CN1116098C - Prepn of hollow alumina fiber film - Google Patents
Prepn of hollow alumina fiber film Download PDFInfo
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- CN1116098C CN1116098C CN 00135448 CN00135448A CN1116098C CN 1116098 C CN1116098 C CN 1116098C CN 00135448 CN00135448 CN 00135448 CN 00135448 A CN00135448 A CN 00135448A CN 1116098 C CN1116098 C CN 1116098C
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Abstract
The present invention relates to a method for preparing a hollow alumina fibre membrane. Aluminium powder, alumina powder and sintering aids are added into acetone for ball milling for 6 to 8 hours, dried powder is dispersed in organic solvent, and polysulphone or polyvinylidene fluoride which is a polymer is added into dispersed suspending liquid to obtain membrane casting liquid. The membrane casting liquid is stirred for 6 to 8 hours with the temperature kept within the range between 60 to 80 DEG C, and then, still standing for bubble removal is kept for 5 to 6 hours. The membrane casting liquid is squeezed out from a spinning jet to be solidified and molded in gel bath, and a molded hollow fibre membrane is soaked to sufficiently cement out the organic solvent. After drying, a certain temperature increasing speed is controlled, and a hollow alumina fibre membrane can be obtained through oxidation and sintering. The hollow alumina fibre membrane of the present invention has the advantages of small shrinkage ratio, high mechanical strength, no needle pore and no cracking in the sintering process.
Description
The present invention relates to a kind of preparation method of diffusion barrier, particularly a kind of aluminium oxide doughnut membrane preparation method.
Inorganic ceramic membrane has that mechanical strength is big, long service life, acid and alkali-resistance, remarkable advantage such as high temperature resistant, now listed the unit process of field of chemical engineering in, separated and catalytic field has a wide range of applications at the Separation of Solid and Liquid of processes such as chemical industry, food, gas.At present, the form of commercial ceramic membrane mainly contains tubular type and multi-channel type.Comparatively speaking, the doughnut form has the advantage that loading density is big, separative efficiency is high.The loading density of general tubular type and multichannel form is lower than 300m
2/ m
3, and doughnut can be up to 30000m
2/ m
3This point is verified in the polymeric membrane field very widely fully in application.The report of relevant aluminium oxide doughnut membrane preparation technology is more common in twentieth century beginning of the nineties, document 1 (K.H.Lee and Y.M.Kim.Asymmetric hollow inorganicmembranes.Key Engineering Materials, 1991,61～62:17～22) reported the method for preparing the aluminium oxide hollow-fibre membrane, its process is aluminium oxide (silica) to be scattered in the dimethylacetamide solution that is dissolved with polysulfones form casting solution, make through spinning, drying, sintering, as supporter, prepare the sol-gel separating layer with made doughnut.The scope of sintering temperature is 1100～1500 ℃, and the mechanical performance of relevant made film is report not, and the major defect of made film is that shrinkage factor is big.Document 2 (J.Smid, C.G.Avci, V.G ǔ nay, R.A.Terpstra, J.P.G.M.VanEijk.Preparation and characterization of microporous ceramic hollow fiber membranes.J.Membrane Sci., 1996,112:85～90) adopt fusion method to prepare aluminium oxide and silicon nitride hollow-fibre membrane, its process is 85-125 ℃ of fusion with raw alumina and silicon nitride and sintering aid yittrium oxide and organic binder bond, granulation, through spinning head is the extrusion modling of in-core medium with the air, and aluminium oxide doughnut moulding sample is through 1350 ℃, silicon nitride doughnut moulding sample makes the hollow-fibre membrane product after 1650 ℃ of heat treatment.Prepared external diameter is 800～2700 μ m, and film thickness is 130～400 μ m, and porosity is 30%～52%.US5707584 has reported that the employing fusion method prepares the method for aluminium oxide/silicon nitride hollow-fibre membrane, and prepared external diameter is 500～2000 μ m, and film thickness is 30～500 μ m, and porosity is 30%～50%.And the research of at present domestic relevant this respect does not appear in the newspapers as yet.
Reaction bonded technology Reaction-bonded aluminum oxide (RBAO) is a kind of novel reaction moulding process for preparing aluminium oxide ceramics that grows up the eighties.This process has that sintering temperature is lower, mechanical property good, volume contraction is little and advantage such as preparation cost is low, and in recent years, this technology causes widely to be paid close attention to.At present, the RBAO technology mainly be with aluminium powder and alumina powder under the situation of not introducing binding agent, by the high pressure compacted under, be used to prepare that porosity is low, good mechanical property, special cermacis that shrinkage factor is little.
Wet method or the made aluminium oxide hollow-fibre membrane of fusion method are done in the employing of being reported in the document 1,2, and shrinkage factor is big, bad mechanical strength.The present invention combines dry-wet spinning and reaction bonded technology, is used to prepare the aluminium oxide hollow-fibre membrane, and the defective of this two aspect is significantly improved.
The object of the present invention is to provide the film that a kind of shrinkage factor is little, mechanical strength is high, prepared can be directly used in micro-filtration, the carrier that also can be used as sol gel film or catalyst is used for the aluminium oxide doughnut membrane preparation method of gas separation or membrane reactor.
The technical solution that realizes purpose of the present invention is: a kind of aluminium oxide doughnut membrane preparation method, it is characterized in that: with aluminium powder, alumina powder and sintering aid ball milling 6～8 hours in acetone, the powder that drying is good is scattered in the organic solvent, polymer polysulfones or Kynoar added in the scattered suspension make casting solution, stir, be incubated 60～80 ℃, 6～8 hours, standing and defoaming 5～6 hours, extruded by spinning head and to enter curing molding in the coagulation bath, the hollow-fibre membrane after the moulding fully cements out organic solvent after soaking, after the drying, control certain heating rate, oxidation, sintering obtains the aluminium oxide hollow-fibre membrane.
Sintering aid in the aluminium oxide doughnut membrane preparation method of the present invention can be titanium oxide, magnesia or kaolin.
Organic solvent in the aluminium oxide doughnut membrane preparation method of the present invention is dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, process strong mixing earlier was 1～2 hour when powder added organic solvent, and then disperseed through 15～30 minutes ultrasonic wave.
Spinning moulding temperature in the aluminium oxide doughnut membrane preparation method of the present invention is 40～70 ℃, and the mode that forms hollow is core liquid method or air-flow method.
Principle of the present invention is: dry-wet spinning and RBAO technology are combined, be applied to go in the preparation of aluminium oxide hollow-fibre membrane, dry-wet spinning technology is adopted in the moulding of aluminium oxide hollow-fibre membrane, aluminium powder, alumina powder and sintering aid are scattered in the organic solvent, add polymer, make the stabilized uniform casting solution, casting solution enters in the coagulation bath through dry-wet spinning and solidifies.Aluminium oxide hollow-fibre membrane after the moulding burns till in air atmosphere, in sintering process, aluminium powder can progressively be oxidized to aluminium oxide, the aluminium oxide that generates is along with the rising of temperature, from amorphous state to the γ phase, change the α phase at last into, owing to be attended by the volumetric expansion effect in the oxidizing process of aluminium, can remedy the volume contraction in the sintering process, the particle of adding newborn aluminium oxide is very tiny, has very high activity, can reduce sintering temperature, in addition, because newborn fine structure makes intensity obtain tangible improvement.Its mechanical strength of hollow-fibre membrane that adopts this method to prepare can reach 2 times of common process.
The present invention compared with prior art, its remarkable advantage is: aluminium oxide hollow-fibre membrane shrinkage factor is little, and mechanical strength is big, free of pinholes, do not have cracking in the sintering process, thickness can be regulated by the control spinning technology parameter between 800～1400 μ m at 120～400 μ m, external diameter; The fiber porosity is 40%～50%, and average pore size can be adjusted in 0.84～8.36 μ m by changing alumina powder jointed particle diameter, and intensity can reach more than the twice that does not add aluminium in the prescription under the condition of same porosity; This film can be directly used in micro-filtration, and the carrier that also can be used as catalyst is used for catalytic reaction or is used for gas as the carrier of sol gel film separating.
Accompanying drawing is the flow chart of aluminium oxide doughnut membrane preparation method of the present invention.
Below in conjunction with accompanying drawing the present invention is further described.
Embodiment 1.
(1). with the aluminium oxide (d of 300 grams
50=0.86 μ m), the wet-milling 8 hours in acetone of 200 gram aluminium powders (cross 200 mesh sieves), 7.5 gram titanium oxide, drum's speed of rotation is 500 rev/mins, dry back is standby;
(2). dried powder is added in the 450 gram dimethyl formamides, strong mixing 2 hours, ultrasonic wave disperseed 15 minutes, and powder is dispersed in the solvent;
(3). 50 gram polysulfones are added in the scattered solvent, 60 ℃ of following stirring and dissolving 8 hours;
(4). standing and defoaming, 6 hours;
(5). under nitrogen pressure, casting solution is extruded through spinning head, the casting solution temperature maintenance is at 60 ℃, and core liquid is deionized water, and the fiber of extruding leaves spinning head through the long air section of 20cm, enters in the coagulation bath and solidifies;
(6). the fiber after the curing is through receiving silk device, closes on the winch spool with the speed of 0.15m/s;
(7). the fiber after the moulding successively is soaked in isopropyl alcohol and the water, residual solvent is leached, at air drying;
(8). place electric furnace to burn till in 2 hours the fiber behind the drying and moulding in 1450 ℃ of insulations, heating rate less than be respectively 1.5 ℃/minute and 3 ℃/minute greater than 1000 ℃;
Hollow-fibre membrane with this method preparation has the characteristics of anisotropic membrane, and porosity is 48.4%, and average pore size is 0.88 μ m, and fiber external diameter 1300 μ m, wall thickness are 300 μ m, and compressive strength is 89.6MPa, bending strength 41.1MPa.Condition lower compression intensity in same porosity can reach more than the twice that does not add aluminium in the prescription.
Embodiment 2.
According to the step among the embodiment 1, preparation casting solution and spinning, sintering.Different is that aluminium oxide adopts d
50The powder of=25.10 μ m, spinning temperature are 40 ℃.The membrane porosity of gained is 47.5%, and average pore size is 8.36 μ m, and fiber external diameter 1360 μ m, thickness are 400 μ m, and compressive strength is 74.9MPa, bending strength 47.1MPa.
Embodiment 3.
According to the step among the embodiment 1, preparation casting solution and spinning, sintering.Different is that spinning temperature is 70 ℃.The membrane porosity of gained is 45.6%, and average pore size is 0.84 μ m, and fiber external diameter 1200 μ m, wall thickness are 120 μ m, and compressive strength is 87.9MPa, bending strength 37.9MPa.Adopt the aluminium oxide hollow-fibre membrane of reaction bonded preparation, it is little to have shrinkage factor, the characteristics that mechanical strength is high.This film can be directly used in micro-filtration, and the carrier that also can be used as catalyst is used for catalytic reaction or is used for gas as the carrier of sol gel film separating.
Claims (6)
1, a kind of aluminium oxide doughnut membrane preparation method, it is characterized in that: with aluminium powder, alumina powder and sintering aid ball milling 6～8 hours in acetone, the powder that drying is good is scattered in the organic solvent, polymer polysulfones or Kynoar added in the scattered suspension make casting solution, stir, be incubated 60～80 ℃, 6～8 hours, standing and defoaming 5～6 hours, extruded by spinning head and to enter curing molding in the coagulation bath, the hollow-fibre membrane after the moulding fully cements out organic solvent after soaking, after the drying, control certain heating rate, oxidation, sintering obtains the aluminium oxide hollow-fibre membrane.
2, aluminium oxide doughnut membrane preparation method according to claim 1, it is characterized in that: sintering aid is titanium oxide, magnesia or kaolin.
3, aluminium oxide doughnut membrane preparation method according to claim 1 and 2, it is characterized in that: organic solvent is dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, process strong mixing earlier was 1～2 hour when powder added organic solvent, and then disperseed through 15～30 minutes ultrasonic wave.
4, aluminium oxide doughnut membrane preparation method according to claim 1 and 2, it is characterized in that: the spinning moulding temperature is 40～70 ℃, the mode that forms hollow is core liquid method or air-flow method.
5, aluminium oxide doughnut membrane preparation method according to claim 1 and 2 is characterized in that: after the fiber after the moulding soaks in isopropyl alcohol and water, organic solvent is leached.
6, aluminium oxide doughnut membrane preparation method according to claim 1 and 2 is characterized in that: the heating rate when oxidation, sintering is 1.5 ℃/minute less than 1000 ℃ the time, is 3 ℃/minute greater than 1000 ℃ the time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00135448 CN1116098C (en) | 2000-12-26 | 2000-12-26 | Prepn of hollow alumina fiber film |
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|---|---|---|---|
| CN 00135448 CN1116098C (en) | 2000-12-26 | 2000-12-26 | Prepn of hollow alumina fiber film |
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| CN1360966A CN1360966A (en) | 2002-07-31 |
| CN1116098C true CN1116098C (en) | 2003-07-30 |
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| CN 00135448 Expired - Fee Related CN1116098C (en) | 2000-12-26 | 2000-12-26 | Prepn of hollow alumina fiber film |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010045430A2 (en) * | 2008-10-15 | 2010-04-22 | National University Of Singapore | Dual-layer hollow fibers with enhanced flux as forward osmosis membranes for water reuses and protein enrichment |
| CN101905121B (en) * | 2010-08-26 | 2012-10-17 | 南京工业大学 | Method for preparing aluminum oxide-based ceramic hollow fibrous membrane |
| CN102877218B (en) * | 2012-10-24 | 2016-03-09 | 厦门大学 | A kind of preparation method of hydrophobic oil suction silicon carbide ceramic fiber felt |
| CN103349918B (en) | 2013-06-19 | 2015-11-11 | 南京工业大学 | A kind of method preparing multichannel ceramic hollow fibrous membrane |
| DE102013012671A1 (en) * | 2013-07-31 | 2015-02-05 | Mann + Hummel Gmbh | Ceramic hollow fiber membranes with improved mechanical properties |
| US10751671B2 (en) * | 2014-01-10 | 2020-08-25 | Asahi Kasei Kabushiki Kaisha | Porous hollow fiber membrane, method for producing same, and water purification method |
| GB2526310A (en) * | 2014-05-20 | 2015-11-25 | Imp Innovations Ltd | Monolith |
| CN110342910B (en) * | 2019-08-21 | 2021-08-31 | 中国石油化工股份有限公司 | Method for preparing ceramic hollow fiber membrane from FCC (fluid catalytic cracking) waste catalyst and ceramic hollow fiber membrane |
| CN114133268B (en) * | 2021-11-29 | 2022-12-20 | 电子科技大学长三角研究院(湖州) | High-flux ceramic support body, preparation method and application thereof |
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