CN116020283A - Composite hollow fiber ceramic membrane and preparation method thereof - Google Patents
Composite hollow fiber ceramic membrane and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 94
- 239000012528 membrane Substances 0.000 title claims abstract description 88
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000005266 casting Methods 0.000 claims abstract description 75
- 239000000654 additive Substances 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 15
- 230000001112 coagulating effect Effects 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000007872 degassing Methods 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 239000000853 adhesive Substances 0.000 claims abstract description 3
- 230000001070 adhesive effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 71
- 238000005345 coagulation Methods 0.000 claims description 27
- 230000015271 coagulation Effects 0.000 claims description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 13
- -1 solsperse3000 Polymers 0.000 claims description 13
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000004695 Polyether sulfone Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229920006393 polyether sulfone Polymers 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 229920005596 polymer binder Polymers 0.000 claims description 6
- 239000002491 polymer binding agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- SHBUUTHKGIVMJT-UHFFFAOYSA-N Hydroxystearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OO SHBUUTHKGIVMJT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 229940072106 hydroxystearate Drugs 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 229940095574 propionic acid Drugs 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229950004959 sorbitan oleate Drugs 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 2
- 229910001220 stainless steel Inorganic materials 0.000 abstract 1
- 239000010935 stainless steel Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000004907 flux Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a composite hollow fiber ceramic membrane and a preparation method thereof, belonging to the technical field of membrane material preparation, wherein the method comprises the following process steps: adding ceramic powder, an additive, a nanoparticle dispersing agent and a nano additive into an organic solvent, fully stirring through a ball mill, and then adding a polymer adhesive to continuously stir to prepare a uniformly dispersed casting solution; degassing the casting solution under vacuum; transferring the casting solution into a stainless steel container and extruding the casting solution into an external coagulating bath from a pipe hole spinneret through a syringe pump to complete the phase inversion process, so as to obtain a hollow fiber ceramic membrane precursor; and drying the precursor at room temperature, and finally obtaining the composite hollow fiber ceramic membrane through high-temperature sintering.
Description
Technical Field
The invention belongs to the technical field of membrane material preparation, and particularly relates to a composite hollow fiber ceramic membrane and a preparation method thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The membrane separation technology is used as an efficient, energy-saving and environment-friendly separation technology, and is widely applied to the fields of liquid and gas separation, sewage treatment, drinking water industry, sea water desalination and the like. According to the external structure of the ceramic membrane, the ceramic membrane can be divided into a flat membrane, a single-pore tubular membrane, a porous tubular membrane and a hollow fiber membrane. Among them, flat sheet membranes are disadvantageous for large-scale industrial applications due to their low packing density, and are mainly used for small-scale industrial applications and laboratory research. The packing density and the membrane strength of the single-channel tubular membrane are also low, so that the low separation efficiency leads to the adverse effect on industrial application; the multi-channel tubular membrane has high production cost although the mechanical strength and the assembly density are improved; the hollow fiber ceramic membrane has high assembly density and simple and convenient preparation process, and has high permeability and separation efficiency due to the asymmetric structure of the hollow fiber membrane, so that the hollow fiber ceramic membrane is widely paid attention to by more researchers.
Because the ceramic material is brittle naturally, brittle fracture is very easy to occur due to stress concentration caused by defects existing on the surface or in the ceramic material, and the reinforcement and toughening of the porous ceramic membrane become a urgent problem to be solved; meanwhile, how to further improve the hydrophilicity of the hollow fiber ceramic membrane so as to obtain higher permeability and lower membrane pollution in the water treatment process is also a problem to be solved.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a composite hollow fiber ceramic membrane and a preparation method thereof, and the preparation method can effectively improve the toughness and the hydrophilicity of the membrane.
The preparation method of the composite hollow fiber ceramic membrane is a phase inversion dry-wet spinning technology, and takes an aqueous solution containing N-methyl pyrrolidone or polyethylene glycol as a coagulating bath, and researches show that adding a solvent into the coagulating bath can reduce the polymer concentration at a membrane interface, and simultaneously can reduce the activity of a non-solvent and the rate of diffusion into the polymer membrane, so that the delamination is further delayed, the membrane has smoother surface and smaller surface roughness, and meanwhile, the produced porous sponge layer can effectively reduce the passing resistance of a permeate and improve the water outlet flux of the membrane.
Yttria stabilized zirconia, zirconia and alumina are used as ceramic powder, silicon carbide, silicon dioxide, molecular sieve or polyethylene glycol are used as nano additives for coating up-conversion nano particles, and research shows that in order to increase the wall strength between the gaps in the porous ceramic, reinforcing materials are required to be added, the most effective additives are carbide and oxide in particle, fiber or tubular form, and in order to avoid the influence of the size of the particles on the membrane pore structure, nano-sized additives are required to be used; meanwhile, when two sizes of ceramic powder and nano additive are mixed, smaller particles can fill unoccupied gaps between large particles. So as long as the proportion of the nano additive is proper, the proportion of the ceramic powder can reach the optimal filling density obtained in the phase of mutual contact, thereby improving the toughness of the ceramic membrane, and simultaneously, the hydrophilicity of the ceramic membrane can be improved due to the inherent hydrophilic property of the nano additive, thereby obtaining higher separation efficiency and better permeability. And citric acid is used as a nano dispersing agent to inhibit agglomeration of the nano additive.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the composite hollow fiber ceramic membrane comprises the following steps:
(1) Adding the additive into an organic solvent, and fully stirring to obtain a casting solution A; sequentially adding ceramic powder, a nanoparticle dispersing agent and a nano additive into the casting solution A, and fully stirring the mixture in a ball mill to obtain casting solution B; adding a polymer adhesive into the casting solution B, and fully stirring to form a uniformly dispersed casting solution C;
(2) Degassing the casting solution C under vacuum; extruding the casting solution C from the pipe hole spinneret into an external coagulating bath through a syringe pump to complete the phase inversion process, so as to obtain a hollow fiber ceramic membrane precursor;
(3) Sintering the composite hollow fiber ceramic membrane: drying the hollow fiber ceramic membrane precursor at room temperature, and sintering at two steps of high temperature in a tube furnace to finally obtain the composite hollow fiber ceramic membrane.
Further, the ceramic powder is Al 2 O 3 、ZrO 2 Yttria is stableOne or more of the defined zirconia powder, the particle size of the powder is 0.3-5 microns, and the addition amount of the powder is 30-60% of the total mass of the casting solution C.
Further, the nano dispersing agent is citric acid, and the addition amount of the nano dispersing agent is 0-1% of the total mass of the casting solution C.
Furthermore, the nano additive is silicon carbide, silicon dioxide, molecular sieve or polyethylene glycol coated up-conversion nano particles, the addition amount of the nano particles does not account for the total amount of the casting solution, and the addition amount of the nano additive is 0-50% of the mass fraction of ceramic powder in the ceramic powder and nano particle additive samples.
Further, the polymer binder is one or more of polyethersulfone, polysulfone and polyetherimide, and the addition amount of the polymer binder is 5-25% of the total mass of the casting solution C.
Further, the organic solvent is one or more of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, and the addition amount of the organic solvent is 35-55% of the total mass of the casting solution C.
Further, the additive is polyvinylpyrrolidone, solsperse3000, polyethylene glycol-30 dimer hydroxystearate, propionic acid, sorbitan oleate, polyethylene oxide or O- (2-aminopropyl) -O · The addition amount of the- (2-methoxyethyl) -polypropylene glycol is 1 to 8 percent of the total mass of the casting solution C.
Further, before addition, the ceramic powder and nanoparticle additives were placed in a 70 ℃ oven dry sufficiently to ensure no moisture retention.
Further, after the casting solution A is sufficiently ground by a planetary ball grinder, adding a polymer binder, continuously grinding until the system is uniformly dispersed, and finally degassing the casting solution A under vacuum to remove excessive bubbles remained in the casting solution A, thereby finally obtaining the casting solution.
Further, in the preparation of the hollow fiber ceramic membrane precursor in the step (2), water or absolute ethyl alcohol is used as a core liquid, water, an aqueous solution containing 1-5% of N-methylpyrrolidone or an aqueous solution containing 1-5% of polyethylene glycol is used as a coagulating bath, the extrusion pressure is 0.03-0.2 MPa, and the casting solution C enters the coagulating bath after passing through an air gap of 2-20 cm and is phase-converted in the coagulating bath for 24 hours.
Further, the high-temperature sintering process of the hollow fiber ceramic membrane precursor in the step (3) is firstly carried out to 400-600 ℃ at a heating rate of 2-6 ℃/min so as to remove organic components in the hollow fiber ceramic membrane precursor, then the temperature is raised to 1000-1600 ℃ at a heating rate of 2-6 ℃/min so as to be kept for 8-12 hours, finally the temperature is gradually reduced to room temperature at a cooling rate of 3-5 ℃/min, and finally the composite hollow fiber ceramic membrane is obtained.
The invention has the advantages that:
through optimizing raw materials and a preparation process, ceramic raw materials with different particle sizes are adopted for blending and nano additive loading, and the optimal filling density is achieved by adjusting the proportion, so that the toughness of the ceramic membrane can be improved, the toughness and the compressive strength of a composite ceramic membrane prepared from a casting membrane solution are further improved, and meanwhile, the hydrophilic performance of the ceramic membrane can be improved due to the nano additive with inherent hydrophilicity; and simultaneously, an aqueous solution containing N-methyl pyrrolidone or an aqueous solution containing polyethylene glycol is used as a coagulating bath, so that the water flux of the finally prepared ceramic membrane is further improved.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
The preparation method of the composite hollow fiber ceramic membrane comprises the following process steps:
step 1: preparation of casting solution
1.1, placing the ceramic powder into a 70 ℃ oven for full drying so as to ensure no water retention;
1.2 adding polyethylene glycol-30 dipolyhydroxystearate into N-methylpyrrolidone, wherein the addition amount of the polyethylene glycol-30 dipolyhydroxystearate is 5%, wherein the addition amount of the N-methylpyrrolidone is 35%, and fully stirring to obtain casting film liquid A;
1.3 adding yttria-stabilized zirconia into the casting solution A and fully stirring the yttria-stabilized zirconia in a ball mill to obtain casting solution B so as to ensure that ceramic particles, a solvent and an additive are fully mixed, wherein the addition amount of the yttria-stabilized zirconia is 40%;
1.4 adding polyethersulfone into the casting solution B, and fully stirring to form a uniformly dispersed casting solution C, wherein the addition amount of polyethersulfone is 20%.
1.5 degassing the casting solution C under vacuum;
step 2: preparation of hollow fiber ceramic membrane precursors
2.1 extruding a casting solution C through a pipe hole spinneret with nitrogen pressure of 0.1MPa, pumping an internal coagulant (core solution) into the hole of the spinneret, immersing the green hollow fiber body into an external coagulation bath for 24 hours after passing through an air gap of 10cm to complete a phase conversion process, and drying the precursor in air at room temperature (25 ℃) to finally obtain a hollow fiber ceramic membrane precursor; wherein the internal coagulation bath: water, internal coagulation bath flow rate: 20mL/min; external coagulation bath: water; extrusion speed: 22mL/min; spinneret size: 1.3mm/2.5mm.
Step 3: sintered composite hollow fiber ceramic membrane
3.1 drying the precursor at room temperature, then raising the temperature to 500 ℃ at the heating rate of 2 ℃/min for 2 hours to remove organic components in the hollow fiber ceramic membrane precursor, raising the temperature to 1500 ℃ at the heating rate of 5 ℃/min for 12 hours, and finally gradually cooling to room temperature at the cooling rate of 5 ℃/min to obtain the porous high-strength hollow fiber ceramic membrane.
Example 2
The preparation method of the composite hollow fiber ceramic membrane comprises the following process steps:
step 1: preparation of casting solution
1.1, placing the ceramic powder into a 70 ℃ oven for full drying so as to ensure no water retention;
1.2 adding polyethylene glycol-30 dipolyhydroxystearate into N-methylpyrrolidone, wherein the addition amount of the polyethylene glycol-30 dipolyhydroxystearate is 5%, wherein the addition amount of the N-methylpyrrolidone is 35%, and fully stirring to obtain casting film liquid A;
1.3 adding yttria-stabilized zirconia into the casting solution A and fully stirring the yttria-stabilized zirconia in a ball mill to obtain casting solution B so as to ensure that ceramic particles, a solvent and an additive are fully mixed, wherein the addition amount of the yttria-stabilized zirconia is 40%;
1.4 adding polyethersulfone into the casting solution B, and fully stirring to form a uniformly dispersed casting solution C, wherein the addition amount of polyethersulfone is 20%.
1.5 degassing the casting solution C under vacuum;
step 2: preparation of hollow fiber ceramic membrane precursors
2.1 extruding a casting solution C through a pipe hole spinneret with nitrogen pressure of 0.1MPa, pumping an internal coagulant (core solution) into the hole of the spinneret, immersing the green hollow fiber body into an external coagulation bath for 24 hours after passing through an air gap of 10cm to complete a phase conversion process, and drying the precursor in air at room temperature (25 ℃) to finally obtain a hollow fiber ceramic membrane precursor; wherein the internal coagulation bath: water, internal coagulation bath flow rate: 20mL/min; external coagulation bath: an aqueous solution containing 4% of N-methylpyrrolidone; extrusion speed: 22mL/min; spinneret size: 1.3mm/2.5mm.
Step 3: sintered composite hollow fiber ceramic membrane
3.1 drying the precursor at room temperature, then raising the temperature to 500 ℃ at the heating rate of 2 ℃/min for 2 hours to remove organic components in the hollow fiber ceramic membrane precursor, raising the temperature to 1500 ℃ at the heating rate of 5 ℃/min for 12 hours, and finally gradually cooling to room temperature at the cooling rate of 5 ℃/min to obtain the porous high-strength hollow fiber ceramic membrane.
Example 3
The preparation method of the composite hollow fiber ceramic membrane comprises the following process steps:
step 1: preparation of casting solution
1.1, placing the ceramic powder into a 70 ℃ oven for full drying so as to ensure no water retention;
1.2 adding polyethylene glycol-30 dipolyhydroxystearate into N-methylpyrrolidone, wherein the addition amount of the polyethylene glycol-30 dipolyhydroxystearate is 5%, wherein the addition amount of the N-methylpyrrolidone is 35%, and fully stirring to obtain casting film liquid A;
1.3 adding yttria-stabilized zirconia into the casting solution A and fully stirring the yttria-stabilized zirconia in a ball mill to obtain casting solution B so as to ensure that ceramic particles, a solvent and an additive are fully mixed, wherein the addition amount of the yttria-stabilized zirconia is 40%;
1.4 adding polyethersulfone into the casting solution B, and fully stirring to form a uniformly dispersed casting solution C, wherein the addition amount of polyethersulfone is 20%.
1.5 degassing the casting solution C under vacuum;
step 2: preparation of hollow fiber ceramic membrane precursors
2.1 extruding a casting solution C through a pipe hole spinneret with nitrogen pressure of 0.1MPa, pumping an internal coagulant (core solution) into the hole of the spinneret, immersing the green hollow fiber body into an external coagulation bath for 24 hours after passing through an air gap of 10cm to complete a phase conversion process, and drying the precursor in air at room temperature (25 ℃) to finally obtain a hollow fiber ceramic membrane precursor; wherein the internal coagulation bath: water, internal coagulation bath flow rate: 20mL/min; external coagulation bath: an aqueous solution containing 4% polyethylene glycol; extrusion speed: 22mL/min; spinneret size: 1.3mm/2.5mm.
Step 3: sintered composite hollow fiber ceramic membrane
3.1 drying the precursor at room temperature, then raising the temperature to 500 ℃ at the heating rate of 2 ℃/min for 2 hours to remove organic components in the hollow fiber ceramic membrane precursor, raising the temperature to 1500 ℃ at the heating rate of 5 ℃/min for 12 hours, and finally gradually cooling to room temperature at the cooling rate of 5 ℃/min to obtain the porous high-strength hollow fiber ceramic membrane.
Example 4
The preparation method of the composite hollow fiber ceramic membrane comprises the following process steps:
step 1: preparation of casting solution
1.1, placing ceramic powder and nano particle additive into a 70 ℃ oven for full drying so as to ensure no water retention;
1.2 adding polyethylene glycol-30 dipolyhydroxystearate into N-methylpyrrolidone, wherein the addition amount of the polyethylene glycol-30 dipolyhydroxystearate is 5%, wherein the addition amount of the N-methylpyrrolidone is 35%, and fully stirring to obtain casting film liquid A;
1.3 adding yttria-stabilized zirconia, silicon carbide and citric acid into the casting solution A and fully stirring the mixture in a ball mill to obtain casting solution B so as to ensure that ceramic particles, a solvent and additives are fully mixed, wherein the addition amount of the yttria-stabilized zirconia is 40%, the addition amount of the citric acid is 0.6%, and the loading amount of the silicon carbide is 5%;
1.4 adding polyethersulfone into the casting solution B, and fully stirring to form a uniformly dispersed casting solution C, wherein the addition amount of polyethersulfone is 19.4%.
1.5 degassing the casting solution C under vacuum;
step 2: preparation of hollow fiber ceramic membrane precursors
2.1 extruding a casting solution C through a pipe hole spinneret with nitrogen pressure of 0.1MPa, pumping an internal coagulant (core solution) into the hole of the spinneret, immersing the green hollow fiber body into an external coagulation bath for 24 hours after passing through an air gap of 10cm to complete a phase conversion process, and drying the precursor in air at room temperature (25 ℃) to finally obtain a hollow fiber ceramic membrane precursor; wherein the internal coagulation bath: water, internal coagulation bath flow rate: 20mL/min; external coagulation bath: an aqueous solution containing 4% of N-methylpyrrolidone; extrusion speed: 22mL/min; spinneret size: 1.3mm/2.5mm.
Step 3: sintered composite hollow fiber ceramic membrane
3.1 drying the precursor at room temperature, then raising the temperature to 500 ℃ at the heating rate of 2 ℃/min for 2 hours to remove organic components in the hollow fiber ceramic membrane precursor, raising the temperature to 1500 ℃ at the heating rate of 5 ℃/min for 12 hours, and finally gradually cooling to room temperature at the cooling rate of 5 ℃/min to obtain the porous high-strength hollow fiber ceramic membrane.
Example 5
The difference from example 4 is that: the silicon carbide loading was 15%.
Example 6
The difference from example 4 is that: the silicon carbide loading was 25%.
Example 7
The difference from example 5 is that: nanoparticle additive: silica.
Example 8
The difference from example 5 is that: nanoparticle additive: polyethylene glycol coats the up-conversion nanoparticles.
Example 9
The difference from example 5 is that: nanoparticle additive: HZSM-5; calcination temperature: 1000 ℃.
Example 10
The difference from example 2 is that: the coagulation bath is as follows: an aqueous solution containing 2% of N-methylpyrrolidone.
Example 11
The difference from example 2 is that: the coagulation bath is as follows: an aqueous solution containing 5% of N-methylpyrrolidone.
Example 12
The difference from example 3 is that: the coagulation bath is as follows: aqueous solution containing 2% polyethylene glycol
Example 13
The difference from example 3 is that: the coagulation bath is as follows: aqueous solution containing 2% polyethylene glycol
Performance test
Performance test data were carried out using the composite hollow fiber ceramic membranes prepared in examples 1 to 13, and the test results are shown in table 1:
TABLE 1
In combination with examples 1, 2 and 3, it can be seen that the composition of different coagulating liquids in the film-forming slurry can have a great influence on the performance of the finally formed hollow fiber ceramic film, and the composition of the coagulating liquid used for the film-forming slurry in example 2 is optimal, so that the prepared hollow fiber ceramic film has the greatest porosity, the highest pure water flux, the best hydrophilicity and the best compressive strength.
In combination with examples 1, 2 and 4, it can be seen that in example 4, silicon carbide and citric acid were added to the casting solution, wherein the addition amount of citric acid was 0.6%, and the loading amount of silicon carbide was 5%; when the coagulating bath is an aqueous solution containing 4% of N-methyl pyrrolidone, the compressive strength and the hydrophilicity of the prepared hollow fiber ceramic membrane are greatly improved under the condition of ensuring good porosity and water flux.
In combination with examples 4, 5 and 6, it can be seen that the loading of the nanoparticle additive silicon carbide added to the casting solution is 5%, 15% and 25%, wherein when the loading of silicon carbide is 15%, the compressive strength and hydrophilicity of the prepared hollow fiber ceramic membrane are improved maximally under the condition of ensuring good porosity and water flux.
In combination with examples 5, 7, 8 and 9, it can be seen that the nanoparticle additives added to the casting solution are silicon carbide, silica, polyethylene glycol coated up-conversion nanoparticles and HZSM-5 (calcination temperature: 1000 ℃), respectively, wherein the compressive strength and hydrophilicity of the hollow fiber ceramic membrane obtained are improved to the greatest extent when the nanoparticle additive added is silicon carbide.
In combination with examples 2, 10 and 11, it can be seen that the concentrations of N-methylpyrrolidone in the external coagulation bath added to the casting solution were 2%, 4% and 5%, respectively, wherein the porosity, water flux and compressive strength of the hollow fiber ceramic membrane were all maximally improved when the concentration of N-methylpyrrolidone in the external coagulation bath was 4%.
In combination with examples 3, 13 and 14, it can be seen that the polyethylene glycol concentration of the external coagulation bath added to the casting solution was 2%, 4% and 5%, respectively, wherein the porosity, water flux and compressive strength of the hollow fiber ceramic membrane were all maximally improved when the polyethylene glycol concentration of the external coagulation bath was 4%.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention. While the foregoing describes the embodiments of the present invention, it should be understood that the present invention is not limited to the embodiments, and that various modifications and changes can be made by those skilled in the art without any inventive effort.
Claims (10)
1. The preparation method of the composite hollow fiber ceramic membrane is characterized by comprising the following steps of:
(1) Adding the additive into an organic solvent, and fully stirring to obtain a casting solution A; sequentially adding ceramic powder, a nanoparticle dispersing agent and a nano additive into the casting solution A, and fully stirring the mixture in a ball mill to obtain casting solution B; adding a polymer adhesive into the casting solution B, and fully stirring to form a uniformly dispersed casting solution C;
(2) Degassing the casting solution C under vacuum; extruding the casting solution C from the pipe hole spinneret into an external coagulating bath through a syringe pump to complete the phase inversion process, so as to obtain a hollow fiber ceramic membrane precursor;
(3) Sintering the composite hollow fiber ceramic membrane: drying the hollow fiber ceramic membrane precursor at room temperature, and sintering at two steps of high temperature in a tube furnace to finally obtain the composite hollow fiber ceramic membrane.
2. The method according to claim 1, wherein the additive is polyvinylpyrrolidone, solsperse3000, polyethylene glycol-30 dimer hydroxystearate, propionic acid, sorbitan oleate, polyethylene oxide or O- (2-ammonia)Propyl) -O · - (2-methoxyethyl) -polypropylene glycol, the addition amount of which is 1-8% of the total mass of the casting solution C; the organic solvent is one or more of N-methyl pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, and the addition amount of the organic solvent is 35-55% of the total mass of the casting solution C.
3. The method according to claim 1, wherein the ceramic powder is Al 2 O 3 、ZrO 2 One or more of yttria-stabilized zirconia powder, wherein the particle size of the powder is 0.3-5 microns, and the addition amount of the powder is 30-60% of the total mass of the casting solution C.
4. The preparation method of claim 1, wherein the nano-dispersing agent is citric acid, and the addition amount of the nano-dispersing agent is 0-1% of the total mass of the casting solution C.
5. The preparation method according to claim 1, wherein the nano additive is silicon carbide, silicon dioxide, molecular sieve or polyethylene glycol coated up-conversion nano particles, and the loading amount is 0-50% of the adding amount of the ceramic powder.
6. The preparation method of claim 1, wherein the polymer binder is one or more of polyethersulfone, polysulfone and polyetherimide, and the addition amount of the polymer binder is 5-25% of the total mass of the casting solution C.
7. The method of claim 1, wherein the ceramic powder and nanoparticle additive are dried at 70 ℃ to ensure no moisture retention prior to addition.
8. The preparation method according to claim 1, wherein after the casting solution A is sufficiently ground by a planetary ball mill, a polymer binder is added to continuously grind until the system is uniformly dispersed, and finally the system is degassed under vacuum to remove excessive bubbles remained in the system, thereby obtaining the casting solution.
9. The method according to claim 1, wherein water or absolute ethyl alcohol is used as a core liquid in the preparation of the hollow fiber ceramic membrane precursor in the step (2), water, an aqueous solution containing 1-5% of n-methylpyrrolidone or an aqueous solution containing 1-5% of polyethylene glycol is used as a coagulation bath, the extrusion pressure is 0.03-0.2 MPa, the casting solution C enters the coagulation bath after passing through an air gap of 2-20 cm, and phase-inversion is performed in the coagulation bath for 24 hours;
or, in the high-temperature sintering process of the hollow fiber ceramic membrane precursor in the step (3), firstly, the temperature is increased to 400-600 ℃ at the heating rate of 2-6 ℃/min so as to remove organic components in the hollow fiber ceramic membrane precursor, then, the temperature is increased to 1000-1600 ℃ at the heating rate of 2-6 ℃/min so as to keep the temperature for 8-12 hours, and finally, the temperature is gradually reduced to room temperature at the cooling rate of 3-5 ℃/min, so that the composite hollow fiber ceramic membrane is finally obtained.
10. A composite hollow fiber ceramic membrane prepared according to the preparation method of any one of the preceding claims.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090120875A1 (en) * | 2007-11-08 | 2009-05-14 | Chunqing Liu | High Performance Mixed Matrix Membranes Incorporating at Least Two Kinds of Molecular Sieves |
| CN102160967A (en) * | 2011-03-21 | 2011-08-24 | 南京工业大学 | Lining enhanced hollow fiber membrane tube and preparation device and preparation method thereof |
| CN102327745A (en) * | 2010-07-12 | 2012-01-25 | 华东理工大学 | Preparation method of alumina hollow fibre membrane containing inorganic additive |
| CN103638822A (en) * | 2013-12-24 | 2014-03-19 | 深圳市诚德来实业有限公司 | Hollow fiber nano-filtration membrane and preparation method thereof |
| US20150053611A1 (en) * | 2013-08-23 | 2015-02-26 | Nanyang Technological University | Hydrophobic organic-inorganic composite hollow fiber membrane and method of forming the same |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090120875A1 (en) * | 2007-11-08 | 2009-05-14 | Chunqing Liu | High Performance Mixed Matrix Membranes Incorporating at Least Two Kinds of Molecular Sieves |
| CN102327745A (en) * | 2010-07-12 | 2012-01-25 | 华东理工大学 | Preparation method of alumina hollow fibre membrane containing inorganic additive |
| CN102160967A (en) * | 2011-03-21 | 2011-08-24 | 南京工业大学 | Lining enhanced hollow fiber membrane tube and preparation device and preparation method thereof |
| US20150053611A1 (en) * | 2013-08-23 | 2015-02-26 | Nanyang Technological University | Hydrophobic organic-inorganic composite hollow fiber membrane and method of forming the same |
| CN103638822A (en) * | 2013-12-24 | 2014-03-19 | 深圳市诚德来实业有限公司 | Hollow fiber nano-filtration membrane and preparation method thereof |
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