CN112755801A - Preparation method of mixed matrix membrane material - Google Patents

Preparation method of mixed matrix membrane material Download PDF

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CN112755801A
CN112755801A CN202011483840.XA CN202011483840A CN112755801A CN 112755801 A CN112755801 A CN 112755801A CN 202011483840 A CN202011483840 A CN 202011483840A CN 112755801 A CN112755801 A CN 112755801A
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郭振济
赵东风
刘忠源
康子曦
逄佳
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China University of Petroleum East China
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2257/7027—Aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
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Abstract

The invention discloses a preparation method of a mixed matrix membrane material, and belongs to the technical field of membrane materials. The preparation method comprises the steps of preparing porous MIL-101(Cr) particles with the particle size of 200-300 nm by adopting a solvothermal synthesis method, uniformly dispersing MIL-101 with different amounts in an MOF dispersion liquid by adopting a stirring-ultrasonic treatment method, adding the MOF dispersion liquid into ethanol/water solution of high polymer polyether block amide, and obtaining a series of mixed matrix membranes with different composition ratios by adopting a natural casting method, wherein the preparation method comprises the steps of preparing MIL-101(Cr), preparing an MIL-101@ Pebax membrane and the like. The comparison graph of the permeability shows that the MIL-101@ Pebax mixed matrix membrane with different composition ratios is used for ethylbenzene/N2All have certain osmotic selectivity, and the permeation rate of the ethylbenzene is increased and the permeability is increased along with the increase of the doping amount of the MIL-101. The invention can be used for separating the waste gas containing VOCs.

Description

Preparation method of mixed matrix membrane material
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a preparation method of a mixed matrix membrane material obtained by doping a metal-organic coordination polymer material into a high molecular compound.
Background
Mixed Matrix Membranes (MMMs), a composite material, are constructed by adding inorganic substances as dispersed particles to a continuous phase of a polymer or copolymer. The mixed matrix membrane is able to combine the easy processability and good mechanical properties of polymer membranes with the good permeability and selectivity of crystalline porous fillers. Therefore, the mixed matrix membrane has great potential in the field of gas separation, particularly in the field of air pollution control such as pervaporation separation of VOCs. However, a large amount of toxic and harmful solvents such as N, N-Dimethylacetamide (DMA), N-methylpyrrolidone (NMP), chloroform (CHCl3), etc. are widely used in the polymer processing process, which causes secondary pollution to some extent. Polyether block amide: the advent and application of Pebax mh1657 (Pebax for short) perfectly solved this problem, as Pebax films could be prepared under relatively mild conditions (80 ℃) by using more environmentally friendly solvents (water/ethanol mixed solutions), which are very environmentally friendly.
As a new nano porous material, a Metal-organic frameworks (MOFs) material is a coordination polymer formed by self-assembly reaction of Metal ions and organic ligands, and has extremely important research value in the fields of gas adsorption, chemical catalysis, biomedicine, electrochemistry and the like. The existing research results prove that the metal-organic framework material has good interface compatibility with a polymer matrix. In addition, the designability of the MOF structure, as well as the uniform pore structure, helps to achieve selective adsorption and diffusion of the target VOCs. However, the poor stability of some MOF structures has hindered their practical application. Therefore, the metal-organic framework material with better chemical stability and the characteristic of a pore structure can meet the requirement of constructing a mixed matrix membrane material. MIL-101(Cr) is a widely studied chromium-based metal-organic framework material, which is formed by connecting terephthalic acid ligands and trimeric chromium (III) octahedral clusters through coordination bond bonding, and the structure of the material has two types of mesoporous cages with diameters of about 2:1
Figure BDA0002838813240000021
And
Figure BDA0002838813240000022
MIL-101 has good structural stability, and is widely applied to the field of gas adsorption/separation.
In conclusion, the high polymer PebaxMH1657 serving as a substrate and containing the stable and porous metal-organic framework doped mixed matrix membrane material has rich research significance and great application prospect in the field of membrane material application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a mixed matrix membrane material.
The technical scheme adopted by the invention for realizing the purpose is as follows: a preparation method of mixed matrix membrane material, which is prepared by mixing MIL-101(Cr) as organic particle additive with Pebax and ethanol/water solvent, is characterized in that the preparation method comprises the following steps:
step S1: firstly, dissolving terephthalic acid and chromium nitrate nonahydrate in deionized water, adding a certain amount of benzoic acid to obtain a mixed solution, stirring and carrying out ultrasonic treatment for 30min, and sealing in a reaction kettle with a polytetrafluoroethylene lining;
step S2: placing the sealed mixed solution in the S1 in a 220 ℃ oven, continuously reacting for 8h, synchronously setting a program for cooling, slowly cooling the oven to room temperature at a cooling rate of 25 ℃/h after 8h, filtering and collecting a generated solid product;
step S3: repeatedly washing and filtering the solid product obtained in the step S3 by using deionized water for 3 times, placing the solid product into a glass bottle with a cover, adding 18-22mL of anhydrous methanol, stirring for 15min, standing for 8h, repeating the process for 3 times, and filtering again to collect the generated precipitate;
step S4: drying the precipitate obtained in the step S3 in a 120 ℃ forced air drying oven for 12h to obtain MIL-101(Cr) crystals with the size of 200-300 nm;
step S5: weighing 0.15-0.6 g of MIL-101(Cr) prepared in the step S4, placing the MIL-101(Cr) in a mortar, grinding for 20min, placing in a glass bottle, sequentially pouring 14mL of ethanol and 6mL of deionized water, stirring at a constant speed for 30min, carrying out ultrasonic treatment for 10min, repeating the above process for 5 times, and continuously stirring at a constant speed for 12h to obtain an MOF dispersion liquid;
step S6: weighing 2.4-2.85 g of PebaxMH1657 particles, placing the particles in a round bottom flask, adding 35mL of ethanol and 15mL of deionized water into the flask, placing the flask in an oil bath kettle at 80 ℃, heating and stirring for 12 hours until the particles are completely dissolved. Dropwise transferring the MOF dispersion liquid in the step S5 into a flask, and continuously heating and stirring for 6 hours until the dispersion is uniform;
step S7: placing a circular glass culture dish with the diameter of 10cm on a completely horizontal fume hood table, slowly pouring the solution prepared in the flask in the step S6 into the culture dish, standing, and taking off the film at the bottom of the culture dish by using tweezers after the solution is volatilized, thus obtaining a circular film with the diameter of 10 cm.
Step S8: and (4) placing the circular film in the step S7 in a vacuum oven at 60 ℃, heating and continuously vacuumizing for 24h at the same time, and finishing the activation of the MIL-101@ Pebax film material.
Preferably, the mass amount of the terephthalic acid used in the step S1 is 0.8 to 1.2 g.
Preferably, the mass ratio of the terephthalic acid, the chromium nitrate nonahydrate, the deionized water and the benzoic acid in the step S1 is 1 (2-2.5): (30-50): 2-2.5).
Preferably, the mass ratio of MIL-101(Cr) to Pebax in the step S4-6 is 1 (4-19).
Preferably, the mass ratio of the ethanol to the deionized water in the step S6 is 7: 3.
Preferably, the solution in the culture dish is kept still for 68-72 hours in the step S7.
The invention has the beneficial effects that: the preparation method of the mixed matrix membrane material comprises the steps of preparing the mixed matrix membrane of MIL-101@ Pebax with different component proportions to ethylbenzene/N2The method has certain osmotic selectivity, the permeation rate of ethylbenzene is increased along with the increase of the doping amount of MIL-101, the osmotic selectivity is increased, and the method can be used for separating waste gas containing VOCs and has the advantages of no pollution, convenience in operation and low energy consumption.
Drawings
FIG. 1 is an XRD spectrum of MIL-101(Cr) in accordance with the present invention;
FIG. 2 is an SEM image of MIL-101(Cr) in accordance with the present invention;
FIG. 3 shows ethylbenzene vapor and N at 298K for MIL-101(Cr) in accordance with the present invention2Adsorption isotherm diagram of (a);
FIG. 4 is an XRD spectrum of a sample of MIL-101@ Pebax film from examples 1-3 herein;
FIG. 5 is an SEM image of film samples of examples 1-3 and comparative examples of the present invention;
FIG. 6 is a graph showing a comparison of gas permeation separation performance of membrane samples in examples 1 to 3 of the present invention and comparative example.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Specific example 1:
(1) the preparation process comprises the following steps: firstly, accurately weighing 2.4g of chromium nitrate nonahydrate, adding the chromium nitrate nonahydrate into a high-pressure reaction kettle with a polytetrafluoroethylene lining, adding 30mL of deionized water, accurately weighing 0.99g of terephthalic acid and 2.2g of benzoic acid, sequentially adding into a reaction kettle, stirring and ultrasonic treating for 30min until completely dissolving, sealing with reaction kettle, placing in oven at 220 deg.C, continuously reacting for 8h, synchronously setting program cooling, slowly cooling the temperature of the oven to room temperature at the cooling rate of 25 ℃/h after 8h, filtering and collecting solid products, repeatedly washing the obtained solid products by deionized water, filtering for 3 times, then placing the products into a 30mL glass bottle with a cover, adding 20mL of anhydrous methanol, stirring for 15min, screwing a bottle cap, standing for 8h, repeating the process for 3 times, filtering and collecting dark green precipitates, and recently placing the precipitates in a forced air drying oven for drying for 12h to obtain activated MIL-101 (Cr); accurately weighing 0.15g of prepared MIL-101(Cr), placing the MIL-101(Cr) into a mortar, grinding for 20min, placing the MIL-101(Cr) into a glass bottle with a cover, pouring 14mL of ethanol and 6mL of deionized water in sequence, stirring for 30min at a constant speed, carrying out ultrasonic treatment for 10min, repeating the process for 5 times, continuously stirring for 12h at a constant speed to obtain an MOF dispersion liquid, accurately weighing 2.85g of PebaxMH1657 particles, placing the PebaxMH1657 particles into a round bottom flask, adding 35mL of ethanol and 15mL of deionized water into the flask, placing the flask into an oil bath kettle at 80 ℃, heating and stirring for 12h until the solution is completely dissolved, dropwise transferring the MOF dispersion liquid into the flask, continuously heating and stirring for 6h until the solution is uniformly dispersed, placing a round glass culture dish with the diameter of 10cm on a completely horizontal ventilation table top of the cabinet, slowly pouring the solution in the culture dish, standing for 72h, after the solution is volatilized, the method comprises the steps of obtaining a circular MIL-10 (15%) @ Pebax film with the diameter of 10cm, wherein the mass fraction of MIL-101(Cr) is 5%, placing the film in a clean culture dish, placing the culture dish in a vacuum oven at the temperature of 60 ℃, and continuously vacuumizing for 24 hours while heating, so that activation of the MIL-101 (5%) @ Pebax film material is completed.
(2) And (3) detection process: characterization of MIL-101@ Pebax film: performing X-ray diffraction spectrum characterization, scanning electron microscope characterization and ethylbenzene/N on the mixed matrix membrane2And (4) testing osmotic separation. When a permeation separation test is carried out, the prepared MIL-101@ Pebax mixed matrix membrane is placed into a mold of a permeation separation device, air containing ethylbenzene is introduced for testing, and the permeation rate P of the membrane to two test gases is obtained after the test is finishedEthylbenzene production、PN2Permeability selectivity is the ratio of the permeation rates (P) of a composite membrane to two gasesEthylbenzene production/PN2) The test results are shown in table 1.
Table 1: ethylbenzene and N2Permeability rate and permselectivity
Figure BDA0002838813240000051
Specific example 2:
(1) the preparation process comprises the following steps: firstly, accurately weighing 2.4g of chromium nitrate nonahydrate, adding the chromium nitrate nonahydrate into a high-pressure reaction kettle with a polytetrafluoroethylene lining, adding 30mL of deionized water, accurately weighing 0.99g of terephthalic acid and 2.2g of benzoic acid, sequentially adding into a reaction kettle, stirring and ultrasonic treating for 30min until completely dissolving, sealing with reaction kettle, placing in oven at 220 deg.C, continuously reacting for 8h, synchronously setting program cooling, slowly cooling the temperature of the oven to room temperature at the cooling rate of 25 ℃/h after 8h, filtering and collecting solid products, repeatedly washing the obtained solid products by deionized water, filtering for 3 times, then placing the products into a 30mL glass bottle with a cover, adding 20mL of anhydrous methanol, stirring for 15min, screwing a bottle cap, standing for 8h, repeating the process for 3 times, filtering and collecting dark green precipitates, and recently placing the precipitates in a forced air drying oven for drying for 12h to obtain activated MIL-101 (Cr); accurately weighing 0.3g of MIL-101(Cr), placing the MIL-101(Cr) into a mortar, grinding for 20min, placing the mixture into a glass bottle with a cover, pouring 14mL of ethanol and 6mL of deionized water, uniformly stirring for 30min, carrying out ultrasonic treatment for 10min, repeating the process for 5 times, continuously and uniformly stirring for 12h to obtain an MOF dispersion solution, accurately weighing 2.7g of PebaxMH1657 particles, placing the PebaxMH1657 particles into a round bottom flask, adding 35mL of ethanol and 15mL of deionized water into the flask, placing the flask into an 80 ℃ oil bath, heating and stirring for 12h until the particles are completely dissolved. Dropwise transferring the MOF dispersion liquid into a flask, continuously heating and stirring for 6 hours until the MOF dispersion liquid is uniformly dispersed, taking a circular glass culture dish with the diameter of 10cm, placing the circular glass culture dish on a completely horizontal table top of a fume hood, slowly pouring the solution in the flask into the culture dish, standing for 72 hours, after the solution is volatilized, removing a film at the bottom of the culture dish by using forceps to obtain a circular MIL-101 (10%) @ Pebax film with the diameter of 10cm, wherein the mass fraction of the MIL-101(Cr) is 10%, placing the film into a clean culture dish, placing the culture dish into a vacuum oven with the temperature of 60 ℃, continuously vacuumizing for 24 hours while heating, and considering that the MIL-101 (10%) @ Pebax film material is activated completely.
(2) And (3) detection process: characterization of MIL-101@ Pebax film: performing X-ray diffraction spectrum characterization, scanning electron microscope characterization and ethylbenzene/N on the mixed matrix membrane2And (4) testing osmotic separation. When a permeation separation test is carried out, the prepared MIL-101@ Pebax mixed matrix membrane is placed into a mold of a permeation separation device, air containing ethylbenzene is introduced for testing, and the permeation rate P of the membrane to two test gases is obtained after the test is finishedEthylbenzene production、PN2Permeability selectivity is the ratio of the permeation rates (P) of a composite membrane to two gasesEthylbenzene production/PN2) The test results are shown in Table 2.
Table 2: ethylbenzene and N2Permeability rate and permselectivity
Figure BDA0002838813240000061
Specific example 3:
(1) the preparation process comprises the following steps: firstly, accurately weighing 2.4g of chromium nitrate nonahydrate, adding the chromium nitrate nonahydrate into a high-pressure reaction kettle with a polytetrafluoroethylene lining, adding 30mL of deionized water, accurately weighing 0.99g of terephthalic acid and 2.2g of benzoic acid, sequentially adding into a reaction kettle, stirring and ultrasonic treating for 30min until completely dissolving, sealing with reaction kettle, placing in oven at 220 deg.C, continuously reacting for 8h, synchronously setting program cooling, slowly cooling the temperature of the oven to room temperature at the cooling rate of 25 ℃/h after 8h, filtering and collecting solid products, repeatedly washing the obtained solid products by deionized water, filtering for 3 times, then placing the products into a 30mL glass bottle with a cover, adding 20mL of anhydrous methanol, stirring for 15min, screwing a bottle cap, standing for 8h, repeating the process for 3 times, filtering and collecting dark green precipitates, and recently placing the precipitates in a forced air drying oven for drying for 12h to obtain activated MIL-101 (Cr); accurately weighing 0.6g of MIL-101(Cr), placing the MIL-101(Cr) into a mortar, grinding for 20min, placing the mixture into a glass bottle with a cover, pouring 14mL of ethanol and 6mL of deionized water, uniformly stirring for 30min, carrying out ultrasonic treatment for 10min, repeating the process for 5 times, continuously and uniformly stirring for 12h to obtain an MOF dispersion liquid, accurately weighing 2.4g of PebaxMH1657 particles, placing the PebaxMH1657 particles into a round bottom flask, adding 35mL of ethanol and 15mL of deionized water into the flask, placing the flask into an oil bath kettle at 80 ℃, heating and stirring for 12h until the solution is completely dissolved, dropwise transferring the MOF dispersion liquid into the flask, continuously heating and stirring for 6h until the solution is uniformly dispersed, placing another round glass culture dish with the diameter of 10cm on a completely horizontal ventilation table top, slowly pouring the solution in the flask into the culture dish, standing for 72h, after the solution is volatilized, removing a film at the bottom of the culture dish by using tweezers to obtain a round MIL-101 (20%) Pebax film with the, wherein the mass fraction of MIL-101(Cr) is 20%, placing the membrane in a clean culture dish, placing the culture dish in a vacuum oven at 60 ℃, heating and continuously vacuumizing for 24h, and then, the MIL-101 (20%) @ Pebax membrane material is considered to be activated completely.
(2) The preparation process comprises the following steps: characterization of MIL-101@ Pebax film: performing X-ray diffraction spectrum characterization, scanning electron microscope characterization and ethylbenzene/N on the mixed matrix membrane2And (4) testing osmotic separation. When a permeation separation test is carried out, the prepared MIL-101@ Pebax mixed matrix membrane is placed into a mold of a permeation separation device, air containing ethylbenzene is introduced for testing, and the permeation rate P of the membrane to two test gases is obtained after the test is finishedEthylbenzene production、PN2Permeability selectivity is the ratio of the permeation rates (P) of a composite membrane to two gasesEthylbenzene production/PN2) The test results are shown in Table 3.
Table 3: ethylbenzene and N2Permeability rate and permselectivity
Figure BDA0002838813240000071
Comparative example:
(1) preparation of pure Pebax membranes: accurately weighing 3.0g of PebaxMH1657 particles, placing the particles in a round bottom flask, adding 14mL of ethanol and 6mL of deionized water into the flask, placing the flask in an oil bath kettle at 80 ℃, heating and stirring for 12 hours until the particles are completely dissolved, placing another round glass culture dish with the diameter of 10cm on a completely horizontal table top of a fume hood, slowly pouring the solution in the flask into the culture dish, standing for 72 hours, removing the film at the bottom of the culture dish by using tweezers after the solution is completely volatilized, and obtaining a round pure Pebax film with the diameter of 10cm, wherein the mass fraction of MIL-101(Cr) is 0%, placing the film in a clean culture dish, placing the culture dish in a vacuum oven at 60 ℃, and continuously vacuumizing for 24 hours while heating, so that the pure Pebax film material is completely activated.
(2) Characterization of pure Pebax membranes: scanning electron microscopy characterization of pure Pebax membranes and ethylbenzene/N2And (4) testing osmotic separation. When performing a permeation separation test, the productPutting the pure Pebax membrane into a mold of a permeation separation device, introducing air containing ethylbenzene for testing, and obtaining the permeation rate P of the membrane to two testing gases after the testing is finishedEthylbenzene production、PN2Permeability selectivity is the ratio of the permeation rates (P) of a pure Pebax membrane to two gasesEthylbenzene production/PN2) The test results are shown in Table 4.
Table 4: ethylbenzene and N2Permeability rate and permselectivity
Figure BDA0002838813240000081
In summary, the following steps:
FIG. 1 is the XRD diffraction pattern of the MIL-101(Cr) powder in examples 1-3, and comparing the simulated XRD diffraction patterns can find that the positions of the peaks in the synthesized pattern are consistent with the simulated standard pattern, which shows that we have successfully synthesized MIL-101 (Cr).
FIG. 2 is an SEM image of the MIL-101(Cr) powder of example 1-3, which shows that the particle size of the MIL-101(Cr) particles is about 200-300 nm.
FIG. 3 shows the MIL-101(Cr) powders obtained in examples 1-3 at 25 deg.C (298K) for ethylbenzene and N, respectively2From the adsorption isotherm plot of (A), it can be seen that the affinity of MIL-101(Cr) for ethylbenzene is much stronger than that of N at this temperature2。
FIG. 4 is the XRD spectra of different types of MIL-101@ Pebax films prepared in examples 1-3, and by comparing the XRD diffraction spectra of different types of films and simulated XRD diffraction spectra, the characteristic peak of MIL-101(Cr) appears in the XRD spectra of the composite films, which shows that MIL-101(Cr) particles are successfully loaded in the Pebax films, the intensity of the characteristic peak of MIL-101(Cr) increases with the increase of doping concentration, and the crystal structure of MIL-101(Cr) is not damaged in the film forming process.
FIG. 5 is a front scanning electron micrograph of a pure Pebax film in a comparative example and different types of composite films made in examples 1-3. The composite film was found to be rough in surface with different sized particulate matter, presumably the incorporated MIL-101(Cr) particles. Fig. 5(a) is a comparative example, fig. 5(b) is example 1, fig. 5(c) is example 2, and fig. 5(d) is example 3.
FIG. 6 shows the p-ethylbenzene/N ratios of different types of composite membranes of examples 1-3 at a test temperature of 25 deg.C, a pressure difference of 0.05MPa between the two sides of the membranes, and an ethylbenzene concentration of 1000ppm2Comparative permeation performance of (c). From the figure, the MIL-101@ Pebax composite membrane p-ethylbenzene/N with different MOF doping amounts can be seen2There is a certain selectivity. With the increase of the MIL-101(Cr) doping amount, the permeation rate of the ethylbenzene is increased, and the permeation selectivity is increased.
In order to determine the doping amount of MIL-101 in the composite membrane, the prepared composite membrane can show more excellent ethylbenzene/N2Separation performance pure Pebax membranes, MIL-101 (5%) @ Pebax, MIL-101 (10%) @ Pebax, MIL-101 (20%) @ Pebax, respectively, without and with a doping amount of 5%, 10%, 20% MIL-101(Cr) were prepared according to the conditions in Table 1.
Table 5: composition conditions of different composite membranes
Figure BDA0002838813240000091
It can be seen that the separation and recovery of organic vapors from waste gas streams using membranes made in accordance with the present invention is an efficient and safe process with the advantages of no pollution, convenient operation and low energy consumption.
The invention relates to relevant test conditions and methods:
x-ray photoelectron diffraction (XRD) spectrum: the XRD test used was an XRD-6000X-ray diffractometer from Shimadzu corporation, Japan. And (3) adopting a Cu emission field, wherein the scanning 2theta range is 5-45 degrees.
Scanning Electron Microscope (SEM) photograph: the SEM used a SU8010 field emission scanning electron microscope from Hitachi, Japan.
Ethylbenzene vapor adsorption isotherm diagram: the vapor adsorption was performed using a 3H-2000PW multistation gravimetric vapor adsorption analyzer from Beijing Bethesed instruments.
N2Adsorption isotherm diagram: n is a radical of2Adsorption used was an ASAP2460 surface area and pore size analyzer from shanghai macrmericek instruments.
In the gas separation test, an SPG-AT01VOC generator (containing a precision injector) of Arois, Suzhou is used for generating ethylbenzene steam, mixed gas of the ethylbenzene steam and air enters a membrane module under the control of a flowmeter, and the pressure difference between two ends of the membrane module is controlled by a backpressure valve AT an outlet end. The gas that permeates is collected by the gas sampling bag, gets into gas chromatography and inspects various gas content in order to confirm the separation effect, and tail gas absorbs or the condensation is retrieved.
Gas Chromatography (GC) analysis: GC-7890B gas chromatograph from Agilent technologies, USA and A91Plus high-end laboratory gas chromatograph from Tokya.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (6)

1. A preparation method of mixed matrix membrane material, which is prepared by mixing MIL-101(Cr) as organic particle additive with Pebax and ethanol/water solvent, is characterized in that the preparation method comprises the following steps:
step S1: firstly, dissolving terephthalic acid and chromium nitrate nonahydrate in deionized water, adding a certain amount of benzoic acid to obtain a mixed solution, stirring and carrying out ultrasonic treatment for 30min, and sealing in a reaction kettle with a polytetrafluoroethylene lining;
step S2: placing the sealed mixed solution in the S1 in a 220 ℃ oven, continuously reacting for 8h, synchronously setting a program for cooling, slowly cooling the oven to room temperature at a cooling rate of 25 ℃/h after 8h, filtering and collecting a generated solid product;
step S3: repeatedly washing and filtering the solid product obtained in the step S3 by using deionized water for 3 times, placing the solid product into a glass bottle with a cover, adding 18-22mL of anhydrous methanol, stirring for 15min, standing for 8h, repeating the process for 3 times, and filtering again to collect the generated precipitate;
step S4: drying the precipitate obtained in the step S3 in a 120 ℃ forced air drying oven for 12h to obtain MIL-101(Cr) crystals with the size of 200-300 nm;
step S5: weighing 0.15-0.6 g of MIL-101(Cr) prepared in the step S4, placing the MIL-101(Cr) in a mortar, grinding for 20min, placing in a glass bottle, sequentially pouring 14mL of ethanol and 6mL of deionized water, stirring at a constant speed for 30min, carrying out ultrasonic treatment for 10min, repeating the above process for 5 times, and continuously stirring at a constant speed for 12h to obtain an MOF dispersion liquid;
step S6: 2.4-2.85 g of Pebax MH1657 particles are weighed and placed in a round bottom flask, 35mL of ethanol and 15mL of deionized water are added into the flask, the flask is placed in an oil bath kettle at 80 ℃, and the mixture is heated and stirred for 12 hours until the mixture is completely dissolved. Dropwise transferring the MOF dispersion liquid in the step S5 into a flask, and continuously heating and stirring for 6 hours until the dispersion is uniform;
step S7: placing a circular glass culture dish with the diameter of 10cm on a completely horizontal fume hood table top, slowly pouring the solution prepared in the flask in the step S6 into the culture dish, standing, and taking off the film at the bottom of the culture dish by using tweezers after the solution is volatilized, thus obtaining a circular film with the diameter of 10 cm;
step S8: and (4) placing the circular film in the step S7 in a vacuum oven at 60 ℃, heating and continuously vacuumizing for 24h at the same time, and finishing the activation of the MIL-101@ Pebax film material.
2. The method of claim 1 for preparing a mixed matrix membrane material, wherein: in the step S1, the mass usage amount of the terephthalic acid is 0.8-1.2 g.
3. The method of claim 1 for preparing a mixed matrix membrane material, wherein: in step S1, the mass ratio of the terephthalic acid, the chromium nitrate nonahydrate, the deionized water and the benzoic acid is 1 (2-2.5): (30-50): 2-2.5).
4. The method of claim 1 for preparing a mixed matrix membrane material, wherein: in the step S4-6, the mass ratio of MIL-101(Cr) to Pebax is 1 (4-19).
5. The method of claim 1 for preparing a mixed matrix membrane material, wherein: the mass ratio of the ethanol to the deionized water in the step S6 is 7: 3.
6. The method of claim 1 for preparing a mixed matrix membrane material, wherein: and in the step S7, the standing time of the solution in the culture dish is 68-72 hours.
CN202011483840.XA 2020-12-16 2020-12-16 Preparation method of mixed matrix membrane material Pending CN112755801A (en)

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