CN104841286A - Spiral inorganic hollow fiber film and preparation method thereof - Google Patents
Spiral inorganic hollow fiber film and preparation method thereof Download PDFInfo
- Publication number
- CN104841286A CN104841286A CN201510230331.9A CN201510230331A CN104841286A CN 104841286 A CN104841286 A CN 104841286A CN 201510230331 A CN201510230331 A CN 201510230331A CN 104841286 A CN104841286 A CN 104841286A
- Authority
- CN
- China
- Prior art keywords
- casting solution
- preparation
- helical form
- inorganic hollow
- hollow fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention belongs to the technical field of inorganic films, and particularly relates to a spiral inorganic hollow fiber film and a preparation method thereof. The preparation method comprises the basic steps of preparing film casting liquid containing an inorganic powder material, a polymer bonder, a solvent and an additive; preparing an inorganic hollow fiber film precursor with a composite membrane asymmetrical structure according to a spinning phase conversion method; uniformly winding the hollow fiber film precursor on a quartz or ceramic die for molding, and sintering to prepare the spiral inorganic hollow fiber film under specific atmosphere by a certain sintering procedure. A softener is added in the film casting liquid to improve the tenacity of the hollow fiber film precursor, and sintering is performed by the specific dies. The prepared hollow fiber film has a spring-like spiral appearance, internally has a typical asymmetric structure of a composite film porous layer plus a separated layer, can overcome the limitation of thermal expansion and chilling shrinkage in a temperature varying operation, and the preparation process is simple without complex equipment demands and convenient for industrialized production.
Description
Technical field
The invention belongs to inorganic membrane technology field, be specifically related to a kind of helical form or spring type inorganic hollow fibers film and preparation method thereof, comprise the preparation of porous ceramic film, dense ceramic membrane and porous metal film.
Background technology
Inoranic membrane is the parting material with selective penetrating quality made by inorganic material such as pottery, metal, glass, it is good that it has chemical stability, mechanical strength is high, acid and alkali resistance, organic solvent are corroded, can at high temperature use, regenerating easily, the advantages such as long service life, are widely used in separation and purification and the chemical reaction process of mixture.But Preparation of inorganic membrane process is complicated, and process route is long, and need repetitious high temperature sintering, thus cost is high, limits its wider application.By making the micro-tubular hollow-fibre membrane of diameter at φ 0.5 ~ 3.0 mm, improving the membrane area of unit volume and reducing effective film thickness, improving the separating property of film, effectively can reduce production and the application cost of inoranic membrane.
In the last few years, people generally adopt a kind of spinning-sintering technology based on polymer solution inversion of phases to prepare inorganic hollow fibers film (Xiaoyao Tan, Shaomin Liu, K. Li, Journal of Membrane Science 188 (2001) 87 – 95), this method only needs one-step shaping and step sintering just to can be made into the inorganic hollow fibers film with porous support layer and effective separating layer asymmetric compound structure, thus greatly simplify filming technology, reduce the production cost of inoranic membrane, what is more important, the micro-structural of hollow-fibre membrane can be regulated by changing preparation manipulation parameter, and then reach the object (Tan little Yao improving Middle hollow fiber membrane performance, Yin Weining, Meng Bo, Meng Xiuxia, a kind of preparation method of composite structural ceramic hollow fiber membrane, Chinese invention patent CN100577606).
But inorganic hollow fibers film, because caliber is little, tube wall is thin, fragility is large, is difficult to the membrane module being assembled into large membrane area.When particularly at high temperature operating, if hollow-fibre membrane two ends are fixed in membrane module, because variations in temperature causes expanding with heat and contract with cold of tunica fibrosa to cause hollow-fibre membrane easily to rupture, even if the other end can be made to close by one end of only fixing hollow-fibre membrane solve the problem of expanding with heat and contract with cold with free-extension method, doughnut film length in membrane module also can not be oversize because being subject to high-temperature sealing material restriction, thus greatly can reduce effective usable floor area of film.A kind of effective solution is that hollow-fibre membrane is done curl or spring-like, even if the hollow-fibre membrane two ends of this shape are fixed, also volume expansion can be changed into because of being expanded by the line of microtubular membrane, thus also can free-extension when variations in temperature, thus avoid causing hollow-fibre membrane to rupture owing to expanding with heat and contract with cold, the more important thing is, because the actual effective length of helical form film can be very long, it can provide very large membrane area in very short membrane module, is particularly suitable for the separation or the course of reaction that need long residence time.But conventional phase-inversion technologies is difficult to obtained this spiral helicine hollow-fibre membrane.The present invention by preparation high-flexibility casting solution, and has obtained different types of helical form inorganic hollow fibers film by controlling sintering process.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology simple, without complex device requirement, the helical form inorganic hollow fibers film being convenient to suitability for industrialized production and preparation method thereof.
The present invention is the improvement that conventional inversion of phases prepares doughnut film method, by adding softening agent, dispersant in casting solution, strengthen the pliability of doughnut film precursor, again by precursor film uniform winding in pottery or quartz ampoule mould on, by certain sintering procedure high temperature sintering in specific atmosphere, obtained helical form inorganic hollow fibers film.The concrete steps of preparation are as follows:
(1) prepare casting solution: be dissolved in organic solvent by softening agent and dispersant, add inorganic material powder, fully stir and powder is soaked, then add polymeric binder in batches, strong stirring makes it dissolve completely, obtained uniform and stable casting solution.
Polymer bonding agent used is the one in polysulfones (PSF), polyether sulfone (PES), polyacrylonitrile (PAN) and PEI (PEI); Organic solvent is the one in 1-METHYLPYRROLIDONE (NMP), DMF (DMF), DMA (DMAc) and dimethyl sulfoxide (DMSO) (DMSO).
Softening agent used is a kind of macromolecular material auxiliary agent, is the one in dioctyl phthalate (DOP), epoxidized soybean oil (ESO), dibutyl phthalate (DBP), dioctyl adipate (DOA), or wherein several mixing; Dispersant used is the one in polyvinylpyrrolidone, ammonium polymethacrylate, polymethyl methacrylate and phosphate, or wherein several mixing.
In described casting solution processed, organic polymer thing bonding agent mass content accounts for the 5-10% of casting solution total amount; Organic solvent accounts for the 20-40% of casting solution total amount; Inorganic powder accounts for the 50-70% of casting solution total amount; Softening agent accounts for the 0.5-3% of casting solution total amount; Dispersant accounts for the 0.5-2% of casting solution total amount.Total amount is 100%.
(2) by above-mentioned steps (1) gained casting solution, inorganic hollow fibers film precursor is prepared by dry-jet wet-spinning silk device.
Casting solution, first through vacuum outgas 20-28 hour (preferred vacuum outgas 24-26 hour), moves in spinning batch can.Under gas pressure, casting solution enters in the coagulation bath of pure water or water/solvent mixed liquor by spinneret, after the solvents of 12 ~ 48 hours-water coke slurry process settings is shaping, applies the washing of a large amount of water soaking, to make solvent complete exchange out, ensure that membrane structure is stablized.Wherein, the size of hollow-fibre membrane, thickness are by the adjustment such as size, gas pressure of spinneret.
(3) above-mentioned steps (2) is prepared gained presoma, uniform winding is shaped in quartz or earthenware mould, dries, be placed in high-temperature atmosphere furnace together with shaping mould, by certain program sintering under particular atmosphere, obtain helical form inorganic hollow fibers film.
Quartz used or the best tool of earthenware mould groove at regular intervals are to limit the ring spacing of helical form film, and the diameter of quartz or earthenware mould is determined as required, is generally φ 3 ~ 20 mm.Adopt multi-steps sintering during sintering, first, control programming rate 1 ~ 3 DEG C/min, be heated to 400 ~ 600 DEG C, heat 20 ~ 100 minutes in still air, part burn off organic polymer; Then, N is changed into
2or H
2atmosphere, with 1 ~ 3 DEG C/min speed, heats to the sintering temperature of membrane material, and wherein sintering temperature is selected according to material, is generally 1050 ~ 1600 DEG C, sinters 1 ~ 10 hour; Cool to about 800-850 DEG C with 1 ~ 3 DEG C/min speed, be finally replaced as air, and continue to cool to room temperature, obtain helical form inorganic hollow fibers film.
In the present invention, described inorganic material both can be ceramic powder, also can be metal-powder.The helical form hollow-fibre membrane made both can be perforated membrane, also can be dense film.
Hollow-fibre membrane prepared by the present invention has the screw type profile of spring shape, inside is the unsymmetric structure of typical composite membrane porous layer+separating layer, and can overcome the restriction of expanding with heat and contract with cold in alternating temperature operation, preparation technology is simple, without complex device requirement, be convenient to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is porous stainless steel doughnut film precursor photo in embodiment 1.
The helical form porous stainless steel hollow-fibre membrane photo of Fig. 2 prepared by embodiment 1.
Electromicroscopic photograph after Fig. 3 helical form stainless steel hollow-fibre membrane sintering prepared by embodiment 1, wherein a is cross section, and b is the cross section of amplifying, and c is inner surface.
Fig. 4 is porous stainless steel doughnut film precursor photo in embodiment 2.
Fig. 5 is porous YSZ doughnut film precursor photo in embodiment 3.
Detailed description of the invention
Below by example, the present invention is described further, but embodiments of the present invention are not limited thereto, can not limiting the scope of the invention be interpreted as.
embodiment 1: preparation helical form porous stainless steel hollow-fibre membrane
Take 1-METHYLPYRROLIDONE solvent 40g, take dioctyl phthalate and the polyvinylpyrrolidone of dosage again, add (500 mL wide-mouth bottle) in 1-METHYLPYRROLIDONE solvent, to dissolve and after mixing, add 316L stainless steel powder 140 g that average grain diameter is 3 microns, stir 30 minutes; Take 10 g polysulfones, divide and add for 5 times, strong stirring makes it dissolve completely, and continues mechanical agitation 48 hours, obtains uniform and stable stainless steel hollow-fibre membrane casting solution.The content of the polymer bonding agent in casting solution, organic solvent, stainless steel powder, softening agent and dispersant accounts for 5%, 20%, 70%, 3% and 2% of casting solution total amount respectively.
The casting solution stirred is transferred in the feed liquid still of device for spinning, vacuum defoamation 1h; Be communicated with high pure nitrogen and keep the steady pressure of 10 Kpa, being extruded from spinning head exit orifice by casting solution enters in deionized water coagulation bath, core liquid (deionized water) is extruded by spinning head endoporus by syringe pump simultaneously, the stainless steel doughnut film precursor of spinning soaks 24h in coagulation bath, then places two days in deionized water to ensure its Stability Analysis of Structures.
By the stainless steel hollow-fibre membrane precursor uniform winding prepared in external diameter be φ 10mm quartz ampoule on, as shown in Figure 1, be placed in high-temperature atmosphere furnace after drying in the lump and sinter, first in still air, be heated to 600 DEG C with the heating rate of 2 DEG C/min, process 20 minutes, then change N into
2: H
2the sintering atmosphere of=3:1, is heated to 1050 DEG C with the heating rate of 3 DEG C/min, sinters 2 hours, then cools to 800 DEG C with 1 DEG C/min speed; Finally change air atmosphere into, continue to drop to room temperature with the cooling rate of 3 DEG C/min, obtain the helical form porous stainless steel hollow-fibre membrane of φ 12 mm, as shown in Figure 2, the micro-structural of porous stainless steel hollow-fibre membrane is as shown in the SEM figure of Fig. 3.
embodiment 2: preparation helical form porous stainless steel hollow-fibre membrane
Take 1-METHYLPYRROLIDONE solvent 48g, take dioctyl phthalate and the polyvinylpyrrolidone of dosage again, add (500 mL wide-mouth bottle) in 1-METHYLPYRROLIDONE solvent, to dissolve and after mixing, add 316L stainless steel powder 130 g that average grain diameter is 3 microns, stir 30 minutes; Take 12g polysulfones, divide and add for 5 times, strong stirring makes it dissolve completely, and continues mechanical agitation 48 hours, obtains uniform and stable stainless steel hollow-fibre membrane casting solution.The content of the polymer bonding agent in casting solution, organic solvent, stainless steel powder, softening agent and dispersant accounts for 6%, 24%, 65%, 3% and 2% of casting solution total amount respectively.
The casting solution stirred is transferred in the feed liquid still of device for spinning, vacuum defoamation 1h; Be communicated with high pure nitrogen and keep the steady pressure of 10 Kpa, being extruded from spinning head exit orifice by casting solution enters in deionized water coagulation bath, core liquid (deionized water) is extruded by spinning head endoporus by syringe pump simultaneously, the stainless steel doughnut film precursor of spinning soaks 24h in coagulation bath, then places two days in deionized water to ensure its Stability Analysis of Structures.
By the stainless steel hollow-fibre membrane precursor uniform winding prepared in external diameter be φ 3.6mm quartz ampoule on, as shown in Figure 4, be placed in high-temperature atmosphere furnace after drying in the lump and sinter, first in still air, be heated to 600 DEG C with the heating rate of 2 DEG C/min, process 20 minutes, then change N into
2: H
2the sintering atmosphere of=3:1, is heated to 1050 DEG C with the heating rate of 3 DEG C/min, sinters 2 hours, then cools to 800 DEG C with 1 DEG C/min speed; Finally change air atmosphere into, continue to drop to room temperature with the cooling rate of 3 DEG C/min, obtain the helical form porous stainless steel hollow-fibre membrane of φ 5 mm.
embodiment 3: preparation helical form porous YSZ hollow-fibre membrane
Take DMF solvent 80g, then take epoxidized soybean oil and the ammonium polymethacrylate of dosage, add (500 mL wide-mouth bottle) in DMF solvent, to dissolve and after mixing, add YSZ powder 100 g that average grain diameter is 80 nanometers, stir 30 minutes; Take 16 g polyether sulfones, divide and add for 5 times, strong stirring makes it dissolve completely, and continues mechanical agitation 48 hours, obtains uniform and stable YSZ hollow-fibre membrane casting solution.The content of the polymer bonding agent in casting solution, organic solvent, YSZ powder, softening agent and dispersant accounts for 8%, 40%, 50%, 1% and 1% of casting solution total amount respectively.
The casting solution stirred is transferred in the feed liquid still of device for spinning, vacuum defoamation 1h; Be communicated with high pure nitrogen and keep the steady pressure of 10 Kpa, being extruded from spinning head exit orifice by casting solution enters in deionized water coagulation bath, core liquid (deionized water) is extruded by spinning head endoporus by syringe pump simultaneously, the YSZ doughnut film precursor of spinning soaks 24h in coagulation bath, then places two days in deionized water to ensure its Stability Analysis of Structures.
By the YSZ hollow-fibre membrane precursor uniform winding prepared in external diameter be φ 10mm quartz ampoule on, as shown in Figure 5, be placed in high-temperature atmosphere furnace after drying in the lump to sinter, first in still air, be heated to 600 DEG C with the heating rate of 2 DEG C/min, process 20 minutes, then change the sintering atmosphere of high pure nitrogen into, be heated to 1400 DEG C with the heating rate of 5 DEG C/min, sinter 4 hours, then cool to 800 DEG C with 1 DEG C/min speed; Finally change air atmosphere into, continue to drop to room temperature with the cooling rate of 3 DEG C/min, obtain the helical form YSZ porous hollow fiber membrane of φ 12 mm.
embodiment 4: preparation helical form porous Al
2
o
3
hollow-fibre membrane
Take DMA solvent 60g, then take dibutyl phthalate and the polymethyl methacrylate of dosage, add N, in N-dimethylacetamide solvent (500 mL wide-mouth bottle), dissolve and after mixing, add the Al that average grain diameter is 1.8 microns
2o
3powder 120 g, stirs 30 minutes; Take 14 g polyacrylonitrile, divide and add for 5 times, strong stirring makes it dissolve completely, and continues mechanical agitation 48 hours, obtains uniform and stable Al
2o
3hollow-fibre membrane casting solution.Polymer bonding agent in casting solution, organic solvent, Al
2o
3the content of powder, softening agent and dispersant accounts for 7%, 30%, 60%, 2.5% and 0.5% of casting solution total amount respectively.
The casting solution stirred is transferred in the feed liquid still of device for spinning, vacuum defoamation 1h; Be communicated with high pure nitrogen and keep the steady pressure of 10 Kpa, casting solution being extruded from spinning head exit orifice and enters in deionized water coagulation bath, while core liquid (deionized water) extruded by spinning head endoporus by syringe pump, the Al of spinning
2o
3doughnut film precursor soaks 24h in coagulation bath, then places two days in deionized water to ensure its Stability Analysis of Structures.
By the Al prepared
2o
3hollow-fibre membrane precursor uniform winding is on the quartz ampoule of φ 10mm in external diameter, be placed in high-temperature atmosphere furnace after drying in the lump to sinter, first in still air, be heated to 600 DEG C with the heating rate of 2 DEG C/min, process 20 minutes, then the sintering atmosphere of high pure nitrogen is changed into, be heated to 1500 DEG C with the heating rate of 5 DEG C/min, sinter 4 hours, then cool to 800 DEG C with 1 DEG C/min speed; Finally change air atmosphere into, continue to drop to room temperature with the cooling rate of 3 DEG C/min, obtain the helical form porous Al of φ 12 mm
2o
3hollow-fibre membrane.
embodiment 5: preparation helical form fine and close LSCF doughnut oxygen permeation membrane
Take dimethyl sulfoxide solvent 60g, then take dioctyl adipate and the phosphate of dosage, add (500 mL wide-mouth bottle) in dimethyl sulfoxide solvent, dissolve and after mixing, add LSCF powder 116 g that average grain diameter is 3 microns, stir 30 minutes; Take 20 g PEIs, divide and add for 5 times, strong stirring makes it dissolve completely, and continues mechanical agitation 48 hours, obtains uniform and stable LSCF hollow-fibre membrane casting solution.The content of the polymer bonding agent in casting solution, organic solvent, LSCF powder, softening agent and dispersant accounts for 10%, 30%, 58%, 0.5% and 1.5% of casting solution total amount respectively.
The casting solution stirred is transferred in the feed liquid still of device for spinning, vacuum defoamation 1h; Be communicated with high pure nitrogen and keep the steady pressure of 10 Kpa, being extruded from spinning head exit orifice by casting solution enters in deionized water coagulation bath, core liquid (deionized water) is extruded by spinning head endoporus by syringe pump simultaneously, the LSCF doughnut film precursor of spinning soaks 24h in coagulation bath, then places two days in deionized water to ensure its Stability Analysis of Structures.
By the LSCF hollow-fibre membrane precursor uniform winding prepared in external diameter be φ 10mm quartz ampoule on, be placed in high-temperature atmosphere furnace after drying in the lump to sinter, first be heated to 800 DEG C in atmosphere with the heating rate of 3 DEG C/min, insulation 1h, 1400 DEG C are heated to again with the heating rate of 2 DEG C/min, sinter 4 hours, then continue to drop to room temperature with the cooling rate of 5 DEG C/min, obtain the helical form fine and close LSCF doughnut oxygen permeation membrane of φ 12 mm.
Claims (9)
1. a preparation method for helical form inorganic hollow fibers film, is characterized in that concrete steps are:
(1) prepare casting solution: be dissolved in organic solvent by softening agent and dispersant, add inorganic material powder, fully stir and powder is soaked, then add polymeric binder in batches, stir and make it dissolve completely, obtained uniform and stable casting solution;
In described casting solution processed, organic polymer thing bonding agent mass content accounts for the 5-10% of casting solution total amount; Organic solvent accounts for the 20-40% of casting solution total amount; Inorganic powder accounts for the 50-70% of casting solution total amount; Softening agent accounts for the 0.5-3% of casting solution total amount; Dispersant accounts for the 0.5-2% of casting solution total amount, and total amount is 100%;
(2) by step (1) gained casting solution, inorganic hollow fibers film precursor is prepared by dry-jet wet-spinning silk device;
(3) step (2) is prepared gained presoma, uniform winding is shaped in helical form quartz or earthenware mould, dries, be placed in high-temperature atmosphere furnace together with shaping mould, under particular atmosphere, sinter by following program:
First, control programming rate 1 ~ 3 DEG C/min, be heated to 400 ~ 600 DEG C, heat 20 ~ 100 minutes in still air, part burn off organic polymer; Then, N is changed into
2or H
2atmosphere, is warmed up to the sintering temperature of membrane material with 1 ~ 3 DEG C/min heating rate, sinter 1 ~ 10 hour; Cool to 800-850 DEG C with 1 ~ 3 DEG C/min speed, be finally replaced as air, and continue to cool to room temperature, obtain helical form inorganic hollow fibers film.
2. the preparation method of helical form inorganic hollow fibers film according to claim 1, it is characterized in that: in step (1), described organic polymer bonding agent is the one in polysulfones, polyether sulfone, polyacrylonitrile and PEI, or wherein several mixing; Described organic solvent is the one in 1-METHYLPYRROLIDONE, DMF, DMA and dimethyl sulfoxide (DMSO).
3. the preparation method of helical form inorganic hollow fibers film according to claim 1, it is characterized in that: in step (1), described softening agent is the one in dioctyl phthalate, epoxidized soybean oil, dibutyl phthalate, dioctyl adipate, or wherein several mixing.
4. the preparation method of helical form inorganic hollow fibers film according to claim 1, it is characterized in that: in step (1), described dispersant is the one in polyvinylpyrrolidone, ammonium polymethacrylate, polymethyl methacrylate and phosphate.
5. the preparation method of helical form inorganic hollow fibers film according to claim 1, is characterized in that: described inorganic material is ceramic powder, or metal-powder.
6. the preparation method of helical form inorganic hollow fibers film according to claim 1, is characterized in that: the operating process of step (2) is: casting solution, first through vacuum outgas 20-28 hour, moves in spinning batch can; Under gas pressure, casting solution enters in the coagulation bath of pure water or water/solvent mixed liquor by spinneret, after the solvents of 12 ~ 48 hours-water coke slurry process settings is shaping, applies the washing of a large amount of water soaking, to make solvent complete exchange out, ensure that membrane structure is stablized.
7. the preparation method of helical form inorganic hollow fibers film according to claim 1, is characterized in that: in step (3), and the diameter of described quartz or earthenware mould is φ 3 ~ 20 mm.
8. the helical form inorganic hollow fibers film prepared by one of claim 1-7 preparation method, has the screw type profile of spring shape, and inside is the unsymmetric structure of composite membrane porous layer+separating layer.
9. helical form inorganic hollow fibers film according to claim 8, is characterized in that for perforated membrane or dense film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510230331.9A CN104841286B (en) | 2015-05-08 | 2015-05-08 | A kind of helical form inorganic hollow fibers film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510230331.9A CN104841286B (en) | 2015-05-08 | 2015-05-08 | A kind of helical form inorganic hollow fibers film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104841286A true CN104841286A (en) | 2015-08-19 |
| CN104841286B CN104841286B (en) | 2017-03-15 |
Family
ID=53841502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510230331.9A Active CN104841286B (en) | 2015-05-08 | 2015-05-08 | A kind of helical form inorganic hollow fibers film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104841286B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544144A (en) * | 2016-11-09 | 2017-03-29 | 中昊(大连)化工研究设计院有限公司 | A kind of preparation of bulkiness tail seal grease of shield |
| CN106588000A (en) * | 2016-11-24 | 2017-04-26 | 上海交通大学 | Manufacturing process of helical wire type ceramic spring |
| CN108786485A (en) * | 2018-06-22 | 2018-11-13 | 北京耐恩环保科技有限公司 | Spiral shape doughnut film device |
| CN112675712A (en) * | 2020-12-10 | 2021-04-20 | 景德镇陶瓷大学 | Preparation method of roll-type ceramic membrane, prepared product and filtration water purifier |
| CN114984772A (en) * | 2022-06-22 | 2022-09-02 | 中国科学院生态环境研究中心 | Polytetrafluoroethylene hollow fiber membrane, preparation method thereof and membrane contact reactor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4348458A (en) * | 1980-09-08 | 1982-09-07 | Monsanto Company | Coiled inorganic monolithic hollow fibers |
| US5837033A (en) * | 1996-03-29 | 1998-11-17 | Praxair Technology, Inc. | Hollow fiber membrane separation apparatus |
| JP3410472B2 (en) * | 1994-07-01 | 2003-05-26 | マイクロリス・コーポレイション | Hollow fiber membrane module made of thermoplastic and method of manufacturing the same |
| WO2003064003A1 (en) * | 2002-01-29 | 2003-08-07 | Amersham Biosciences Membrane Separations Corp. | Convoluted surface hollow fiber membranes |
| CN102107122A (en) * | 2011-01-12 | 2011-06-29 | 北京交通大学 | Membrane fiber structure for membrane bioreactor and membrane bioreactor |
-
2015
- 2015-05-08 CN CN201510230331.9A patent/CN104841286B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4348458A (en) * | 1980-09-08 | 1982-09-07 | Monsanto Company | Coiled inorganic monolithic hollow fibers |
| JP3410472B2 (en) * | 1994-07-01 | 2003-05-26 | マイクロリス・コーポレイション | Hollow fiber membrane module made of thermoplastic and method of manufacturing the same |
| US5837033A (en) * | 1996-03-29 | 1998-11-17 | Praxair Technology, Inc. | Hollow fiber membrane separation apparatus |
| WO2003064003A1 (en) * | 2002-01-29 | 2003-08-07 | Amersham Biosciences Membrane Separations Corp. | Convoluted surface hollow fiber membranes |
| CN102107122A (en) * | 2011-01-12 | 2011-06-29 | 北京交通大学 | Membrane fiber structure for membrane bioreactor and membrane bioreactor |
Non-Patent Citations (1)
| Title |
|---|
| 徐南平著: "《面向应用过程的陶瓷膜材料设计、制备与应用》", 31 March 2005, 徐南平著 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544144A (en) * | 2016-11-09 | 2017-03-29 | 中昊(大连)化工研究设计院有限公司 | A kind of preparation of bulkiness tail seal grease of shield |
| CN106544144B (en) * | 2016-11-09 | 2019-06-07 | 中昊(大连)化工研究设计院有限公司 | A kind of bulkiness tail seal grease of shield and preparation method thereof |
| CN106588000A (en) * | 2016-11-24 | 2017-04-26 | 上海交通大学 | Manufacturing process of helical wire type ceramic spring |
| WO2018094860A1 (en) * | 2016-11-24 | 2018-05-31 | 上海交通大学 | Manufacturing process of spiral ceramic spring |
| CN108786485A (en) * | 2018-06-22 | 2018-11-13 | 北京耐恩环保科技有限公司 | Spiral shape doughnut film device |
| CN112675712A (en) * | 2020-12-10 | 2021-04-20 | 景德镇陶瓷大学 | Preparation method of roll-type ceramic membrane, prepared product and filtration water purifier |
| CN112675712B (en) * | 2020-12-10 | 2022-07-15 | 景德镇陶瓷大学 | Preparation method of roll-type ceramic membrane, prepared product and filtration water purifier |
| CN114984772A (en) * | 2022-06-22 | 2022-09-02 | 中国科学院生态环境研究中心 | Polytetrafluoroethylene hollow fiber membrane, preparation method thereof and membrane contact reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104841286B (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104841286A (en) | Spiral inorganic hollow fiber film and preparation method thereof | |
| JP6170245B2 (en) | Manufacturing method of multi-channel ceramic hollow fiber membrane | |
| CN100579638C (en) | Modified polyvinyl chloride hollow fiber microporous memebrane and method for preparing the same | |
| WO2013143345A1 (en) | Preparation method for homogeneously-enhanced polyvinylidene fluoride hollow fiber membrane | |
| US20080176056A1 (en) | Composite Ceramic Hollow Fibers, Method for Their Production and Their Use | |
| WO2018094860A1 (en) | Manufacturing process of spiral ceramic spring | |
| CN104923083B (en) | Stainless steel doped perovskite ceramic two-phase composite hollow fiber oxygen-permeating membrane and preparation method thereof | |
| CN105536559A (en) | Mullite ceramic hollow fiber membrane and preparation method for same | |
| CN107096396A (en) | A kind of polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof | |
| KR101913178B1 (en) | Method for manufacturing of ceramic hollow fiber membrane and the ceramic hollow fiber membrane thereby | |
| US8491716B2 (en) | Inorganic hollow yarns and method of manufacturing the same | |
| CN105032198A (en) | Porous nickel flat sheet membrane preparation method and porous nickel flat sheet membrane prepared by using same | |
| CN106268356B (en) | Method for preparing ultrahigh molecular weight polyethylene composite hollow fiber by thermally induced phase separation | |
| KR101561606B1 (en) | The method for preparing porous hollow fiber membrane and porous hollow fiber membrane thereby | |
| CN101961611B (en) | Hollow polyester fiber microporous membrane and preparation method thereof | |
| KR100748999B1 (en) | Preparation method of membrane using oxidized metal and carbon powder | |
| CN102512987B (en) | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane | |
| KR20150014718A (en) | The method for preparing porous hollow fiber membrane and porous hollow fiber membrane thereby | |
| CN110981453B (en) | Preparation method of light ceramic filtering membrane | |
| CN105435654A (en) | Method for preparing single-skin-layer hollow fiber membrane | |
| US20200062657A1 (en) | Method for preparing composite metal oxide hollow fibre | |
| CN104607057B (en) | There is the preparation method of the doughnut film support of Gao Zhidu and intensity | |
| KR100819418B1 (en) | Membrane using metallic powder and ceramic powder | |
| CN108636129A (en) | A kind of preparation method of Ceramic Hollow Fiber oxygen permeation membrane | |
| CN108043249B (en) | Method for preparing hollow fiber membrane from lignin modified polyacrylonitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 201506 Jinshan District, Jinshan Industrial Zone, Shanghai Road, Lane No. 285, No. 5 Co-patentee after: Tianjin Polytechnic University Patentee after: Shanghai Sui Hua Industrial Limited by Share Ltd Address before: 201506 Jinshan District, Jinshan Industrial Zone, Shanghai Road, Lane No. 285, No. 5 Co-patentee before: Tianjin Polytechnic University Patentee before: Shanghai Huishan Industrial Co., Ltd. |