CN107803117B - High-stability mesoporous polymer confined ionic liquid supported liquid membrane and preparation method and application thereof - Google Patents
High-stability mesoporous polymer confined ionic liquid supported liquid membrane and preparation method and application thereof Download PDFInfo
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- CN107803117B CN107803117B CN201610814000.4A CN201610814000A CN107803117B CN 107803117 B CN107803117 B CN 107803117B CN 201610814000 A CN201610814000 A CN 201610814000A CN 107803117 B CN107803117 B CN 107803117B
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Abstract
The invention belongs to the technical field of gas membrane separation, and particularly relates to a preparation method of a high-stability mesoporous polymer confinement ionic liquid supported liquid membrane and application thereof in CO2Use in separation. The supported liquid membrane is an ionic liquid supported liquid membrane of a mesoporous polymer confinement formed by growing a layer of mesoporous polymer membrane on the surface of a porous substrate and then carrying ionic liquid with a separation function in a pore passage of the mesoporous polymer membrane, wherein the pore diameter of the ionic liquid supported liquid membrane is 1-20nm, and the thickness of the ionic liquid supported liquid membrane is 5nm-100 mu m. The ionic liquid supported liquid membrane prepared by the invention can stably work under higher transmembrane pressure difference, and can be widely applied to CO purification, flue gas treatment and the like2The field of separation. The preparation method has the advantages of simple equipment, convenient operation, simple steps and strong practicability.
Description
Technical Field
The invention belongs to the technical field of gas membrane separation, and particularly relates to a preparation method of a high-stability mesoporous polymer confinement ionic liquid supported liquid membrane and application thereof in CO2Use in separation.
Background
The membrane separation method has small investment, low energy consumption and easy realization of skid-mounting, and is the CO which is developed most rapidly at present2One of the separation techniques. CO 22The separation membrane is mainly divided into a polymer membrane and a supported liquid membrane. The separation performance of polymer membranes is limited by the upper limit of Robeson and it is difficult to achieve both high selectivity and high permeate flux. The ionic liquid supported liquid membrane is prepared by supporting ionic liquid on a porous substrate. Because the diffusion coefficient of gas in ionic liquid is several orders of magnitude larger than that in polymer film, and CO2Can be generated with ionic liquidThe ionic liquid supported liquid membrane has higher gas permeation rate and selectivity due to the reverse physical or chemical action, and is widely concerned by researchers.
The ionic liquid supported liquid membrane is mainly used for CO2And N2、CH4The separation performance of the gas system approaches or even exceeds the upper limit of Robeson. Such as Paul Scovazzo et al [ J Membr Sci,2009,327,41, university of Missississippi, USA]PVDF and PES membranes with pore diameter of 0.1 mu m are used for supporting ionic liquid [ EMIM ]][BF4]、[EMIM][DCA]、[EMIM][CF3SO3]、[EMIM][Tf2N]、[C6MIM][Tf2N]、[BMIM][BETI]Discovery of CO2/CH4Selectivities of 22, 23, 18.5, 12.2, 8.5 and 9.9, respectively, and CO2/N2Selectivity was 44, 57, 40.5, 23, 15 and 16.7, exceeding the Robeson upper limit.
The ionic liquid supported liquid membrane has high penetration flux and selectivity at the same time, but the ionic liquid supported liquid membrane is not applied to large scale in industry, and the main reason is that the supported liquid membrane is unstable. The substrate for supporting the liquid membrane is usually a microfiltration membrane with a pore diameter of 0.1-0.45 mu m, such as polyvinylidene fluoride (PVDF), polyether sulfone (PES), polypropylene (PP), a nylon membrane, a ceramic membrane and the like. Transmembrane pressure difference due to wide pore size distribution of the substrate: (<1bar) is larger than the capillary force between the ionic liquid in the largest pore of the substrate and the pore wall, so that the ionic liquid in the largest pore of the substrate is lost, and the separation performance of the membrane is reduced or even disappears. Chinese patent with application number of 201110037748.5, takes polytetrafluoroethylene PTFE, PES, PVDF, polysulfone PS and polyacrylonitrile PAN membranes as porous substrates and adopts an impregnation method to prepare ionic liquid supported liquid membrane separation N2、CH4、CO、H2S、H2、O2And CO2The separation factor is 8-40, but the patent does not test its long-term stability.
For the disadvantage of poor stability of the supported liquid membrane, methods are generally adopted to (1) reduce the pore size of the membrane and (2) replace the ionic liquid with gel ionic liquid or even fix polyionic liquid in the substrate pore canal. Gan et al [ J Membr Sci,2006,280,948]Using nanofiltration membrane as substrate and ionic liquid BMIM][Tf2N]、[C10MIM][Tf2N]、[N8881][Tf2N]、[C8Py][Tf2N]Doing membrane liquid research H2、O2、N2And CO gas inThe separation performance in the supported liquid membrane was found to increase exponentially and to be very stable when the pressure was increased from 3.0 to 7.0bar, the supported liquid membrane being able to withstand pressures much higher than those of the supported liquid membrane using a microfiltration membrane as a substrate (< 0.1 bar). Richard D. noble et al [ J Membr Sci,2008,321, 3; ind Eng Chem Res,2013,52,8812]Covering or polymerizing a layer of gel ionic liquid and polyionic liquid on the surfaces and pores of the nylon membrane, PVDF and PTFE substrates, and supporting a liquid membrane to be capable of bearing transmembrane pressure difference of 2.7-6bar at most. The Chinese patent with the application number of 201210124953.X adopts a dipping method and a pressure permeation method to add the gel factor nano SiO2And imidazole type ionic liquid of carbon nanotube fixed on PVDF membrane, PTFE membrane, PS membrane, PES membrane, nylon membrane, silica membrane and porous Al membrane2O3The supported liquid film, CO, is obtained in the pores of the membrane substrate2/CH4The ideal selectivity reaches 8-25, and the stable operation is carried out for more than 24 hours at the transmembrane pressure difference of 100-200 kPa. Both of these methods, while improving the stability of the supported liquid membrane, result in a significant reduction in the permeate flux of the supported liquid membrane. Therefore, how to obtain a high-stability high-permeation-flux supported liquid membrane becomes a main challenge for industrial application.
Disclosure of Invention
The invention aims to provide an ionic liquid supported liquid membrane with high stability and mesoporous polymer confinement, a preparation method thereof and application thereof in CO2Use in separation.
In order to achieve the purpose, the invention adopts the technical scheme that:
the supported liquid membrane is an ionic liquid supported liquid membrane of a mesoporous polymer confinement, wherein a layer of mesoporous polymer membrane grows on the surface of a porous substrate, and then ionic liquid playing a role in separation is supported in a pore passage of the mesoporous polymer membrane to form the ionic liquid supported liquid membrane of the mesoporous polymer confinement, the pore diameter of which is 1-20nm, and the thickness of which is 5nm-100 mu m.
The method comprises the steps of coating a layer of mesoporous polymer precursor on the surface of a porous substrate, taking a surfactant triblock copolymer as a structure directing agent, forming an ordered structure between the polymer precursor and the structure directing agent, and then removing the structure directing agent, so that a layer of mesoporous polymer film with uniform aperture and high porosity is grown on the surface of the porous substrate, ionic liquid for separation is carried in pore channels of the mesoporous polymer film, and further an ionic liquid supported liquid film of a mesoporous polymer confinement is formed.
Wherein the structure directing agent is a triblock copolymer F127 or P123.
Carrying ionic liquid in a pore channel of the mesoporous polymer film on the surface of the substrate by adopting a dipping method, a negative pressure suction-coating method or a pressure permeation method on the porous substrate with the mesoporous polymer film formed on the surface, thereby obtaining an ionic liquid supported liquid film of the mesoporous polymer confinement; the ionic liquid is salt formed by anions and cations, the cations are imidazole cations, ammonium salt cations, pyridine cations, phosphine cations or guanidine cations, and the anions are tetrafluoroborate, hexafluoroborate, trifluoromethanesulfonate, bistrifluorosulfonyl imide and amino acid radicals.
A preferred ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroborate ([ emim [ ])][BF4]) 1-butyl-3-methylimidazolium hexafluoroborate ([ bmim ]][BF4]) Or 1-ethyl-3-methylimidazolium bistrifluorosulfonylimide salt ([ emim][Tf2N])。
A preparation method of an ionic liquid supported liquid membrane of a high-stability mesoporous polymer confinement comprises the steps of coating a layer of mesoporous polymer precursor on the surface of a porous substrate, taking a surfactant triblock copolymer as a structure directing agent, forming an ordered structure between the polymer precursor and the structure directing agent, removing the structure directing agent, growing a layer of mesoporous polymer membrane with uniform aperture and high porosity on the surface of the porous substrate, and supporting ionic liquid with a separation effect in pore channels of the mesoporous polymer membrane to form the ionic liquid supported liquid membrane of the mesoporous polymer confinement. Wherein the structure directing agent is a triblock copolymer F127 or P123.
Further comprising:
(1) adding melted phenol into NaOH solution and formaldehyde solution, adding the phenol into the NaOH solution and the formaldehyde solution, stirring the mixture for 30-180min at 50-80 ℃, cooling the mixture to room temperature, adjusting the pH value of the mixed solution to 7 after cooling, drying the mixed solution in vacuum to obtain resol, and dissolving the resol in ethanol for later use; wherein the molar ratio of phenol, NaOH and formaldehyde is 10:1: 20;
(2) dissolving the triblock copolymer in ethanol, and adding the ethanol solution of the obtained resol to form mesoporous polymer sol; wherein, the mol ratio of the triblock copolymer to the phenol to the formaldehyde to the ethanol in the mesoporous polymer sol is 0.001-0.01:1:2: 30-80;
(3) coating the mesoporous polymer sol on the surface of a porous substrate, sealing for 30min-5h after coating to slowly volatilize ethanol in the sol, and further volatilizing ethanol for 2-5 h; drying for 24-72h at 50-100 ℃ after volatilization to further polymerize the mesoporous polymer; removing the triblock copolymer after polymerization, thereby growing a mesoporous polymer film with uniform aperture and high porosity on the surface of the porous substrate; the steps of coating the mesoporous polymer sol, volatilizing ethanol, polymerizing in an oven and removing the triblock copolymer are repeated for 2-4 times to make up for defects possibly formed in the process of removing the triblock copolymer.
(4) And (3) carrying the ionic liquid in the pore channel of the mesoporous polymer membrane by adopting an immersion method, a negative pressure suction-coating method or a pressure permeation method, thereby forming the ionic liquid supported liquid membrane of the mesoporous polymer confinement.
The triblock copolymer is removed by calcination under an inert atmosphere or by solvent extraction.
The removing of the triblock copolymer comprises the steps of calcining the substrate at the temperature of 300-500 ℃ for 2-8h under the protection of inert atmosphere, and further removing the triblock copolymer; wherein the inert atmosphere is N2And Ar atmosphere;
carrying out reflux extraction on the substrate in ethanol at the temperature of 30-80 ℃ for 2-48h, and further removing the triblock copolymer;
refluxing and extracting the substrate in 20-60 wt.% sulfuric acid at 60-120 ℃ for 2-48h, and further removing the triblock copolymer;
or reflux-extracting the substrate in 60-80 deg.C hydrochloric acid ethanol solution for 2-48h to remove triblock copolymer, and concentrating hydrochloric acid and anhydrous ethanol at ratio of 1: 1-5.
Application of high-stability mesoporous polymer confined ionic liquid supported liquid membrane in separation of CO2And CH4、N2、H2、O2And application in CO gas.
The invention has the following advantages:
the mesoporous polymer confined ionic liquid supported liquid membrane prepared by the method has the characteristics of high permeation flux and high stability. Specifically, the higher porosity of the mesoporous polymer is beneficial to improving the permeation flux of the supported liquid membrane, and the smaller pore diameter and the uniform pore diameter distribution can effectively avoid the loss of the ionic liquid and ensure the higher stability of the supported liquid membrane. Therefore, a mesoporous polymer film with uniform pore diameter and high porosity is grown on the surface of the porous substrate and carries the ionic liquid, and meanwhile, the mesoporous polymer film has high permeation flux and high stability. The invention is beneficial to separating CO2And CH4、N2And the like in the field of gas separation.
Description of the drawings:
fig. 1 is a characteristic XRD spectrum of cubic mesoporous polymer powder FDU16 according to embodiment 1 of the present invention.
Fig. 2 is a TEM photograph of cubic phase mesoporous polymer powder FDU16 according to embodiment 1 of the present invention.
Fig. 3 is a cross-sectional SEM photograph of a mesoporous polymer film according to embodiment 2 of the present invention. Fig. 3b is a partial enlarged view of fig. 3 a.
FIG. 4 shows a mesoporous polymer/[ emim ] according to example 2 of the present invention][BF4]Scanning electron micrograph of the cross section of the supported liquid film and C, B, F, N and Al element phase analysis. Al under the white line2O3The element phase of the substrate has high Al element content; the white line is a mesoporous polymer film loaded with ionic liquid, contains C, B, F and N elements, and indicates that the mesoporous polymer film successfully grows on Al2O3On a substrate, an ionic liquid [ emim][BF4]Loaded into the pore canal of the mesoporous polymer membrane.
FIG. 5 shows Al of example 2 of the present invention2O3Substrate, mesoporous polymer film and mesoporous polymer/[ emim][BF4]An infrared spectrum of the supported liquid film. The characteristic peak of the infrared spectrogram indicates that the mesoporous polymer film successfully grows on Al2O3On a substrate, an ionic liquid [ emim][BF4]Loaded into the pore canal of the mesoporous polymer membrane.
FIG. 6 shows a mesoporous polymer/[ emim ] according to example 2 of the present invention][BF4]Supported liquid film CO2、N2Permeability coefficient and selectivity of pure gas and mixed gas. FIG. 6a shows the CO2And N2Permeability coefficient of pure gas, CO2/N2The ideal selectivity of the method reaches more than 40; FIG. 6b shows the CO measured at a volume ratio of 1:12And N2The pressure of the mixed gas is increased from 0 to 2.55bar, and the selectivity of the mixed gas is increased from 14 to 26.
FIG. 7 shows a mesoporous polymer/[ emim ] according to example 2 of the present invention][BF4]Supporting the liquid film with PES/[ emim][BF4]Contrast graph of the stability of the supported liquid film. Mesoporous polymer/[ emim][BF4]The supported liquid membrane still stably works when the delta P is increased to 2.5atm, and PES/[ emim][BF4]The supported liquid membrane loses separation performance due to ionic liquid loss when deltap is increased to 1 atm.
FIG. 8 shows a mesoporous polymer/[ emim ] according to example 2 of the present invention][BF4]Stability of the supported liquid film.
FIG. 9 shows a mesoporous polymer/[ emim ] according to example 2 of the present invention][BF4]Gas chromatography for supported liquid membrane test.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is further illustrated by the following examples, it should be noted that the scope of the present invention is not limited to the specific examples, and the preparation method and application are not limited to the preparation method in the following examples.
Coating a layer of resol polymer precursor on the surface of a porous substrate, and growing a mesoporous polymer film on the surface of the porous substrate by a self-assembly method by taking a triblock copolymer F127 as a structure directing agent; and filling the mesoporous polymer membrane pore canal with ionic liquid by adopting a negative pressure suction-coating method to obtain a supported liquid membrane. The mesoporous polymer film has smaller aperture and uniform aperture, ensures higher stability of the supported liquid film, and avoids the flow of ionic liquid in the largest hole in the supported liquid filmThe separation performance decreases and disappears due to the loss. The ionic liquid supported liquid membrane prepared by the invention can stably work under higher transmembrane pressure difference, and can be widely applied to CO purification, flue gas treatment and the like2The field of separation. The preparation method has the advantages of simple equipment, convenient operation, simple steps and strong practicability.
Example 1
(1) Synthesis of resol sol: 0.61g (94.11g/mol, 6.5mmol) of phenol was melted at 40-42 ℃ and then 0.13g of 20% NaOH solution (containing NaOH 0.026g, 0.65mmol, 40g/mol) was slowly added thereto for 10min with stirring. Then, 1.05g of formalin solution (37%, containing 0.39g of formaldehyde, 13.0mmol) was added dropwise thereto, and the reaction was continued at 70 ℃ for 60min with continuous stirring. Cooled to room temperature and the pH adjusted to 7 with 0.6M hydrochloric acid. And vacuum drying at a temperature of less than 50 ℃ to obtain the product of resol (molecular weight less than 500) and dissolving in 7.5g of ethanol for later use.
(2) Preparation of cubic phase mesoporous polymer FDU16 sol: 0.5g F127 (3.9683X 10)-5mol) was dissolved in 7.5g of ethanol (46g/mol, 0.163mol) and the oligomeric phenol-formaldehyde resin (containing 0.61g of 6.5mmol phenol, 0.39g of 13.0mmol formaldehyde, 7.5g of ethanol) was slowly added over 10min with stirring to form a homogeneous solution. Wherein, the molar ratio of F127, phenol, formaldehyde and ethanol in the homogeneous solution is F127, phenol, formaldehyde and ethanol is 0.005-0.006:1:2: 50.
(3) Preparation of cubic phase mesoporous polymer FDU16 powder: pouring the FDU16 sol into a culture dish, slowly volatilizing ethanol for 5-8h, and then putting into an oven at 100 ℃ for polymerization for 24h to obtain the phenolic resin polymer. Hanging the polymer from the culture dish, grinding into powder, and placing into a 350 ℃ tube furnace N2Calcining for 5h under protection to obtain FDU16 powder, wherein the heating and cooling rates are both 1 ℃/min. The pore structure of the FDU powder is body centered cubic with a pore size of about 7nm (see fig. 1 and 2). Similar to the preparation method of the cubic phase mesoporous polymer FDU16 powder, the pore channel structure of the mesoporous polymer film grown on the surface of the porous substrate is also body-centered cubic, and the pore diameter is about 7 nm.
In addition, the pore size depends on factors such as calcination temperature, calcination time, and surfactant ratio. The calcination temperature is increased and the calcination time is longer because the pore size is reduced due to shrinkage of the polymer skeleton. The use amount of the block copolymer is different, so that critical micelles with different forms are formed, and different pore diameters are finally formed.
Example 2
(1) Preparation of Al by dropping coating method2O3Mesoporous polymer primary membrane: mixing Al2O3Flatly placing the microporous filter membrane on an experiment table, dripping a thin layer of FDU16 sol with the thickness of 50nm-1mm on the surface of the microporous filter membrane, tightly covering the microporous filter membrane with a small culture dish to slowly volatilize ethanol in the FDU16 sol, naturally volatilizing the ethanol for 2-3h, then solidifying the ethanol, and then drying the sol for 24h at the temperature of 100 ℃ to obtain Al high polymer2O3-a mesoporous polymeric primary membrane.
(2) Calcining to remove F127 to prepare a mesoporous polymer film: mixing Al2O3Primary membrane of mesoporous polymer in N2And (3) calcining at 350 ℃ for 5h at the heating and cooling rate of 0.8 ℃/min under protection to obtain the mesoporous polymer film, and repeating the step (2) twice to make up for possible defects formed in the calcining process.
(3) Preparation of a supported liquid film: placing the mesoporous polymer film on a filter, and dropwise adding a thin layer of 5nm-100 μm ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate ([ emim ] on the surface of the mesoporous polymer film][BF4]) Then pumping the mesoporous polymer layer by a vacuum pump with the vacuum degree of 0.02-0.08MPa to ensure that the ionic liquid enters the mesoporous polymer layer to obtain an ionic liquid supported liquid membrane (see attached figures 3-5). Figures 3-5 illustrate that the mesoporous polymer layer successfully grows on the surface of the porous substrate and the ionic liquid enters the pore channels of the mesoporous polymer film.
(4) Testing of the supported liquid film: connection N as shown in FIG. 92Steel cylinder, CO2Steel cylinder, CH4Steel cylinder, pressure reducing valve, mass flowmeter, filter, pressure gauge, needle valve, permeator and chromatogram. First, the flow rate of 20mL/min is measured by using N2、CO2And CH4Purging the corresponding line for 30min, and then adjusting N2Flow rate of 6mL/min, CO2The flow rate is 6mL/min, CH4The flow rate is 1mL/min in terms of CH4Testing of CO for purge gas2、N2Permeation flux of (see FIGS. 6-9), CO is illustrated by FIG. 62And N2The ideal selectivity of the catalyst is more than 40 percent, and the mixture isThe gas separation factor reaches 26 (CO)2And N2Volume ratio of 1: 1). FIGS. 7 and 8 illustrate that the stability of the ionic liquid supported liquid membrane of the mesoporous polymer confinement prepared by the invention is higher than that of the ionic liquid supported liquid membrane prepared by the ionic liquid supported by the conventional porous substrate.
Example 3
The difference from the above embodiment 2 is that the ionic liquid enters the pore channels by a pressurization method, specifically:
preparation of a supported liquid film: putting the mesoporous polymer film on a filter, and dropwise adding a thin layer of ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate ([ emim ] on the surface of the mesoporous polymer film][BF4]) And then pressurizing to enable the ionic liquid to enter the mesoporous polymer layer to obtain an ionic liquid supported liquid membrane.
Example 4
The difference from the above example 2 is that the ionic liquid is introduced into the pore channels by impregnation, specifically:
preparation of a supported liquid film: placing a thin layer of ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate ([ emim ] in a culture dish][BF4]) Then, the mesoporous polymer membrane is soaked in a culture dish for 30min, and the ionic liquid on the surface of the supported liquid membrane is carefully wiped off by using filter paper to obtain the ionic liquid supported liquid membrane.
Claims (7)
1. A high-stability mesoporous polymer confined ionic liquid supported liquid membrane is characterized in that: the supported liquid membrane is an ionic liquid supported liquid membrane of a mesoporous polymer confinement formed by growing a layer of mesoporous polymer membrane on the surface of a porous substrate and then carrying ionic liquid with a separation function in a pore passage of the mesoporous polymer membrane, wherein the pore diameter of the ionic liquid supported liquid membrane is 1-20nm, and the thickness of the ionic liquid supported liquid membrane is 5nm-100 mu m;
coating a layer of mesoporous polymer precursor on the surface of the porous substrate, taking a surfactant triblock copolymer as a structure directing agent, forming an ordered structure between the polymer precursor and the structure directing agent, and then removing the structure directing agent, so that a layer of mesoporous polymer film with uniform aperture and high porosity is grown on the surface of the porous substrate, ionic liquid for separation is carried in pore channels of the mesoporous polymer film, and further an ionic liquid supported liquid film of the mesoporous polymer confinement is formed.
2. The high stability mesoporous polymer confined ionic liquid supported liquid membrane of claim 1, wherein: carrying ionic liquid in a pore channel of the mesoporous polymer film on the surface of the substrate by adopting a dipping method, a negative pressure suction-coating method or a pressure permeation method on the porous substrate with the mesoporous polymer film formed on the surface, thereby obtaining an ionic liquid supported liquid film of the mesoporous polymer confinement; wherein the ionic liquid is salt formed by anions and cations, the cations are imidazole cations, ammonium salt cations, pyridine cations, phosphine cations or guanidine cations, and the anions are tetrafluoroborate, hexafluoroborate, trifluoromethanesulfonate, bistrifluorosulfonyl imide or amino acid radicals.
3. The preparation method of the ionic liquid supported liquid membrane with high stability mesoporous polymer confinement, which is disclosed by claim 1, is characterized by comprising the following steps: coating a layer of mesoporous polymer precursor on the surface of a porous substrate, taking a surfactant triblock copolymer as a structure directing agent to form an ordered structure between the polymer precursor and the structure directing agent, and then removing the structure directing agent, so that a layer of mesoporous polymer film with uniform aperture and high porosity is grown on the surface of the porous substrate, ionic liquid with separation function is carried in pore channels of the mesoporous polymer film, and further an ionic liquid supported liquid film of a mesoporous polymer confinement is formed.
4. The method for preparing the ionic liquid supported liquid membrane with high stability mesoporous polymer confinement as claimed in claim 3, which is characterized in that:
(1) adding melted phenol into NaOH solution and formaldehyde solution, adding the phenol into the NaOH solution and the formaldehyde solution, stirring the mixture for 30-180min at 50-80 ℃, cooling the mixture to room temperature, adjusting the pH value of the mixed solution to 7 after cooling, drying the mixed solution in vacuum to obtain resol, and dissolving the resol in ethanol for later use; wherein the molar ratio of phenol to NaOH to formaldehyde is phenol to NaOH to formaldehyde =10:1: 20;
(2) dissolving the triblock copolymer in ethanol, and adding the ethanol solution of the obtained resol to form mesoporous polymer sol; wherein the mole ratio of the triblock copolymer, phenol, formaldehyde and ethanol is triblock copolymer phenol to formaldehyde to ethanol =0.001-0.01:1:2: 30-80;
(3) coating the mesoporous polymer sol on the surface of a porous substrate, sealing for 30min-5h after coating to slowly volatilize ethanol in the sol, and further volatilizing ethanol for 2-5 h; drying for 24-72h at 50-100 ℃ after volatilization to further polymerize the mesoporous polymer; removing the triblock copolymer after polymerization, thereby growing a mesoporous polymer film with uniform aperture and high porosity on the surface of the porous substrate; repeating the steps of coating the mesoporous polymer sol, volatilizing ethanol, polymerizing in an oven and removing the triblock copolymer for 2-4 times to make up for possible defects formed in the process of removing the triblock copolymer;
(4) and (3) carrying the ionic liquid in the pore channel of the mesoporous polymer membrane by adopting an immersion method, a negative pressure suction-coating method or a pressure permeation method, thereby forming the ionic liquid supported liquid membrane of the mesoporous polymer confinement.
5. The method for preparing the ionic liquid supported liquid membrane with high stability mesoporous polymer confinement as claimed in claim 4, wherein the method comprises the following steps: the triblock copolymer is removed by calcination under an inert atmosphere or by solvent extraction.
6. The method for preparing the ionic liquid supported liquid membrane with high stability mesoporous polymer confinement as claimed in claim 5, is characterized in that: the removing of the triblock copolymer comprises the steps of calcining the substrate at the temperature of 300-500 ℃ for 2-8h under the protection of inert atmosphere, and further removing the triblock copolymer; wherein the inert atmosphere is N2And Ar atmosphere;
or reflux-extracting the substrate in ethanol at 30-80 deg.C for 2-48h to remove triblock copolymer;
or refluxing and extracting the substrate in 20-60 wt.% sulfuric acid at 60-120 deg.C for 2-48h to remove triblock copolymer;
or refluxing and extracting the substrate in an ethanol solution of hydrochloric acid at the temperature of 60-80 ℃ for 2-48h, and further removing the triblock copolymer, concentrated hydrochloric acid: absolute ethanol =1: 1-5.
7. The application of the ionic liquid supported liquid membrane with high stability mesoporous polymer confinement, which is disclosed by claim 1, is characterized in that: the liquid film is separating CO2And CH4、N2、H2、O2And application in CO gas.
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| CN112191110B (en) * | 2019-07-08 | 2022-07-05 | 中国科学院青岛生物能源与过程研究所 | Nano metal organic frame ZIF-8 supported ionic liquid composite membrane and preparation method and application thereof |
| CN113041851B (en) * | 2019-12-27 | 2023-04-14 | 中国科学院理化技术研究所 | Nano-pore seawater antifouling liquid film and preparation method and application thereof |
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