CN103721577B - The preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure - Google Patents
The preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure Download PDFInfo
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Abstract
The present invention relates to separation membrane technical field, the specifically method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure and preparation thereof, the pure matter silicon carbide film of multichannel symmetrical structure consists of pure matter carborundum, formed by 10-200 μ m silicon-carbide particle sintering, there is three-dimensional connectivity gap structure, percent opening, at 35-65%, filters and characterizes pore diameter range between 1-20 micron; Film material is tubulose multi-channel structure, forms new carborundum and sinter bonded by binding agent as silicon carbide precursor body cracking reaction, and sintering temperature is at 900-1500 DEG C. Prepared silicon carbide film has that purity is high, porosity is high, intensity is large, flux is large, the feature of long service life, preparation method has advantages of that energy consumption is low, raw material is easy to get, moulding easily, be applicable to industry customization, meet large-scale production.
Description
Affiliated technical field
Patent of the present invention relates to separation membrane technical field, and particularly inoranic membrane technical field of separation materials, is specially oneThe preparation method of the pure matter silicon carbide film of multichannel symmetrical structure.
Background technology
Membrane separation technique is the new and high technology of an emerging multidisciplinary intersection, the material of film relate to polymer chemistry and inorganic chemistry,The preparation of film, separation characteristic, transmittance process relate to hydrodynamics, thermodynamics, chemical engineering kinetics, Process Design etc. many-sideSubject. The application of membrane separation technique relates to industry-by-industry, and applied range, interrelationship between industries are large. With other isolation technics ratios, it have efficient, energy-conservation, process is easy to control, easy to operate, environmental friendliness, be convenient to amplify, take up an area little, easily and otherThe advantages such as technology is integrated. The in the situation that energy shortage in the world today, water resources shortage and environmental pollution being day by day serious, film skillArt more obtains the great attention of countries in the world, has become the national pillar industry development of promotion, improves environment for human survival, has improved peopleThe common technology of quality of life.
Existing separation membrane is mainly divided into organic film and the large class of inoranic membrane two, and wherein organic film adopts organic polymer to make,Be limited to the character of material, have that flux is little, the life-span is short, an easy pollution, easily aging, cracky, difficult recoil, pretreatment requirementThe shortcomings such as height; And inoranic membrane is made up of inorganic material, there is the incomparable strength and stability of organic film, especially high temperature resistant,Anti-pollution, long service life are the focuses of current membrane material exploitation. At present inoranic membrane kind is less, only has oxidesinteringFew several such as ceramic membrane, metal powder sintered metal film, have limited the application of inoranic membrane, can not meet day by day complicatedFilm separate the market demand.
Silicon carbide film is subject to researcher's attention day by day as a kind of new separation membrane, what have based on silicon carbide film is goodCharacter, can be applicable under the environmental condition of various harshnesses, and existing market application study mainly concentrates in the purification of high-temperature gas,And the silicon carbide film research that meets liquid system filtration is less. It is pure that patent CN102659446B and CN102659447B proposeThe patent of matter silicon carbide film pipe and filter course, mainly utilizes coarse granule carborundum, silica or silica flour as stock, utilizesMacromolecular material is as bonding agent, and mix, utilizes cold isostatic press bag cover compacting supporter, under 1500-2400 DEG C of high temperature,The carbon source forming with organic substance decomposing by silica or silica flour react the new carborundum of generation, by thick silicon-carbide particle sintering oneRise, form pure matter silicon carbide film pipe and filter course. Above method exists that sintering temperature is high, energy consumption is high, technique controlling difficulty is large etc.Problem.
Summary of the invention
The object of the invention is for the few situation of existing inoranic membrane parting material kind, provide a kind of moulding easily, production costThe pure matter silicon carbide film of low multichannel symmetrical structure, is tubulose multi-channel structure, and film pipe can be that circle can be also square or justHexagon, passage number, between 7-3000, enlarges markedly elementary membrane area, strengthens film pipe intensity, and product diversification, canMeet the designing requirement under different occasions.
Another problem that the present invention will solve is: avoid that existing carborundum filtering material purity is low, corrosion resistance is not strong, mechanicalInsufficient strength, the problem that unit filter area is little, provide a kind of carborundum composition more than 99wt%, porosity is high, intensity is large,Flux is large, the silicon carbide film of long service life.
The problem that the present invention also will solve is: improve that existing pure matter silicon carbide film sintering temperature is high, equipment requirement is high, energy consumptionGreatly, problem that cost is high, provide a kind of sintering temperature 900-1500 DEG C, raw material be easy to get, prepare simple, moulding easily, rawProduce low, the applicable industrial preparation method who customizes, meets the multichannel symmetrical structure silicon carbide film of large-scale production of cost.
For solving the technical problem existing in silicon carbide film material preparation process, technical solution of the present invention is as follows:
A preparation method for the pure matter silicon carbide film of multichannel symmetrical structure, the pure matter silicon carbide film of multichannel symmetrical structure usesRaw material comprises silicon-carbide particle, binding agent, pore creating material, curing agent, dispersant and solvent, wherein: silicon-carbide particle can beα-SiC particle or β-SiC micro mist, grain diameter scope is at 10-200 μ m, and it is 1-20 μ m that corresponding formation film characterizes pore size filter,Adopt the good silicon-carbide particle of aperture concentration degree, can form and characterize the silicon carbide film of aperture concentration degree more than 80%; Binding agentFor organosilicon polymer, specifically comprise a kind of of Polycarbosilane, polysilazane, polysiloxanes, silicone oil, poly dimethyl silane orMore than one, the cementation that this binding agent rose is embodied in normal temperature sizing and high temperature sintering chains, and effect is as carborundumPresoma, at high temperature reacts with carbon source and generates new carborundum, thereby realizes the connection of the same component between silicon-carbide particle; MakeHole agent is one or more of carboxymethyl cellulose, starch, dusty yeast, organic polymer microballoon, by controlling pore creating materialThe porosity of the adjustable silicon carbide film of addition; Curing agent is carboxyalkyl acid amides, phenolic resins, epoxy resin, petroleum cokeOne or more, effect is the mechanical strength that contributes to strengthen idiosome in the time of extrusion molding; Dispersant be polymine,One or more of TMAH, effect is the uniformity that strengthens carborundum powder slurry, contributes to increase multichannelThe filtering accuracy of symmetrical structure silicon carbide film; Solvent is mainly ethanol, toluene or water.
By the combination of above raw material, coordinate sintering process, can realize pore size filter controlled, filtering accuracy is high, porosity is high,Large, corrosion-resistant, the resistant to pollution silicon carbide film of compression strength, preparation method's step is as follows:
(1) batching
By silicon-carbide particle, binding agent, pore creating material, curing agent and dispersant within the scope of 10-200 μ m according to mass percent be(90wt%-65wt%): (20wt%-5wt%): (30wt%-10wt%): (1wt%-5wt%): (0.2wt%-0.8wt%), standardReally formula accurately weighs, join in the container that fills solvent, wherein silicon-carbide particle, binding agent, pore creating material, curing agent,Dispersant gross mass sum is 100%, and solvent accounts for the 10-40% of amount of the mixture; Slurry after batching is through batch mixer machineryStir 20-60min, and then enter the mixing 20-60min of extruding in pug mill, form and mix more evenly and have good plasticitySlurry mud.
(2) extrusion molding
According to the multichannel extrusion die of designing requirement processing definite shape, be arranged on cross-head place, above-mentioned slurry mud is addedEnter in extruder feed bin, then extrude the multi-channel membrane idiosome of design shape by extruder, control extrusion pressure and be less than 20MPa,Extruded velocity is less than 50mm/s, and outlet of extruder place arranges infrared flash dryer, makes idiosome fast shaping obtain prefabricated multichannelFilm idiosome; Multi-channel membrane idiosome is by naturally drying or the mode of oven for drying is further shaped, and natural flash-off time is little at 2-48Time; Oven for drying time 1-10 hour, oven temperature is controlled at 20-50 DEG C.
(3) sintering
By prefabricated multi-channel membrane idiosome under the protective atmosphere of vacuum, nitrogen or inert gas, sintering, heating rate is3-10 DEG C/min, be first warming up to 150-300 DEG C, insulation 20-120min, carries out Degumming Procedures; And then with 3-10 DEG C/minHeating rate is warming up to 900-1500 DEG C, and insulation 20-180min, carries out sintering circuit; And then with the cooling of 1-10 DEG C/minSpeed, temperature is down to 300-500 DEG C, and insulation 30-60min, finally naturally cools to room temperature with stove; Obtain multichannel symmetrical junctionThe pure matter silicon carbide film of structure.
As preferably, the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure, described silicon carbide film consists of pure matterCarborundum, film characterizes aperture value between 1-20 μ m, is formed film by the silicon-carbide particle between 10-200 μ m by binding agent sinteringPorosity, between 35-65%, has the pore structure that three-dimensional is communicated with.
As preferably, the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure, described silicon carbide film profile is tubuloseMulti-channel structure, can be circular tube shaped or square tube type or hexagon tubulose, and channel shape can be circular or square or hexagon,Film material external diameter or the length of side between 10-500mm, length between 100-2000mm, single membrane channels number between 7-3000,Membranous wall is thick between 0.05-10mm, and single film effective filtration area is at 0.1-50m2Between.
As preferably, the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure, described silicon carbide film is symmetrical structure,Film characterize pore size filter between 1-20 micron, as preferred film characterize pore size filter be chosen as 1 micron, 3 microns, 5 microns,10 microns, 20 microns, pore size filter concentration degree is more than 80%.
As preferably, the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure, the multichannel knot of described silicon carbide filmStructure is by multichannel mould head, extrudes realization by extruder, for the idiosome collapse-deformation that prevents from just having extruded, is provided with redOuter drying unit carries out fast shaping; For preventing that idiosome from, in dry link cracking and distortion, having adopted and naturally having dried or internal-external temperature differenceLittle heat is dried.
As preferably, the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure, described silicon carbide film carborundum contentMore than 99wt%, the inner carborundum crystals combination of film is by binding agent (Polycarbosilane, polysilazane, polysiloxanes, siliconOne or more of oil, poly dimethyl silane) the new carborundum that forms as silicon carbide precursor body cracking reaction and sintering knotClose, do not exist clay or other oxides in conjunction with phase.
As preferably, the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure, is characterized in that: multichannel symmetrical junctionThe pure matter silicon carbide film of structure sintering furnace sintering maximum temperature is between 900-1500 DEG C, and sintering time is between 20-180min.
The preparation method's of the pure matter silicon carbide film of a kind of multichannel symmetrical structure of the present invention technical scheme has following beneficial effect:
1. the pure matter silicon carbide film of multichannel symmetrical structure of the present invention has single carborundum composition, can fully demonstrate carbonThe various characteristics of SiClx material on film separates, produces high flux, anti-pollution, corrosion resistant feature, especially in oxide combinationUnder reducing atmosphere and high-alkali, high chlorine corrosion environment that carborundum filtering material is not suitable for using, have good stability, guarantee that material is longService life.
2. the pure matter silicon carbide film of multichannel symmetrical structure of the present invention is tubulose multi-channel structure, is meeting the feelings of requirement of strengthUnder condition, can enlarge markedly film material size and effective filtration area, can increased efficiency, reduce putamina and number of seals, excellentChange and filter fluid distribution, minimizing project occupation of land, significantly reduce investment and use cost.
3. the pure matter silicon carbide film of multichannel symmetrical structure of the present invention is symmetrical structure, does not establish filter course, and film characterizes filtering holesFootpath is between 1-20 micron, and rete can not come off, and tolerance 10MPa is with interior kickback pressure, successfully manages water hammer effect, canBe applied in cross-flow filtration, dead-end filtration, half dead-end filtration and dynamic membrane filtering technique, or as unsymmetric structure filmBase material, range of application is more extensive.
4. the porosity of the pure matter silicon carbide film of multichannel symmetrical structure of the present invention, at 35-65%, is communicated with by three dimensionsUniform pore size forms, and has ensured that filter medium, at space diverging flow more widely, reduces filtration resistance, can significantly promote anti-Rush cleaning performance, thereby increase filtration flux and stability.
5. the pure matter silicon carbide film of multichannel symmetrical structure of the present invention preparation method adopts organosilicon polymer as carborundumPresoma, reaction at a lower temperature generates new carborundum in conjunction with original silicon-carbide particle, has ensured that membrane material is pure carborundum;With respect to other reaction-sintereds and recrystallization sintering, sintering temperature is reduced in 1500 DEG C above from 2000 DEG C, thereby reducesEnergy consumption and operation requirements, also significantly reduce the requirement of sintering furnace, can reduce investment and operating cost.
6. the pure matter silicon carbide film of multichannel symmetrical structure of the present invention preparation method technology controlling and process is flexible, can design as requiredThe product of different size, with short production cycle, cost is low, is easy to realize, and can ensure properties of product.
7. the pure matter silicon carbide film of multichannel symmetrical structure of the present invention application is wide, can be used for chemical industry, biofermentation, makesThe industry special separation such as paper, food and drink, mineral processing, also can carry mark transformation, waste water place for tap water purifying, sewageThe links such as reason and recovery utility, middle water reuse, also can be applicable to purifying vehicle exhaust, the filtration of Coal Chemical Industry raw gas, high temperatureThe gas purifications such as flue gas processing.
Brief description of the drawings
The pure matter silicon carbide film of Fig. 1 multichannel symmetrical structure dimensional drawing, description of reference numerals: carborundum film body 1, passage 2.
The pure matter silicon carbide film of Fig. 2 multichannel symmetrical structure internal structure
Detailed description of the invention:
Further illustrate the present invention below in conjunction with example, but be not any restriction of context of the present invention.
Embodiment 1
50-100 μ m silicon-carbide particle, polysiloxanes, carboxymethyl cellulose, phenolic resins, polymine are pressed to quality hundredPoint ratio is 65: 12: 19.5: blend in 3: 0.5 is in toluene, and toluene level accounts for the 30wt% of total amount, ball after mechanical agitationGrind 0.5 hour to obtain dense thick slurry, and then enter the mixing 30min of extruding in pug mill, form and mix more evenly and have goodThe slurry mud of plasticity. Above-mentioned slurry mud is packed in extruder, and cross-head adopts cylindrical inner circle 31 hole multichannel moulds, controlExtrusion pressure 5MPa processed, extruded velocity 10mm/s, outlet of extruder place adopts ultra redray drier flash baking sizing, adoptsHigh temperature resistant graphite pallet is accepted idiosome, and it is 500mm that control idiosome is extruded length; Just the idiosome of one-step forming be transferred to drying room dry intoOne step sizing, 40 DEG C of drying room temperature, drying time 5 hours.
In the vacuum drying oven that is 0.05Pa at air pressure by the idiosome after drying, carry out sintering, heating rate is 4 DEG C/min, first heats upTo 220 DEG C, insulation 30min; And then be warming up to 1100 degrees Celsius with 6 DEG C/min heating rate, insulation 60min; ThenWith the rate of temperature fall of 5 DEG C/min, temperature is down to 350 DEG C again, and insulation 30min, finally naturally cools to room temperature with stove; Obtain manyThe pure matter silicon carbide film of passage symmetrical structure.
As shown in Figure 1, the pure matter silicon carbide film of this multichannel symmetrical structure is circular tube shaped film material, and channel shape is circular, port numberAmount is 31, and monofilm effective filtration area is 0.15 square metre, and burst strength 18MPa has realized increase filter area and filmThe object of material intensity.
As shown in Figure 2, the pure matter silicon carbide film of multichannel symmetrical structure particle is by newly-generated carborundum in conjunction with tight, and hole isStereoscopic three-dimensional structure is communicated with, is evenly distributed, and be symmetric form filter course, can guarantee that membrane porosity is high, filtration pressure drop is little, flux is largeRequirement; Obtaining film sign pore size filter is 3 μ m, and porosity is 45%, and pure water filtration flux is 57000L.m-2.H-1.bar-1。
Embodiment 2
Difference from Example 1 is:
Raw material adopts 20-50 micron silicon-carbide particle, Polycarbosilane, dusty yeast, carboxyalkyl acid amides, TMAH to pressMass percent example is 70: 10: 15.5: blend in 4: 0.5 is in ethanol, and ethanol content accounts for the 20wt% of total amount, and then entersEnter the mixing 30min of extruding in pug mill, form the slurry mud that mixes more evenly and have good plasticity. Above-mentioned slurry mud is packed intoIn extruder, cross-head adopts cylindrical inner circle 31 hole multichannel moulds, controls extrusion pressure 6MPa, extruded velocity 5mm/s,Extruding length is 1013mm; Just the idiosome of one-step forming is transferred to drying room and dries further sizing, and 35 DEG C of drying room temperature, when oven dryBetween 6 hours.
Idiosome after drying is carried out to sintering in the vacuum drying oven of 0.05Pa, and heating rate is 3.5 DEG C/min, is first warming up to200 DEG C, insulation 30min; And then be warming up to 1000 degrees Celsius with 5 DEG C/min heating rate, insulation 120min; And thenWith the rate of temperature fall of 5 DEG C/min, temperature is down to 400 DEG C, and insulation 30min, finally naturally cools to room temperature with stove; Led to moreThe pure matter silicon carbide film of road symmetrical structure.
As shown in Figure 1, the pure matter silicon carbide film of this multichannel symmetrical structure is circular tube shaped film material, and channel shape is circular, port numberAmount is 31, and monofilm effective filtration area is 0.33 square metre, and burst strength 11MPa has realized increase filter area and filmThe object of material intensity.
As shown in Figure 2, the pure matter silicon carbide film of multichannel symmetrical structure particle is by newly-generated carborundum in conjunction with tight, and hole isStereoscopic three-dimensional structure is communicated with, is evenly distributed, and be symmetric form filter course, can guarantee that membrane porosity is high, filtration pressure drop is little, flux is largeRequirement; Obtaining film sign pore size filter is 1 μ m, and porosity is 42%, and pure water filtration flux is 51000L.m-2.H-1.bar-1。
Embodiment 3
Difference from Example 1 is:
Raw material adopts 150-200 micron silicon-carbide particle, polysilazane, starch, carboxyalkyl acid amides, TMAH to pressMass percent example is 80: 8: 10: blend in 1.8: 0.2 is in ethanol, and ethanol content accounts for the 25wt% of total amount, and then entersThe mixing 30min of extruding in pug mill, forms the slurry mud that mixes more evenly and have good plasticity. Above-mentioned slurry mud is packed into crowdedGo out in machine, cross-head adopts round outside but spuare inside 1035 hole multichannel moulds, controls extrusion pressure 8MPa, extruded velocity 2mm/s,Extruding length is 500mm; Just the idiosome of one-step forming is transferred to drying room and dries further sizing, 35 DEG C of drying room temperature, drying time10 hours.
Idiosome after drying is carried out to sintering in the vacuum drying oven of nitrogen atmosphere, and heating rate is 3 DEG C/min, is first warming up to280 DEG C, insulation 50min; And then be warming up to 1300 degrees Celsius with 4 DEG C/min heating rate, insulation 150min; And thenWith the rate of temperature fall of 5 DEG C/min, temperature is down to 450 DEG C, and insulation 30min, finally naturally cools to room temperature with stove; Led to moreThe pure matter silicon carbide film of road symmetrical structure.
The pure matter silicon carbide film of this multichannel symmetrical structure is circular tube shaped film material, and channel shape is square, and number of channels is 1035,Monofilm effective filtration area is 5 square metres, and burst strength 10MPa has realized the object that increases filter area and film material intensity.
As shown in Figure 2, the pure matter silicon carbide film of multichannel symmetrical structure particle is by newly-generated carborundum in conjunction with tight, and hole isStereoscopic three-dimensional structure is communicated with, is evenly distributed, and be symmetric form filter course, can guarantee that membrane porosity is high, filtration pressure drop is little, flux is largeRequirement; Obtaining film sign pore size filter is 20 μ m, and porosity is 58%, and pure water filtration flux is 89000L.m-2.H-1.bar-1。
The above, be only patent preferred embodiment of the present invention, can not limit successively scope of the invention process, according to thisPatent of invention scope and description equivalence change and modify, all should belong in the scope that the present invention contains.
Claims (4)
1. a preparation method for the pure matter silicon carbide film of multichannel symmetrical structure, is characterized in that: the pure matter carbon of multichannel symmetrical structureSiClx film consist of pure matter silicon-carbide particle, film material is formed by 10-200 μ m silicon-carbide particle reaction-sintered, has three dimensionsInterconnected pore structure, percent opening is at 35-65%, pore diameter range is between 1-20 μ m; Film material is tubulose multi-channel structure, is roundTubulose or square tube type or hexagon tubulose, channel shape is circular or square or hexagon;
The preparation method of the described pure matter silicon carbide film of multichannel symmetrical structure, using 10-200 μ m silicon-carbide particle as main materialMaterial, binding agent, pore creating material, curing agent, dispersant are as auxiliary material, and solubilizer mixing is made into slurry, utilizes solid shapeMould extrusion molding, obtain the pure matter silicon carbide film of multichannel symmetrical structure through sintering, concrete implementation step is as follows:
(1) batching
By 10-200 μ m silicon-carbide particle, binding agent, pore creating material, curing agent, dispersant and solvent according to mass percent be(85wt％-55wt％)：(20wt％-5wt％)：(35wt％-10wt％)：(1wt％-5wt％)：(0.2wt％-0.8wt％)：(10wt%-30wt%) mix, each constituent mass percentage sum is 100%; Through batch mixer mechanical agitation 20-60min, soAfter enter again the mixing 20-60min of extruding in pug mill, form the slurry mud that mixes more evenly and have good plasticity;
(2) extrusion molding
According to the multichannel mould of designing requirement processing definite shape, be arranged on cross-head place, above-mentioned slurry is added and extrudedIn machine feed bin, then extrude the multi-channel membrane idiosome of design shape, outlet of extruder place arranges infrared flash dryer, makes idiosomeFast shaping obtains prefabricated multi-channel membrane idiosome, and prefabricated multi-channel membrane idiosome naturally dries or dries further shapes;
(3) sintering
By moulding prefabricated multi-channel membrane idiosome sintering under the protective atmosphere of vacuum or inert gas, heating rate is 3-10 DEG C/min,First be warming up to 150-300 DEG C, insulation 20-120min; And then be warming up to 900-1500 DEG C with 3-10 DEG C/min heating rate,Insulation 20-180min; And then with the rate of temperature fall of 1-10 DEG C/min, temperature is down to 300-500 DEG C, insulation 30-60min; ?After naturally cool to room temperature with stove, obtain the pure matter silicon carbide film of multichannel symmetrical structure;
Silicon-carbide particle particle diameter is between 10-200 μ m; Binding agent comprises the one or of Polycarbosilane, polysilazane, polysiloxanesMore than kind; Pore creating material is one or more of carboxymethyl cellulose, starch, dusty yeast, organic polymer microballoon; SolidifyAgent is one or more of carboxyalkyl acid amides, phenolic resins, epoxy resin, petroleum coke; Dispersant be polymine,One or more of TMAH; Solvent is mainly ethanol, toluene or water.
2. the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure according to claim 1, is characterized in that:The carborundum diffusion barrier that the pure matter silicon carbide film of multichannel symmetrical structure is a kind of symmetrical structure, pore size filter can be controlled in 1-20 μ m modelIn enclosing, directly isolated by filtration target substance, or as the silicon carbide film supporter of unsymmetric structure.
3. the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure according to claim 1, is characterized in that:The pure matter silicon carbide film of multichannel symmetrical structure is tubulose multi-channel structure, is circular tube shaped or square tube type or hexagon tubulose, tunnel-shapedShape is circular or square or hexagon, and film material external diameter is at 10-500mm, and length is at 100-2000mm, and passage number is 7-3000Individual, wall thickness is at 0.1-10mm.
4. the preparation method of the pure matter silicon carbide film of a kind of multichannel symmetrical structure according to claim 1, is characterized in that:The pure matter silicon carbide film of multichannel symmetrical structure carborundum content is more than 99wt%, and the combination of material internal carborundum crystals is by stickyKnot agent forms new carborundum and sinter bonded as silicon carbide precursor body cracking reaction, binding agent be Polycarbosilane, polysilazane,One or more of polysiloxanes.
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| CN102985171A (en) * | 2010-07-14 | 2013-03-20 | 日本碍子株式会社 | Ceramic filter |
| CN202715364U (en) * | 2012-07-13 | 2013-02-06 | 江苏合兴环保科技有限公司 | Multichannel ceramic membrane filter pipe |
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| CN103721577A (en) | 2014-04-16 |
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