CN112354381B - 'full polyimide' mixed matrix gas separation membrane and preparation method and application thereof - Google Patents
'full polyimide' mixed matrix gas separation membrane and preparation method and application thereof Download PDFInfo
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- B01D71/06—Organic material
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- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a full polyThe hyperbranched microporous polyimide used in the invention has the advantages of high specific surface area, acid resistance and heat resistance, and is suitable for natural gas separation in high-temperature and acid environments, and compared with the existing inorganic particle modified mixed matrix membrane, the hyperbranched microporous polyimide can effectively improve the compatibility of two phases, thereby reducing the defect of nonselectivity between interfaces caused by the phase separation of the continuous phase and the dispersed phase and improving the selectivity of the mixed matrix gas separation membrane 2 /CH 4 、CO 2 /N 2 、H 2 /CO 2 、H 2 /CH 4 、O 2 /N 2 Can maintain selectivity while increasing permeability coefficient.
Description
Technical Field
The invention belongs to the field of membrane separation in gas separation, and particularly relates to a mixed matrix membrane and application thereof in CO (carbon monoxide) 2 /CH 4 、CO 2 /N 2 、H 2 /CO 2 、H 2 /CH 4 、O 2 /N 2 Use in separation.
Background
Syngas separation (H) 2 /CO 2 ) Separation of natural gas and biogas (CO) 2 /CH 4 ) Is a problem to be solved urgently in industry. In addition, hydrogen purification and recovery (H) 2 /CH 4 ) Thermal power plant flue gas emission Control (CO) 2 /N 2 ) Air separation (O) 2 /N 2 ) And the like are all the contents of the invention of the project worthy of study. The membrane separation method is a means for enriching a certain gas in a mixed gas according to the difference of the transmission permeability of different gases in a membrane material. As a novel gas separation technology, the membrane separation has the advantages of low energy consumption, simple equipment, normal-temperature continuous operation, easy amplification of the process and the like, and is very efficient in specific gas separation. The membrane material is of course the core of membrane separation technology, classified according to the membrane material,there are inorganic membrane, polymer membrane and mixed matrix membrane.
The mixed matrix membrane prepared by adding the porous inorganic particles into the polymer matrix has the advantages of high flux of the inorganic membrane and high selectivity of the polymer membrane, but besides the performances of the polymer and the inorganic filler, the transmission process of gas in the mixed matrix membrane is influenced by the compatibility between the matrix and the filler and interface defects.
Disclosure of Invention
In order to solve the above problems, it is an object of the present invention to provide a "full polyimide" mixed matrix gas separation membrane, in which both phases are polyimide, which solves the compatibility problem in conventional mixed matrix membranes.
Another object of the present invention is to provide a method for preparing the above-mentioned "all polyimide" mixed matrix gas separation membrane.
It is also an object of the present invention to apply the above-mentioned "all polyimide" mixed matrix gas separation membrane to CO 2 /CH 4 、CO 2 /N 2 、H 2 /CO 2 、H 2 /CH 4 、O 2 /N 2 Separation of (4).
In order to achieve the above object, the object of the present invention is achieved by: a method for preparing a 'full polyimide' mixed matrix gas separation membrane is characterized in that: the mixed matrix gas separation membrane is prepared by adopting hyperbranched microporous polyimide as a dispersion phase and a polyimide continuous phase.
The 'full polyimide' mixed matrix gas separation membrane prepared by the preparation method.
The 'full polyimide' mixed matrix gas separation membrane is used in CO 2 /CH 4 、CO 2 /N 2 、H 2 /CO 2 、H 2 /CH 4 、O 2 /N 2 Use in separation.
The beneficial effects of the invention are as follows: the hyperbranched microporous polyimide used in the invention has the advantages of high specific surface area, acid resistance and heat resistance, is suitable for natural gas separation in high-temperature and acid environments, and the disperse phase and the continuous phase are polyimideCompared with the existing inorganic particle modified mixed matrix membrane, the amine mixed matrix membrane can effectively improve the compatibility of two phases, thereby reducing the defect of nonselectivity between interfaces caused by the phase separation of a continuous phase and a disperse phase and improving the selectivity of a mixed matrix gas separation membrane 2 /CH 4 、CO 2 /N 2 、H 2 /CO 2 、H 2 /CH 4 、O 2 /N 2 Can maintain selectivity while increasing permeability coefficient.
Drawings
FIG. 1 shows the N at 77K of the hyperbranched microporous polyimide in example 1 of the present invention 2 Adsorption isotherms, the abscissa being the relative pressure and the ordinate being the adsorption capacity.
FIG. 2 is a Scanning Electron Microscope (SEM) cross-section view of a two-step chemical imide process for preparing an "all polyimide" mixed matrix membrane in example 1 of the present invention.
FIG. 3 is a two-step chemical imide process for preparing "all polyimide" mixed matrix films thermo-gravimetric analysis (TGA) in example 1 of this invention with temperature on the abscissa and mass fraction on the ordinate.
FIG. 4 is a SEM cross-sectional view of a two-step chemical imide process for preparing an "all polyimide" mixed matrix membrane in example 2 of the present invention.
FIG. 5 is a TGA graph of a two-step chemical imide process for preparing "all polyimide" mixed matrix films according to example 2 of the present invention with temperature on the abscissa and mass fraction on the ordinate.
FIG. 6 is an SEM image of the cross section of a mixed matrix membrane made of "all polyimide" by the two-step thermal imide method in example 3 of the present invention.
FIG. 7 is a TGA graph of a two-step thermal imide process for preparing a "full polyimide" mixed matrix film in example 3 of the present invention with temperature on the abscissa and mass fraction on the ordinate.
FIG. 8 is a SEM image of a cross section of a pure membrane prepared by the two-step chemical imide method in comparative example 1.
FIG. 9 is an SEM image of a cross section of a pure membrane prepared by the two-step thermal imide method in comparative example 2.
Detailed Description
The invention relates to a preparation method of a 'full polyimide' mixed matrix gas separation membrane, which is prepared by adopting hyperbranched microporous polyimide as a dispersed phase and a polyimide continuous phase. Preferably the following specific steps:
step (1): the hyperbranched microporous polyimide disperse phase is synthesized by a one-step method: dissolving triamine or tetramine monomer and dianhydride monomer (amine and anhydride are equal molar ratio) in high boiling point solvent, adding catalyst, making temperature programmed reaction, then making precipitation, filtering and soxhlet extraction so as to obtain the invented hyperbranched microporous polyimide dispersed phase powder. The temperature-programmed reaction is preferably: reacting at 30-60 deg.C for 80-150min, at 70-100 deg.C for 80-150min, at 110-150 deg.C for 10-15h, at 150-180 deg.C for 80-150min, and at last at 190-210 deg.C for 5-15h; most preferably: reacting at 50 ℃ for 2h, at 80 ℃ for 2h, at 120 ℃ for 2h, at 160 ℃ for 2h, and finally at 200 ℃ for 8h.
More preferably, the total mass percent concentration of the triamine or tetramine monomer and the dianhydride monomer in the high boiling point solvent is 10-30%.
More preferably, the BET specific surface area of the hyperbranched microporous polyimide is 400-1000m 2 /g。
More preferably, the high boiling point solvent is one or more of m-cresol (m-cresol), N-methyl pyrrolidone (NMP), 1,3, 5-trimethylbenzene (mesitylene) and imidazole; the catalyst is one or more than two of pyridine, isoquinoline and triethylamine.
More preferably, the triamine or tetramine monomer has one or more structures as follows:
the dianhydride monomer is one or more of the following structures:
most preferably, the dianhydride is pyromellitic dianhydride (PMDA). Most preferably, the solvent is a mixed solvent of NMP: mesitylene = 1.
Step (2): the polyimide continuous phase is prepared by a two-step method, which is divided into chemical imidization or thermal imidization, wherein: the chemical imidization is to take equivalent diamine monomer and dianhydride monomer to dissolve in solvent, then react for 8-24h at-5-10 ℃ to prepare polyamide acid Precursor (PAA), after the room temperature is recovered, catalyst and dehydrating agent are added to react for 4-12h to form polyimide, and polyimide continuous phase is obtained through precipitation, filtration and Soxhlet extraction; the thermal imidization is to add equivalent diamine monomer and dianhydride monomer into a reaction kettle with a water separator to be dissolved in a solvent, then react for 8-24h at-5-10 ℃ to prepare polyamide acid Precursor (PAA), restore the room temperature, then add catalyst and toluene, react for 4-12h at 180-200 ℃ to form polyimide, and obtain the polyimide continuous phase through precipitation, filtration and Soxhlet extraction.
More preferably, in the chemical imidization or thermal imidization, the total mass percentage concentration of the diamine monomer and the dianhydride monomer in the solvent is 10 to 30%.
More preferably, the polyimide is one or more of the following structures:
wherein n =100-3000.
More preferably, the solvent is one or more of chloroform, N' -Dimethylformamide (DMF), m-cresol (m-cresol) and N-methylpyrrolidone (NMP), the catalyst is one or more of pyridine, isoquinoline and triethylamine, and the dehydrating agent is acetic anhydride.
Most preferably, in chemical imidization, the dianhydride monomer is hexafluoro dianhydride (6 FDA), the diamine is tetramethyl-p-phenylenediamine (Durene), and the solvent is DMF; in the thermal imidization, the dianhydride monomer is hexafluorodianhydride (6 FDA), the diamine is 4,4' -diaminodiphenyl ether (ODA), and the solvent is NMP.
In the precipitation in the steps (1) and (2), preferably, a poor solvent is added for precipitation after the system is cooled, and more preferably, the poor solvent is methanol.
The Soxhlet extraction in steps (1) and (2) uses methanol as a mobile phase.
And (3): dissolving a polyimide continuous phase in a solvent to prepare a casting solution with the solid content of 10-20wt%, adding a hyperbranched microporous polyimide dispersion phase, and uniformly dispersing by ultrasonic; after defoaming treatment, pouring the mixture on a dust-free glass plate, forming the mixture by a blade coating method, a tape casting method or a spin coating method, and drying the mixture until a solvent is volatilized to form the 'full polyimide' mixed matrix gas separation membrane.
Preferably, the load of the hyperbranched microporous polyimide dispersed phase in the 'full polyimide' mixed matrix gas separation membrane is 1-30wt%.
More preferably, the film thickness is 400-600 μm formed by blade coating, tape casting or spin coating, then the film is placed into a vacuum oven at 80-160 ℃ for drying until the solvent is volatilized, a 'full polyimide' mixed matrix gas separation film is formed, finally the film is automatically peeled off in deionized water, and the film is dried in a blast drying oven at 60-80 ℃ and has the film thickness of 10-80 μm.
The 'full polyimide' mixed matrix gas separation membrane prepared by the preparation method.
The 'full polyimide' mixed matrix gas separation membrane is used in CO 2 /CH 4 、CO 2 /N 2 、H 2 /CO 2 、H 2 /CH 4 、O 2 /N 2 Use in separation.
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
The present embodiment is a "full polyimide" mixed matrix gas separation membrane, which uses self-made hyperbranched microporous polyimide as a dispersed phase (tris (4-aminophenyl) amine (TAPA) as a monomer), and two-step chemical imidization self-made polyimide as a continuous phase, wherein the filling content of the dispersed phase is 5wt%. The preparation process comprises the following steps:
1) 0.40g TAPA and 0.45g PMDA were weighed into a three-necked flask with mechanical stirring. Adding 10ml of mixed solvent of N-methyl pyrrolidone and 1,3, 5-trimethylbenzene, adding 0.5ml of isoquinoline after complete dissolution, reacting at 50 ℃ for 2h, reacting at 80 ℃ for 2h, reacting at 120 ℃ for 2h, reacting at 160 ℃ for 2h, and finally reacting at 200 ℃ for 8h. And after the system is cooled, adding methanol for precipitation, filtering, performing Soxhlet extraction by using methanol, and drying to obtain brown powder-AP.
FIG. 1 shows AP 77K N 2 Adsorption, BET specific surface area: 520m 2 /g, pore volume (t plot method): 0.138cm 3 /g。
2) 1.64g of Durene was dissolved in 35ml of DMF, and then 6FDA4.44g was added and dissolved, followed by reaction at 0 ℃ for 8 hours to form a polyamic acid solution. After the reaction temperature was returned to room temperature, 1ml of pyridine as a catalyst and 5ml of acetic anhydride as a dehydrating agent were added to the reaction mixture, and the reaction was carried out at room temperature for 8 hours. Methanol was injected for precipitation, filtered and soxhlet extracted with methanol. And drying to obtain the polyimide continuous phase 6F-Du.
3) 0.95g of 6F-Du was weighed out and dissolved in 5.5ml of DMF. And adding 0.05g of AP after the continuous phase is completely dissolved, and performing ultrasonic dispersion to form a membrane casting solution. And (3) casting the film casting solution on a dust-free glass plate after defoaming treatment, carrying out blade coating forming, putting the glass plate into a vacuum oven at 150 ℃ for 2 hours, and volatilizing the solvent to form a film. And (3) after the room temperature is recovered, soaking and stripping the membrane by using deionized water, and drying the membrane to obtain the full polyimide mixed matrix gas separation membrane 5AP.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a 5AP cross section showing good compatibility. Fig. 3 is a 5AP thermogravimetric analysis (TGA) graph, and it can be seen that the mixed matrix gas separation membrane obtained in this example has good thermal stability.
Example 2
The present example is a "full polyimide" mixed matrix gas separation membrane, which uses self-made hyperbranched microporous polyimide as a dispersed phase (TAPA is a monomer), and two-step chemical imidization self-made polyimide as a continuous phase, wherein the filling content of the dispersed phase is 10wt%. The preparation process comprises the following steps:
1) Dispersed phase AP was prepared as in example 1.
2) Continuous phase 6F-Du was prepared as in example 1.
3) 0.90g of 6F-Du was weighed out and dissolved in 5.5ml of DMF. And adding 0.10g of AP after the continuous phase is completely dissolved, and performing ultrasonic dispersion to form a membrane casting solution. And (3) removing bubbles of the casting solution, pouring the casting solution on a dust-free glass plate, carrying out blade coating forming, putting the glass plate into a vacuum oven at 150 ℃ for 2 hours, and volatilizing the solvent to form a film. And (3) after the room temperature is recovered, soaking and stripping the membrane by using deionized water, and drying the membrane to obtain the full polyimide mixed matrix gas separation membrane 10AP.
FIG. 4 is an SEM image of a 10AP cross-section showing good compatibility. Fig. 5 is a 10AP TGA graph, and it can be seen that the mixed matrix gas separation membrane of the present embodiment has good thermal stability.
Example 3
The present embodiment is a "full polyimide" mixed matrix gas separation membrane, which uses self-made hyperbranched microporous polyimide as a dispersed phase (TAPA is a monomer), and uses self-made polyimide as a continuous phase through two-step thermal imidization. The preparation process comprises the following steps:
1) AP was prepared as in example 1.
2) 2.00g of ODA was dissolved in 35ml of DMF, and then 6FDA4.44g was added and dissolved, and reacted at 0 ℃ for 8 hours to form a polyamic acid solution. And (3) recovering the room temperature, adding 1ml of isoquinoline and 10ml of toluene, reacting at 180 ℃ for 10 hours to form polyimide, injecting methanol for precipitation, filtering, performing Soxhlet extraction by using methanol, and drying to obtain the polyimide continuous phase 6F-ODA.
3) 0.95g of 6F-ODA0 was weighed out and dissolved in 5.5ml of DMF. And after the continuous phase is completely dissolved, adding 0.05g of AP, and performing ultrasonic dispersion to form a membrane casting solution. And (3) casting the film casting solution on a dust-free glass plate after defoaming treatment, carrying out blade coating forming, putting the glass plate into a vacuum oven at 150 ℃ for 2 hours, and volatilizing the solvent to form a film. And (3) after the room temperature is recovered, soaking and stripping the membrane by using deionized water, and drying the membrane to obtain the full polyimide mixed matrix gas separation membrane.
FIG. 6 is a SEM cross-section of a two-step hot acyl "full polyimide" mixed matrix gas separation membrane, showing good compatibility. Fig. 7 is a TGA diagram of a two-step thermal acyl "full polyimide" mixed matrix gas separation membrane, and it can be seen that the mixed matrix gas separation membrane of the present embodiment has good thermal stability.
Comparative example 1 (a two-step chemical imidization homemade 6F-Du pure film)
1.64g of Durene was weighed out and dissolved in 35ml of DMF, and then 6FDA4.44g was added and dissolved, and reacted at 0 ℃ for 8 hours to form a polyamic acid solution. After the reaction is returned to room temperature, 1ml of pyridine catalyst and 5ml of acetic anhydride dehydrating agent are added to react for 8 hours at room temperature. Methanol was injected for precipitation, filtered and soxhlet extracted with methanol. And drying to obtain the polyimide continuous phase 6F-Du.
6F-Du 1.00g was weighed and dissolved completely in 5.5ml of DMF to form a casting solution. And (3) removing bubbles of the casting solution, pouring the casting solution on a dust-free glass plate, carrying out blade coating forming, putting the glass plate into a vacuum oven at 150 ℃ for 2 hours, and volatilizing the solvent to form a film. And (4) recovering the room temperature, soaking and stripping the film by using deionized water, and drying the film to obtain the 6F-Du pure film.
FIG. 8 is a SEM image of a cross section of a two-step hot acyl "full polyimide" mixed matrix membrane.
Comparative example 2 (two-step thermal imidization self-made 6F-ODA pure film)
2.00g of ODA was dissolved in 35ml of DMF, and then 6FDA4.44g was added and dissolved to react at 0 ℃ for 8 hours to form a polyamic acid solution. And recovering the room temperature, adding 1ml of isoquinoline and 10ml of toluene, reacting at 180 ℃ for 10 hours to form polyimide, injecting methanol for precipitation, filtering, performing Soxhlet extraction by using methanol, and drying to obtain the polyimide continuous phase 6F-ODA.
1.00g of 6F-ODA was weighed and completely dissolved in 5.5ml of DMF to form a casting solution. And (3) removing bubbles of the casting solution, pouring the casting solution on a dust-free glass plate, carrying out blade coating forming, putting the glass plate into a vacuum oven at 150 ℃ for 2 hours, and volatilizing the solvent to form a film. And (4) after the room temperature is recovered, soaking and stripping the membrane by using deionized water, and drying the membrane to obtain the 6F-ODA pure membrane.
FIG. 9 is a SEM cross-section of a two-step hot acyl "full polyimide" mixed matrix membrane.
The membrane separation performance of the examples and the comparative examples was tested at 7bar,30 ℃ by a constant volume pressure variation method in a differential pressure method, and the gas was a single component gas.
TABLE 1
As can be seen from the data in Table 1, "full Polyacyl" prepared by adding hyperbranched, microporous polyimide as a dispersed phaseImine "mixed matrix membranes, CO 2 、H 2 And CH 4 The permeability coefficients are all improved, and the greater the permeability coefficient, the greater the gas transmission capacity of the membrane. In examples 1 and 2, the high-flux substrate membrane material 6F-Du is selected, and the obtained 'full polyimide' mixed substrate membrane is used for CO 2 /CH 4 、H 2 /CH 4 The separation coefficient decreased slightly. In example 3, a low flux substrate membrane material of 6F-ODA was selected and the resulting "all polyimide" mixed substrate membrane was paired with CO 2 /CH 4 、H 2 /CH 4 The separation coefficient can also be improved.
In conclusion, the invention discloses a 'full polyimide' mixed matrix membrane, hyperbranched microporous polyimide has the advantages of high specific surface area and light weight, and the gas permeability coefficient can be improved by adding a polyimide substrate. In addition, as the dispersion phase and the continuous phase are both polyimide, the two phases have good compatibility, and the defect of non-selection can be effectively reduced. The prepared full polyimide mixed matrix membrane can be applied to gas separation under high-temperature and acidic environments.
The above examples are only for further illustration of the present invention, and the present invention is not limited to the examples.
Claims (7)
1. A method for preparing a 'full polyimide' mixed matrix gas separation membrane is characterized in that the mixed matrix gas separation membrane is prepared by taking hyperbranched microporous polyimide as a disperse phase and a polyimide continuous phase; the hyperbranched microporous polyimide dispersed phase is synthesized by a one-step method: dissolving triamine or tetramine monomer and dianhydride monomer in a high boiling point solvent according to the equal molar ratio of amine to anhydride, adding a catalyst, reacting at 30-60 ℃ for 80-150min,70-100 ℃ for 80-150min,110-150 ℃ for 10-15h,150-180 ℃ for 80-150min, and finally 190-210 ℃ for 5-15h, and obtaining hyperbranched microporous polyimide dispersed phase powder through precipitation, filtration and Soxhlet extraction; the BET specific surface area of the hyperbranched microporous polyimide is 400-1200m 2 (ii)/g; the high boiling point solvent is one or more of m-cresol, N-methyl pyrrolidone, 1,3, 5-trimethylbenzene and imidazole; the catalyst is pyridine,One or more than two of isoquinoline and triethylamine; the triamine or tetramine monomer has one or more structures as follows:
the dianhydride monomer used for preparing the hyperbranched microporous polyimide dispersed phase is one or more of the following structures:
the polyimide continuous phase is prepared by a two-step method and is divided into chemical imidization or thermal imidization, wherein: the chemical imidization is to take equivalent diamine monomer and dianhydride monomer to dissolve in solvent, then react for 8-24h at-5-10 ℃ to prepare polyamic acid precursor, restore the room temperature, then add catalyst and dehydrating agent to react for 4-12h to form polyimide, and obtain polyimide continuous phase through precipitation, filtration and Soxhlet extraction; the thermal imidization is to add equivalent diamine monomer and dianhydride monomer into a reaction kettle with a water separator to be dissolved in a solvent, then react for 8-24h at-5-10 ℃ to prepare a polyamic acid precursor, restore the room temperature, then add a catalyst and toluene, react for 4-12h at 180-200 ℃ to form polyimide, and obtain a polyimide continuous phase through precipitation, filtration and Soxhlet extraction.
2. The method of claim 1, wherein: the polyimide is one or more of the following structures:
wherein n =100-3000.
3. The method of claim 1, wherein: the solvent for preparing the polyimide continuous phase is one or more of chloroform, N' -dimethylformamide, m-cresol and N-methylpyrrolidone, the catalyst is one or more of pyridine, isoquinoline and triethylamine, and the dehydrating agent is acetic anhydride.
4. The production method according to claim 1, characterized in that: dissolving a polyimide continuous phase in a solvent to prepare a casting solution with the solid content of 10-20wt%, adding a hyperbranched microporous polyimide dispersion phase, and uniformly dispersing by ultrasonic; after defoaming treatment, pouring the mixture on a dust-free glass plate, forming the mixture by a blade coating method, a tape casting method or a spin coating method, and drying the mixture until a solvent is volatilized to form a 'full polyimide' mixed matrix gas separation membrane; the load capacity of the hyperbranched microporous polyimide dispersed phase in the 'full polyimide' mixed matrix gas separation membrane is 1-30wt%.
5. The method of claim 4, wherein: the film thickness is 400-600 μm formed by blade coating, tape casting or spin coating, then the film is put into a vacuum oven at 80-160 ℃ for drying until the solvent is volatilized to form a full polyimide mixed matrix gas separation film, finally the film is automatically stripped after being put into deionized water, and the film is dried in a blast drying oven at 60-120 ℃ to have the film thickness of 10-80 μm.
6. A "full polyimide" mixed matrix gas separation membrane prepared by the method of any one of claims 1 to 5.
7. The "all polyimide" mixed matrix gas separation membrane of claim 6 in the presence of CO 2 /CH 4 、CO 2 /N 2 、H 2 /CO 2 、H 2 /CH 4 、O 2 /N 2 Use in separation.
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