CN114515515B - 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 PDF

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CN114515515B
CN114515515B CN202210089394.7A CN202210089394A CN114515515B CN 114515515 B CN114515515 B CN 114515515B CN 202210089394 A CN202210089394 A CN 202210089394A CN 114515515 B CN114515515 B CN 114515515B
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张国亮
张旭
孟琴
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof in alcohol/water rectification. The method comprises the steps of adopting polyphenol to etch MOFs to form hollow MOFs, simultaneously having rich reaction sites, carrying out super-hydrophobic modification on the hollow MOFs to obtain the 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 preparation method has the advantages that the prepared superhydrophobic hollow MOFs modified hollow fiber composite membrane greatly reduces mass transfer resistance under the condition of reducing membrane wetting and has good market application prospect.

Description

Super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof
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 world economic development faces serious challenges. Fuel alcohols (ethanol, isopropanol, etc.) have become a growing point of research as renewable energy sources. Most industries have high purity requirements for fuel alcohols and they are prone to form azeotropes with water. However, in alcohol/water separation applications, conventional azeotropic rectification, extractive rectification, and the like are high in energy consumption and low in separation efficiency. In view of this, researchers have proposed using hollow fiber membranes as normal packing to carry out alcohol/water rectification, which has a large contact surface compared with conventional rectification, and gas-liquid two phases are in indirect contact, avoiding the occurrence of phenomena that seriously affect the rectification performance, such as flooding, channeling, and the like.
The current research shows that improving the hydrophobicity of the membrane can effectively improve the rectification performance of the membrane. However, the current commonly used hydrophobic polymer coating is PDMS, but the structure is compact, so that the resistance of substance exchange in the membrane rectification process is greatly increased; meanwhile, the PDMS water contact angle is 100 degrees, and a large lifting space is provided.
In order to solve the problems of poor hydrophobicity and low microporosity of the traditional hollow fiber membrane, the invention provides a hydrophobic hollow MOFs material for improving the microporosity of the hollow fiber membrane and the hydrophobicity of the membrane. The improvement of the microporosity 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 solve the defects of low microporosity, poor hydrophobicity and the like in the existing hollow fiber membrane, the invention provides a super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof in alcohol/water rectification, and the super-hydrophobic hollow MOFs modified hollow fiber composite membrane has higher rectification efficiency.
In order to achieve the above purpose, the present 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 steps:
(1) Preparation of superhydrophobic hollow MOF: uniformly dispersing MOF materials in water to obtain MOF dispersion liquid of 5-20 mg/mL (preferably 10 mg/mL), adding polyphenol solution of 1-5 mg/mL (preferably 3 mg/mL), stirring for 2-8 min (preferably 5 min), centrifuging, sequentially cleaning the obtained precipitate with methanol and hexane A, re-suspending in hexane B, adding silane coupling agent, stirring at 50-100 ℃ for reaction for 6-48 h (preferably 80 ℃ for reaction for 24 h), 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 the 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 is hexane, A, B is merely to distinguish between different stages of hexane and has no other meaning.
(2) Super-hydrophobic hollow MOF modified hollow fiber composite membrane: uniformly dispersing the super-hydrophobic hollow MOF in the step (1) in 1-20wt% (preferably 10wt%) Polydimethylsiloxane (PDMS) solution, adding a catalyst and a cross-linking agent, and reacting for 10-2 h (preferably 20 min) at room temperature to obtain a coating liquid; injecting the coating liquid into the inner cavity of the hollow fiber membrane, soaking for 1-10 min (preferably 5 min), pouring out the residual coating liquid, blowing nitrogen to evaporate the solvent, and carrying out ventilation drying to obtain the superhydrophobic hollow MOFs modified hollow fiber composite membrane; the mass ratio of the polydimethylsiloxane, the catalyst and the cross-linking agent contained in the superhydrophobic hollow MOF and the polydimethylsiloxane solution is 1-20:20:1-10:5-20 (preferably 2:20:5:10); the catalyst is dibutyl tin dilaurate; the cross-linking agent is vinyl trimethoxy silane, tetraethyl orthosilicate, phenyl triethoxy silane (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. Specifically, the preparation method comprises the following steps:
and uniformly mixing the metal salt solution and the organic ligand solution under stirring, standing at room temperature for reaction for 12-48 h, centrifuging, washing the obtained precipitate, and drying to obtain the MOF material.
Further, the metal salt contained in the metal salt solution is 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 100 mL/g) based on the mass of the MOF material.
Further, the post-treatment in the step (1) is as follows: and centrifuging the reaction liquid, 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, the silane coupling agent in the step (1) is at least one of vinyl trimethoxy silane, chloro silane, n-propyl trimethoxy silane, n-octyl trimethoxy silane, n-dodecyl trimethoxy silane or a mixture of two or more of them (preferably n-dodecyl trimethoxy silane).
Further, in the step (2), the hollow fiber membrane 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 more of hexane, heptane, and cyclohexane (preferably heptane).
In the step (2), 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 application of the super-hydrophobic hollow MOFs modified hollow fiber composite membrane in alcohol-water solution rectification.
Preferably, the alcohol contained in the alcohol-water solution is isopropyl alcohol.
The invention discovers a super-hydrophobic hollow MOFs modified hollow fiber composite membrane, and 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 the one hand, the polyphenols change MOFs into a hollow structure, so that the MOFs form a structure with a shell layer with a micropore structure and a cavity with a mesoporous structure; on the other hand, reaction sites are provided for further hydrophobic functionalization, so that the microporosity of the hollow fiber membrane is effectively improved, and 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 that the super-hydrophobic hollow MOFs modified hollow fiber composite membrane can be well prepared by the modification method, has good alcohol/water rectification performance, and can be applied to concentrating volatile fuel alcohols such as ethanol, isopropanol and the like.
Drawings
Fig. 1 is a schematic diagram of the preparation of superhydrophobic hollow MOFs materials.
Fig. 2 (a) transmission electron microscopy images of the superhydrophobic hollow MOFs of example 3, (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 are intended to be included within the technical scope of the present invention without departing from the spirit and scope of the present invention.
The volume of the heptane solution of PDMS below is the volume of heptane, the heptane density is 0.68g/mL, the mass of PDMS in 5mL of heptane is 0.3824g, the mass fraction is 10wt%.
Example 1:
(1) Preparation of ZIF-8: respectively configure 100mL ZnCl 2 And (2) and 2-methylimidazole (2 mol/L), then uniformly mixing the methanol solution and the methanol solution under stirring, standing at room temperature for reaction for 24 hours, and washing and drying by using centrifugal methanol to obtain the ZIF-8 material.
(2) Preparation of super-hydrophobic hollow ZIF-8: and dispersing the ZIF-8 material in 30mL of water by ultrasonic stirring to obtain 10mg/mL of ZIF-8 dispersion, adding 30mL of 3mg/mL of aqueous solution of tea polyphenol, stirring for 5min, centrifuging, sequentially washing with methanol and hexane, dispersing the material in 30mL of hexane again, adding 1mL (0.89 g) of n-dodecyl trimethoxysilane, stirring and reacting for 24h at 80 ℃, centrifuging, washing with hexane, and drying to obtain the super-hydrophobic hollow ZIF-8 material.
(3) Super-hydrophobic hollow ZIF-8 modified hollow fiber composite membrane and component: PS polymer hollow fiber is used as a support membrane (the molecular weight cut-off is 6 ten thousand, tianjin membrane Tianmembrane engineering company). Dispersing 0.038g of the super-hydrophobic hollow ZIF-8 prepared in the step (2) into 5mL of PDMS heptane solution (10 wt%) by stirring and ultrasonic, adding 0.0956g of catalyst dibutyltin dilaurate and 0.1912g of cross-linking agent tetraethyl orthosilicate (PDMS: mass ratio of the catalyst to the cross-linking agent is 20:5:10), and stirring and reacting for 20min at room temperature to obtain a coating liquid. Then fixing the hollow fiber membrane assembly on an iron stand, injecting prepared coating liquid into the membrane assembly, immersing the membrane assembly in the hollow fiber membrane for 5min, pouring out the membrane preparation liquid, then purging with nitrogen to evaporate the solvent, and then placing the membrane assembly on a clean workbench for ventilation and drying to obtain the super-hydrophobic hollow ZIF-8 modified hollow fiber composite membrane and the super-hydrophobic hollow ZIF-8 modified hollow fiber composite membrane assembly.
The prepared super-hydrophobic hollow ZIF-8 modified hollow fiber composite membrane is applied to isopropanol/water rectification as follows:
the membrane distillation experiment is carried out under total reflux, the separation system is 20v/v% isopropanol/water solution (5.5 mol/mol%) and the heating power is 90W. The results showed that the molar concentration of isopropanol in the rectification product was 66.5mol/mol and the height of the mass transfer unit (HTU) was 3.4cm.
Example 2:
(1) Preparation of ZIF-7: respectively configure 100mL ZnCl 2 And (2) uniformly mixing the methanol solution (1 mol/L) of the (2 mol/L) benzimidazole and the methanol solution of the (2 mol/L) under stirring, standing at room temperature for reaction for 24 hours, and washing and drying by using centrifugal methanol to obtain the ZIF-7 material.
(2) Preparation of super-hydrophobic hollow ZIF-7: and dispersing the ZIF-7 material in water by ultrasonic stirring to obtain 10mg/mL ZIF-7 dispersion, adding 30mL of 3mg/mL aqueous solution of tea polyphenol, stirring for 5min, centrifuging, sequentially washing with methanol and hexane, dispersing in 30mL of hexane again, adding 1mL (0.89 g) of n-dodecyl trimethoxysilane, stirring for reaction at 80 ℃ for 24h, and washing and drying with centrifugal hexane to obtain the super-hydrophobic hollow ZIF-7 material.
(3) Super-hydrophobic hollow ZIF-7 modified hollow fiber composite membrane and component: PS polymer hollow fiber is used as a support membrane (the molecular weight cut-off is 6 ten thousand, tianjin membrane Tianmembrane engineering company). Dispersing 0.038g of the super-hydrophobic hollow ZIF-7 prepared in the step (2) into 5mL of PDMS heptane solution (10 wt%) by stirring and ultrasonic treatment, adding 0.0956g of catalyst dibutyltin dilaurate and 0.1912g of cross-linking agent tetraethyl orthosilicate (PDMS: mass ratio of the catalyst to the cross-linking agent is 20:5:10), and stirring and reacting for 20min at room temperature to obtain a coating liquid. Then fixing the hollow fiber membrane assembly on an iron stand, injecting prepared coating liquid into the membrane assembly, immersing the membrane assembly in the hollow fiber membrane for 5min, pouring out the membrane preparation liquid, then purging with nitrogen to evaporate the solvent, and then placing the membrane assembly on a clean workbench for ventilation and drying to obtain the super-hydrophobic hollow ZIF-7 modified hollow fiber composite membrane and the super-hydrophobic hollow ZIF-7 modified hollow fiber composite membrane assembly.
The prepared super-hydrophobic hollow ZIF-7 modified hollow fiber composite membrane is applied to isopropanol/water rectification as follows:
the membrane distillation experiment is carried out under total reflux, the separation system is 20v/v% isopropanol/water solution (molar concentration 5.5%), and the heating power is 90W. The results showed that the molar concentration of isopropanol in the rectification product was 65.8mol/mol and the height of the mass transfer unit (HTU) was 3.8cm. Example 3:
(1) Preparation of ZIF-67: respectively configure 100mL CoCl 2 And (2) and 2-methylimidazole (2 mol/L), then uniformly mixing the methanol solution and the methanol solution under stirring, standing at room temperature for reaction for 24 hours, and washing and drying by using centrifugal methanol to obtain the ZIF-67 material.
(2) Preparation of super-hydrophobic hollow ZIF-67: and dispersing the ZIF-67 material in water by ultrasonic stirring to obtain 10mg/mL ZIF-67 dispersion, adding 30mL of 3mg/mL aqueous solution of tea polyphenol, stirring for 5min, centrifuging, sequentially washing with methanol and hexane, dispersing in 30mL of hexane again, adding 1mL (0.89 g) of n-dodecyl trimethoxysilane, stirring for reaction at 80 ℃ for 24h, and washing and drying with centrifugal hexane to obtain the super-hydrophobic hollow ZIF-67 material.
(3) Super-hydrophobic hollow ZIF-67 modified hollow fiber composite membrane and component: PS polymer hollow fiber is used as a support membrane (the molecular weight cut-off is 6 ten thousand, tianjin membrane Tianmembrane engineering company). Dispersing 0.038g of the super-hydrophobic hollow ZIF-67 prepared in the step (2) into 5mL of a heptane solution (10 wt%) of PDMS by stirring and ultrasonic treatment, adding 0.0956g of catalyst dibutyltin dilaurate and 0.1912g of cross-linking agent tetraethyl orthosilicate (PDMS: mass ratio of the catalyst to the cross-linking agent is 20:5:10), and stirring and reacting for 20min at room temperature to obtain a coating liquid. Then fixing the hollow fiber membrane assembly on an iron stand, injecting prepared coating liquid into the membrane assembly, immersing the membrane assembly in the hollow fiber membrane for 5min, pouring out the membrane preparation liquid, then purging with nitrogen to evaporate the solvent, and then placing the membrane assembly on a clean workbench for ventilation and drying to obtain the super-hydrophobic hollow ZIF-67 modified hollow fiber composite membrane and the super-hydrophobic hollow ZIF-67 modified hollow fiber composite membrane assembly.
The prepared super-hydrophobic hollow ZIF-67 modified hollow fiber composite membrane is applied to isopropanol/water rectification as follows:
the membrane distillation experiment is carried out under total reflux, the separation system is 20v/v% isopropanol/water solution (molar concentration 5.5%), and the heating power is 90W. The results showed that the molar concentration of isopropanol in the rectification product was 66.7mol/mol% and the height of the mass transfer unit (HTU) was 3.2cm.
Comparative example 1:
hollow fiber composite membrane and module: PS polymer hollow fiber is used as a support membrane (the molecular weight cut-off is 6 ten thousand, tianjin membrane Tianmembrane engineering company). To 5mL of a heptane solution (10 wt%) of PDMS, 0.0956g of dibutyltin dilaurate as a catalyst and 0.1912g of tetraethyl orthosilicate as a crosslinking agent (PDMS: catalyst: crosslinking agent mass ratio: 20:5:10) were added, and the mixture was stirred at room temperature for reaction for 20 minutes to obtain a coating liquid. Then fixing the hollow fiber membrane module on an iron stand, injecting the prepared coating liquid into the membrane module, immersing the membrane module in the hollow fiber membrane for 5min, pouring out the membrane preparation liquid, then purging with 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 composite membrane module.
The prepared hollow fiber composite membrane is applied to isopropanol/water rectification as follows:
the membrane distillation experiment is carried out under total reflux, the separation system is 20v/v% isopropanol/water solution (molar concentration 5.5%), and the heating power is 90W. The results showed that the molar concentration of isopropanol in the rectification product was 60.1mol/mol and the height of the mass transfer unit (HTU) was 9.2cm.
Comparative example 2:
(1) Preparation of ZIF-8: respectively configure 100mL ZnCl 2 And (2) and 2-methylimidazole (2 mol/L), then uniformly mixing the methanol solution and the methanol solution under stirring, standing at room temperature for reaction for 24 hours, and washing and drying by using centrifugal methanol to obtain the ZIF-8 material.
(2) ZIF-8 modified hollow fiber composite membrane and component: PS polymer hollow fiber is used as a support membrane (the molecular weight cut-off is 6 ten thousand, tianjin membrane Tianmembrane engineering company). Dispersing 0.038g ZIF-8 prepared in the step (1) into 5mL of PDMS heptane solution (10 wt%) by stirring and ultrasonic, adding 0.0956g of catalyst dibutyltin dilaurate and 0.1912g of cross-linking agent tetraethyl orthosilicate (PDMS: catalyst: cross-linking agent mass ratio is 20:5:10), and stirring and reacting for 20min at room temperature to obtain a coating liquid. Then fixing the hollow fiber membrane assembly on an iron stand, injecting the prepared coating liquid into the membrane assembly, immersing the membrane assembly in the hollow fiber membrane for 5min, pouring out the membrane preparation liquid, then purging with nitrogen to evaporate the solvent, and then placing the membrane assembly 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 composite membrane assembly.
The prepared ZIF-8 modified hollow fiber composite membrane is applied to isopropanol/water rectification as follows:
the membrane distillation experiment is carried out under total reflux, the separation system is 20v/v% isopropanol/water solution (molar concentration 5.5%), and the heating power is 90W. The results showed that the molar concentration of isopropanol in the rectification product was 63.4mol/mol and the height of the mass transfer unit (HTU) was 5.9cm.

Claims (8)

1. The application of the super-hydrophobic hollow MOFs modified hollow fiber composite membrane in alcohol-water solution rectification is characterized in that the super-hydrophobic hollow MOFs modified hollow fiber composite membrane is prepared according to the following method:
(1) Preparation of superhydrophobic hollow MOF: uniformly dispersing MOF materials in water to obtain MOF dispersion liquid of 5-20 mg/mL, adding polyphenol solution of 1-5 mg/mL, stirring for 2-8 min, centrifuging, sequentially cleaning the obtained precipitate with methanol and hexane A, then re-suspending the precipitate in hexane B, adding 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 the polyphenol contained in the MOF material to the silane coupling agent is 10:1-5:1-60; the MOF material is ZIF-67; the polyphenol solution comprises tea polyphenol;
(2) Super-hydrophobic hollow MOF modified hollow fiber composite membrane: uniformly dispersing the super-hydrophobic hollow MOF in the step (1) in 1-20wt% of polydimethylsiloxane solution, adding a catalyst and a crosslinking agent, and reacting for 10 min-2 h at room temperature to obtain a coating liquid; injecting the coating liquid into the inner cavity of the hollow fiber membrane, soaking for 1-10 min, pouring out the residual coating liquid, blowing nitrogen to evaporate the solvent, and carrying out ventilation drying to obtain the super-hydrophobic hollow MOFs modified hollow fiber composite membrane; the mass ratio of the polydimethylsiloxane, the catalyst and the cross-linking agent contained in the superhydrophobic hollow MOF and the polydimethylsiloxane solution is 1-20:20:1-10:5-20; the catalyst is dibutyl tin dilaurate; the cross-linking agent is vinyl trimethoxy silane, tetraethyl orthosilicate or phenyl triethoxy silane.
2. The use according to claim 1, wherein: the volume of hexane B in step (1) is 20-100mL/g based on the mass of the MOF material.
3. The use according to claim 1, wherein the post-treatment of step (1) is: and centrifuging the reaction liquid, washing the obtained precipitate with hexane, and drying to obtain the super-hydrophobic hollow MOF material.
4. The use according to claim 1, wherein: the polyphenol solution in the step (1) also contains one or more than two of catechol, resorcinol and tannic acid.
5. The use according to 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.
6. The use according to claim 1, wherein: the hollow fiber membrane in the step (2) is made of polysulfone, polyethersulfone, polyvinylidene fluoride or polyacrylonitrile.
7. The use according to claim 1, wherein: the solvent of the polydimethylsiloxane solution in the step (2) is one or more than two of hexane, heptane and cyclohexane.
8. The use according to claim 1, wherein: the alcohol contained in the alcohol-water solution is isopropanol.
CN202210089394.7A 2022-01-25 2022-01-25 Super-hydrophobic hollow MOFs modified hollow fiber composite membrane and application thereof Active CN114515515B (en)

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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

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