CN114632430B - Covalent organic polymer material nanosheet composite matrix membrane for gas separation and preparation method thereof - Google Patents
Covalent organic polymer material nanosheet composite matrix membrane for gas separation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a covalent organic polymer material nanosheet composite matrix membrane for gas separation and a preparation method thereof. The method comprises the following steps: (1) Preparing a series of covalent organic polymer nanosheets with 1,3, 5-triacyl phloroglucinol as a central monomer by a solvothermal method; (2) Doping a covalent organic polymer nanosheet material into a high molecular polymer, and preparing a composite membrane liquid, wherein the high molecular polymer is polysulfone, polyimide, polyamide and polyvinylidene fluoride; (3) Preparing a self-supporting composite matrix film material by adopting a blade coating method; and (4) drying the composite membrane. The preparation process has high repeatability, and the obtained membrane material has high stability, high gas permeation and high selectivity.
Description
Technical Field
The invention belongs to the field of membrane separation, and relates to a covalent organic polymer material nanosheet composite matrix membrane for gas separation and a preparation method thereof.
Background
CO resulting from burning fossil fuels in large quantities in industrial production 2 Excessive emission of tail gas and resulting global temperature rise destroy ecosystem are one of common problems facing people all over the world. The membrane separation method has the advantages of low energy consumption, environmental friendliness, simplicity in operation, high mechanical/thermal/chemical stability and the like, and is widely applied to the field of gas separation. Using membrane material to remove CO 2 From mixed gases with H 2 、N 2 、CH 4 And hydrocarbon and other components, and has great practical significance in the domestic production processes of gas purification before production, tail gas treatment after production, gas transportation, tertiary oil recovery and the like.
For CO 2 The membrane materials for separation and capture can be classified into three major groups according to the difference of components: porous inorganic membrane material and compact organic polymerMembrane materials and composite matrix membrane materials. Wherein the porous inorganic film is on CO 2 The gas has high permeability and selectivity and good chemical stability, but the preparation process is complex, the cost is high, the repeatability is poor, and the gas is difficult to be widely applied. Most organic membranes are in CO 2 The selectivity and permeability of the gas show a tendency to trade off, the separation effect is difficult to break through the limit of the upper Robinson limit, and the CO is simultaneously 2 The plasticizing phenomenon greatly reduces the gas selectivity of the organic film. The composite matrix membrane is a gas separation membrane formed by mutually compounding inorganic/organic materials and a polymer matrix, and the membrane material has the inherent pore screening characteristic of a porous doped phase, also has the advantages of easy processing, high mechanical strength and the like of the polymer, and has great commercialization potential.
The covalent organic polymer material is a novel crystalline state nano-porous material formed by periodically connecting different organic functional groups, has the characteristics of high specific surface, polyfunctional groups, designable structure, good stability and the like, and is CO 2 The ideal material for adsorption and separation has considerable prospect for industrial synthesis. Due to the rigid skeleton and stable physicochemical properties of the covalent organic framework material, the homogeneous pure phase membrane material is difficult to synthesize. The full organic framework characteristic of the covalent organic framework material can enhance the affinity of the covalent organic framework material and the continuous polymer matrix phase, and the affinity is favorable for eliminating non-selective gaps between the matrix material and the filling material in the mixed matrix membrane and improving the separation efficiency of the gas separation membrane. Thus, covalent organic framework materials are an excellent choice for gas separation composite membrane packing. Zhao Dan et al in 2016 doped nanosheets of two covalent organic framework materials (NUS-2, NUS-3) into a chain-like organic polymer
And &>
The obtained composite membrane has certain gas separation effect and low permeability (CO) 2 Less than 20 Barrer). Gascon et al general chemical formula ACOF-1 powder and Polymer>
5218 doping to prepare composite membrane material, CO of composite gas separation membrane doped with ACOF-1, compared with pure polymer membrane 2 Permeability is doubled, but CO 2 /CH 4 The selectivity increase is not significant. Therefore, the composite membrane prepared by doping the covalent organic framework material and the high molecular polymer material has good research and development prospects in the aspect of improving the gas separation and permeation effects. Tp series covalent organic polymer materials are: a series of crystalline microporous materials prepared by condensation of 1,3, 5-triacyl phloroglucinol (Tp) and diamine monomer through Schiff base reaction are hopeful to be used in CO due to the amino groups with higher density on the structural framework 2 The application and development of the field of adsorption and separation membrane materials. />
Disclosure of Invention
The invention aims to provide a covalent organic polymer material doped composite membrane and a preparation method thereof.
The invention provides a preparation method of a covalent organic polymer material nanosheet composite matrix membrane for gas separation, which comprises the following steps:
(1) Preparation of covalent organic polymeric materials:
a trialdehyde monomer (1, 3, 5-trimethyloylphloroglucinol (Tp)) and a diamine monomer (selected from hydrazine (Hz), p-phenylenediamine (Pa-1), 2, 5-dimethyl-1, 4-phenylenediamine (Pa-2) and o-nitro-p-phenylenediamine (Pa-NO) 2 ) 2,4,5, 6-tetrafluoro-1, 3-phenylenediamine (TpPa-F) 4 ) Benzidine (BD), o-tolidine (BD-Me) 2 ) Dianisidine (BD- (OMe) 2 ) Dinitrobenzidine (BD- (NO) 2 ) 2 ) And one of p-diaminoazobenzene (Azo) to generate a covalent organic polymer material (two-dimensional layered covalent compound precursor material);
wherein the mass ratio of the trialdehyde monomer to the diamine monomer is 2:3, performing Schiff base reaction by using an ammonia pump method, taking 1, 4-dioxane and 1,3, 5-trimethylbenzene as solvents, taking acetic acid as a catalyst, and reacting at the temperature of 120-140 ℃ for 72-96 hours;
the total amount of the solvent (1, 4-dioxane and 1,3, 5-trimethylbenzene) is not critical as long as the raw materials (the trialdehyde monomer and the diamine monomer) can be dispersed, wherein the volume ratio of the 1, 4-dioxane to the 1,3, 5-trimethylbenzene is 1.
Preferably, the concentration of the catalyst acetic acid is 3mol/L, and the volume ratio of the 1, 4-dioxane, the 1,3, 5-trimethylbenzene and the acetic acid is 3.
Washing and drying the product to obtain a two-dimensional layered covalent compound precursor material; wherein the washing of the product comprises washing with tetrahydrofuran, methanol and acetone respectively, and soxhlet extraction washing with ethanol and dichloromethane.
The covalent organic polymeric material prepared by the above method is selected from: tpPa-1 (doi: 10.1021/ja308278 w), tpPa-2 (doi: 10.1021/ja308278 w), NO 2 -TpPa(doi：10.1021/ja408121p)，TpHz(doi：10.1002/chem.201501206)，TpPa-F 4 ，TpBD，TpBD-Me 2 ，TpBD-(OMe) 2 ，TpBD-(NO 2 ) 2 And TpAzo (doi: 10.1039/c5ta07998 e).
The covalent organic polymeric material is most preferably TpPa-2.
(2) Preparation of covalent organic polymeric material nanosheets:
mixing the covalent organic polymer material with an organic solvent a, and then carrying out ball milling to obtain a nanosheet-organic solvent mixed system uniform dispersion liquid; and freeze-drying the nanosheet mixed dispersion liquid to obtain covalent organic polymer nanosheet powder.
Wherein the mass ratio of the covalent organic polymer material to the organic solvent a is 1: 10-1: 100.
preferably, the ball milling speed is 30-300 r/min, and the ball milling time is 30-200 min.
Preferably, the organic solvent a is selected from alcohols, ethers, esters, aromatic hydrocarbons or their mixed solvents, preferably methanol, ethanol,One or a mixed solvent of n-propanol, isopropanol, n-butanol, isoamyl alcohol, ethyl acetate, acetone, chloroform, dimethyl sulfoxide and tetrahydrofuran; most preferred are dimethyl sulfoxide (TpPa-2) and n-butanol (NO) 2 TpPa), ethyl acetate (TpPa-1 and TpHz);
preferably, the method also comprises a separation step after ball milling, and the nanosheet-organic solvent mixed system uniform dispersion liquid is obtained by standing separation or centrifugal separation. The standing separation is to stand the ball-milled system for 4 hours to 1 month, preferably 72 hours to 1 month. The centrifugal separation operation parameters comprise: the centrifugal speed is 500-900 r/min, and the centrifugal time is 30-90 min.
Preferably, the nanosheet mixed dispersion is subjected to liquid nitrogen treatment, then vacuum freeze-dried at the temperature of-70 ℃ to-20 ℃ (vacuum pressure is 0.002-0.2 mbar), the freeze-dried powder is subjected to soxhlet extraction with ethanol for 36-48 hours, and then vacuum drying is carried out at 120 ℃ for 48-72 hours;
(3) Preparing a composite membrane liquid:
the selected organic high molecular material (high molecular polymer material) is one of polysulfone, polyimide (6 FDA-DAM), polyamide and polyvinylidene fluoride, the high molecular polymer material and the organic solvent b are mixed according to the mass ratio of 2-30 wt% of the high molecular material, and the mixture is uniformly dispersed under 30-1000 watts for 1-30 minutes by ultrasonic waves to obtain a mixed solution of the high molecular polymer material and the organic solvent b; selecting the Tp series (TpPa-1, tpPa-2 2 -TpPa、TpHz、TpPa-F 4 、TpBD、TpBD-Me 2 、TpBD-(OMe) 2 、TpBD-(NO 2 ) 2 And TpAzo nanosheet) material, wherein the mass ratio of the covalent organic polymer nanosheet material powder to the high molecular polymer material is 0.05-30 wt%, preferably 1:50 to 1:10 (the doping amount of the covalent organic polymer nanosheet material powder is 2wt% -10 wt%) is added into the mixed solution of the high molecular polymer material and the organic solvent b which are uniformly mixed, the mixture is uniformly mixed by ultrasonic for 1-30 minutes under 30-1000 watts, and then the mixture is stirred for 12 hours and then is kept stand for 12-24 hours;
wherein the organic solvent b is one of N, N-Dimethylformamide (DMF), N-methylpyrrolidone, trichloromethane, toluene, ethanol and methanol, preferably DMF;
preferably, the high molecular polymer material and the organic solvent b are mixed according to the mass ratio of the high molecular polymer material of 5-30 wt%;
preferably, the stirring speed is 500 to 1000rpm, preferably 700rpm.
(4) Preparation of covalent organic polymer nanosheet composite membrane
Taking a proper amount of the composite membrane liquid prepared in the step (3), uniformly coating the composite membrane liquid on a proper position in front of a scraper, adjusting the running speed of the scraper and the temperature of a heating platform until the substrate (a silicon wafer, a ceramic wafer, a stainless steel sheet, a glass sheet or a mica sheet) scrapes out a uniform composite membrane material, and exchanging a solvent to obtain a transparent self-supporting composite membrane (a covalent organic polymer nano-sheet composite membrane);
wherein the height of the scraper is 50-500 mu m; film making parameters, namely the speed of a scraper is 3-21 mm/s, and the temperature of a heating table is 50-120 ℃; the solvent used for solvent exchange is one of water, methanol, ethanol and acetone.
(5) And (3) drying the film:
the composite membrane material (transparent self-supporting composite membrane) is dried in vacuum at 120 ℃ for 48 to 96 hours, taken out and put into a dryer for storage and standby.
The invention also relates to a covalent organic polymer material nanosheet composite matrix membrane prepared by the method, which is a planar self-supporting membrane with the thickness of 10-100 microns and can be applied to various carriers and different environments.
Another aspect of the present invention is to provide the use of the above covalent organic polymer material nanosheet composite matrix membrane in gas separation.
Has the advantages that: the invention provides a preparation method of Tp series covalent organic polymer composite matrix membrane material, firstly preparing a series of covalent organic polymer nanosheet materials with 1,3, 5-triacyl phloroglucinol as a central monomer by a solvothermal method; doping the covalent organic polymer nano sheet material into a high molecular polymer to prepare a composite membrane liquid; then, preparing a self-supporting composite matrix membrane material by adopting a blade coating method; and finally drying the composite membrane. The preparation operation is simple and efficient, the application range is wide, the repeatability is high, and the obtained membrane material has high stability and excellent gas permeation, selectivity and separation performance.
Drawings
The invention is shown in the attached figure 5, which respectively comprises the following components:
FIG. 1 is an X-ray diffraction pattern of a Tp series covalent organic polymer material nanosheet synthesized in example 1;
FIG. 2 is a scanning electron micrograph of Tp series covalent organic polymeric material nanosheets synthesized in example 1;
FIG. 3 is a scanning electron microscope photograph of the surface of the composite film prepared in example 2;
FIG. 4 is a scanning electron micrograph of a cross section of the composite film prepared in example 2;
FIG. 5 is a graphical representation of the gas separation performance of the composite membrane prepared in example 2.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
EXAMPLE 1 preparation of covalent organic Polymer Material TpPa-2
31 mg of 1,3, 5-trialdehyde phloroglucinol (Tp) and 30 mg of 2, 5-dimethyl-1, 4-phenylenediamine (Pa-2) powder were charged into a Pyrex tube. 1.5 ml of 1, 4-dioxane and 1,3, 5-trimethylbenzene were added as solvents. 0.5 ml of 3mol/l acetic acid was added as catalyst. The mixture was mixed well after 10 minutes of sonication at 300W. And then putting the pyrex glass tube into a liquid nitrogen bath for freezing, switching on a vacuum oil pump for pumping after the liquid in the tube is solidified, and then taking the sample tube out of the liquid nitrogen bath for waiting for the liquid to be melted, wherein the freeze-pump-melt cycle needs to be carried out for three times. And (3) putting the vacuum sealed sample tube into an oil bath at 120 ℃ for heating for 72 hours to obtain dark red powder. The powder is washed by tetrahydrofuran, methanol and acetone respectively, soxhlet extraction and washing are carried out on ethanol and dichloromethane, and the powder is dried for 12 hours at the temperature of 120 ℃ in vacuum to obtain the TpPa-2.
And dispersing 10 mg of the prepared TpPa-2 powder in 100 ml of ethyl acetate solution, sealing in a ball milling tank with the volume of 500 ml, and carrying out ball milling for 1 hour at the rotating speed of 60 r/min to obtain the TpPa-2 nanosheet dispersion liquid. The ethyl acetate dispersion of the nanoplatelets was then removed and allowed to stand for 15 days to remove the large unpeeled particles. Treating the TpPa-2 nanosheet-ethyl acetate mixed dispersion liquid with liquid nitrogen, carrying out vacuum freeze-drying at-55 ℃ (vacuum pressure is 0.002-0.2 mbar), soxhlet extracting the freeze-dried powder with ethanol for 48 hours, and then carrying out vacuum drying at 120 ℃ for 72 hours to obtain TpPa-2 nanosheet powder;
x-ray diffraction confirmed the product to have a crystalline structure (as in fig. 1), and the scanning electron microscope pictures showed the product to have a particle size in the micrometer range with a flake morphology (as in fig. 2).
Comparative example 16 FDA-DAM high molecular polymer membrane material preparation
Preparing 5 ml of DMF solution with the mass fraction of 20% from 0.47g of 6FDA-DAM polymer powder, uniformly mixing under the condition of 300W ultrasonic water bath, magnetically stirring at 700rpm for 24 hours, continuously uniformly mixing, and standing the mixed membrane solution for 12 hours at room temperature to discharge air bubbles;
placing a scraper on a smooth silicon wafer (20 x 20cm), coating 5 ml of membrane liquid in the front of the advancing direction of the scraper, setting the temperature of a heating table at 80 ℃, and setting the advancing speed of the scraper at 20mm/s;
after DMF in the film liquid on the silicon chip is completely volatilized, the silicon chip is placed in deionized water to be soaked for 5 minutes for solvent exchange, and the membrane can fall off from the silicon chip in the deionized water to form a transparent self-supporting film;
the high molecular polymer membrane can be subjected to a gas separation experiment after vacuum drying at 120 ℃ for 48 hours.
Example 2 preparation of composite mechanism membrane material of TpPa-2 nanosheet and 6FDA-DAM
Preparing 5 ml of DMF solution with the mass fraction of 20% from 0.47g of 6FDA-DAM polymer powder, uniformly mixing for 30 minutes under the condition of 300W ultrasonic water bath, adding the TpPa-2 nanosheet powder prepared in the example 1 into the mixed solution, magnetically stirring at 700rpm for 24 hours, uniformly mixing, and standing the mixed membrane solution for 12 hours at room temperature to discharge air bubbles;
placing a scraper on a smooth silicon wafer (20-20 cm/20 cm), coating 5 ml of membrane liquid in the advance direction of the scraper, setting the temperature of a heating table at 80 ℃, and setting the advance speed of the scraper at 20mm/s;
after DMF in the film liquid on the silicon chip is completely volatilized, the silicon chip is placed in deionized water to be soaked for 5 minutes for solvent exchange, and the membrane can fall off from the silicon chip in the deionized water to form a transparent self-supporting film;
the composite matrix membrane can be subjected to a gas separation experiment after vacuum drying at 120 ℃ for 48 hours.
The scanning electron microscope pictures show that the composite film has a relatively uniform surface and a thickness of about 10-20 μm (see fig. 3 and 4).
Example 3 gas separation Performance of 6FDA-DAM Polymer Membrane and TpPa-2 nanosheet-6 FDA-DAM composite matrix Membrane
The membranes prepared in comparative example 1 and example 2 were subjected to a gas separation test at room temperature with a pressure difference of 1mpa between both sides of the membrane 2 ，CO 2 ，N 2 ，CH 4 As shown in fig. 5 and the following table, it can be seen that the composite membrane doped with TpPa-2 nanosheets has higher permeability and separation effect compared to the membrane prepared from pure polymer material.
| CO 2 Penetration quantity (Barrer) | CH 4 Penetration amount (Barrer) | CO 2 /CH 4 Selecting the separation ratio | |
| High molecular polymer film | 671.3 | 29.3 | 22.9 |
| Composite matrix membrane | 1126.7 | 43 | 26.2 |
Claims (3)
1. Covalent organic polymer material composite matrix membrane in CO 2 /CH 4 The application in separation is characterized in that the thickness of the covalent organic polymer material composite matrix membrane is 10 to 100 mu m, and the preparation method of the covalent organic polymer material composite matrix membrane comprises the following steps:
(1) Preparation of covalent organic polymeric materials
Using acetic acid as a catalyst, 1, 4-dioxane and 1,3, 5-trimethylbenzene as solvents, and reacting a trialdehyde monomer with a diamine monomer to generate a covalent organic polymer material;
wherein the trialdehyde monomer is 1,3, 5-triacyl phloroglucinol, the diamine monomer is one of hydrazine, p-phenylenediamine, 2, 5-dimethyl-1, 4-phenylenediamine, o-nitro-p-phenylenediamine, 2,4,5, 6-tetrafluoro-1, 3-phenylenediamine, benzidine, o-tolidine, dianisidine, dinitrobenzidine and p-diaminoazobenzene, and the mass ratio of the trialdehyde monomer to the diamine monomer is 2:3, the reaction temperature is 120-140 DEG o C, the reaction time is 72-96 hours;
(2) Preparation of covalent organic polymeric material nanosheets
Mixing the covalent organic polymer material obtained in the step (1) with an organic solvent a, and then carrying out ball milling to obtain a nanosheet-organic solvent mixed system uniform dispersion liquid; then, freeze-drying the nanosheet mixed dispersion liquid to obtain covalent organic polymer nanosheet powder;
wherein the organic solvent a is selected from alcoholsEthers, esters, aromatic hydrocarbons or mixed solvents thereof; the mass ratio of the covalent organic polymer material to the organic solvent a is 1:10 to 1:100, respectively; the ball milling speed is 30 to 300 revolutions per minute, and the ball milling time is 30 to 200 minutes; the freeze-drying conditions are as follows: -70 o C ~ -20 o C, vacuum freeze-drying, wherein the vacuum pressure is 0.002 to 0.2 mbar;
(3) Preparation of composite membrane liquid
Uniformly mixing a high-molecular polymer material and an organic solvent b, adding the covalent organic polymer nanosheet powder obtained in the step (2), uniformly mixing, and standing for 12-24 hours to obtain a composite membrane liquid;
wherein the high molecular polymer material is one of polysulfone, polyimide, polyamide and polyvinylidene fluoride; the organic solvent b is one of N, N-dimethylformamide, N-methylpyrrolidone, trichloromethane, toluene, ethanol and methanol; the mass ratio of the high-molecular polymer material to the organic solvent b is 2-30%; the mass ratio of the covalent organic polymer material nanosheet powder to the high molecular polymer material is 0.05% -30%;
(4) Preparation of covalent organic polymer nanosheet composite membrane
Scraping the composite membrane liquid obtained in the step (3) on a substrate to obtain a composite membrane material by adopting a scraping method under a heating condition, and exchanging a solvent to obtain a covalent organic polymer nanosheet composite membrane;
wherein the solvent used for solvent exchange is one of water, methanol, ethanol and acetone; the speed of the scraper is 3-21 mm/s, and the heating temperature is 50-120 o C；
(5) Dry film
The covalent organic polymer nano-sheet composite film obtained in the step (4) is placed at 120 o And C, vacuum drying for 48-96 hours.
2. The use according to claim 1, wherein in the step (2), the organic solvent a is selected from one or a mixture of methanol, ethanol, n-propanol, isopropanol, n-butanol, isoamyl alcohol, ethyl acetate, acetone, chloroform, dimethyl sulfoxide and tetrahydrofuran.
3. The use according to claim 1, wherein in step (4), the height of the scraper is 50-500 μm; the substrate is a silicon wafer, a ceramic wafer, a stainless steel sheet, a glass sheet or a mica sheet.
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