CN1044988C - Prodn process and equipment for high-pure ceramic membranous canal - Google Patents
Prodn process and equipment for high-pure ceramic membranous canal Download PDFInfo
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- CN1044988C CN1044988C CN 95102519 CN95102519A CN1044988C CN 1044988 C CN1044988 C CN 1044988C CN 95102519 CN95102519 CN 95102519 CN 95102519 A CN95102519 A CN 95102519A CN 1044988 C CN1044988 C CN 1044988C
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Abstract
The present invention relates to a device for producing highly purified ceramic membrane tube. The mould of the tube is a double-layer tube mould composed of a supporting external layer and a meltable inner layer, the double-layer tube mould is connected with a motor, and the motor drives the tube mould to rotate. The method of producing the highly purified ceramic membrane tube comprises: slurry is added into the double-layer tube mould to be moulded; drying the membrane pipe; demoulding; baking the membrane pipe into a finished product. During the use of the method and the device of the present invention, additives are not necessary to be added into powdery materials, the demoulding of the membrane pipe is easy, the finished product obtained has high purity and strength and large throughput, and is directly applicable to the fields of separation, catalytic reaction, etc.
Description
The present invention relates to the porous ceramic articles field.
Inoranic membrane in the application of various fields such as chemical industry, food, medicine more and more widely, it and organic film relatively have stable performance, are difficult for advantages such as burn into is high temperature resistant, easy cleaning, are expected more and more in order to replace traditional separation, purification, consersion unit.Have high temperature resistant, corrosion-resistant, steady performance just because of inoranic membrane than organic film, its importance is more and more paid attention to by numerous scientific workers, be widely used in experimental study and production practices, obtained increasing application in fields such as chemical industry, food and drink production, water treatment, enriched gas, gas purifications.
The separable bacterium of inoranic membrane of aperture 0.1～0.2 μ m, virus are expected to replace traditional pasteurization processes; Wherein the micro-filtration ceramic membrane can be used in milk sterilization, concentrate, carry dense, also can be used for wastewater treatment, juice clarification, gas separation etc.
Repay examination in the chemical reaction field effort that the inorganic ceramic membrane pipe is applied to traditional unit process has also been obtained gratifying progress, according to the scope of membrane aperture, ceramic membrane can be divided into micro-filtration membrane (0.1～10 μ m), milipore filter (5nm～0.1 μ m) and reverse osmosis membrane (＜5nm), the screening (＜10 ) of molecular level.Micro-filtration membrane can be separated fine particle, big colloidal particle, bacterium etc.; Milipore filter can be used to carry out the separation of emulsion, colloidal particle, big molecule (macromolecule), protein; Reverse osmosis membrane can separate the salt that has dissolved, little organic particle; The screening of molecular level can make the molecule of a certain molecular radius by very high selection permeability is arranged.
Relevant in recent years inorganic ceramic membrane pipe is more and more in the research of high temperature gas-solid catalystic converter system, catalysis control oxidation system, inoranic membrane can be used as novel reaction tube, catalytic reaction agent carrier or new catalyst, has to select to see through performances such as a certain material, electro-catalysis.
The production process of ceramic-film tube generally is: powder is injected the mould internal shaping, obtain the porous ceramic film pipe after the roasting of taking-up base substrate.
The method of the at present general acquisition micropore and the ceramic-film tube of ultramicropore is further to modify on the porous ceramic film pipe that producer provides, the modification means have colloidal sol---methods such as gel method, chemical vapour deposition technique, vacuum deposition, the quality of modification effect is except outside the Pass having with modification means and modification level, also be limited by the performance indications of the porous ceramic pipe that producer provides greatly, just the performance indications of our said matrix pipe or supporter pipe.As long as so to say that the outstanding matrix pipe of performance is arranged, always can achieve the goal by modification, the preparation of the matrix pipe that visible performance is outstanding is a railing of inorganic ceramic membrane pipe extensive use.
Ceramic-film tube is the difference of ceramic substrate pipe according to its raw material of selecting for use, and plurality of classes such as aluminium oxide, zirconia, silica are arranged.Than flat sheet membrane difficulty, the key issue that the application of ceramic-film tube at first must solve is how to prepare to satisfy having certain pore size, even aperture distribution, having and select permeability, again the ceramic-film tube of certain flux arranged of our needs to tubular membrane at aspects such as shapings.Especially high-pure ceramic membranous canal, because raw material is the ridge material, there was the not high shortcoming of demoulding difficulty, intensity in the plasticity extreme difference in the past aspect the shaping of film pipe.
The powder forming method is generally adopted in the preparation of ceramic-film tube.Existing powder forming technology has press forming, castable etc.
1, press forming method
Press forming is that powder (ooze suitable additives such as binding agent be pre-mixed it can be flowed freely) is poured in the mould, and exerting pressure makes it compacting again.Additive adopts dextrin, starch, PVA, methyl fiber purple, natural gum etc.But adopt this method can not once obtain the gradient column that different apertures are formed, take coating, impregnating method to add transition zone again after the green tube of compacting can only being burnt till, such gradient column layer with the layer between combine bad, and tube wall will be thickeied many, cause flux to reduce, increased the transmission resistance.
2, castable method
Pottery cast at room temperature is that the powder particle that will float on a liquid injects in the mould of porous, and the special liquid of mould absorbs, and the fine grained base substrate is stayed in the mould.The most frequently used technology is that slurry casting is shaped, and generally all will contain the feldspar clay of some in the former slip, makes green compact that certain shrinkage be arranged, and green compact and the mould of being convenient to pipe break away from.This method may make high-pure ceramic membranous canal hardly, when matrix powder content 99% when above, the green compact of pipe can't be deviate from from plaster mold.
The physical property of ceramic-film tube is relevant with its purity, and high more its resistance to compression of purity, bending resistance, acid-alkali-corrosive-resisting are good more.
For the micropore ceramics film pipe that is used to separate with catalytic reaction, on the physical property of pipe, different requirements is arranged with common earthenware, except basic demands such as intensity, hardness, resistance to acids and bases, the uniformity in the porosity of prior film pipe in addition, pore size, hole, these parameters all influence the intensity of pipe again, to reduce the intensity of pipe as the increase of porosity, and it can not be reached separate and the requirement of catalytic reaction earthenware.
The preparation of micropore ceramics film pipe all is at method plated films such as the porous ceramics matrix Guan Shangyong of traditional ceramics explained hereafter SOL-GEL, further modifies to obtain required micropore ceramics film pipe.The preparation of traditional porous ceramics matrix pipe is identical with the preparation of general pottery, just in slurry, added pore former, general press forming, the castable method of adopting is shaped, this just requires to add additives such as bonding agent, clay, plasticizer in slurry, and the adding of these additives has a significant impact the intensity and the pore-size distribution of antipriming pipe.And for being used to separate the ceramic-film tube with the catalytic reaction purposes, then require earthenware under the high intensity of trying one's best, the big porosity of trying one's best to be arranged, and require that the aperture is certain, pore-size distribution is narrow as far as possible,, require that the aperture of pipe is descending from the skin to the internal layer to be changed in gradient in order to guarantee flux.When with methods such as SOL-GEL the porous ceramic film pipe being carried out the film modified preparation micropore ceramics of key film pipe, specification requirement is high especially, and phenomenon appears chapping, peeling off etc. in microporous barrier that these methods plate easily in coating process or in the drying, roasting, use.And existing ceramic-film tube manufacturing process and equipment thereof all can't be produced the ceramic-film tube of this high-purity, high performance requirements.
The objective of the invention is to defective, a kind of device of producing high-pure ceramic membranous canal is provided, make the ceramic-film tube base substrate be easy to the demoulding at the prior art existence.
The present invention also aims to provide a kind of device of producing high-pure ceramic membranous canal, the product of producing with this device both can be the outstanding matrix pipe of performance, also can be need just can not be applied to water treatment, micro-filtration even ultrafiltration purposes through modifying.
The present invention also aims to provide a kind of method of producing high-pure ceramic membranous canal, once produce the aperture by the gradient microporous pipe of micropore to the ultramicropore distribution gradient, as long as the particle of original powder is enough trickle, just can obtain micropore, ultramicropore ceramic-film tube, directly apply to micro-filtration, ultrafiltration, field of catalytic reactions.
When producing ceramic-film tube, wait performance requirement for the pore-size distribution that reaches earthenware is narrow, the powder that will as far as possible select for use the high granularity of purity to concentrate, single in theory particle size can provide 30% desirable space, as be equivalent to the maximum interspace size particle mix, pore volume is reduced to 26% and is added the third littler particle again, can make the voidage volume reduce to 23%, so require particle size that certain grating is arranged when producing the ceramic-film tube product.But in the actual production process, deposit when requiring the product certain intensity, certain aperture be arranged, and pore size distribution range is narrow more good more, this must cause becoming out difficulty, demoulding difficulty, the easy problems of crack of base substrate.
In order to solve these difficulties, the inventor utilizes the meltability mould overcoming demoulding difficulty, and utilizes action of centrifugal force that the powder in the slurry is well invested on the pipe die wall, makes well behaved ceramic-film tube.Just can once obtain the gradient column of art from coarse to fine as long as in forming process, inject the slurry that variable grain degree size is made in order with the aperture composition, although the certainly not unique particle diameter of the powder of the slurry of Zhu Ruing but be that the certain granules degree distributes once, but (r ∝ 1/F, i.e. r ∝ 1/ ω because the particle diameter of centrifugal force and the particulate that can drive is inversely proportional to
2, wherein r is a diameter of particle, F is a centrifugal force, ω is a rotating speed), be attached to the process of pipe die inwall from large to small so the process of quickening is exactly a particulate in the slurry, and, just can obtain the enough thin ceramic-film tube in aperture as long as the particle of raw material is enough thin.If the employing super fine is a raw material, we just can easily make the gradient micro-filtration or the ultrafiltration ceramic-film tube that can guarantee flux.
The apparatus features of production high-purity ceramic-film tube of the present invention is that pipe die of the present invention is made of two-layer, but outer stainless steel by proof strength, aluminium, metals such as copper and alloy thereof or nonmetally form as materials such as glass, internal layer is made up of the mixture of meltability material or meltability material, the meltability material can be wax material such as paraffin, beeswax, microwax, ceresine, insect wax montan wax etc., rosin and derivative thereof such as newtrex, rosin vinegar etc., high molecular polymer such as polyethylene, polystyrene, ethene---vinyl acetate copolymer resins etc., these meltability materials are in fusion more than 50 ℃, and the not influence of ceramic-film tube performance to forming.Utilize this novel pipe die to make ceramic-film tube, treat that heating promptly removes pipe die behind the green compact bone dry, obtain wall thickness evenly, smooth surface, tubular circle be straight, porous ceramic film pipe that certain green strength is arranged.
The apparatus features of production high-purity ceramic-film tube of the present invention is to comprise that also drives the motor that pipe die rotates, when the driven by motor pipe die rotates, the slurry of different-grain diameter is attached in the pipe die from large to small by action of centrifugal force in pipe die and measures, as long as the particle of raw material is enough thin, just can obtain the enough thin ceramic-film tube in aperture.If the employing super fine is a raw material, we just can easily make the gradient micro-filtration and the ultrafiltration ceramic-film tube that can guarantee flux and directly apply to fields such as chemical reaction.Fig. 1 is the structural representation of apparatus of the present invention, motor, and 1 is connected with pipe die 2, and pouring basin 4 pours into slurry and forms ceramic-film tubes 3 in the pipe die 2.Fig. 2 is the structural representation of pipe die of the present invention, and as shown in the figure, pipe die 2 of the present invention is made of skin 2 (1) and internal layer 2 (2).Skin is a support body layer, and internal layer is the meltability layer, and ceramic-film tube 3 is within the meltability layer.
The method of production high-purity ceramic-film tube of the present invention may further comprise the steps: the first step, slurry is added in the double-deck pipe die, start motor, slurry is shaped; Film pipe drying after second step, the shaping; The 3rd goes on foot, is heated to fusion mould internal layer more than 50 ℃, takes out film pipe body; The 4th step, roasting film pipe body get product.
The present invention compared with prior art has following advantage:
1, adopt the meltability mould, the ceramic-film tube green compact can easily spin off from pipe die, and its performance is unaffected.
2, slurry can add or not doping less, helps improving the purity of film pipe, can make the high-pure ceramic membranous canal more than 99%.
3, adopt flospinning, green density is all compared evenly in all fields, not yielding and cracking when burning till.
4, can once obtain the gradient column of aperture distribution gradient, not only satisfy the requirement (promptly optionally requiring) in film pore footpath but also can satisfy the requirement of flux.
5, the ceramic-film tube smooth in appearance that makes, film pipe up rightness is good.
160～200 order aluminium oxide powders are made into water content 50%, pH value is 4.0 not contain the slurry of additive, the aluminium, paraffin and the stearic acid that inject φ 20mm, wall thickness 2mm are total to the double-deck pipe die of molten thing, be shaped in about two minutes down for 1500 rev/mins at rotating speed, be heated to 50 ℃ of demouldings after the drying, make the tubular inorganic membrane that wall thickness is about 1.5mm.It can be used as the supporter ceramic-film tube, and big porosity and high flux are arranged.
With average particle size is that the silica powder of 1 μ m is a raw material, the slurry that to be made into moisture 100%PH value be about 5.0, do not contain additive, inject the double-deck pipe die of stainless steel, paraffin of φ 20mm, wall thickness 2mm, under about 5000 rev/mins of rotating speeds, be shaped in about 1.5 minutes, be heated to 60 ℃ of demouldings after the drying, make the high-pure ceramic membranous canal that wall thickness is about 1mm, it can directly be used in separation field, as the micro-filtration membrane element of water treatment etc.
With average particle size is that the alumina powder of 5 μ m is that raw material is made into moisture 30%, pH value is about 4.7, the slurry that does not contain additive, inject φ 20mm, the aluminium alloy of thick 2mm, in the double-deck pipe die of rosin ester, change commentaries on classics shaping in 2 minutes under 1 minute 2500, making wall thickness is high-purity (＞99.9%) ceramic-film tube of 1.5mm, after the dry demoulding at 1500 ℃ of sintering, one-tenth pipe behind the sintering has been carried out the Electronic Speculum sign, find its surperficial even compact, it is 2.8 μ m that the bubble rule obtains its most probable aperture, and the gas permeation rate of this film pipe (seeing through oxygen down with normal temperature is example) is 227.448L/hr.m
2This ceramic die pipe can be directly used in fields such as separation.
Embodiment 4
With the superfine zirconia powder is raw material, is made into the slurry of water content 100%, injects the double-deck pipe die of copper, polyethylene of φ 20mm, thick 2mm, about 7000 rev/mins are changeed shaping in 1.5 minutes down, the dry back demoulding gets the ceramic-film tube that wall thickness is about 1.5mm, can be used for separating and field of catalytic reactions.
Claims (2)
1, a kind of device of producing high-pure ceramic membranous canal is characterized in that double-deck pipe die is connected with motor, and the double-deck pipe die of motor-driven rotates and produces centrifugal force, and double-deck pipe die is made of supporter skin and meltability internal layer.
2. a method of producing high-pure ceramic membranous canal is characterized in that comprising the following steps: the first step, slurry is added in the double-deck pipe die, starts motor, and slurry is shaped; Film pipe drying after second step, the shaping; The 3rd goes on foot, is heated to fusion mould internal layer more than 50 ℃, takes out film pipe body; The 4th step, roasting film pipe body get product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95102519 CN1044988C (en) | 1995-04-06 | 1995-04-06 | Prodn process and equipment for high-pure ceramic membranous canal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95102519 CN1044988C (en) | 1995-04-06 | 1995-04-06 | Prodn process and equipment for high-pure ceramic membranous canal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1132680A CN1132680A (en) | 1996-10-09 |
| CN1044988C true CN1044988C (en) | 1999-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95102519 Expired - Fee Related CN1044988C (en) | 1995-04-06 | 1995-04-06 | Prodn process and equipment for high-pure ceramic membranous canal |
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| CN (1) | CN1044988C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489166B (en) * | 2011-12-06 | 2014-01-15 | 深圳恒通源水处理科技有限公司 | Ultrafiltration membrane processing system and processing technology thereof |
| CN104707489A (en) * | 2015-03-25 | 2015-06-17 | 中国科学院城市环境研究所 | Phase conversion pouring preparation process and forming device for inorganic porous ceramic tubular membrane |
| CN107376659B (en) * | 2017-07-31 | 2023-03-28 | 成都易态科技有限公司 | Manufacturing equipment for asymmetric tubular filter element blank |
| CN107551826B (en) * | 2017-07-31 | 2023-11-14 | 成都易态科技有限公司 | Apparatus for manufacturing an asymmetrical tubular filter element blank |
| CN112706277B (en) * | 2020-12-24 | 2022-04-01 | 湖北科技学院 | Preparation method of large mica tube |
| CN113624656A (en) * | 2021-07-14 | 2021-11-09 | 南京三乐集团有限公司 | Device and method for nondestructive testing of uniformity of barium-tungsten cathode substrate |
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1995
- 1995-04-06 CN CN 95102519 patent/CN1044988C/en not_active Expired - Fee Related
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| CN1132680A (en) | 1996-10-09 |
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