CN105693276B - A kind of silicon carbide filter film layer and its low temperature preparation method - Google Patents
A kind of silicon carbide filter film layer and its low temperature preparation method Download PDFInfo
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- CN105693276B CN105693276B CN201410699493.2A CN201410699493A CN105693276B CN 105693276 B CN105693276 B CN 105693276B CN 201410699493 A CN201410699493 A CN 201410699493A CN 105693276 B CN105693276 B CN 105693276B
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 116
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 58
- 238000001914 filtration Methods 0.000 claims abstract description 49
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000007921 spray Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 16
- 238000006073 displacement reaction Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 238000013461 design Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000000428 dust Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 3
- 238000005245 sintering Methods 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 239000003245 coal Substances 0.000 abstract description 10
- 239000000919 ceramic Substances 0.000 abstract description 8
- 230000035939 shock Effects 0.000 abstract description 8
- 238000002309 gasification Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 208000016791 bilateral striopallidodentate calcinosis Diseases 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003546 flue gas Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000010248 power generation Methods 0.000 abstract description 2
- -1 vehicle exhaust Substances 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011214 refractory ceramic Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000011856 silicon-based particle Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Filtering Materials (AREA)
- Ceramic Products (AREA)
Abstract
The invention belongs to porous ceramic film material field, specially a kind of silicon carbide filter film layer and its low temperature preparation method.The group of silicon carbide filter film layer becomes pure matter SiC, superficial film is combined by the accumulation of fine grained silicon carbide, aperture 20nm~20 μm, film layer porosity have the characteristics that high pass porosity, low pressure drop, intensity are high, thermal shock resistance is good, high using temperature between 40~50%.Membrane layer pulp is prepared using thin silicon-carbide particle, organosilane precursor, pore-creating agent addition agent, film layer is prepared using sprayed surface, after drying, sintering obtains pure matter silicon carbide film layer.The present invention is cracked to form using organosilane precursor in conjunction with phase, sintering temperature is low, pore structure control is easy, prepared film layer can use under oxidizing atmosphere, it can also use under reducing atmosphere, acid and alkali resistance corrosive nature is strong, can be used for the various high and low temperature filtering flow purifications such as coal gasification chemical industry and IGCC, PFBC coal gasification power generation, high-temperature flue gas, vehicle exhaust, Water warfare.
Description
Technical field
The invention belongs to porous ceramic film material field, specially a kind of silicon carbide filter film layer and its low temperature preparation method.
Background technique
Refractory ceramics filtering material generally all works under the conditions of various harsh environments, is made pottery as gas purification with high temperature
Porcelain filtering material, which usually requires that, includes (1) high mechanical strength, high temperature resistant (300~900 DEG C) and excellent medium corrosion resistance
Energy；(2) high filtering accuracy and filtering gas velocity and low pressure drop；(3) it is easy to blowback, stable operation, filter efficiency height；
(4) there is good thermal stability, be able to bear thermal shock caused by the blowback of frequent high-voltage pulse cold air.Meanwhile
It is required according to its application, High Temperature Ceramic Filter must be able to bear the shadow of the influence change of component of air-flow chemical characteristic variation
The influence vibrated when ringing, spraying into superfine grit, and higher efficiency of dust collection is kept, keep high flow capacity etc. to require.The ceramics of selection
Material not only has the chemistry of heat, mechanical stability, should also have durability and high reliability；Especially in high-temperature and high-pressure conditions
Under, when there are gas phase sulfur, alkali, chlorine element corrosion the case where when, also require ceramic material have high chemical stability.
Strainability, high high-temp stability and the roadholding of refractory ceramics filtering material and long-term operation it is reliable
Performance is the key that the design of refractory ceramics filtering material.Refractory ceramics mistake with filtering, desulfurization or denitration multifunctional all
Filter material material will be the further developing direction of gas purification material.In all kinds of ceramic filter materials, before most having development with SiC ceramic
Scape, because SiC has compared with oxide ceramics, high thermal conductivity, low-expansion coefficient, thermal shock resistance are good, use temperature height (1000
DEG C or more) the characteristics of, therefore it is preferred in terms of the industrial fields high temperature fluid filtering such as vehicle exhaust, coal chemical industry, molten metal
Material.
It but is mostly at present that the oxides such as clay combine using most silicon carbide filters in terms of high temperature air filtration
SiC ceramic causes thermal shock resistance poor the disadvantage is that thermal conductivity is low, so that ceramic filter material is difficult to bear big thermic load
Fluctuation；Especially in high-temperature coal gasification generation technology (such as IGCC, PFBC), because containing sodium metasilicate, NaCl composition, coal in coal
The Na2Si2O5 meeting heavy corrosion oxide combined silicon carbide filtering material being converted to after burning, causes the destruction of filter to be lost
Effect, and research shows that pure SiC ceramic material not by above-mentioned corrosion, while pure matter carbofrax material in high-temperature oxydation and
It can be used under reducing atmosphere, but technology is few in terms of pure matter silicon carbide filters development at present, resulting product intensity
The shortcomings that low, pore-size distribution is unevenly, filter efficiency is not high, filtering pressure drop is big, pore structure is not easy to blowback cleaning, limit carbon
The application process of SiClx filtering material.
Filtering material is attached to filtering material support body surface in use, to what filtering accuracy played a decisive role
The filtering film layer in face, supporter play the role of intensity, and the gradient-structure formed by the two can not only be required with proof strength, but also can be with
Guarantee filter effect, it is contemplated that filtration resistance problem, filtering film layer is made general very thin, this requires that filtering film layer has height
Tolerance and high filtration performance.Existing silicon carbide supporter filtering material film layer is mostly the oxides material such as aluminium oxide, mullite
Matter, in order to preferably match with silicon carbide supporter, people it is expected to prepare pure matter silicon carbide film layer always, but due to silicon carbide
Not easy-sintering, sintering temperature height (1900~2400 DEG C) are difficult to guarantee again while controlling film layer pore structure brilliant in film layer
The silicon carbide film layer intensity of the good combination of grain, conventional method preparation is low, and resistance to erosion, service life be not low.Therefore, high using temperature,
Resistance to various dielectric corrosions, high intensity, low pressure drop, are easy to regenerate, the silicon carbide filter that preparation method is reliable, at low cost intensity height
Film layer is that people are expected.
Summary of the invention
The purpose of the present invention is to provide a kind of silicon carbide filter film layer and its low temperature preparing methods, specifically solve skill as above
Art problem:
The invention solves a technical problem be: avoiding existing filtering material material surface filtering film layer is mostly not
The material composition for carrying out the oxide ceramics such as stone, aluminium oxide, provides a kind of pure matter silicon carbide filters, and material group becomes 99wt%
The above silicon carbide enables such material media-resistant corrosive power under various atmospheric conditions stronger.
Another technical problem to be solved by the present invention is that: avoid existing filtering material material surface filtering film layer technology of preparing
In shortcoming, provide that a kind of pore structure is controllable, porosity is big, the high and low pressure drop of intensity, regenerating easily, it is reusable
Ideal pure matter silicon carbide porous filter film layer.
The invention solves another technical problem be: using be different from Conventional silicon carbide high-sintering process low temperature system
Preparation Method, provide a kind of raw material be easy to get, form be easy, sintering temperature is low, high yield rate, film layer pore structure more easily regulate and control
The silicon carbide filter film layer preparation method suitable for large-scale production.
In order to solve technical problem present in the preparation of silicon carbide filter film layer, the technical solution used in the present invention is:
The group of a kind of silicon carbide filter film layer, silicon carbide filter film layer becomes pure matter SiC, and superficial film is carbonized by fine grained
Silicon stack product is combined into, and aperture 20nm~20 μm, film layer porosity is between 40~50%.
The silicon carbide filter film layer, in silicon carbide filter film layer, pure matter SiC content in 99wt% or more, material by
Organosilane precursor cracking silicon carbide combination original silicon carbide silicon particle is sintered composition certainly.
The preparation method of the silicon carbide filter film layer, is added using thin silicon-carbide particle, organosilane precursor, pore creating material
Add agent and organic solvent to prepare membrane layer pulp, film layer is prepared using sprayed surface, after drying, sintering obtains silicon carbide film layer.
The preparation method of the silicon carbide filter film layer, the specific steps are as follows:
(1) membrane layer pulp prepares
By thin silicon-carbide particle, organosilane precursor, pore-creating agent addition agent, organic solvent by mass percentage example be (6~
4): (5~3)): (2~1): (8~6) are blended, and ball milling obtains membrane layer pulp after mechanical stirring；
(2) superficial film coats
Superficial film is carried out using spraying method, spraying method: will be starched the film layer that step (1) obtains using gas spray gun
Material is sprayed on the precast support body of rotation, controls thicknesses of layers by adjusting relative displacement between supporter and spray gun,
Superficial film is obtained after drying, drying temperature is 60~80 DEG C and keeps the temperature 0.5~1.5 hour, then proceedes to be warming up to 180~220
DEG C heat preservation 1.5~2.5 hours；
(3) it is sintered
By the filtering material supporter after coating surface film layer under the protective atmosphere of vacuum, argon gas or other inert gases
Sintering, is warming up to 600~800 DEG C, heat preservation makes organosilane precursor basic in 0.5~1 hour by 1~3 DEG C/min of heating rate
Cracking；Heating rate is 5~15 DEG C/min afterwards, temperature are as follows: 1100~1600 DEG C, keeps the temperature 0.5~5 hour, obtains with silicon carbide
Filter film layer；
(4) silicon carbide film layer for obtaining (3) step, 750~850 DEG C of oxidation processes 0.5~1.5 are small in air atmosphere
When, pore-forming additive is removed, so that film layer porosity is promoted to design level.
The preparation method of the silicon carbide filter film layer, in step (1), the granularity of thin silicon-carbide particle is in 20nm~40
Between μm, organosilane precursor is polymethyl silicane；Pore-forming additive is carbon dust, and granularity is between 20nm~10 μm；It is organic molten
Agent is toluene or dimethylbenzene.
The preparation method of the silicon carbide filter film layer, in step (2), spraying method: using gas spray gun by slurry
It is sprayed on the precast support body of rotation, the flow velocity of spray gun membrane layer pulp is 10~20 Grams Per Seconds, and rotation speed is 5~30rpm/
Min controls thicknesses of layers by adjusting 50~100mm/min of relative displacement between supporter and spray gun, obtains after dry
Superficial film.
The preparation method of the silicon carbide filter film layer, in step (3), by the control of spraying process, pure matter carbonization
Silicon film thickness control is between 50~1000 μm.
The present invention has the advantage that with prominent effect:
1. there is silicon carbide filter film layer of the invention single silicon carbide to form, it ensure that material in various high-temperature mediums
Under corrosion resistance, especially oxide membranous layer filtering material be not suitable for using reducing atmosphere and high-alkali corrosive environment under,
It has good stability, it is ensured that the material long life.
2. silicon carbide filter film layer of the invention have fine pore structure, guarantee material have good filtering accuracy and
Filter efficiency, and it is conducive to the realization of blowback cleaning, regeneration is easy, reusable.
3. silicon carbide filter film layer crystal grain combination of the invention be secondary silicon carbide combination original silicon carbide silicon particle, two
Person is qualitative unanimously to guarantee that intercrystalline is firmly combined, and guarantees that material has high intensity and thermal shock resistance.
4. silicon carbide filter film layer preparation method technique sintering temperature of the invention is sintered temperature well below Conventional silicon carbide
Degree, pore structure are easy to finely control, and preparation cost is low, can design the product of different size as needed, with short production cycle, at
This is low, it is easy to accomplish, it can ensure properties of product.
5. silicon carbide filter film material application field provided by the invention is wide, in oxidation, reduction, high chlorine, alkali, sulphur, silicon
Etc. use when can be long under atmosphere, can more be used at a high temperature of 1000 DEG C, can be used for coal chemical industry and high-temperature coal gasification generation technology
The various industrial smokes such as raw gas filtering, high-temperature boiler can also be used in sewage water filtration processing.
In short, this kind of silicon carbide filter film layer group becomes pure matter silicon carbide, there is no oxides etc. to combine phase, has high pass
Porosity, low pressure drop, intensity are high, thermal shock resistance is good, using the high feature of temperature, and preparation method is easily achieved, Neng Goubao
Demonstrate,prove properties of product.
Detailed description of the invention
Fig. 1: silicon carbide filter film surface shape appearance figure.
Fig. 2: silicon carbide filter film surface enlarged drawing.
Fig. 3: silicon carbide filter film layer port shape appearance figure.
Fig. 4: silicon carbide filter film layer and supporter interface cohesion figure.
Specific embodiment
In a specific embodiment, silicon carbide filter film layer of the invention and its low temperature preparation method, superficial film raw material
Group is divided into (according to the mass fraction):
| Thin silicon-carbide particle (20nm~40 μm) | 6~4 |
| Organosilane precursor (polymethyl silicane) | 5~3 |
| Pore-creating agent addition agent (carbon dust, 20nm~10 μm) | 2~1 |
| Organic solvent (toluene or dimethylbenzene) | 8~6 |
In the constitutive material of silicon carbide filter film layer, organosilane precursor crack during the sintering process be transformed into silicon carbide and
The silicon carbide of small amounts silicon, generation combines original silicon carbide silicon particle, provides intensity for film layer and guarantees, and wherein few
The silica of amount reacts to form silicon carbide with carbon dust in raw material, avoids the presence of impurity phase, then in subsequent oxidation process
Pore-forming additive is removed, film layer porosity is remarkably improved, so that the group of material becomes silicon carbide.Pure matter silicon carbide film layer pair
It plays an important role in improving the strength of materials, heat shock resistance, high-temperature stability and creep rupture life.
In material preparation, different raw material compositions, granularity selection, it is ensured that silicon carbide filter film layer has high through-hole
Gap rate and reasonable pore structure guarantee that material permeability is good, have low filter pressure, while fine film layer design can
With good guarantee filtering accuracy.
The preparation method of pure matter silicon carbide filter film layer of the invention, using thin silicon-carbide particle, organosilane precursor, makes
Hole agent addition agent, organic solvent prepare film layer raw material, are prepared and are filtered in filtering material supporting body surface using spin coating process
Film layer, after drying, sintering and oxidation removal pore creating material obtain pure matter silicon carbide filter film layer, mainly comprise the steps that
(1) membrane layer pulp prepares
By thin silicon-carbide particle, organosilane precursor, pore-creating agent addition agent, organic solvent by mass percentage example be (6~
4): (5~3): (2~1): (8~6) blending and stirring obtains membrane layer pulp through ball milling, and Ball-milling Time is 1~2 hour, for use.
Carborundum granularity is between 20nm~40 μm, and pore-forming additive (carbon dust) is between 20nm~10 μm, before organosilicon
It drives body and selects polymethyl silicane；Organic solvent is toluene or dimethylbenzene.
(2) superficial film coating preparation
Superficial film is carried out using spin coating process, spraying method: the film that will be obtained step (1) using gas spray gun
Layer slurry is sprayed on the filtering material supporter of rotation, and the flow velocity of spray gun membrane layer pulp is 10~20 Grams Per Seconds, and rotation speed is
5~30rpm/min controls thicknesses of layers by adjusting relative displacement (50~100mm/min) between supporter and spray gun,
Superficial film is obtained after drying.By dry caudacoria pipe outside diameter measurement, superficial film thickness is controlled between 50~1000 μm.
(3) it is sintered
Film layer then proceeded to be warming up to 180~220 DEG C, drying in 1.5~2.5 hours through 60~80 DEG C, 0.5~1.5 hour
After processing, by the filtering material supporter after coating surface film layer under the protective atmosphere of vacuum, argon gas or other inert gases
Sintering: 1~3 DEG C/min of heating rate of starting is warming up to 600~800 DEG C, and heat preservation makes organosilane precursor in 0.5~1 hour
Basic cracking；It then proceedes to heat up, heating rate is 5~15 DEG C/min, and temperature is 1100~1600 DEG C, and heat preservation 0.5~5 is small
When, it obtains with silicon carbide filter film layer.Wherein,
Drying process of the film layer Jing Guo two stages different temperatures, feature and effect are: low-temperature zone keeps organic solvent slow
Volatilization, and be allowed to remove, it can avoid acutely bubble occur in inside due to organic solvent vaporization, generate hole；High temperature section is
The organosilane precursor cure treatment stage can avoid the generation of organosilane precursor temperature flowing phenomenon, it is ensured that organic very well
Silicon precursor is evenly distributed.
Film layer uses the sintering processes of two stages different temperatures, and feature and effect are: low-temperature region is organosilicon forerunner
Body cleavage stages, rate of cleavage is too fast, and being easy a large amount of deflation good can be controlled so that film layer cracks using slow heating rate
Heating rate processed avoids the generation of defect；Organosilane precursor breeds rank of growing up into carborundum grain after slowly cracking
Section, heating rate can be accelerated, and preparation efficiency can be improved.
(4) by silicon carbide filter film layer, 750~850 DEG C oxidation processes 0.5~1.5 hour in air atmosphere, removal is made
Macroporous additive, so that film layer porosity is promoted to design level.
In the present invention, the average pore size of silicon carbide filter film layer between 20nm~20 μm, porosity 40~50% it
Between.In the pure matter silicon carbide filter film layer, for pure matter SiC content in 99wt% or more, surplus is impurity element, and material internal is brilliant
Burl conjunction is combined by silicon-carbide particle completely, and clay or other oxide combination phases are not present.
In the following, being described in further detail by the embodiment present invention.
Embodiment 1
It is 4:5:2:8 blending, warp by 20nm silicon-carbide particle, polymethyl silicane, 20nm carbon dust, dimethylbenzene example in mass ratio
Obtain membrane layer pulp within ball milling 1.5 hours after mechanical stirring.
Slurry is sprayed on the filtering material supporter of rotation using gas spray gun, by adjust supporter and spray gun it
Between relative displacement control thicknesses of layers, obtain superficial film after dry.Spray gun material flow is 10 Grams Per Seconds, filtering support
Pipe revolving speed 10rpm/ minutes.Supporter and spray gun relative displacement are 70mm/min, after spraying, film layer through 70 DEG C, 1 hour,
It then proceedes to be warming up to 200 DEG C, drying process in 2 hours, film layer after drying is sintered under vacuum, originates 1 DEG C/minute of heating rate
Clock is warming up to 600 DEG C, and heat preservation cracks organosilane precursor substantially in 0.5 hour；It then proceedes to heat up, heating rate 5
DEG C/min, temperature is 1100 DEG C, keeps the temperature 2 hours, obtains with silicon carbide filter film layer.
Again by above-mentioned silicon carbide filter film layer 800 DEG C oxidation processes 1 hour in air atmosphere, pore-forming additive is removed,
So that film layer porosity is promoted to design level.
To which obtaining silicon carbide filter thicknesses of layers is 400 μm, average pore size 20nm, porosity 45%, film
1000 DEG C of heatproof of layer.
Embodiment 2
It is 5:3:1:6 blending by 40 μm of silicon-carbide particles, polymethyl silicane, 20 μm of carbon dusts, toluene example in mass ratio, through machine
Obtain membrane layer pulp within ball milling 1 hour after tool stirring.
Slurry is sprayed on the filtering material supporter of rotation using gas spray gun, by adjust supporter and spray gun it
Between relative displacement control thicknesses of layers, obtain superficial film after dry.Spray gun material flow is 20 Grams Per Seconds, filtering support
Pipe revolving speed 30rpm/ minutes.Supporter and spray gun relative displacement are 50mm/min, after spraying, film layer through 70 DEG C, 1 hour,
It then proceedes to be warming up to 200 DEG C, drying process in 2 hours, film layer after drying is sintered under vacuum, originates 3 DEG C/minute of heating rate
Clock is warming up to 800 DEG C, and heat preservation cracks organosilane precursor substantially in 1 hour；Then proceed to heat up, heating rate be 10 DEG C/
Minute, temperature is 1400 DEG C, keeps the temperature 2 hours, obtains silicon carbide filter film layer.
Again by above-mentioned silicon carbide filter film layer 800 DEG C oxidation processes 1 hour in air atmosphere, pore-forming additive is removed,
So that film layer porosity is promoted to design level.
So that 1000 μm of silicon carbide filter thicknesses of layers are obtained, and 20 μm of average pore size, porosity 42%, film layer
1000 DEG C of heatproof.
Embodiment 3
It is 5.5:4:2:7 blending by 10 μm of silicon-carbide particles, polymethyl silicane, 500nm carbon dust, toluene example in mass ratio,
Obtain membrane layer pulp within ball milling 1 hour after mechanical stirring.
Slurry is sprayed on the filtering material supporter of rotation using gas spray gun, by adjust supporter and spray gun it
Between relative displacement control thicknesses of layers, obtain superficial film after dry.Spray gun material flow is 10 Grams Per Seconds, filtering support
Pipe revolving speed 10rpm/ minutes.Supporter and spray gun relative displacement are 5mm/min, and after spraying, film layer was through 70 DEG C, 1 hour, so
After be continuously heating to 200 DEG C, 2 hours be dried, film layer after drying is sintered under vacuum, originate 2 DEG C/minute of heating rate
Clock is warming up to 800 DEG C, and heat preservation cracks organosilane precursor substantially in 0.5 hour；It then proceedes to heat up, heating rate 15
DEG C/min, temperature is 1600 DEG C, keeps the temperature 5 hours, obtains silicon carbide filter film layer.
Again by above-mentioned silicon carbide filter film layer 800 DEG C oxidation processes 1 hour in air atmosphere, pore-forming additive is removed,
So that film layer porosity is promoted to design level.
So that 1000 μm of silicon carbide filter thicknesses of layers, average pore size 500nm are obtained, and porosity 50%, film layer
1000 DEG C of heatproof.
As shown in Figure 1, the film surface flatness that can be seen that present invention preparation film layer from film surface pattern is high, have equal
Even pore structure.
As shown in Fig. 2, aperture uniform level is high from film surface amplification as can be seen that film layer inner pore is evenly distributed, it can
Guarantee film layer filtering accuracy with higher.
As shown in figure 3, can be seen that film layer inside original silicon carbide silicon particle by organosilane precursor from film layer port pattern
The silicon carbide cladding being cracked to form is combined together, it is ensured that film layer intensity with higher.
As shown in figure 4, can be seen that film layer and supporter interface cohesion is secured from film layer and support body interface, film layer is not
It is easy to fall off, it can be ensured that film layer service life.
Embodiment the result shows that, the present invention provides a kind of silicon carbide filter film layer and its low temperature preparation method, this kind of carbon
It is 99% silicon carbide that SiClx, which filters film layer composition, and there is no oxides etc. to combine phase, has high pass porosity, low pressure drop, intensity
It is high, thermal shock resistance is good, using the high feature of temperature, preparation method is easily achieved, and can guarantee properties of product.The present invention adopts
It is cracked to form with organosilane precursor (polymethyl silicane Polymethylsilane, PMS) in conjunction with phase, sintering temperature is low, hole
Structure control is easy, and prepared film layer can use under oxidizing atmosphere, can also be used under reducing atmosphere, and acid and alkali resistance is rotten
Corrosion can be strong, and it is various to can be used for coal gasification chemical industry and IGCC, PFBC coal gasification power generation, high-temperature flue gas, vehicle exhaust, Water warfare etc.
The purification of high and low temperature filtering flow.
Claims (3)
1. a kind of preparation method of silicon carbide filter film layer, which is characterized in that specific step is as follows:
It is 4:5:2:8 blending by 20nm silicon-carbide particle, polymethyl silicane, 20nm carbon dust, dimethylbenzene example in mass ratio, through machinery
Obtain membrane layer pulp within ball milling 1.5 hours after stirring；
Slurry is sprayed on the filtering material supporter of rotation using gas spray gun, by adjusting phase between supporter and spray gun
To displacement rate controlling membrane thickness degree, superficial film is obtained after dry；Spray gun material flow is 10 Grams Per Seconds, and filtering support tube turns
It is 10rpm/ minutes fast；Supporter and spray gun relative displacement are 70mm/min, and after spraying, film layer was through 70 DEG C, 1 hour, then
It is continuously heating to 200 DEG C, 2 hours to be dried, film layer after drying is sintered under vacuum, originates 1 DEG C/min of heating rate,
600 DEG C are warming up to, heat preservation cracks organosilane precursor substantially in 0.5 hour；It then proceedes to heat up, heating rate is 5 DEG C/minute
Clock, temperature are 1100 DEG C, keep the temperature 2 hours, obtain with silicon carbide filter film layer；
Again by above-mentioned silicon carbide filter film layer 800 DEG C oxidation processes 1 hour in air atmosphere, pore-forming additive is removed, so that
Film layer porosity is promoted to design level；
To which obtaining silicon carbide filter thicknesses of layers is 400 μm, and average pore size 20nm, porosity 45%, film layer is resistance to
1000 DEG C of temperature.
2. a kind of preparation method of silicon carbide filter film layer, which is characterized in that specific step is as follows:
It is 5:3:1:6 blending by 40 μm of silicon-carbide particles, polymethyl silicane, 20 μm of carbon dusts, toluene example in mass ratio, is stirred through machinery
Mix rear ball milling 1 hour to obtain membrane layer pulp；
Slurry is sprayed on the filtering material supporter of rotation using gas spray gun, by adjusting phase between supporter and spray gun
To displacement rate controlling membrane thickness degree, superficial film is obtained after dry；Spray gun material flow is 20 Grams Per Seconds, and filtering support tube turns
It is 30rpm/ minutes fast；Supporter and spray gun relative displacement are 50mm/min, and after spraying, film layer was through 70 DEG C, 1 hour, then
It is continuously heating to 200 DEG C, 2 hours to be dried, film layer after drying is sintered under vacuum, originates 3 DEG C/min of heating rate,
800 DEG C are warming up to, heat preservation cracks organosilane precursor substantially in 1 hour；It then proceedes to heat up, heating rate is 10 DEG C/minute
Clock, temperature are 1400 DEG C, keep the temperature 2 hours, obtain silicon carbide filter film layer；
Again by above-mentioned silicon carbide filter film layer 800 DEG C oxidation processes 1 hour in air atmosphere, pore-forming additive is removed, so that
Film layer porosity is promoted to design level；
So that 1000 μm of silicon carbide filter thicknesses of layers are obtained, and 20 μm of average pore size, porosity 42%, film layer heatproof
1000℃。
3. a kind of preparation method of silicon carbide filter film layer, which is characterized in that specific step is as follows:
It is 5.5:4:2:7 blending by 10 μm of silicon-carbide particles, polymethyl silicane, 500nm carbon dust, toluene example in mass ratio, through machine
Obtain membrane layer pulp within ball milling 1 hour after tool stirring；
Slurry is sprayed on the filtering material supporter of rotation using gas spray gun, by adjusting phase between supporter and spray gun
To displacement rate controlling membrane thickness degree, superficial film is obtained after dry；Spray gun material flow is 10 Grams Per Seconds, and filtering support tube turns
It is 10rpm/ minutes fast；Supporter and spray gun relative displacement are 5mm/min, after spraying, film layer through 70 DEG C, 1 hour, then after
It is continuous to be warming up to 200 DEG C, drying process in 2 hours, film layer after drying is sintered under vacuum, originates 2 DEG C/min of heating rate, is risen
For temperature to 800 DEG C, heat preservation cracks organosilane precursor substantially in 0.5 hour；It then proceedes to heat up, heating rate is 15 DEG C/minute
Clock, temperature are 1600 DEG C, keep the temperature 5 hours, obtain silicon carbide filter film layer；
Again by above-mentioned silicon carbide filter film layer 800 DEG C oxidation processes 1 hour in air atmosphere, pore-forming additive is removed, so that
Film layer porosity is promoted to design level；
So that 1000 μm of silicon carbide filter thicknesses of layers, average pore size 500nm are obtained, and porosity 50%, film layer heatproof
1000℃。
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| CN109678522A (en) * | 2018-12-20 | 2019-04-26 | 中国科学院上海硅酸盐研究所 | A kind of normal pressure solid-phase sintered silicon carbide film support and preparation method thereof |
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| CN102659447A (en) * | 2012-03-31 | 2012-09-12 | 中国科学院金属研究所 | Pure silicon carbide filtering membrane and preparation method thereof |
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| CN102659447A (en) * | 2012-03-31 | 2012-09-12 | 中国科学院金属研究所 | Pure silicon carbide filtering membrane and preparation method thereof |
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