CN112717711A - Preparation method of polyimide-based mixed matrix hollow fiber membrane - Google Patents
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- CN112717711A CN112717711A CN202011471013.9A CN202011471013A CN112717711A CN 112717711 A CN112717711 A CN 112717711A CN 202011471013 A CN202011471013 A CN 202011471013A CN 112717711 A CN112717711 A CN 112717711A
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- 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
- B01D69/147—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded adsorbents
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- 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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- 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
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- 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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- 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
- B01D2256/16—Hydrogen
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- 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
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- 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
Abstract
The invention discloses a preparation method of a polyimide-based mixed matrix hollow fiber gas separation membrane. The gas separation membrane takes polyimide as a high-molecular continuous phase and inorganic or organic porous materials as a disperse phase, and the preparation process comprises (1) blending the polyimide and porous dispersed particles to prepare uniform membrane casting liquid; (2) dry-wet spinning and forming; (3) solvent exchange and cleaning; (4) naturally drying; (5) and (4) temperature programmed heat treatment. In the heat treatment process, the solvent adsorbed in the micropores of the porous dispersed phase is desorbed by controlling the heat treatment time, temperature and atmosphere composition, so that the dispersed phase presents better gas adsorption and separation performance; the flexibility of the polyimide chain segment is increased in the heat treatment stage, the joint surface between the organic phase and the inorganic phase is tighter, and the defect of the interface between the two phases is eliminated; the polyimide is partially crosslinked at high temperature, so that the separation selectivity of the membrane is improved, and the anti-plasticizing pressure is obviously increased. The preparation method is simple and easy to operate, does not introduce a third component, does not produce waste liquid to pollute the environment, and is easy to realize industrialization.
Description
Technical Field
The invention belongs to the field of membrane separation, and particularly relates to a preparation method of a polyimide-based mixed matrix hollow fiber membrane.
Background
The membrane separation technology is an energy-saving and environment-friendly separation technology, has a huge application prospect in the fields of resource recovery, water treatment, gas purification and the like, and is receiving more and more attention. Among them, the first industrial application of gas separation membranes began in the last 80 th century for the recovery of hydrogen from the purge gas of ammonia synthesis. With the development of the technology, the method has wide application prospect in the fields of air separation, hydrogen recovery, natural gas purification, carbon capture and the like.
The core problem of research on the gas membrane separation technology is that the membrane is a membrane material with high gas permeation separation performance, which can not only improve the processing capacity of the separation process, but also reduce the production cost, reduce the occupied space of equipment and the like, so how to further optimize and improve the separation capacity of the membrane is the key point of research of the current scholars. Membrane materials and membrane structures are two major factors that affect the performance of gas separation membranes. In the aspect of membrane materials, organic membrane materials are low in price and easy to process and prepare asymmetric membranes, wherein polyimide is good in gas separation performance, high in temperature resistance and high in mechanical strength, is the most potential polymer material at present, and the gas permeability coefficient and the separation coefficient of the organic membrane are limited by the relation of 'trade-off'. The mixed matrix membrane improves the gas permeation and separation performance of the organic membrane by introducing inorganic particles into the organic membrane, keeps the characteristics of good toughness and easy processing and forming of the organic membrane, and can realize the advantage complementation of the organic membrane and the inorganic membrane. In terms of membrane structure, polymer membrane modules for gas separation mainly have a plate-and-frame type, a spiral wound type and a hollow fiber type. Wherein, the hollow fiber type has the characteristics of high filling density, large specific surface area and the like, so that the cost of the gas membrane is greatly reduced. And the hollow fiber membrane has a self-supporting structure, high pressure resistance stability, relatively simple preparation process, good gas hydrodynamic condition in the membrane component and good application advantages. Therefore, polyimide-based mixed matrix hollow fiber membranes are one of the research hotspots in the art.
The biggest problem in the preparation process of the mixed matrix membrane is how to avoid the defect of void between organic and inorganic phases, for example, chinese patent CN201911348858.6 discloses a method for improving the compatibility between MOF material and polyimide polymer matrix by modifying the MOF surface, which is not only complicated in process but also causes more environmental pollution. For the hollow fiber membrane forming process, a dry-wet spinning process is usually adopted, and a preparation method of a single-outer-skin-layer PES hollow fiber gas separation membrane disclosed in Chinese patent CN107626187A, the hollow fiber membrane filaments formed by solidification need to be exchanged by low-boiling-point solvents such as water, alcohol and hexane, or coated by silicon rubber, the process flow is complex, and organic solvent waste liquid and waste gas can be generated. Chinese patent CN109745869 also discloses a preparation method of hollow fiber mixed matrix membrane for removing carbon dioxide from natural gas, in order to obtain hollow fiber membrane with high separation selectivity, the membrane still needs to be sequentially replaced by low boiling point organic solvent after being formed, and then is dried and coated by silicon rubber. And the formed film still has the possibility of existence of interface defects.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a polyimide-based mixed matrix hollow fiber membrane, which can eliminate the interface defect between a polyimide matrix and an inorganic dispersion phase, simplify the process flow, reduce the generation of waste gas/waste liquid and has more industrial production advantages.
The preparation method of the polyimide-based mixed matrix hollow fiber membrane provided by the invention comprises the following steps:
1) blending the porous dispersed particles and polyimide to prepare a casting solution, and defoaming the obtained casting solution in vacuum;
2) dry-wet spinning forming: extruding the defoamed casting solution from a spray head, and entering a coagulating bath for phase inversion molding after passing through an air section;
3) soaking the obtained hollow fiber membrane in clear water cleaning bath, and naturally drying after solvent exchange is completed;
4) and (4) carrying out high-temperature treatment after the temperature is programmed to be high, thus obtaining the product.
In the step 1), the porous dispersed particles may be one or a mixture of several of metal organic framework compounds (MOFs), Covalent Organic Frameworks (COFs), molecular sieves, porous graphene, activated carbon, porous carbon nanotubes, and porous metal oxides; specifically ZIF-8;
the polyimide can be specifically polyimide and polyetherimide; more specifically, the polyimide may be prepared by copolymerizing one or two of hexafluoro dianhydride (6FDA), Benzophenone Tetracarboxylic Dianhydride (BTDA), diphenyl ether tetracarboxylic dianhydride (ODPA), and pyromellitic dianhydride (PMDA) with one or two of diaminotoluene (PDA), trimethylphenylenediamine (DMA), and biphenyldiamine (TDA).
The operation of blending and preparing the casting solution is as follows: firstly, blending porous dispersed particles and a solvent, performing ultrasonic treatment or stirring to uniformly disperse the porous dispersed particles into the solvent, then adding polyimide into the obtained solution in batches, and continuously stirring to obtain a membrane casting solution;
the solvent can be one or a mixture of more of NMP, DMAc, DMF, DMSO, dichloromethane, chloroform, tetrahydrofuran and the like;
the casting solution also contains a pore structure directing agent;
the pore structure directing agent can be one or more of methanol, ethanol, propanol, formic acid, acetic acid, propionic acid, ethylene glycol, glycerol, water, chloroform, tetrahydrofuran, polyethylene glycol and polyvinylpyrrolidone;
the mass ratio of the porous dispersed particles to the polyimide may be 1: 9-1: 2, specifically 3: 17;
the ratio of the pore structure directing agent to the solvent may be 1: 19-1: 4, specifically 1: 10;
the solid content of the casting solution (the mass percentage of (polyimide + porous dispersed particles) in the casting solution) can be 15-40 wt%, and specifically, the solid content of the casting solution can be 25-35 wt%;
in the step 2) of the method, the length (dry spinning distance) of the air section can be 0.1-50 cm, and specifically can be 1-10 cm; more specifically 6 cm;
the spinning temperature is 25-120 deg.C, more specifically 50-70 deg.C;
the coagulating bath is filled with water at the temperature of 20 ℃,
in the step 3), the soaking time can be 10-100h, specifically 20-50 h, and more specifically 48 h;
in the step 4), the temperature programming rate can be 5-50 ℃/h, specifically 10-30 ℃/h, more specifically 20 ℃/h;
the temperature of the high-temperature treatment can be 150-500 ℃, specifically 200-400 ℃, 180-220 ℃, 220-260 ℃, and more specifically 220 ℃.
The high-temperature treatment time can be 10-100h, specifically 40-55h, more specifically 48 h;
the high temperature treatment is carried out in a nitrogen or air atmosphere.
The polyimide-based mixed matrix hollow fiber membrane prepared by the method also belongs to the protection scope of the invention.
The polyimide-based mixed matrix hollow fiber membrane is used for removing CO from natural gas/methane2Hydrogen recovery, airThe application in gas separation also belongs to the protection scope of the invention.
The invention has the beneficial effects that: the preparation method is simple and easy to operate, does not introduce a third component, generates little waste water/waste liquid and the like, and is easy to realize industrialization. In the heat treatment process, the solvent adsorbed in the micropores of the porous dispersed phase is desorbed by controlling the heat treatment time, temperature and atmosphere composition, so that the dispersed phase presents better gas adsorption and separation performance; the flexibility of the polyimide chain segment is increased in the heat treatment stage, the joint surface between the organic phase and the inorganic phase is tighter, and the defect of the interface between the two phases is eliminated; the polyimide is partially crosslinked at high temperature, so that the separation selectivity of the membrane is improved, and the anti-plasticizing pressure is obviously increased.
The invention improves the preparation method of the hollow fiber mixed matrix membrane, which can simplify the process flow and eliminate the defect of two-phase interface, thereby preparing the high-selectivity hollow fiber mixed matrix membrane.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) cross-sectional view of a mixed matrix hollow fiber membrane prepared in example 1 of the present invention.
FIG. 2 is a cross-sectional Scanning Electron Microscope (SEM) image of the mixed matrix hollow fiber membrane prepared in example 1 of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the outer skin layer of the mixed matrix hollow fiber membrane prepared in example 1 of the present invention.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
CO used in the following examples of the invention2、CH4、N2、O2All are high purity gases. The test was carried out in the following examples using a self-made constant-pressure variable-volume gas separation and evaluation apparatus. The part belongs to a conventional test characterization method, and is shown in ZIF-8 pairs
Research on influence of hollow fiber gas separation membrane performance, membrane science and technology, 2020.
Example 1
Blending 15g of ZIF-8 and 250g of NMP, performing ultrasonic treatment for 30 min/stirring for 30min, and repeating the ultrasonic treatment for three times to uniformly disperse the ZIF-8 in the NMP. 85g
Added to the ZIF-8 solution in portions. And after the polymer is added, stirring for 12h, adding 25g of ethanol, and continuously stirring for 6h to prepare a uniform membrane casting solution. And (5) defoaming the casting solution in vacuum for 6 hours. Spinning at the dry spinning distance of 6cm and the spinning temperature of 70 ℃, solidifying and forming in water at the temperature of 20 ℃, soaking in clear water for 48 hours, then cleaning with clear water for three times, and naturally drying in air for 24 hours. Gradually heating to 200 ℃ at the heating rate of 20 ℃/h, and keeping the temperature at 180 ℃ for 48 h.
FIG. 1 is a Scanning Electron Microscope (SEM) cross-sectional view of the prepared mixed matrix hollow fiber membrane.
FIG. 2 is a cross-sectional enlarged Scanning Electron Microscope (SEM) image of the prepared mixed matrix hollow fiber membrane.
Fig. 3 is a Scanning Electron Microscope (SEM) image of the outer skin layer of the prepared mixed matrix hollow fiber membrane.
As can be seen from fig. 1-3: ZIF-8 is uniformly dispersed, and ZIF-8 is tightly combined with Ultem1000 without phase interface gaps.
Example 2
The preparation process of the hollow fiber membrane is the same as that of the hollow fiber membrane in the example 1, the maximum heat treatment temperature is 200 ℃, and the high-temperature heat treatment time is 48 hours.
Example 3
The preparation process of the hollow fiber membrane is the same as that of the hollow fiber membrane in the example 1, the maximum heat treatment temperature is 220 ℃, and the high-temperature heat treatment time is 48 hours.
Example 4
The preparation process of the hollow fiber membrane is the same as that of the hollow fiber membrane in the example 1, the maximum heat treatment temperature is 240 ℃, and the high-temperature heat treatment time is 48 hours.
Example 5
The preparation process of the hollow fiber membrane is the same as that of the hollow fiber membrane in the embodiment 1, the maximum heat treatment temperature is 260 ℃, and the high-temperature heat treatment time is 48 hours.
Comparative example
Ethanol (pore structure directing agent) is not added in the preparation process of the hollow fiber membrane in the embodiment 1, other operations are not changed, the maximum heat treatment temperature is 220 ℃, and the high-temperature heat treatment time is 48 h.
TABLE 1 gas permeation flux and gas selectivity of different membranes
As can be seen from Table 1, high temperature post-treatment of CO on polyimide based ZIF-8 mixed matrix hollow fiber membranes2/CH4Separation performance and CO resistance2The plasticizing pressure has a relatively significant effect. 180-220 ℃, CO along with the increase of the post-treatment temperature2Permeability coefficient gradually decreases while CO2/CH4The separation performance is obviously improved, and CO2The plasticizing pressure is also obviously increased; 220-260 ℃ of CO with the increase of the post-treatment temperature2The permeability coefficient is slightly increased, and CO2/CH4The separation coefficient remains substantially constant, CO2The plasticizing pressure also remains substantially constant.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The invention is not the best known technology.
Claims (8)
1. A method for preparing a polyimide-based mixed matrix hollow fiber membrane comprises the following steps:
1) blending the porous dispersed particles and polyimide to prepare a casting solution, and defoaming the obtained casting solution in vacuum;
2) dry-wet spinning forming: extruding the defoamed casting solution from a spray head, and entering a coagulating bath for phase inversion molding after passing through an air section;
3) soaking the obtained hollow fiber membrane in clear water cleaning bath, and naturally drying after solvent exchange is completed;
4) and (4) carrying out high-temperature treatment after the temperature is programmed to be high, thus obtaining the product.
2. The method of claim 1, wherein: in the step 1), the porous dispersion particles are one or a mixture of several of metal organic framework compounds, covalent organic frameworks, molecular sieves, porous graphene, activated carbon, porous carbon nanotubes and porous metal oxides; specifically ZIF-8;
the polyimide is polyimide or polyetherimide;
the mass ratio of the porous dispersed particles to the polyimide is 1: 9-1: 2.
3. the method according to claim 1 or 2, characterized in that: the operation of blending and preparing the casting solution is as follows: firstly, blending porous dispersed particles and a solvent, performing ultrasonic treatment or stirring to uniformly disperse the porous dispersed particles into the solvent, then adding polyimide into the obtained solution in batches, and continuously stirring to obtain a membrane casting solution;
the solvent is one or a mixture of more of NMP, DMAc, DMF, DMSO, dichloromethane, chloroform, tetrahydrofuran and the like;
the casting solution also contains a pore structure directing agent;
the pore structure guiding agent is one or more of methanol, ethanol, propanol, formic acid, acetic acid, propionic acid, ethylene glycol, glycerol, water, chloroform, tetrahydrofuran, polyethylene glycol and polyvinylpyrrolidone;
the ratio of the pore structure directing agent to the solvent is 1: 19-1: 4.
4. the method according to any one of claims 1-3, wherein: the solid content of the casting solution is 15-40 wt%.
5. The method according to any one of claims 1-4, wherein: in the step 2), the length of the air section is 0.1-50 cm;
the spinning temperature is 25-120 ℃;
the coagulating bath is filled with water at the temperature of 20 ℃,
in the step 3), the soaking time is 10-100 h.
6. The method according to any one of claims 1-5, wherein: in the step 4), the temperature programming rate is 5-50 ℃/h;
the temperature of the high-temperature treatment is 150-500 ℃;
the high-temperature treatment time is 10-100 h;
the high temperature treatment is carried out in a nitrogen or air atmosphere.
7. A polyimide-based mixed matrix hollow fiber membrane prepared by the method of any one of claims 1 to 6.
8. The polyimide-based mixed matrix hollow fiber membrane of claim 7 for CO removal from natural gas/biogas2And hydrogen recovery and air separation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113368712A (en) * | 2021-05-17 | 2021-09-10 | 北京化工大学 | Efficient air filtration composite nanofiber membrane and preparation method thereof |
| CN113368692A (en) * | 2021-07-16 | 2021-09-10 | 滁州学院 | Liquefied walnut shell solvent-resistant composite nanofiltration membrane and preparation method thereof |
| CN114377562A (en) * | 2022-01-17 | 2022-04-22 | 天津众泰材料科技有限公司 | For CO2/CH4Mixed matrix membrane for gas separation and preparation method thereof |
| CN114950147A (en) * | 2022-05-10 | 2022-08-30 | 中海油天津化工研究设计院有限公司 | For CO 2 Separated Trnano's Base type polyimide hybrid membrane and preparation method thereof |
| CN115337791A (en) * | 2022-09-02 | 2022-11-15 | 万华化学集团股份有限公司 | Hollow fiber porous membrane and preparation method and application thereof |
| CN116099377A (en) * | 2023-03-07 | 2023-05-12 | 哈尔滨工业大学 | Preparation method of high-strength charged hollow fiber membrane applied to MABR |
| CN116571098A (en) * | 2023-05-23 | 2023-08-11 | 山东仁丰特种材料股份有限公司 | Hydrogen separation membrane and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113368712A (en) * | 2021-05-17 | 2021-09-10 | 北京化工大学 | Efficient air filtration composite nanofiber membrane and preparation method thereof |
| CN113368692A (en) * | 2021-07-16 | 2021-09-10 | 滁州学院 | Liquefied walnut shell solvent-resistant composite nanofiltration membrane and preparation method thereof |
| CN114377562A (en) * | 2022-01-17 | 2022-04-22 | 天津众泰材料科技有限公司 | For CO2/CH4Mixed matrix membrane for gas separation and preparation method thereof |
| CN114950147A (en) * | 2022-05-10 | 2022-08-30 | 中海油天津化工研究设计院有限公司 | For CO 2 Separated Trnano's Base type polyimide hybrid membrane and preparation method thereof |
| CN115337791A (en) * | 2022-09-02 | 2022-11-15 | 万华化学集团股份有限公司 | Hollow fiber porous membrane and preparation method and application thereof |
| CN115337791B (en) * | 2022-09-02 | 2024-05-03 | 万华化学集团股份有限公司 | Hollow fiber porous membrane and preparation method and application thereof |
| CN116099377A (en) * | 2023-03-07 | 2023-05-12 | 哈尔滨工业大学 | Preparation method of high-strength charged hollow fiber membrane applied to MABR |
| CN116099377B (en) * | 2023-03-07 | 2024-04-19 | 哈尔滨工业大学 | Preparation method of high-strength hollow fiber membrane applied to MABR |
| CN116571098A (en) * | 2023-05-23 | 2023-08-11 | 山东仁丰特种材料股份有限公司 | Hydrogen separation membrane and preparation method thereof |
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