CN114377562A - For CO2/CH4Mixed matrix membrane for gas separation and preparation method thereof - Google Patents
For CO2/CH4Mixed matrix membrane for gas separation and preparation method thereof Download PDFInfo
- Publication number
- CN114377562A CN114377562A CN202210051166.0A CN202210051166A CN114377562A CN 114377562 A CN114377562 A CN 114377562A CN 202210051166 A CN202210051166 A CN 202210051166A CN 114377562 A CN114377562 A CN 114377562A
- Authority
- CN
- China
- Prior art keywords
- membrane
- reaction
- mixing
- mixed matrix
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- 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
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for preparing CO2/CH4The mixed matrix membrane for gas separation and the preparation method thereof comprise the following steps: mixing an SBA-15 molecular sieve, a solvent and an amination reagent, heating until the reaction is complete, filtering and drying to obtain an amination filler; mixing 6FDA, ODA and DMAC, carrying out heat preservation reaction, adding a dehydrating agent and a catalyst, mixing the reaction solution after the reaction with ethanol, washing, drying and separating out precipitated solids to obtain polyimide; uniformly mixing polyimide, aminated filler and solvent to obtain a membrane casting solution, coating the membrane casting solution on a template, drying to obtain a prefabricated membrane, and carrying out high-temperature heat treatment on the prefabricated membrane to obtain the required mixed matrix membrane. The invention is used for CO2/CH4Mixed matrix membranes for gas separation by addition of ammoniaThe basic filler reduces the close packing of polymer chains, maintains good mechanical property and enhances CO2So that CO is permeated2/CH4Selectivity enhancement, mixed matrix membrane compared to polymer matrix membrane, CO2The separation performance is obviously improved.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to a method for separating CO2/CH4A mixed matrix membrane for gas separation and a method for preparing the same.
Background
With the rapid development of human society, people have increasingly increased demands for energy. However, the new energy technology has not been broken through, fossil fuel is still the leading of the energy market, and is accompanied by a series of byproducts brought by the fossil fuel, wherein the greenhouse gas CO is2The most serious pollution to the environment is about three quarters of the world's CO2Derived from the combustion of fossil fuels. According to statistics, the global CO is 20352The concentration of the carbon dioxide reaches 435ppm, and the high concentration of the carbon dioxide causes natural disasters such as global warming, glacier melting, sea level rising and the like, which causes immeasurable loss to human beings and seriously threatens the survival development of the human beings. Thus, CO2Have become a problem that humans must face and await solution.
At present, the separation and capture of carbon dioxide are mainly carried out by physical and chemical adsorption methods, cryogenic distillation, membrane separation, and other techniques. Compared with the traditional method, the membrane separation technology has the advantages of low energy consumption, small occupied area, no toxic and harmful byproducts and the like. After decades of development, the membrane separation technology is continuously perfected and developed, and remarkable results are obtained. Gas separation membranes are generally classified into inorganic membranes, polymeric membranes, and mixed matrix membranes. Compared with the former two, the mixed matrix membrane not only has good processability of a polymer membrane, but also has excellent separation performance of an inorganic membrane. Meanwhile, the mixed matrix membrane has the characteristics of simple preparation process, low price and the like.
The filler of the mixed matrix membrane mainly comprises graphene, carbon nano tubes, molecular sieves, Metal Organic Frameworks (MOFs) and other materials. Compared with other fillers, the molecular sieve has the advantages of simple synthesis, low price, environmental friendliness and the like. However, it has a problem of poor interfacial compatibility with the polymer, resulting in CO of the mixed matrix film2The separation performance is poor, which seriously limits the scale of the molecular sieve mixed matrix membrane.
Disclosure of Invention
In view of the above, the present invention is directed to a method for CO2/CH4Mixed matrix membrane for gas separation and method for preparing the same, and method for preparing the sameSolves the problem that the gas separation membrane prepared by the prior method is used for CO2/CH4Low separation performance, poor compatibility between the filler and the polymer matrix interface and the like, and improves the CO content of the mixed matrix membrane2Separation performance.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
for CO2/CH4The preparation method of the mixed matrix membrane for gas separation comprises the following steps:
(1) mixing an SBA-15 molecular sieve and ethanol through magnetic stirring, heating to a certain temperature, slowly dripping an amination reagent, cooling to room temperature after complete reaction, filtering to obtain a white solid, washing with ethanol, and drying to obtain an amination filler;
(2) mixing and dissolving hexafluoro dianhydride (6FDA) and DMAC, adding ODA at a certain temperature, keeping the temperature and reacting for a certain time, adding a dehydrating agent and a catalyst, reacting completely to obtain a reaction solution, mixing the reaction solution with ethanol, separating out a solid, washing the solid with ethanol, and drying at a certain temperature to obtain polyimide;
(3) mixing polyimide and DMAC (dimethylacetamide) until the polyimide and the DMAC are completely dissolved, adding an aminated filler, ultrasonically stirring and uniformly mixing to obtain a membrane casting solution, coating the membrane casting solution on a polytetrafluoroethylene template, drying a solvent to obtain a prefabricated membrane, and carrying out high-temperature heat treatment on the prefabricated membrane to obtain the required mixed matrix membrane.
Further, the mass ratio of the SBA-15 molecular sieve to the amination reagent in the step (1) is 20: 1-2.
Further, the reaction temperature in the step (1) is 60 ℃, and the reaction time is 8-15 h.
Further, the amination reagent comprises 3-aminopropyltriethoxysilane.
Further, the temperature in the step (2) is kept at 0-25 ℃, preferably 25 ℃, the reaction time is kept at 8-24h, and the reaction time is 8-12h after adding the dehydrating agent and the catalyst.
Further, the dehydrating agent comprises acetic anhydride and the catalyst comprises triethylamine.
Furthermore, the mass ratio of the polyimide to the aminated filler in the step (3) is 500: 1-5.
Further, the temperature of the high-temperature heat treatment is 100-200 ℃; preferably 150 deg.c.
Further, the preparation method of the SBA-15 molecular sieve comprises the following steps: mixing a template agent and 2-3mol/L hydrochloric acid, magnetically stirring at 20-50 ℃ until the template agent is completely dissolved, then dropwise adding ethyl orthosilicate under full stirring, stirring for 8-12h, putting into a stainless steel reaction kettle, crystallizing at a certain temperature for 10-30h, taking out, cooling, filtering, washing with deionized water, drying the obtained white powder at 80-150 ℃ overnight, and finally putting the white powder into a muffle furnace at 300-600 ℃ for calcining for 4-8h to remove the template agent to obtain the SBA-15 molecular sieve; preferably, the templating agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
Prepared according to the preparation method for CO2/CH4A gas separated mixed matrix membrane.
The principle of the invention is that the traditional SBA-15 molecular sieve is subjected to amination modification to obtain the filler N-SBA-15 containing a large number of amino groups, and the filler N-SBA-15 contains a large number of organic groups and has hydrogen bond acting force with a polymer, so that the problem of poor interface compatibility between a polymer matrix and the filler is solved to a great extent, and the amino groups on the filler promote CO2Selectivity of (2). Provides certain basic preparation for the industrial production of the mixed matrix membrane.
Compared with the prior art, the method for CO disclosed by the invention2/CH4The mixed matrix membrane for gas separation and the preparation method thereof have the following advantages:
(1) the invention is used for CO2/CH4The mixed matrix membrane for gas separation takes polyimide as a high molecular membrane material, and the close stacking of high molecular chains is reduced and good mechanical property is maintained by adding the aminated filler, so that CO is enhanced2The permeation flux of (c); the aminated fillers contain a large number of amino groups, which react with CO2Has stronger affinity, keeps no interface defect between the filler and the base film, and simultaneously leads CO to be2/CH4Selectivity enhancement, mixed matrix membrane compared to polymer matrix membrane, CO2The separation performance is obviously improved;
(2) the invention is used for CO2/CH4The preparation method of the mixed matrix membrane for gas separation is simple and environment-friendly, and is CO2The scaling of gas separation membranes provides a foundation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is an SEM image of an SBA-15 molecular sieve made according to an example of the present invention;
FIG. 2 is an SEM image of an aminated filler prepared in accordance with an embodiment of the present invention;
FIG. 3 is an X-ray diffraction pattern of a separation membrane according to an example of the present invention and a comparative example;
FIG. 4 shows CO of separation membranes prepared in examples of the present invention and comparative examples2/CH4The gas separation effect is shown schematically;
fig. 5 is a schematic view of a connection structure of a high molecular polymer gas separation performance test apparatus according to an embodiment of the present invention.
Description of reference numerals:
1. a membrane tank; 2. a vacuum pump; 3. an air storage tank.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Examples
Preparation of (I) SBA-15 molecular sieve
Weighing 4g of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), dissolving in 120mL of 2.5mol/L hydrochloric acid, magnetically stirring at 40 ℃ to completely dissolve the triblock copolymer, then dropwise adding 8mL of Tetraethoxysilane (TOES) under full stirring, continuously stirring for 10h, then placing into a stainless steel reaction kettle, and crystallizing at a certain temperature for 24 h. Taking out and cooling, and washing with deionized water. The resulting white powder was dried at 100 ℃ overnight. And (3) putting the white powder into a muffle furnace at 500 ℃ to be calcined for 8h to remove the template agent, so as to obtain the SBA-15 molecular sieve, wherein the SEM picture is shown in figure 1.
Preparation of (di) aminated Filler N-SBA-15
Adding 2g of SBA-15 molecular sieve into ethanol, magnetically stirring until the mixture is uniform, raising the temperature to 60 ℃, slowly adding 200mg of 3-Aminopropyltriethoxysilane (APTES) into a reaction system, reacting at a certain temperature for 12 hours, turning off heating, cooling to room temperature, filtering to obtain a white solid, washing with ethanol, and drying at 80 ℃ for 12 hours to obtain the aminated filler N-SBA-15, wherein an SEM picture of the aminated filler is shown in figure 2.
Preparation of (III) polyimide
2g of hexafluorodianhydride (6FDA) was dissolved in 10mL of DMAC to give a colorless transparent solution, and 0.9g of ODA was weighed and added to the reaction solution while maintaining the reaction temperature at 25 ℃ to react for 12 hours. To the reaction mixture were added 0.9mL of triethylamine and 2.8mL of acetic anhydride, and the solution quickly became viscous and the reaction was continued at room temperature for 12 h. The reaction solution was poured into 300mL of ethanol, and a large amount of white filaments were precipitated, and the solution was filtered and washed with ethanol for 12 hours. The washed solid was dried in vacuo at 150 ℃ for 24h to give 3g of a white polyimide, denoted as PI (6 FDA-ODA).
(IV) preparation of Mixed matrix Membrane (N-SBA-15/6FDA-ODA)
Dissolving 0.5g of 6FDA-ODA in DMAc, doping 2mg of N-SBA-15 in the DMAc, stirring and carrying out ultrasonic treatment for 5 hours respectively to obtain a casting solution, pouring the casting solution on a polytetrafluoroethylene plate, placing the polytetrafluoroethylene plate in an oven for drying at 60 ℃ for 8 hours, forming and then shedding, and carrying out vacuum drying at 150 ℃ for 24 hours to obtain a mixed matrix membrane, which is marked as N-SBA-15/6FDA-ODA, wherein the X-ray diffraction spectrum of the mixed matrix membrane is shown in figure 3.
Comparative example
Dissolving 0.5g of PI (6FDA-ODA) in 7mL of DMAC (dimethylacetamide), uniformly coating on a polytetrafluoroethylene plate after ultrasonic defoaming, placing the polytetrafluoroethylene plate in an oven to dry for 8h at 60 ℃, forming and then dropping off, and then drying in vacuum for 24h at 150 ℃ to obtain a polymer gas separation membrane, which is marked as 6FDA-ODA, and the X-ray diffraction spectrum of the polymer gas separation membrane is shown in figure 3.
Experiment of gas separation Performance
CO treatment of the membranes obtained in the examples and comparative examples2/CH4In the gas separation performance experiment, a connection structure of a gas separation performance test device is shown in fig. 5, wherein F1-8 are valves, and the specific experimental steps are as follows:
(1) after the membranes prepared in the examples and the comparative examples are respectively loaded into the membrane pool 1, the vacuum pumps 2, F3, F6 and F7 are started firstly, then F4 and F5 are started, and then F8 is slowly started to simultaneously suck air from the upper membrane pool 1 and the lower membrane pool 1, wherein F1 and F2 are in a closed state; when the vacuum degree reaches 3.0 multiplied by 10-2Testing can be carried out when the temperature is below Torr;
(2) firstly, sequentially closing F4 and F8, then opening F1 to fill test gas with certain pressure into a gas storage tank 3, repeatedly opening F2 to replace gas for three times, adjusting the sample injection pressure, closing F3, F6, F7 and a vacuum pump 2, opening F4, and starting data acquisition, wherein F1 and F2 are still in a closed state;
(3) and after the test is finished, opening the vacuum pumps 2, F3, F6 and F7, closing the pressure reducing valve, opening F1 and F2 to exhaust gas in the sample injection pipeline, closing F1 and F2, and slowly opening F8 to simultaneously exhaust gas.
The permeability coefficient P of the gas can be calculated by testing the curve of the gas pressure of the upper membrane pool along with the change of time. Separation Membrane pairs prepared in the examples CO2/CH4Separation performance, as shown in fig. 4. As can be seen from the analysis of FIG. 4, the mixed matrix membrane N-SBA-15/6FDA-ODA obtained according to the technical scheme provided by the invention is compared with the polymer gas separation membrane 6FDA-ODA in CO2CO is obviously improved while the permeation flux is obviously improved2/CH4Selectivity is also increased, and excellent CO is obtained2/CH4The separation performance of (3).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. For CO2/CH4The preparation method of the mixed matrix membrane for gas separation is characterized by comprising the following steps:
(1) mixing an SBA-15 molecular sieve, a solvent and an amination reagent, heating until the reaction is complete, filtering and drying to obtain an amination filler;
(2) mixing 6FDA, ODA and DMAC, carrying out heat preservation reaction, adding a dehydrating agent and a catalyst, reacting completely to obtain a reaction solution, mixing the reaction solution with ethanol, washing, drying and separating precipitated solids to obtain polyimide;
(3) uniformly mixing polyimide, aminated filler and solvent to obtain a membrane casting solution, coating the membrane casting solution on a template, drying to obtain a prefabricated membrane, and carrying out high-temperature heat treatment on the prefabricated membrane to obtain the required mixed matrix membrane.
2. The method of claim 1, wherein: in the step (1), the mass ratio of the SBA-15 molecular sieve to the amination reagent is 20: 1-2.
3. The method of claim 1, wherein: in the step (1), the reaction temperature is 60 ℃, and the reaction time is 8-15 h.
4. The method of claim 1, wherein: the amination reagent comprises 3-aminopropyltriethoxysilane.
5. The method of claim 1, wherein: and (3) in the step (2), the heat preservation reaction temperature is 0-25 ℃, the heat preservation reaction time is 8-24h, and the reaction time is 8-12h after the dehydrating agent and the catalyst are added.
6. The method of claim 1, wherein: the dehydrating agent comprises acetic anhydride, and the catalyst comprises triethylamine.
7. The method of claim 1, wherein: the mass ratio of the polyimide to the aminated filler in the step (3) is 500: 1-5.
8. The method of claim 1, wherein: the temperature of the high-temperature heat treatment is 100-200 ℃.
9. The method of claim 1, wherein the SBA-15 molecular sieve is prepared by a method comprising the steps of: mixing a template agent and hydrochloric acid until the template agent and the hydrochloric acid are completely dissolved, dropwise adding ethyl orthosilicate, stirring for 8-12h, putting into a reaction kettle, crystallizing for 10-30h, cooling, filtering, washing, drying and calcining to obtain an SBA-15 molecular sieve; preferably, the templating agent is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
10. Use for CO, prepared according to the preparation process of claims 1-92/CH4A gas separated mixed matrix membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210051166.0A CN114377562A (en) | 2022-01-17 | 2022-01-17 | For CO2/CH4Mixed matrix membrane for gas separation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210051166.0A CN114377562A (en) | 2022-01-17 | 2022-01-17 | For CO2/CH4Mixed matrix membrane for gas separation and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114377562A true CN114377562A (en) | 2022-04-22 |
Family
ID=81201337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210051166.0A Pending CN114377562A (en) | 2022-01-17 | 2022-01-17 | For CO2/CH4Mixed matrix membrane for gas separation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114377562A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870655A (en) * | 2022-05-10 | 2022-08-09 | 河北工业大学 | Preparation method and application of mixed matrix membrane for realizing efficient gas separation through in-situ crosslinking |
| CN115025647A (en) * | 2022-06-20 | 2022-09-09 | 江西师范大学 | Preparation method and application of mixed matrix membrane material filled with molecular sieve |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070022877A1 (en) * | 2002-04-10 | 2007-02-01 | Eva Marand | Ordered mesopore silica mixed matrix membranes, and production methods for making ordered mesopore silica mixed matric membranes |
| CN101084052A (en) * | 2004-11-19 | 2007-12-05 | 切夫里昂美国公司 | Mixed matrix membrane with mesoporous particles and methods for making the same |
| CN101959577A (en) * | 2007-06-01 | 2011-01-26 | 环球油品公司 | Functionalization of polymers molecular sieve/mixed with polymers matrix membrane that UV is crosslinked |
| CN102418168A (en) * | 2011-06-02 | 2012-04-18 | 华东理工大学 | Porous-particle-doped polyimide hollow fibrous membrane, preparation method thereof, and application thereof |
| WO2012092980A1 (en) * | 2011-01-07 | 2012-07-12 | Statoil Petroleum As | Process for removing acid gas from natural gas |
| CN108404690A (en) * | 2018-04-16 | 2018-08-17 | 哈尔滨工业大学 | A kind of preparation method of MOF- polyimide composite films material |
| CN112717711A (en) * | 2020-12-14 | 2021-04-30 | 中海石油(中国)有限公司 | Preparation method of polyimide-based mixed matrix hollow fiber membrane |
| CN113731198A (en) * | 2021-09-28 | 2021-12-03 | 天津众泰材料科技有限公司 | Preparation method of high-selectivity polyimide gas separation membrane |
| CN113893700A (en) * | 2021-11-24 | 2022-01-07 | 常州大学 | Rapid preparation method and application of dual-functionalized mixed matrix membrane with high carbon dioxide selectivity |
-
2022
- 2022-01-17 CN CN202210051166.0A patent/CN114377562A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070022877A1 (en) * | 2002-04-10 | 2007-02-01 | Eva Marand | Ordered mesopore silica mixed matrix membranes, and production methods for making ordered mesopore silica mixed matric membranes |
| CN101084052A (en) * | 2004-11-19 | 2007-12-05 | 切夫里昂美国公司 | Mixed matrix membrane with mesoporous particles and methods for making the same |
| CN101959577A (en) * | 2007-06-01 | 2011-01-26 | 环球油品公司 | Functionalization of polymers molecular sieve/mixed with polymers matrix membrane that UV is crosslinked |
| WO2012092980A1 (en) * | 2011-01-07 | 2012-07-12 | Statoil Petroleum As | Process for removing acid gas from natural gas |
| CN102418168A (en) * | 2011-06-02 | 2012-04-18 | 华东理工大学 | Porous-particle-doped polyimide hollow fibrous membrane, preparation method thereof, and application thereof |
| CN108404690A (en) * | 2018-04-16 | 2018-08-17 | 哈尔滨工业大学 | A kind of preparation method of MOF- polyimide composite films material |
| CN112717711A (en) * | 2020-12-14 | 2021-04-30 | 中海石油(中国)有限公司 | Preparation method of polyimide-based mixed matrix hollow fiber membrane |
| CN113731198A (en) * | 2021-09-28 | 2021-12-03 | 天津众泰材料科技有限公司 | Preparation method of high-selectivity polyimide gas separation membrane |
| CN113893700A (en) * | 2021-11-24 | 2022-01-07 | 常州大学 | Rapid preparation method and application of dual-functionalized mixed matrix membrane with high carbon dioxide selectivity |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870655A (en) * | 2022-05-10 | 2022-08-09 | 河北工业大学 | Preparation method and application of mixed matrix membrane for realizing efficient gas separation through in-situ crosslinking |
| CN115025647A (en) * | 2022-06-20 | 2022-09-09 | 江西师范大学 | Preparation method and application of mixed matrix membrane material filled with molecular sieve |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114377562A (en) | For CO2/CH4Mixed matrix membrane for gas separation and preparation method thereof | |
| CN105289337A (en) | Crosslinking polyimide gas separation membrane and preparation method | |
| CN113209841B (en) | Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol, and preparation method and application thereof | |
| CN114377561A (en) | Efficient CO separation2/CH4Mixed matrix membrane of (1) and process for producing the same | |
| CN103084078A (en) | Mixed matrix membrane of polyetherimide and fumed silicon dioxide, and preparation and application thereof | |
| CN113731198B (en) | Preparation method of high-selectivity polyimide gas separation membrane | |
| CN113477102A (en) | Preparation and application of polymer-aminated transition metal carbide blended film | |
| CN114522669A (en) | Integral solid amine adsorbent and preparation method thereof | |
| CN110776522B (en) | Copper metal organic framework material and preparation method thereof, gas capture method and gas separation method | |
| CN113385055B (en) | Preparation method of composite material UiO-66@ HNT-based mixed matrix film | |
| CN111821812B (en) | CO (carbon monoxide)2Absorbent and synthesis and application thereof | |
| CN110270231B (en) | MOF (Metal organic framework) derivative gas separation membrane as well as preparation method and application thereof | |
| CN101733029A (en) | Method for preparing CO2 separation membrane material and composite membrane | |
| CN115253714B (en) | Mixed matrix membrane doped with molybdenum disulfide nanosheet modified material, and preparation method and application thereof | |
| CN111389369A (en) | Synthesis method of metal organic framework mesoporous material and its application in CO2Application in adsorption | |
| CN112717723B (en) | Preparation method of amino carbon dot and polyimide mixed matrix membrane for gas separation | |
| CN106582307B (en) | A kind of application of the preparation method and blend film of blend film | |
| CN116351265A (en) | Preparation and application of high-performance mixed matrix gas separation membrane based on ionic liquid coordination | |
| CN104525006B (en) | Macromolecule-carboxylic acid functional nano-hydrogel composite membrane, preparation method and application | |
| CN112755801A (en) | Preparation method of mixed matrix membrane material | |
| CN110787658A (en) | Preparation method of Pebax/ATP mixed matrix membrane | |
| CN115228311B (en) | Preparation method of PIM-1 mixed matrix membrane based on amidoxime group modified UiO-66 material | |
| CN115582032A (en) | Preparation method of 6 FAP-based high-selectivity polyimide gas separation membrane | |
| CN111298667B (en) | Polymer-based blended film, and preparation method and application thereof | |
| CN114950390A (en) | Integer CO 2 Adsorbent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |