CN104524987A - Honeycomb-shaped hollow fiber ceramic ultrafiltration membrane and production method thereof - Google Patents
Honeycomb-shaped hollow fiber ceramic ultrafiltration membrane and production method thereof Download PDFInfo
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- CN104524987A CN104524987A CN201510021083.7A CN201510021083A CN104524987A CN 104524987 A CN104524987 A CN 104524987A CN 201510021083 A CN201510021083 A CN 201510021083A CN 104524987 A CN104524987 A CN 104524987A
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Abstract
The invention relates to a honeycomb-shaped hollow fiber ceramic ultrafiltration membrane and production method of the honeycomb-shaped hollow fiber ceramic ultrafiltration membrane. The honeycomb-shaped hollow fiber ceramic ultrafiltration membrane comprises a main body, the main body is in the shape of a circular rod, and is made out of ceramic material. Nano-scale micropores are densely distributed in the main body. The honeycomb-shaped hollow fiber ceramic ultrafiltration membrane is characterized in that through holes are distributed in the main body in the longitudinal direction, so that the cross section of the main body is honeycomb-shaped. According to the honeycomb-shaped hollow fiber ceramic ultrafiltration membrane, a nano-scale ceramic powder is poured into a polymer adhesive solution to make suspended liquid. A green body is formed only through one of the hollow fiber of the dry and wet processing, and then the solidification and the sintering is conducted. The honeycomb-shaped hollow fiber ceramic ultrafiltration membrane has the advantages that the effective filtration area in a unit volume is large, the relative strength is high, a relative longer size can be made, and the application range is wide. By using the nano-scale nano-scale ceramic powder as the raw material, the filter fineness of the membrane is further improved, the complexity of multiple layers, multiple times and repeating sintering in the conventional process, and the practicability and reliability of the membrane is enhanced.
Description
Technical field
The present invention relates to technical field of membrane separation, is a kind of cellular doughnut ceramic super-filtering film and production method thereof specifically.
Background technology
UF membrane is that a kind of operation is comparatively simple, consume energy low separating technology, it can utilize membrane module and core component filter membrane, reclaim and recycle the component in mixture, being thus widely used in bioengineering, oil, chemical industry, metallurgy, medicine and other fields.At present, the filter membrane used in technical field of membrane separation point mainly contains two kinds in material, i.e. organic film and inoranic membrane, inoranic membrane is again based on ceramic membrane.Ceramic membrane, compared with organic film, has that high temperature resistant, resistance to chemical attack, mechanical strength are high, the advantage such as even aperture distribution, long service life, is therefore with a wide range of applications.
Existing ceramic membrane mainly contains dull and stereotyped and tubular type two kinds of structures, and its shortcoming mainly contains following 2 points:
1. ceramic membrane is compared to the film of doughnut structure, its loading density is lower, in unit volume, effective filtration area is less, existing hollow fiber ceramic membrane product adopts single hollow silk structure, but because the draw ratio of individual thread is larger, and the fragility of ceramic material is large, its relative intensity must reduce, therefore the length of this hollow fiber ceramic membrane generally can not more than 450 millimeters, compared with the hollow fiber filtering membrane of common organic polymer, less than the half of its length, its usage range is limited by very large;
2. the manufacturing cycle of ceramic membrane is longer, complex technical process, and preparation cost is high, especially along with separation accuracy by micro-filtration to ultrafiltration again to the development of nanofiltration, the preparation process of its repeatedly coating process, more tediously long, complicated.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of cellular doughnut ceramic super-filtering film, effective filtration area in this cellular doughnut ceramic super-filtering film unit volume is larger, and relative intensity is higher, can be made into longer size, the scope of application is comparatively extensive.
Another problem that the present invention will solve is to provide a kind of production method of cellular doughnut ceramic super-filtering film, the method adopts nano level ceramic powder as raw material, further increase the filtering accuracy of film, the complexity avoid common process multilayer, repeatedly, repeatedly sintering, improves practicality and the reliability of film.
For solving the problem, take following technical scheme:
Cellular doughnut ceramic super-filtering film of the present invention comprises body, and this body is round bar shape and is made up of ceramic material, is densely covered with nanometer level microporous in body.Be characterized in the through hole be evenly equipped with in described body along its longitudinal direction, make the cross section of body be cellular.
Wherein, the external diameter of described body is 5 ~ 15mm, and length is 50 ~ 1500mm, and the internal diameter of described through hole is 0.5 ~ 5mm.The quantity of described through hole is 3,5,7,19 or 37.
The feature of the production method of cellular doughnut ceramic super-filtering film of the present invention comprises the following steps:
First, polymer adhesive is dissolved in polymer adhesive solvent, makes polymer binder solution;
Then, nanometer scale ceramics powder is poured in polymer binder solution, and adds auxiliary agent, form the suspension of stable and uniform; Comprise the nanometer scale ceramics powder of 50 ~ 75 weight portions, the auxiliary agent of 1 ~ 3 weight portion, the polymer adhesive of 5 ~ 10 weight portions in this suspension, residual components is polymer adhesive solvent;
Afterwards, by the spinning process of above-mentioned suspension by the doughnut of dry, wet processing, with the spinning head containing multiple inner core tube, one-shot forming goes out the base substrate of cellular doughnut pottery;
Afterwards, base substrate spinning made directly imports in coagulant, by the automatic exchange of polymer adhesive solvent and coagulant, this base substrate is solidified;
Finally, the base substrate solidified is heated as in high temperature furnace, in heating process, make the polymer adhesive volatilization in base substrate remove, and blank sintering becomes inner densely covered by nanometer level microporous cellular doughnut ceramic super-filtering film the most at last.
Wherein, described polymer adhesive is polyether sulfone, Kynoar or polyimides.Described polymer adhesive solvent is N.N dimethyl formamide, N.N dimethyl formamide, N methyl-2-pyrrolidones, dimethyl sulfoxide (DMSO), carrene or acetone.Described nanometer scale ceramics powder is one or the mixture of aluminium oxide, zirconia or titanium dioxide, and its average grain diameter is between 20 ~ 200nm.Described auxiliary agent is the surfactant of poly amic acid, polyvinylpyrrolidone, polyethylene glycol-400, or glacial acetic acid, nitric acid, propionic acid PH Auto-regulator, or KH-560 organo-silicon coupling agent.
Take such scheme, have the following advantages:
The through hole along its longitudinal direction is evenly equipped with in body due to cellular doughnut ceramic super-filtering film of the present invention, the cross section of body is made to be cellular, namely its filtering surface is the inwall of multiple longitudinal hole in body, therefore the effective filtration area in its unit volume is relatively large, when filtering requirement is identical, effectively can reduce the draw ratio of hollow fiber ceramic membrane, be conducive to producing and application.And, this cellular doughnut ceramic super-filtering film is when being subject to External Force Acting, the stress distribution of body interior is comparatively disperseed, be not easy the position occurring that stress is concentrated, therefore its relative intensity is higher, not easy fracture, can be made into longer size according to user demand, be applicable to the requirement of most occasion and installation dimension, the scope of application is comparatively extensive.
Adopt nanometer scale ceramics powder as raw material in production method due to cellular doughnut ceramic super-filtering film of the present invention, and be cellular doughnut through spinning, sinter molding, its inside nanometer level microporous finer and closely woven, even, while raising filter membrane intensity, effectively raise the filtering accuracy of film.And its production craft step is simple, the complexity avoid common process multilayer, repeatedly, repeatedly sintering, is conducive to producing and application, improves practicality and the reliability of film.
Accompanying drawing explanation
Fig. 1 is the structural representation of cellular doughnut ceramic super-filtering film of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail.
As shown in Figure 1, cellular doughnut ceramic super-filtering film of the present invention comprises body 1, and this body 1 is round bar shape and is made up of ceramic material, is densely covered with nanometer level microporous in body 1.Be evenly equipped with the through hole 2 along its longitudinal direction in described body 1, make the cross section of body 1 be cellular.
Wherein, the external diameter of described body 1 is 5 ~ 15mm, and length is 50 ~ 1500mm, and the internal diameter of described through hole 2 is 0.5 ~ 5mm.The quantity of described through hole 2 can be 3,5,7,19 or 37, determines according to specific requirement when using.In the present embodiment, the quantity of described through hole 2 is 7.
Be described in further details below in conjunction with the production method of embodiment to cellular doughnut ceramic super-filtering film of the present invention.
Embodiment one
First, polymer adhesive is dissolved in polymer adhesive solvent, makes polymer binder solution.
Then, nanometer scale ceramics powder is poured in polymer binder solution, and adds auxiliary agent, form the suspension of stable and uniform.Comprise the nanometer scale ceramics powder of 50 weight portions, the auxiliary agent of 1 weight portion, the polymer adhesive of 5 weight portions in this suspension, residual components is polymer adhesive solvent.
Afterwards, by the spinning process of above-mentioned suspension by the doughnut of dry, wet processing, with the spinning head containing multiple inner core tube, one-shot forming goes out the base substrate of cellular doughnut pottery.
Afterwards, base substrate spinning made directly imports in coagulant, by the automatic exchange of polymer adhesive solvent and coagulant, this base substrate is solidified.
Finally, the base substrate solidified is heated as in high temperature furnace, in heating process, make the polymer adhesive volatilization in base substrate remove, and blank sintering becomes inner densely covered by nanometer level microporous cellular doughnut ceramic super-filtering film the most at last.
Described polymer adhesive is polyether sulfone, Kynoar or polyimides.
Described polymer adhesive solvent is N.N dimethyl formamide, N.N dimethyl formamide, N methyl-2-pyrrolidones, dimethyl sulfoxide (DMSO), carrene or acetone.
Described nanometer scale ceramics powder is one or the mixture of aluminium oxide, zirconia or titanium dioxide, and its average grain diameter is between 20nm.
Described auxiliary agent is the surfactant of poly amic acid, polyvinylpyrrolidone, polyethylene glycol-400, or glacial acetic acid, nitric acid, propionic acid PH Auto-regulator, or KH-560 organo-silicon coupling agent.
Embodiment two
First, polymer adhesive is dissolved in polymer adhesive solvent, makes polymer binder solution.
Then, nanometer scale ceramics powder is poured in polymer binder solution, and adds auxiliary agent, form the suspension of stable and uniform.Comprise the nanometer scale ceramics powder of 60 weight portions, the auxiliary agent of 2 weight portions, the polymer adhesive of 7 weight portions in this suspension, residual components is polymer adhesive solvent.
Afterwards, by the spinning process of above-mentioned suspension by the doughnut of dry, wet processing, with the spinning head containing multiple inner core tube, one-shot forming goes out the base substrate of cellular doughnut pottery.
Afterwards, base substrate spinning made directly imports in coagulant, by the automatic exchange of polymer adhesive solvent and coagulant, this base substrate is solidified.
Finally, the base substrate solidified is heated as in high temperature furnace, in heating process, make the polymer adhesive volatilization in base substrate remove, and blank sintering becomes inner densely covered by nanometer level microporous cellular doughnut ceramic super-filtering film the most at last.
Described polymer adhesive is polyether sulfone, Kynoar or polyimides.
Described polymer adhesive solvent is N.N dimethyl formamide, N.N dimethyl formamide, N methyl-2-pyrrolidones, dimethyl sulfoxide (DMSO), carrene or acetone.
Described nanometer scale ceramics powder is one or the mixture of aluminium oxide, zirconia or titanium dioxide, and its average grain diameter is between 100nm.
Described auxiliary agent is the surfactant of poly amic acid, polyvinylpyrrolidone, polyethylene glycol-400, or glacial acetic acid, nitric acid, propionic acid PH Auto-regulator, or KH-560 organo-silicon coupling agent.
Embodiment three
First, polymer adhesive is dissolved in polymer adhesive solvent, makes polymer binder solution.
Then, nanometer scale ceramics powder is poured in polymer binder solution, and adds auxiliary agent, form the suspension of stable and uniform.Comprise the nanometer scale ceramics powder of 75 weight portions, the auxiliary agent of 3 weight portions, the polymer adhesive of 10 weight portions in this suspension, residual components is polymer adhesive solvent.
Afterwards, by the spinning process of above-mentioned suspension by the doughnut of dry, wet processing, with the spinning head containing multiple inner core tube, one-shot forming goes out the base substrate of cellular doughnut pottery.
Afterwards, base substrate spinning made directly imports in coagulant, by the automatic exchange of polymer adhesive solvent and coagulant, this base substrate is solidified.
Finally, the base substrate solidified is heated as in high temperature furnace, in heating process, make the polymer adhesive volatilization in base substrate remove, and blank sintering becomes inner densely covered by nanometer level microporous cellular doughnut ceramic super-filtering film the most at last.
Described polymer adhesive is polyether sulfone, Kynoar or polyimides.
Described polymer adhesive solvent is N.N dimethyl formamide, N.N dimethyl formamide, N methyl-2-pyrrolidones, dimethyl sulfoxide (DMSO), carrene or acetone.
Described nanometer scale ceramics powder is one or the mixture of aluminium oxide, zirconia or titanium dioxide, and its average grain diameter is between 200nm.
Described auxiliary agent is the surfactant of poly amic acid, polyvinylpyrrolidone, polyethylene glycol-400, or glacial acetic acid, nitric acid, propionic acid PH Auto-regulator, or KH-560 organo-silicon coupling agent.
During use, liquid to be filtered is imported in the through hole 2 of this cellular doughnut ceramic super-filtering film, liquid is via in the nanometer level microporous process infiltrated into outside body 1 on body 1, the molecule that cannot dissolve in liquid is just tackled in through hole completely, thus achieves the function of filter membrane.
Claims (8)
1. a cellular doughnut ceramic super-filtering film, comprises body (1), and this body (1) is in round bar shape and be made up of ceramic material, is densely covered with nanometer level microporous in body (1); It is characterized in that being evenly equipped with the through hole (2) along its longitudinal direction in described body (1), the cross section making body (1) is cellular.
2. cellular doughnut ceramic super-filtering film as claimed in claim 1, it is characterized in that the external diameter of described body (1) is 5 ~ 15mm, length is 50 ~ 1500mm, and the internal diameter of described through hole (2) is 0.5 ~ 5mm.
3. cellular doughnut ceramic super-filtering film as claimed in claim 1, is characterized in that the quantity of described through hole (2) is 3,5,7,19 or 37.
4. produce the method for cellular doughnut ceramic super-filtering film as claimed in claim 1, it is characterized in that comprising the following steps:
First, polymer adhesive is dissolved in polymer adhesive solvent, makes polymer binder solution;
Then, nanometer scale ceramics powder is poured in polymer binder solution, and adds auxiliary agent, form the suspension of stable and uniform; Comprise the nanometer scale ceramics powder of 50 ~ 75 weight portions, the auxiliary agent of 1 ~ 3 weight portion, the polymer adhesive of 5 ~ 10 weight portions in this suspension, residual components is polymer adhesive solvent;
Afterwards, by the spinning process of above-mentioned suspension by the doughnut of dry, wet processing, with the spinning head containing multiple inner core tube, one-shot forming goes out the base substrate of cellular doughnut pottery;
Afterwards, base substrate spinning made directly imports in coagulant, by the automatic exchange of polymer adhesive solvent and coagulant, this base substrate is solidified;
Finally, the base substrate solidified is heated as in high temperature furnace, in heating process, make the polymer adhesive volatilization in base substrate remove, and blank sintering becomes inner densely covered by nanometer level microporous cellular doughnut ceramic super-filtering film the most at last.
5. the production method of cellular doughnut ceramic super-filtering film as claimed in claim 4, is characterized in that described polymer adhesive is polyether sulfone, Kynoar or polyimides.
6. the production method of cellular doughnut ceramic super-filtering film as claimed in claim 4, is characterized in that described polymer adhesive solvent is N.N dimethyl formamide, N.N dimethyl formamide, N methyl-2-pyrrolidones, dimethyl sulfoxide (DMSO), carrene or acetone.
7. the production method of cellular doughnut ceramic super-filtering film as claimed in claim 4, it is characterized in that described nanometer scale ceramics powder is one or the mixture of aluminium oxide, zirconia or titanium dioxide, its average grain diameter is between 20 ~ 200nm.
8. the production method of cellular doughnut ceramic super-filtering film as claimed in claim 4, it is characterized in that described auxiliary agent is the surfactant of poly amic acid, polyvinylpyrrolidone, polyethylene glycol-400, or glacial acetic acid, nitric acid, propionic acid PH Auto-regulator, or KH-560 organo-silicon coupling agent.
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Cited By (2)
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| CN105384216A (en) * | 2015-12-11 | 2016-03-09 | 大连远东新材料科技有限公司 | Separating device of ceramic membrane for waste liquid cycling filtration |
| CN109845531A (en) * | 2019-04-02 | 2019-06-07 | 杨俊奎 | The double-deck special-shaped multi-functional tube of townhouse formula |
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| CN102811969A (en) * | 2010-02-17 | 2012-12-05 | 昆士兰大学 | Method of manufacture for hollow fibre ceramic membrane |
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Application publication date: 20150422 |