-05-11 | 中山大学附属第一医院 | Antibacterial composite hydrogel and preparation method and application thereof |
| CN113346116A (en) * | 2021-05-20 | 2021-09-03 | 华中科技大学 | Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof |
-
2022
- 2022-01-25 CN CN202210089394.7A patent/CN114515515B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816814A (en) * | 2014-03-06 | 2014-05-28 | 北京工业大学 | Porous granule MCM-41-ZIF-8/PDMS pervaporation hybrid membrane, preparation and application |
| WO2017124101A2 (en) * | 2016-01-15 | 2017-07-20 | The Broad Institute Inc. | Semi-permeable arrays for analyzing biological systems and methods of using same |
| CN109224861A (en) * | 2017-07-10 | 2019-01-18 | 浙江工业大学 | A kind of modified nanofiltration/reverse osmosis membrane of metal organic framework and its application |
| CN112778772A (en) * | 2020-12-31 | 2021-05-11 | 中山大学附属第一医院 | Antibacterial composite hydrogel and preparation method and application thereof |
| CN113346116A (en) * | 2021-05-20 | 2021-09-03 | 华中科技大学 | Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| PENGCHENG SU,ET,AL: "Distillation of alcohol/water solution in hybrid metal-organic framework hollow fibers", 《ALCHE JOURNAL》 * |
| SHUNFENG LI,ET.AL: "Improving the perbaporation performance of PDMS membranes for n-butanol by incorporating silane-modified ZIF-8 particles", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114515515B (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20210260535A1 (en) | Uio-66-nh2 doped organosilicon high salinity wastewater treatment membrane and a preparation method thereof | |
| CN110237725B (en) | Organic amine modified graphene oxide/polymer composite membrane and preparation and application thereof | |
| CN113209841B (en) | Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol, and preparation method and application thereof | |
| CN110773127B (en) | Hydrophobic active carbon material, preparation method and application thereof | |
| WO2017185874A1 (en) | Hydroxyl silicone oil and continuous method for preparing same | |
| CN110105580B (en) | Hierarchical pore zeolite imidazole ester framework material and preparation method thereof | |
| US20180021728A1 (en) | Pervaporation and Vapor-Permeation Separation of Gas-Liquid Mixtures and Liquid Mistures by SAPO-34 Molecular Sieve Membrane Prepared in Dry-Gel Process | |
| CN113346116A (en) | Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof | |
| CN109627814A (en) | A kind of silicon dioxide nano composite material and its preparation method and application | |
| CN106905526A (en) | Rigid backbone porous polymer with gas absorption performance and its preparation method and application | |
| CN105688985A (en) | Immobilized ionic liquid catalyst and preparation method thereof | |
| CN111617645A (en) | Preparation method of low-resistance high-selectivity mixed matrix membrane based on hollow MOFs (metal-organic frameworks) material | |
| CN114050375A (en) | Preparation method of modified aluminum oxide and PMMA mixed slurry coating diaphragm | |
| CN108976169A (en) | A kind of glyoxaline ion liquid and its preparation method and application | |
| CN114180581B (en) | Synthetic method of silicon dioxide aerogel | |
| CN114515515B (en) | Super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof | |
| CN111036089A (en) | Preparation method of modified PDMS/ZIF pervaporation hybrid membrane | |
| CN110152503A (en) | A kind of preparation method for the solvent resistant nanofiltration membrane that graphene oxide is compound with tool microporous polymer certainly | |
| CN110776788A (en) | Heat-insulation self-cleaning hybrid coating and preparation method thereof | |
| CN109037743A (en) | A kind of graphene aerogel denatured fuel battery proton exchange membrane and preparation method thereof | |
| CN111841612A (en) | CO of nitrogen-sulfur in-situ doped hollow porous carbon microsphere2Reduced electrocatalyst and method of making same | |
| CN113480741B (en) | Chelating Cu 2+ Preparation method of metal organic framework material and application of metal organic framework material in chitosan composite anion membrane | |
| KR20200129231A (en) | Organic- Inorganic composite solution, procedure for producing the same, organic-inorganic hybrid composite membrane and the application using the same | |
| CN113801353A (en) | Preparation method of quaternized chitosan-ethyl silicate organic/inorganic hybrid membrane | |
| CN111569673B (en) | SiO with preferential alcohol permeability2Preparation method of PVDF hybrid membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |