CN114471201A - Polyether-ether-ketone hollow fiber membrane, preparation method thereof and membrane absorption application - Google Patents
Polyether-ether-ketone hollow fiber membrane, preparation method thereof and membrane absorption application Download PDFInfo
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Abstract
The invention discloses a polyether-ether-ketone hollow fiber membrane, a preparation method thereof and membrane absorption application. The method comprises the following steps: A. premixing a high-temperature resistant plasticizer, a hydrophobic additive, polyether-ether-ketone resin and a co-melting polymer pore-foaming agent, and performing blending extrusion and grain cutting through an extruder to obtain spinning granules; B. melting the spinning granules by a screw extruder, quantitatively extruding the spinning granules by a hollow spinning pack, introducing inert gas or a high-temperature-resistant braided tube into the pack, cooling and solidifying the spinning melt, and performing heat setting treatment, dissolution, extraction, cleaning and drying to obtain the polyether-ether-ketone hollow fiber membrane. The invention solves the problems of difficult hydrophobic modification and insufficient stability of the polyether-ether-ketone through simple premixing and melt blending spinning, the prepared membrane does not need secondary hydrophobic modification such as surface grafting, coating and the like, the water contact angle is more than 110 degrees, the liquid permeation pressure is high, the hydrophobic stability is strong, the membrane can be stably maintained under severe conditions such as high temperature, strong acid and alkali, organic solvents and the like, and the invention is suitable for the membrane absorption process in severe environment.
Description
Technical Field
The invention relates to the technical field of membranes, in particular to a polyether-ether-ketone hollow fiber hydrophobic membrane for membrane absorption and a preparation method thereof.
Background
The global warming trend is still continuing and the risk of extreme weather events is further exacerbated, which has become a focus of governments and the public in various countries. Separation and recovery of the main greenhouse gas carbon dioxide (CO)2) Has become a hot spot of research. At present, CO2The separation technique of gas includes: chemical absorption of solution, low-temperature fractionation, pressure swing adsorption, cryogenic separation, membrane absorption and the like.
In recent years, the research of removing acid gas from mixed gas by using hollow fiber porous membrane has been gradually attracting attention. In the absorption and desorption process based on the hollow fiber membrane technology, the existence of the membrane component obviously increases the gas-liquid contact area of unit volume, avoids the problems of flooding, foaming, entrainment, channeling and the like in the chemical absorption process, has a module structure, is easy to realize process amplification, and is considered to be a carbon capture technology with prospect. The hollow fiber membrane microporous membrane is used as a gas-liquid two-phase contact interface in the membrane absorption process, and the requirements on the hollow fiber membrane microporous membrane mainly comprise: good solvent resistance, fine membrane outer diameter, high porosity, good hydrophobicity, high liquid osmotic pressure and the like.
Polyether-ether-ketone (PEEK) is a semi-crystalline novel special engineering plastic, has the long-term heat resistance of more than 250 ℃, and has the characteristics of chemical corrosion resistance, excellent mechanical property and the like, so that the polyether-ether-ketone (PEEK) has good application potential in the high-temperature flue gas decarburization process. In addition, during the membrane absorption process, gas and liquid phases flow at two sides of the membrane respectively, and the gas needs to fill the micropores on the membrane, so that the separation occurs at the membrane orifice at the liquid side. Once the pore channels are wetted by the absorption liquid, the mass transfer resistance will be greatly increased, thereby causing a drastic deterioration in the operating efficiency of the membrane contactor. Usually for CO2The water solution of the absorbent is absorbed, so that a larger contact angle can be generated by using the hydrophobic membrane, the liquid phase breakthrough pressure is increased, and the wettability problem of the membrane is effectively relieved. However, the PEEK has a water contact angle of 85 degrees and insufficient hydrophobicity, and the hydrophobicity needs to be improved. Due to excellent chemical stability and extremely high performance of PEEKProcessing temperature, hydrophobic modification of which is difficult. At present, the method for improving the hydrophobic property of PEEK is realized by generating active groups on the surface of PEEK through high-energy irradiation such as plasma, gamma rays and the like or a wet chemical method and grafting fluorine-containing oligomer. For example, Li (Journal of membrane science, 2013, 430: 79-86) or the like first produces-OH on the PEEK surface by reacting monoethanolamine with PEEK, and then grafts perfluorooligomer to obtain a superhydrophobic PEEK porous film. The Chinese patent CN201810419272.3 firstly obtains the PEEK hollow fiber membrane through melt spinning, annealing and extraction treatment, and then prepares the hydrophobic PEEK hollow fiber membrane through fluorination treatment. However, the process of improving the hydrophobicity of the membrane by secondary modification is complex, the uniformity is difficult to ensure, and the stability is insufficient under the conditions of strong acid, alkali, high temperature and organic solvent. In addition, the fluorine fluorination treatment needs to be performed on equipment, and is more harmful to the environment.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problems to be solved by the invention are that the traditional membrane for absorbing has insufficient hydrophobicity and osmotic pressure, and the polyether-ether-ketone hollow fiber membrane has the defects of difficult hydrophobic modification, complex process, poor hydrophobic stability and the like.
The technical scheme for solving the technical problems is to provide a polyether-ether-ketone hollow fiber membrane, a preparation method thereof and membrane absorption application.
The invention provides a preparation method of a polyether-ether-ketone hollow fiber membrane, which comprises the following steps:
step 1, weighing the pre-dried PEEK resin, the co-molten polymer pore-foaming agent, the high-temperature resistant plasticizer and the perfluorinated polymer according to the following formula: 30-60 wt% of PEEK resin, 25-50 wt% of co-molten polymer pore-foaming agent, 10-40 wt% of high-temperature resistant plasticizer and 5-20 wt% of perfluoropolymer, wherein the sum of the components is 100%; after fully mixing, blending, extruding and granulating by an extruder to obtain uniform spinning granules;
the co-melting polymer pore-foaming agent is at least one of polyetherimide, polyethylene oxide, polyimide, polyarylsulfone, polyethersulfone, polyphenylene sulfide sulfone and polyarylate;
the high-temperature resistant plasticizer is one or a combination of more of diphenyl sulfone, diphenyl isophthalate, diphenyl terephthalate, benzophenone and the like, the plasticizer mixing process plays a role in dispersing a perfluorinated polymer, the melt viscosity is reduced in the spinning process, the spinnability is improved, and the pore is formed by extraction and dissolution after spinning, so that the connectivity of a membrane pore is improved; preferably diphenyl sulfone;
the perfluorinated polymer is one or a combination of more of polytetrafluoroethylene and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and polymer micro powder is preferred;
heating the high-temperature-resistant plasticizer to 200-300 ℃, adding the perfluoropolymer into the high-speed mixing and stirring uniformly, adding the PEEK resin, heating to 310-360 ℃, fully swelling and uniformly mixing, cooling, crushing and grinding to obtain uniform particles, and fully and uniformly mixing the particles and the co-molten polymer pore-foaming agent through a high-speed mixer;
step 2, fully melting the spinning granules obtained in the step 1 at 310-360 ℃ through a screw extruder, extruding a spinning melt through a hollow spinning assembly, rotating the screw at the speed of 5-15 r/min, introducing inert gas or a high-temperature-resistant braided tube into the assembly, solidifying the spinning melt in an air bath, cooling and solidifying the spinning melt through a coagulating bath, heating and shaping, dissolving the co-melting polymer pore-forming agent through a solvent, extracting the high-temperature-resistant plasticizer through the solvent, cleaning and drying to obtain the PEEK hollow fiber membrane;
the hollow braided tube is formed by braiding at least one of high-temperature-resistant fiber filaments such as polyether-ether-ketone, aramid fibers, glass fibers, basalt fibers or carbon fibers by adopting a two-dimensional braiding technology, can keep the original form at the temperature of 340-390 ℃, and is not decomposed or melted; the outer diameter of the hollow braided tube is 1.0-2.5 mm; preferably homogeneous polyetheretherketone fibres;
the heating and shaping mode is that the material is subjected to fixed-length heat treatment in a hot stretching machine, the length is 30-110 cm, the heat treatment temperature is 150-250 ℃, and the treatment time is 3-5 h;
the dissolving and extracting solution is one or a combination of more of water, dichloromethane, N-methylpyrrolidone, monoethanolamine, dichloroethane, N-dimethylacetamide and N, N-dimethylformamide; the dissolution and extraction processes are kept under tension to prevent shrinkage.
The invention provides a polyether-ether-ketone hollow fiber membrane prepared by the method, namely a polyether-ether-ketone hollow fiber hydrophobic membrane.
The invention provides CO of the polyether-ether-ketone hollow fiber membrane2Gas membrane absorption applications.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the PEEK hollow fiber hydrophobic membrane is prepared by melt blending of the high-temperature-resistant hydrophobic perfluorinated polymer, secondary surface fluorination treatment is not needed, the problem of hydrophobic property reduction in the long-term application process is avoided, and the melt blending of the perfluorinated polymer particles is firmly embedded into the membrane, so that strong hydrophobicity is given to the membrane, and the stability is high. The hydrophobic polymer is prepared and mixed by the high-temperature plasticizer and the hydrophobic polymer to disperse the hydrophobic polymer, so that agglomeration is effectively avoided, and the melt spinning preparation process is simple, easy to amplify and capable of realizing continuous large-scale preparation.
(2) The PEEK hollow fiber membrane is subjected to fixed-length heat treatment by adopting a heat stretcher, and meanwhile, the dissolving and extracting processes are always carried out under tension, so that the PEEK is effectively prevented from shrinking, and the membrane structure is stabilized;
(3) the PEEK hollow fiber membrane prepared by the invention has strong hydrophobicity and high liquid permeation pressure, keeps stable hydrophobicity under the conditions of high temperature, strong acid and alkali and organic solvent, and is used for absorbing CO by the membrane2The process effectively slows down the membrane wetting phenomenon, improves the separation efficiency, prolongs the service life of the membrane and reduces the operation and investment cost.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of a PEEK hollow fiber membrane for membrane absorption obtained in example 1 of the present invention;
FIG. 2 is a partially enlarged scanning electron microscope image of a cross section of a hollow fiber membrane of polyetheretherketone for membrane absorption obtained in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the outer surface of a hollow fiber membrane of polyetheretherketone for membrane absorption obtained in example 1 of the present invention.
Detailed Description
Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The test reagents used in the following examples are all commercially available conventional chemical reagents unless otherwise specified, and the test methods used therein are all conventional methods unless otherwise specified.
Example 1
Step 1, heating 10 wt% of diphenyl sulfone to 180 ℃ for melting, adding 5 wt% of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer micro powder, mixing and stirring uniformly at a high speed, adding 45 wt% of PEEK resin, heating to 340 ℃, fully swelling and mixing uniformly, cooling, crushing and grinding to obtain uniform particles, and fully mixing the uniform particles and 40 wt% of polyetherimide pore-foaming agent uniformly through a high-speed mixer; blending, extruding and granulating by a high-temperature and corrosion resistant screw extruder to obtain uniform spinning granules;
and 2, fully melting the spinning granules obtained in the step 1 at 340 ℃ through a screw extruder, quantitatively extruding the spinning granules through a hollow spinning assembly at the screw rotation speed of 8 r/min, introducing 100 ℃ nitrogen into the assembly, solidifying the spinning melt in an air bath, cooling the spinning melt in a solidification bath, and solidifying the spinning melt to obtain the nascent hollow fiber membrane. Cutting 100 cm of membrane filaments, holding in a 220 ℃ stretching machine, carrying out fixed length treatment for 3h, continuing to keep the fixed length state, soaking for 24 h by using dichloromethane and alcohol, and cleaning and drying to obtain a PEEK hollow fiber membrane;
as shown in the attached figures 1-3, the cross section of the membrane and the surface electron microscope show, the obtained cross section is of uniform microporous structure, the surface roughness is large, the surface hydrophobicity of the membrane is improved, the water contact angle of the membrane is 116 degrees (after the membrane is treated by sodium hydroxide, hydrochloric acid, acetone, carbon tetrachloride and other solvents, the water contact angle of the membrane filament is basically unchanged), the average pore diameter is 28 nm, the liquid osmotic pressure is 0.86 MPa, and CO is absorbed by the membrane2Flux of 2.1X 10-3 mol/(m2·s)。
Example 2
Step 1, heating 10 wt% of diphenyl sulfone to 180 ℃ for melting, adding 5 wt% of polytetrafluoroethylene micro powder, mixing and stirring uniformly at a high speed, adding 50 wt% of PEEK resin, heating to 330 ℃, fully swelling and mixing uniformly, cooling, crushing and grinding to obtain uniform particles, and fully mixing the uniform particles with 35 wt% of polyetherimide pore-foaming agent by a high-speed mixer; blending, extruding and granulating by a high-temperature and corrosion resistant screw extruder to obtain uniform spinning granules;
and 2, fully melting the spinning granules obtained in the step 1 at 340 ℃ through a screw extruder, quantitatively extruding the spinning granules through a hollow spinneret assembly, wherein the rotating speed of the screw is 8 r/min, the interior of the assembly is a PEEK hollow braided tube with the outer diameter of 1.6 mm, and the winding speed is 7 m/min. And solidifying the spinning melt in an air bath, cooling by a coagulating bath, and solidifying to obtain the nascent hollow fiber membrane. Cutting 100 cm of membrane filaments, holding in a 220 ℃ stretching machine, carrying out fixed length treatment for 3h, continuing to keep the fixed length state, soaking for 24 h by using N-methylpyrrolidone and monoethanolamine, and cleaning and drying to obtain a PEEK hollow fiber membrane;
the water contact angle of the membrane obtained by testing is 122 degrees (after the membrane is treated by sodium hydroxide, hydrochloric acid, acetone, carbon tetrachloride and other solvents, the water contact angle of membrane filaments is basically unchanged), the average pore diameter is 22 nm, the liquid osmotic pressure is 1.12 MPa, and CO is absorbed by the membrane2Flux of 1.3X 10-3 mol/(m2·s)。
Example 3
Step 1, heating 14 wt% of diphenyl isophthalate to 150 ℃ for melting, adding 6 wt% of polytetrafluoroethylene micropowder, mixing and stirring uniformly at a high speed, adding 45 wt% of PEEK resin, heating to 340 ℃, fully swelling and mixing uniformly, cooling, crushing and grinding to obtain uniform particles, and fully mixing the uniform particles and 35 wt% of polyetherimide pore-foaming agent by a high-speed mixer; blending, extruding and granulating by a high-temperature and corrosion resistant screw extruder to obtain uniform spinning granules;
and 2, fully melting the spinning granules obtained in the step 1 at 340 ℃ through a screw extruder, quantitatively extruding the spinning granules through a hollow spinning assembly, wherein the rotating speed of the screw is 5 r/min, the internal outer diameter of the hollow glass fiber braided tube of which the inside is 1.8 mm is wound at the speed of 7 m/min, and after the spinning melt is solidified in an air bath, cooling and solidifying the spinning melt through a solidification bath to obtain the nascent hollow fiber membrane. Cutting 80 cm of membrane filaments, holding in a 230 ℃ stretching machine, carrying out fixed length treatment for 3h, continuing to keep the fixed length state, soaking for 24 h by using dichloromethane and alcohol, and cleaning and drying to obtain a PEEK hollow fiber membrane;
the water contact angle of the membrane obtained by testing is 127 degrees (after the membrane is treated by sodium hydroxide, hydrochloric acid, acetone, carbon tetrachloride and other solvents, the water contact angle of membrane filaments is basically unchanged), the average pore diameter is 35 nm, the liquid osmotic pressure is 0.79 MPa, and CO is absorbed by the membrane2Flux of 2.5X 10-3 mol/(m2·s)。
Example 4
Step 1, heating 14 wt% of diphenyl sulfone to melt at 200 ℃, adding 6 wt% of polytetrafluoroethylene micropowder, mixing and stirring uniformly at a high speed, adding 45 wt% of PEEK resin, heating to 350 ℃, fully swelling and mixing uniformly, cooling, crushing and grinding to obtain uniform particles, and fully mixing the uniform particles with 35 wt% of polyether sulfone pore-forming agent by a high-speed mixer; blending, extruding and granulating by a high-temperature and corrosion resistant screw extruder to obtain uniform spinning granules;
and 2, fully melting the spinning granules obtained in the step 1 at 350 ℃ through a screw extruder, quantitatively extruding the spinning granules through a hollow spinning assembly at the screw rotation speed of 5 r/min, introducing 80 ℃ nitrogen into the assembly, solidifying the spinning melt in an air bath, cooling the spinning melt in a solidification bath, and solidifying the spinning melt to obtain the nascent hollow fiber membrane. Cutting 100 cm of membrane filaments, holding in a 230 ℃ stretching machine, carrying out fixed length treatment for 5 h, continuing to keep the fixed length state, heating and soaking for 24 h by using N-methylpyrrolidone, and cleaning and drying to obtain a PEEK hollow fiber membrane;
the water contact angle of the membrane obtained by testing is 129 degrees (after the membrane is treated by sodium hydroxide, hydrochloric acid, acetone, carbon tetrachloride and other solvents, the water contact angle of membrane filaments is basically unchanged), the average pore diameter is 41 nm, the liquid osmotic pressure is 0.82 MPa, and CO is absorbed by the membrane2Flux of 3.1X 10-3 mol/(m2·s)。
Nothing in this specification is said to apply to the prior art.
Claims (9)
1. A preparation method of a polyether-ether-ketone hollow fiber membrane is characterized by comprising the following steps:
step 1, weighing the pre-dried PEEK resin, the co-molten polymer pore-foaming agent, the high-temperature resistant plasticizer and the perfluorinated polymer according to the following formula: 30-60 wt% of PEEK resin, 25-50 wt% of co-molten polymer pore-foaming agent, 10-40 wt% of high-temperature resistant plasticizer and 5-20 wt% of perfluoropolymer, wherein the sum of the components is 100%; after premixing, carrying out blending extrusion and grain cutting by an extruder to obtain uniform spinning granules;
wherein the co-melting polymer pore-foaming agent is one or a combination of more of polyetherimide, polyethylene oxide, polyimide, polyarylsulfone, polyethersulfone, polyphenylene sulfide sulfone and polyarylate,
the high-temperature resistant plasticizer is one or a combination of diphenyl sulfone, diphenyl isophthalate and diphenyl terephthalate,
the perfluorinated polymer is one or a combination of polytetrafluoroethylene and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer;
and 2, fully melting the spinning granules obtained in the step 1 at 310-360 ℃ through a screw extruder, extruding a spinning melt through a hollow spinning assembly, rotating the screw at the speed of 5-15 r/min, introducing inert gas or a high-temperature-resistant braided tube into the assembly, solidifying the spinning melt in an air bath, cooling and solidifying the spinning melt through a solidification bath, heating and shaping, dissolving the co-melting polymer pore-forming agent through a solvent, extracting the high-temperature-resistant plasticizer through the solvent, and cleaning and drying to obtain the PEEK hollow fiber membrane.
2. The method of claim 1, wherein the high temperature plasticizer of step 1 is diphenyl sulfone.
3. The method according to claim 1, wherein the perfluoropolymer in step 1 is a polymer fine powder having a particle size of less than 5 μm.
4. The method of claim 1, wherein the premixing step of step 1 is as follows: heating the high-temperature-resistant plasticizer to 200-300 ℃, adding the perfluoropolymer into the mixture, mixing and stirring the mixture at a high speed, adding the PEEK resin into the mixture, heating the mixture to 310-360 ℃, fully swelling the mixture, uniformly mixing the mixture, cooling the mixture, crushing and grinding the mixture to obtain uniform particles, and fully and uniformly mixing the particles with the co-molten polymer pore-forming agent through a high-speed mixer.
5. The preparation method according to claim 1, characterized in that the hollow braided tube of step 2 is at least one of polyetheretherketone, aramid fiber, glass fiber, basalt fiber or carbon fiber, and is braided by a two-dimensional braiding technique; the hollow braided tube has high temperature resistance range of 340-390 ℃ and an outer diameter of 1.0-2.5 mm.
6. The preparation method according to claim 1, wherein the heating and setting step in step 2 is a fixed length heat treatment in a hot stretching machine, the length is 30-110 cm, the heat treatment temperature is 150-250 ℃, and the treatment time is 3-5 h.
7. The preparation method according to claim 1, wherein the solvent in step 2 is one or more of water, dichloromethane, N-methylpyrrolidone, monoethanolamine, dichloroethane, N-dimethylacetamide and N, N-dimethylformamide; the dissolution and extraction processes are kept under tension.
8. A hollow fiber membrane of polyetheretherketone produced by the method of any one of claims 1 to 7.
9. CO of the hollow fiber membrane of polyetheretherketone according to claim 82Gas membrane absorption applications.
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| CN115369517A (en) * | 2022-08-30 | 2022-11-22 | 烟台民士达特种纸业股份有限公司 | Preparation method and application of polyether-ether-ketone nanofiber membrane |
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| CN115369517A (en) * | 2022-08-30 | 2022-11-22 | 烟台民士达特种纸业股份有限公司 | Preparation method and application of polyether-ether-ketone nanofiber membrane |
| CN115369517B (en) * | 2022-08-30 | 2023-09-01 | 烟台民士达特种纸业股份有限公司 | Preparation method and application of polyether-ether-ketone nanofiber membrane |
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