CN105688684B - With three gradient pore structured pure matter foam silicon carbon supporter membrane tubes and preparation method - Google Patents
With three gradient pore structured pure matter foam silicon carbon supporter membrane tubes and preparation method Download PDFInfo
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- CN105688684B CN105688684B CN201410696037.2A CN201410696037A CN105688684B CN 105688684 B CN105688684 B CN 105688684B CN 201410696037 A CN201410696037 A CN 201410696037A CN 105688684 B CN105688684 B CN 105688684B
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- 239000006260 foam Substances 0.000 title claims abstract description 133
- 239000011148 porous material Substances 0.000 title claims abstract description 109
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000012528 membrane Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000012298 atmosphere Substances 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 235000013312 flour Nutrition 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
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- 150000001282 organosilanes Chemical class 0.000 claims description 10
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- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 8
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- 238000001035 drying Methods 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 8
- 238000001764 infiltration Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011496 polyurethane foam Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920005546 furfural resin Polymers 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 229960004011 methenamine Drugs 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000009825 accumulation Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 229940116315 oxalic acid Drugs 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 4
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000007767 bonding agent Substances 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims description 2
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- 238000009413 insulation Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229920001807 Urea-formaldehyde Polymers 0.000 claims 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 10
- 239000003245 coal Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 238000002309 gasification Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- -1 vehicle exhaust Substances 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
- 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
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- 238000011069 regeneration method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 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
- 229910021431 alpha silicon carbide Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Ceramic Products (AREA)
Abstract
The invention belongs to porous ceramic film material field, is specially that one kind has three gradient pore structured pure matter foam silicon carbon supporter membrane tubes and preparation method thereof.The foam silicon carbon supporter membrane tube forms three gradient filtration structures by double gradient pore structured pure matter foam silicon carbon supporters and superficial film, supporter is made up of double gradient pore structured pure matter foam silicon carbon supporters, 300~500 μm of outer layer average pore size, between 1~3mm of internal layer average pore size, supporter porosity is between 35~65%；Superficial film is combined into by silicon carbide powder, and aperture 50nm~20 μm, the film layer porosity is between 35~50%.Preparation method includes that dispensing, foam support be body formed, supporter sintering successively, and film layer is prepared and burnt till.The present invention can use under oxidizing atmosphere and reducing atmosphere, and acid and alkali resistance corrosive nature is strong, available 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, is specially that one kind has three gradient pore structured pure matter foam silicon carbons
Supporter membrane tube and preparation method thereof.
Background technology
Refractory ceramics filtering material typically all works under the conditions of various harsh environments, is made pottery as gas purification with high temperature
Porcelain filtering material usually requires that have：(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, frequently thermal shock caused by the blowback of high-voltage pulse cold air can be born.Meanwhile
Required according to its application scenario, High Temperature Ceramic Filter must be able to bear the shadow of the influence change of component of air-flow chemical characteristic change
Ring, spray into the influence vibrated during superfine grit, and keep higher efficiency of dust collection, keep high flow capacity etc. to require.The ceramics of selection
Material not only has chemistry, the mechanical stability of heat, should also have durability and high reliability；Especially in high-temperature and high-pressure conditions
Under, when gas phase sulfur, alkali, chlorine element corrosion be present, also require that ceramic material has high chemical stability.
First, the strainability of refractory ceramics filtering material, high high-temp stability and roadholding and long-term operation
Unfailing performance, be refractory ceramics filtering material design key.High temperature with filtering, desulfurization or denitration multifunctional all
Ceramic filter material will be the further developing direction of gas purification material.In all kinds of ceramic filter materials, most have with SiC ceramic
Development prospect, because SiC has compared with oxide ceramics, high thermal conductivity, low-expansion coefficient, thermal shock resistance are good, temperature in use is high
The characteristics of (more than 1000 DEG C), therefore in terms of the industrial field high temperature fluid filtering such as vehicle exhaust, coal chemical industry, molten metal
Preferred material.
But it 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, shortcoming are low thermal conductivities, cause thermal shock resistance poor so that ceramic filter material is difficult to bear big thermic load
Fluctuation；Particularly in high-temperature coal gasification generation technology (such as IGCC, PFBC), because containing sodium metasilicate, NaCl compositions, coal in coal
The Na changed into after burning2Si2O5Meeting heavy corrosion oxide combined silicon carbide filtering material, cause the damage inactivation of filter,
And study and show pure SiC ceramic material not by above-mentioned corrosion, while pure matter carbofrax material is in high-temperature oxydation and also
It can be used under Primordial Qi atmosphere, but technology is few in terms of pure matter silicon carbide filters development at present, resulting product low intensity,
The shortcomings that pore-size distribution is uneven, filter efficiency is not high, filtering pressure drop is big, pore structure is not easy to blowback cleaning, limitation carbonization
The application process of silicon filtering material.
Secondly, existing carborundum membrane tube supporter is mostly powder method extrusion or compressing, by coarse granule carborundum and is glued
Connect agent accumulation and burn till combination, its hole is that particle packing gap is formed, and pore-size is in tens micro-meter scales so that membrane tube pressure
Drop is big, and blowback pressure is big during pulse cleaning, and regeneration is difficult.
Therefore, temperature in use is high, resistance to various dielectric corrosions, intensity height, high intensity, low pressure drop, is easy to regeneration, preparation method
Reliably, the low pure matter carborundum membrane tube filtering material of cost is that people are expected.
The content of the invention
It is an object of the invention to provide one kind have three gradient pore structured pure matter foam silicon carbon supporter membrane tubes and
Its preparation method, it is specific to solve as above technical problem：
The invention solves a technical problem be：It is mostly the oxides such as clay to avoid existing silicon carbide filters
The material composition that part combines, there is provided a kind of pure matter silicon carbide filters, material composition is more than 99wt% carborundum so that
Such a material can under various atmospheric conditions media-resistant corrosive power it is stronger.
Another technical problem to be solved by the present invention is that：Avoid the deficiency in existing carborundum membrane tube supporter technology
Place, there is provided one kind has double gradient foam pore structures, and this kind of foam pores structure has millimetre-sized hole, and hole is
Three-dimensional UNICOM, porosity is big, low pressure drop, is easy to regenerate, reusable preferably pure matter carborundum porous ceramics membrane tube.
The invention solves another technical problem be：There is provided a kind of raw material be easy to get, prepare simple, shaping easily, production
The preparation method for the pure matter carborundum membrane tube suitable for large-scale production that cycle is short, high yield rate, production cost are low.
In order to solve technical problem present in silicon carbide filters preparation, the technical solution used in the present invention is：
One kind has three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, three gradient pore structured foam carbonizations
The composition of silicon fiml pipe is pure matter SiC, and gradient filtration structure is formed by support body layer and superficial film；Wherein, supporter is by double ladders
Spend the pure matter foam silicon carbon supporter of pore structure to form, 300~500 μm of outer layer average pore size, 1~3mm of internal layer average pore size
Between；Superficial film is combined into by silicon carbide powder accumulation, and aperture 50nm~20 μm, the membrane tube entirety porosity is 35~65%
Between.
Described has three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, three gradient pore structured pure matter bubbles
The length of foam carborundum supporter membrane tube is 100~2000mm, 30~50MPa of bending strength.
Described has three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, three gradient pore structured foamy carbons
In SiClx supporter membrane tube, pure matter SiC content is in more than 99wt%.
The described preparation method with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, with solid powder
Particle, organic polymer resin, curing agent, organic solvent are stock, mixed preparing slurry, mould are used as by the use of organic foam
Plate, infusion process prepare supporter presoma, and low-temperature carbonization sintering is molten after machine-shaping to ooze sintering, then is obtained through high temperature purification treatment
After double gradient pore structured pure matter foam silicon carbon supporters, added using silicon carbide powder, silica flour or silicon oxide powder, pore creating material
Add agent and organosilane precursor to prepare film layer raw material, film layer is prepared using spraying or dipping method surface, after drying, sintered
To finished product membrane tube.
The described preparation method with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes is specific to prepare step
It is rapid as follows：
(1) supporter shaping raw material prepares
It is (5~4) by solid powder particle, organic polymer resin, curing agent, organic solvent example in mass ratio：(2~
1)：(0.1~0.2)：(0.3~0.2) it is blended, ball milling obtains slurry after mechanical agitation；
Organic foam uses polyurethane foam, and for internal layer from foam average pore size between 1~3mm, outer layer selects foam
Aperture is 300~500 μm；
Solid powder particle is carborundum powder, silica flour or the two mixed-powder；Organic polymer resin is selected from asphalt mixtures modified by epoxy resin
The one or more of fat, phenolic resin and furfural resin；Curing agent is：P-methyl benzenesulfonic acid, urotropine, oxalic acid or lemon
Acid；Organic solvent is ethanol or formaldehyde；
(2) support body formed
The foam that internal layer needs, which is cut into, first needs the hollow cylindrical of size, and outer foam cuts into 1~2mm's
Thin-walled hollow cylinder, and cause outer hollow cylinder internal diameter to be equal to inner foam external diameter, then both are nested together, in step
(1) soaked in ready slurry, take out and unnecessary slurry is removed by the method for centrifugation, air-blowing, keep foamed open cell, dry
Solidization, then repeatedly said process, obtain needed for solid volume fraction double gradient pore structured pure matter foam silicon carbon branch
Support body presoma short tube, wherein solid volume fraction are controlled between 35~65%, and baking and curing temperature is 120~180 DEG C；
(3) spicing forming type
The supporter presoma short tube that (2) step obtains is machined into the structure that can be mutually inserted, utilizes material of the same race
Slurry is used as bonding agent, by supporter presoma short tube grafting bonding into the foam support body for needing size, is then pyrolyzed, then warp is molten
The composition for oozing sintering is remaining Si and SiC foam silicon carbon supporter；
(4) high temperature purification treatment
The non-pure matter foam silicon carbon supporter that (3) are obtained carries out at high temperature, introducing the processing of carbon atmosphere so that remaining
Si reacts to form carborundum with carbon atmosphere, obtains double gradient pore structured pure matter foam silicon carbon supporters；
During the high temperature purification treatment, technical process and technological parameter are as follows：Carbon atmosphere using acetylene or methane with
Example is 1 by volume for argon gas or helium:1 composition, temperature are 1800~1950 DEG C, and heating rate is 10~20 DEG C/min, insulation
0.5~5 hour, obtain double gradient pore structured pure matter foam silicon carbon supporters；
(5) film layer raw material prepares
Silicon carbide powder, silica flour or silicon oxide powder, organosilane precursor, pore-creating agent addition agent, organic solvent are pressed into matter
Amount ratio is (8~6)：(2~1)：(2~1)：(2~1)：(5~8) it is blended, ball milling obtains membrane layer pulp after mechanical agitation；
(6) prepared by superficial film
Carried out in double gradient pore structured pure matter foam silicon carbon supporting body surfaces that (4) step obtains using brushing method
Film bottom is uniformly after coating, then carried out using spraying coating process；
(7) film layer sinters
By the membrane tube precast body after coating surface film layer under the protective atmosphere of vacuum, argon gas or other inert gases, burn
Knot, 1~10 DEG C/min of heating rate, 1000~1400 DEG C are warming up to, are incubated 0.5~1 hour, Temperature fall cooling, had
There are three gradient pore structured pure matter foam silicon carbon supporter membrane tubes.
The described preparation method with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, in step (1),
Solid powder particle granularity is between 5~20 μm；Organic polymer resin be selected from epoxy resin, phenolic resin and furfural resin it
It is one or more kinds of；Curing agent is p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid；Organic solvent is ethanol or formaldehyde.
The described preparation method with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, in step (3)：
The technical process and technological parameter of pyrolysis are as follows：The protective atmosphere of argon gas, nitrogen or other inert gases, Huo Zhe
Under vacuum condition, 1~10 DEG C/min of heating rate, 800~1200 DEG C are warming up to, are incubated 0.5~2 hour, generate double gradient pores
The pure matter foam silicon carbon supporter of gap structure；
The technical process and technological parameter of melting infiltration sintering are as follows：The raw material selected in infiltration reaction-sintered is silicon, argon gas,
Siliconising is sintered under the protective atmosphere of nitrogen or other inert gases, or is sintered siliconising under vacuum, heating rate
For 5~15 DEG C/min, melt temperature is：1600~1900 DEG C, 0.5~5 hour is incubated, obtains non-pure matter foam silicon carbon membrane tube
Supporter.
The described preparation method with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, in step (5),
Silicon carbide powder granularity is between 0.5~100 μm, and silica flour or silicon oxide powder granularity are between 0.5~20 μm；Before organosilicon
Drive body is triethyl silicane, tetramethylsilane；Solvent is toluene or dimethylbenzene, and pore-forming additive is PVAC polyvinylalcohol or first
Base cellulose.
The described preparation method with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, in step (6),
The technical process of spraying is as follows：Slurry is sprayed on the precast support body of rotation using gas spray gun, by adjusting supporter
Relative displacement controls thicknesses of layers between spray gun, and superficial film is obtained after drying.
The described preparation method with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, in step (7),
Superficial film thickness is between 50~500 μm.
The present invention has the advantage that and prominent effect：
1. the pure matter silicon carbide film pipe of the present invention has single carborundum composition, it ensure that material in various high-temperature mediums
Under corrosion resistance, be especially not suitable for the reducing atmosphere that uses and high caustic corrosion ring in oxide combined silicon carbide filtering material
Under border, have good stability, the unification of film layer and supporter composition can ensure both harmonious property, it is ensured that material length uses the longevity
Life.
2. the three gradient pore structured pure matter foam silicon carbon membrane tubes of the present invention are uniform gradient pore structured with enriching,
The macroporous structure of double gradient pore structured pure matter foam silicon carbon supporters ensure that materials'use mesolow drop, Thief zone
Rate, and be easy to regenerate, the fine pore structure of superficial film ensures that material has good filtering accuracy and filter efficiency, and
Beneficial to the realization of blowback cleaning, regeneration is easy, reusable.
3. the three gradient pore structured pure matter foam silicon carbon membrane tube crystal grain combinations of the present invention are reaction generation carbonization
Silicon combination original silicon carbide silicon grain, the two is qualitative unanimously to ensure that intercrystalline is firmly combined with, and ensures that material has high intensity
And thermal shock resistance.
4. the three gradient pore structured pure matter foam silicon carbon membrane tube preparation method technology controlling and process of the present invention are flexible, can basis
The product of design different size is needed, with short production cycle, cost is low, it is easy to accomplish, properties of product can be ensured.
5. three gradient pore structured pure matter foam silicon carbon membrane tube materials application field provided by the invention is wide, oxidation,
Use when can be long under the atmosphere such as reduction, high chlorine, alkali, sulphur, silicon, can more be used at a high temperature of 1300 DEG C, available for coal chemical industry and
The various industrial smokes such as the filtering of high-temperature coal gasification generation technology raw gas, high-temperature boiler, it can be additionally used in sewage water filtration processing.
In a word, this kind of pure matter silicon carbide film pipe has by double gradient pore structured pure matter foam silicon carbon supporters and surface
Film layer composition it is three gradient pore structured, form as pure matter carborundum, combine phase in the absence of oxide etc., there is high pass hole
Rate, low pressure drop, intensity are high, thermal shock resistance is good, temperature in use is high, is easy to the distinguishing feature of pulse cleaning, and preparation method is easy
In realization, properties of product can be ensured.
Brief description of the drawings
The gradient pore structured pure matter foam silicon carbon membrane tube XRD diffraction patterns of Fig. 1 tri-.
The double gradient-structures of the gradient pore structured pure matter foam silicon carbon membrane tube supporters of Fig. 2 tri-.
The gradient pore structured pure matter foam silicon carbon membrane tube superficial films of Fig. 3 a-b tri- and foam joint portion (Fig. 3 a) and film
Layer pore structure (Fig. 3 b).
The gradient pore structured pure matter foam silicon carbon membrane tube photos of Fig. 4 tri-.
Embodiment
In a specific embodiment, three gradient pore structured pure matter foam silicon carbon supporter membrane tubes of the invention be with
The pure matter carbofrax material of three gradients of different pore structures, which is fired, to be formed, including double gradient pore structured pure matter foam silicon carbon branch
Support body and superficial film.Wherein：
(1) support body layer raw material components is (according to the mass fraction)：
| Solid powder particle (silicon carbide powder and/or silica flour, 5~20 μm) | 5~4 |
| Organic polymer resin (one or more of epoxy, phenolic aldehyde and furfural resin) | 2~1 |
| Curing agent (p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid) | 0.1~0.2 |
| Organic solvent (ethanol or formaldehyde) | 0.3~0.2 |
| Organic foam (polyurethane foam) |
(2) superficial film raw material components is (according to the mass fraction)：
| Silicon carbide powder (0.5~100 μm) | 8~6 |
| Silica flour or silicon oxide powder (0.5~20 μm) | 2~1 |
| Organosilane precursor (triethyl silicane or tetramethylsilane) | 2~1 |
| Pore-creating agent addition agent (PVAC polyvinylalcohol or methylcellulose etc.) | 2~1 |
| Organic solvent (toluene or dimethylbenzene) | 5~8 |
Foam silicon carbon supporter is prepared in constitutive material, and carbon source is first converted into organic resin sintering process, with original
Silica flour reaction-sintered in material, intensity guarantee can be provided for supporter, then through high temperature purification treatment so that wherein remaining Si phases with
C reaction generation SiC in sintering atmosphere, final material forms all original silicon carbide silicon and reaction generation carborundum phase, and gives birth to
Play a part of into carborundum phase with reference to original silicon carbide silicon grain, ensure that the pure matter of material, see accompanying drawing 1XRD diffracting spectrums.
Because foam silicon carbon supporter is double gradient-structures, internal layer is large aperture, and outer layer is micron order aperture, is coated beneficial to film layer,
There is the pore structure of three-dimensional network connection by organic foam material simultaneously, it is ensured that supporter has low pressure drop, is easy to blowback
The advantages of, see Fig. 2.
In film layer preparing raw material composition, organosilane precursor is decomposed to form carborundum phase at a certain temperature, and then combines
Original silicon carbide silicon grain, form close particle packing and combine, while the abjection of pore creating material so that film layer is internally formed hole,
Because film layer and supporter material are all carborundum, the two coefficient of expansion, high temperature resistance atmosphere corrosion performance it is harmonious, for
Improve the strength of materials, heat shock resistance, high-temperature stability and creep rupture life and play good effect.
The preparation method of the three gradient pore structured pure matter foam silicon carbon supporter membrane tubes of the present invention, with solid powder
Grain, organic polymer resin, curing agent, organic solvent are stock, mixed preparing slurry, mould are used as by the use of organic foam
Plate, infusion process prepare supporter presoma, and low-temperature carbonization sintering is molten after machine-shaping to ooze sintering, then is obtained through high temperature purification treatment
After double gradient pore structured pure matter foam silicon carbon supporters, added using silicon carbide powder, silica flour or silicon oxide powder, pore creating material
Add agent and organosilane precursor to prepare film layer raw material, film layer is prepared using spraying or dipping method surface, after drying, sintered
It is as follows to finished product membrane tube, specific preparation process：
(1) supporter shaping raw material prepares
It is (5~4) by solid powder particle, organic polymer resin, curing agent, organic solvent example in mass ratio：(2~
1)：(0.1~0.2)：(0.3~0.2) it is blended, ball milling obtains slurry after mechanical agitation；
Organic foam uses polyurethane foam, and internal layer from organic foam average pore size between 1~3mm, select by outer layer
Organic foam aperture is 300~500 μm；
Solid powder particle is carborundum powder, silica flour or the two mixed-powder, between 5~20 μm of powder diameter；It is organic
Macromolecule resin is selected from the one or more of epoxy resin, phenolic resin and furfural resin；Curing agent be p-methyl benzenesulfonic acid,
Urotropine, oxalic acid or citric acid；Organic solvent is ethanol or formaldehyde；
(2) support body formed
The organic foam that internal layer needs, which is cut into, first needs the hollow cylindrical of size, and outer layer organic foam is cut into
1~2mm thin-walled hollow cylinder, and cause outer hollow cylinder internal diameter to be equal to internal layer organic foam external diameter, then both are covered
Together, soaked in step (1) in ready slurry, take out and unnecessary slurry is removed by the method for centrifugation, air-blowing, protect
Hold machine foamed open cell, baking and curing, then repeatedly said process, obtain needed for volume fraction double gradient pore structured pure matter
Foam silicon carbon supporter presoma short tube, wherein solid volume fraction are controlled between 35~65%, and baking and curing temperature is
120~180 DEG C；
(3) spicing forming type
The supporter presoma short tube that (2) step obtains is machined into the structure that can be mutually inserted, utilizes material of the same race
Slurry is used as bonding agent, by supporter presoma short tube grafting bonding into the foam support body for needing size, is then pyrolyzed, then warp is molten
The composition for oozing sintering is remaining Si and SiC foam silicon carbon supporter.
Pyrolytic process is：The protective atmosphere of argon gas, nitrogen or other inert gases, or under vacuum, heating speed
1~10 DEG C/min of rate, 800~1200 DEG C are warming up to, are incubated 0.5~2 hour.
Sintering process is：The raw material selected in infiltration reaction-sintered is silicon, in the guarantor of argon gas, nitrogen or other inert gases
Siliconising is sintered under shield atmosphere, or is sintered siliconising under vacuum, heating rate is 5~15 DEG C/min, melt temperature
For：1600~1900 DEG C, it is incubated 0.5~5 hour.
(4) high temperature purification treatment
The non-pure matter foam silicon carbon supporter that (3) are obtained carries out at high temperature, introducing the processing of carbon atmosphere so that remaining
Si reacts to form carborundum with carbon atmosphere, obtains double gradient pore structured pure matter foam silicon carbon supporters.Carbon atmosphere uses acetylene
Or example is 1 by volume for methane and argon gas or helium:1 composition, temperature be 1800~1950 DEG C, heating rate be 10~20 DEG C/
Minute, 0.5~5 hour is incubated, obtains double gradient pore structured pure matter foam silicon carbon supporters.
(5) film layer raw material prepares
Silicon carbide powder, silica flour or silicon oxide powder, organosilane precursor, pore-creating agent addition agent, organic solvent are pressed into matter
Amount ratio is (8~6)：(2~1)：(2~1)：(2~1)：(5~8) it is blended, ball milling obtains membrane layer pulp after mechanical agitation；
Silicon carbide powder granularity is between 0.5~100 μm, and silica flour or silicon oxide powder granularity are between 0.5~20 μm；
Organosilane precursor is triethyl silicane, tetramethylsilane；Organic solvent is toluene or dimethylbenzene, and pore-forming additive is polyethylene
Alcohol PVA or methylcellulose.
(6) prepared by superficial film
Carried out in double gradient pore structured pure matter foam silicon carbon supporting body surfaces that (4) step obtains using brushing method
Film bottom is uniformly after coating, then carried out using spraying coating process；
(7) film layer sinters
By the membrane tube precast body after coating surface film layer under the protective atmosphere of vacuum, argon gas or other inert gases, burn
Knot, 1~10 DEG C/min of heating rate, 1000~1400 DEG C are warming up to, are incubated 0.5~1 hour, Temperature fall cooling, had
There are three gradient pore structured pure matter foam silicon carbon supporter membrane tubes.
In the present invention, the composition of foam silicon carbon membrane tube is pure matter SiC, by double gradient pore structured pure matter foam silicon carbons
Support body layer and superficial film form three gradient filtration structures；Wherein, supporter is double gradient pore structured pure matter foam carbonizations
Silicon supporter, there is the macroporous structure of three-dimensional network connection, superficial film is combined into by silicon carbide powder accumulation, aperture
0.1~20 μm (being preferably 0.2~5 μm), the membrane tube entirety porosity is between 35~65%.It is described have it is three gradient pore structured
The length of pure matter foam silicon carbon supporter membrane tube is 100~2000mm, 30~50MPa of bending strength.It is described that there are three gradients
In the pure matter foam silicon carbon supporter membrane tube of pore structure, pure matter SiC content is in more than 99wt%, and surplus is impurity element, material
Expect that internal grain is combined completely by silicon-carbide particle from sinter bonded, in the absence of clay or other oxide combination phases.
Below, the present invention is described in further detail by embodiment and accompanying drawing.
Embodiment 1
It is 5 by 5 μm of silicon carbide powders, phenolic resin, p-methyl benzenesulfonic acid, ethanol example in mass ratio：2：0.1：0.3 blending,
Ball milling obtains the body formed slurry of foam support after mechanical agitation.
It is respectively internal layer from tri- kinds of aperture polyurethane foams of 1mm, 2mm, 3mm, cuts into external diameter Φ 56mm (internal diameter Φ
40mm) × 300mm hollow cylinders, from 300 μm, 400 μm, 500 μm of three kinds of aperture polyurethane foams be outer layer, cut into external diameter
After Φ 60mm (Φ 56mm) × 300mm hollow cylinders, polyurethane foam inside and outside different pore size is nested together, it is double to obtain 9 kinds of combinations
Gradient organic foam (is respectively 1mm and 300 μm, 2mm and 300 μm, 3mm and 300 μm, 1mm and 400 μm, 2mm and 400 μm, 3mm
With 400 μm, 1mm and 500 μm, 2mm and 500 μm, 3mm and 500 μm), dip forming slurry, after centrifugation removes additional size, 120
DEG C baking and curing, repeat more than dipping baking step, it is respectively 35%, 45%, 55%, 65% to obtain four kinds of solid volume fractions
Double gradient pore structured pure matter foam silicon carbon supporter presoma short tubes, above-mentioned short tube is processed into connected structure, is used in combination
Slurry of the same race is joined together, baking and curing, obtains tri- kinds of length support body precast bodies of 1000mm, 1500mm, 2000mm.
Supporter precast body after above-mentioned processing is pyrolyzed, 800 DEG C of temperature, 5 DEG C/min of heating rate, protective atmosphere is
Argon gas, after Temperature fall takes out, load sintering furnace；The raw material selected in infiltration reaction-sintered is silicon, is carried out under vacuum
Siliconising is sintered, heating rate is 5 DEG C/min, and melt temperature is：1900 DEG C, 0.5 hour is incubated, obtains non-pure matter foam silicon carbon
Membrane tube supporter.
High temperature purification treatment, carbon atmosphere use methane and argon gas by volume example for 1:1 composition, temperature are 1800 DEG C, are risen
Warm speed is 10 DEG C/min, is incubated 5 hours, obtains double gradient pore structured pure matter foam silicon carbon supporters.
The strength of materials is obtained mainly to be determined by solid volume fraction, 35%, 45%, 55%, 65% 4 kind of volume fraction it is curved
Qu Qiangdu is respectively 35MPa, 40MPa, 45MPa, 50MPa, measure under supporter 5mm/s gas flow rates droop loss 2%~
Between 5%, mutual gap is smaller.
Embodiment 2
Difference from Example 1 is, by 10 μm of silicon carbide powders, epoxy resin, methenamine, formaldehyde in mass ratio
Example is 4：1：0.2：0.2 blending, ball milling obtains the body formed slurry of foam support after mechanical agitation.
From several polyurethane foam compositions of the same identical of embodiment 1, dip forming post-processing bonding, pyrolysis sintering.
1200 DEG C of pyrolysis temperature, 1 DEG C/min of heating rate, protective atmosphere is argon gas, after Temperature fall takes out, loads and burns
Freezing of a furnace；The raw material selected in infiltration reaction-sintered is silicon, and siliconising is sintered under the conditions of argon gas, and heating rate is 10 DEG C/minute
Clock, melt temperature are：1600 DEG C, 5 hours are incubated, obtains non-pure matter foam silicon carbon membrane tube supporter.
High temperature purification treatment, carbon atmosphere use propane and argon gas by volume example for 1:1 composition, temperature are 1900 DEG C, are risen
Warm speed is 20 DEG C/min, is incubated 0.5 hour, obtains double gradient pore structured pure matter foam silicon carbon supporters.
Obtain the strength of materials and droop loss level is substantially the same manner as Example 1.
Embodiment 3
It is prepared by superficial film：
By silicon carbide powder (2 μm), silica flour (2 μm), triethyl silicane, pore-creating agent addition agent (PVA), toluene in mass ratio
Example is 8：2：2：1：5 blendings, ball milling obtains membrane layer pulp after mechanical agitation.
By obtained embodiment 1 and the double gradient pore structured pure matter foam silicon carbon support body surfaces obtained in embodiment 2
One layer of membrane layer pulp is brushed in face, and then drying polishes smooth, then is sprayed with spraying method：Slurry is sprayed on using gas spray gun
On the precast support body of rotation, thicknesses of layers is controlled by adjusting relative displacement between supporter and spray gun, after drying
To superficial film.Control spray gun material flow obtains three kinds of thickness surface film layers, respectively 50 μm, 300 μm, 500 μm of membrane tubes.
By the membrane tube after coating surface film layer under the protective atmosphere of argon gas, sintering, 5 DEG C/min of heating rate, it is warming up to
1200 DEG C, be incubated 1 hour, obtain with different pairs of gradient pore structured pure matter foam silicon carbon supporters and thicknesses of layers with
Three gradient pore structured pure matter foam silicon carbon supporter membrane tubes.
It is 0.3 μm that above-mentioned difference, which has three gradient pore structured pure matter foam silicon carbon support film periosteum layer hole, hole
Gap rate 38%；Pressure fall-off test level shows that supporter influences less for integral membrane tube voltage drop is horizontal, and thicknesses of layers is main shadow
The factor of sound, corresponding to 50 μm, 300 μm, 500 μm of thicknesses of layers, under 5mm/s gas flow rates droop loss be respectively 7%,
12%th, 23%.Filtering accuracy test result, for 0.2 μm of powder particle, precision is respectively 98%, 99.5%, 99.8%, material
Expect that heatproof is not less than 1200 DEG C.
Embodiment 4
It is with the film layer preparing raw material difference of embodiment 3, by silicon carbide powder (10 μm), silica powder (1 μm), four
Methyl-monosilane, pore-creating agent addition agent (methylcellulose), dimethylbenzene example in mass ratio are 6：1：2：2：8 blendings, through mechanical agitation
Ball milling obtains membrane layer pulp afterwards, and supporter selection and film layer coating method are same as Example 3.
With the sintering temperature of embodiment 3 by the membrane tube after coating surface film layer under the protective atmosphere of argon gas, sintering, heating speed
2 DEG C/min of rate, 1400 DEG C are warming up to, are incubated 0.5 hour, obtained with different double gradient pore structured pure matter foam silicon carbon branch
Support body and thicknesses of layers have three gradient pore structured pure matter foam silicon carbon supporter membrane tubes.
The obtained three gradient pore structured pure matter foam silicon carbon support film periosteum layer hole that have are 2 μm, porosity
40%；Pressure fall-off test level shows, supporter for integral membrane tube voltage drop it is horizontal influence it is little, thicknesses of layers for it is main influence because
Element, corresponding to 50 μm, 300 μm, 500 μm of thicknesses of layers, under 5mm/s gas flow rates droop loss be respectively 6%, 9%,
17%.Filtering accuracy test result, for 0.2 μm of powder particle, precision is respectively 85%, 91%, 95%, for 1 μm of powder
Particle, precision are respectively 98%, 99.2%, 999.9%；Material heatproof is not less than 1300 DEG C.
As shown in figure 1, it can be seen that material group from three gradient pore structured pure matter foam silicon carbon membrane tube XRD diffraction patterns
As pure matter carborundum, it is made up of reaction generation β-SiC and α-SiC, wherein β-SiC are reaction generation phase, are played with reference to original
α-SiC are acted on.
As shown in Fig. 2 it can be seen that from the double gradient-structures of three gradient pore structured pure matter foam silicon carbon membrane tube supporters
Outer layer aperture has<500 μm, internal layer aperture>1mm, internal layer aperture gauge structure coat beneficial to superficial film, and overall three-dimensional network connects
Logical structure ensures that membrane tube has low pressure drop level, and is beneficial to pulse cleaning.
As shown in Fig. 3 a-b, from three gradient pore structured pure matter foam silicon carbon membrane tube superficial films and foam joint portion
(Fig. 3 a) and film layer pore structure (Fig. 3 b), which can be seen that, shows that film layer has micrometer grade hole gap structure, plays a role in filtering, film
Layer is firmly combined with supporter.
As shown in figure 4, it can be seen that prepared by the present invention from three gradient pore structured pure matter foam silicon carbon membrane tube photos
The membrane tube preparation method degree of reliability is high, and membrane tube deformation rate is low, high yield rate.
Embodiment result shows that the invention provides a kind of three gradient pore structured pure matter foam silicon carbon membrane tubes and its system
Preparation Method, the pure matter silicon carbide film pipe with three-dimensional networking with by connecting the double gradient pore structured pure matter foamy carbons in large aperture
SiClx supporter and fine surface film layer composition it is three gradient pore structured, material composition is pure matter carborundum, in the absence of oxidation
Thing etc. combines phase, and with high pass porosity, low pressure drop, intensity is high, thermal shock resistance is good, temperature in use is high, is easy to blowback again
The characteristics of raw, it can use, can also use under reducing atmosphere under oxidizing atmosphere, acid and alkali resistance corrosive nature is strong, available for coal
The various high and low temperature filtering flows such as chemical industry and IGCC, PFBC coal gasification power generation, high-temperature flue gas, vehicle exhaust, Water warfare that gasify are net
Change；The preparation method includes dispensing, supports body formed, film layer to prepare and burn till successively, and its technique is simple, and cost is low, is easy to
Realize, properties of product can be ensured.
Claims (10)
1. one kind has three gradient pore structured pure matter foam silicon carbon supporter membrane tubes, it is characterised in that：Three gradient-porosity knots
The composition of structure foam silicon carbon membrane tube is pure matter SiC, and gradient filtration structure is formed by support body layer and superficial film；Wherein, prop up
Support body is made up of double gradient pore structured pure matter foam silicon carbon supporters, and 300~500 μm of outer layer average pore size, internal layer is average
Between 1~3mm of aperture；Superficial film is combined into by silicon carbide powder accumulation, aperture 50nm~20 μm, the membrane tube entirety porosity
Between 35~65%.
2. having three gradient pore structured pure matter foam silicon carbon supporter membrane tubes according to described in claim 1, its feature exists
In：The length of three gradient pore structured pure matter foam silicon carbon supporter membrane tubes is 100~2000mm, bending strength 30~
50MPa。
3. having three gradient pore structured pure matter foam silicon carbon supporter membrane tubes according to described in claim 1, its feature exists
In：In three gradient pore structured foam silicon carbon supporter membrane tubes, pure matter SiC content is in more than 99wt%.
A kind of 4. preparation side with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes described in claim 1
Method, it is characterised in that：Using solid powder particle, organic polymer resin, curing agent, organic solvent as stock, mixing is matched somebody with somebody
Slurrying material, by the use of organic foam as template, infusion process prepares supporter presoma, and low-temperature carbonization sintering is molten after machine-shaping
Ooze sintering, then after high temperature purification treatment obtains double gradient pore structured pure matter foam silicon carbon supporters, using silicon carbide powder,
Silica flour or silicon oxide powder, pore-creating agent addition agent and organosilane precursor prepare film layer raw material, using spraying or dipping method table
Face prepares film layer, and after drying, sintering obtains finished product membrane tube.
5. according to the preparation side with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes described in claim 4
Method, it is characterised in that specific preparation process is as follows：
（1）Supporter shaping raw material prepares
It is by solid powder particle, organic polymer resin, curing agent, organic solvent example in mass ratio（5~4）：（2~1）：
（0.1~0.2）：（0.3~0.2）Blending, ball milling obtains slurry after mechanical agitation；
Organic foam uses polyurethane foam, and for internal layer from foam average pore size between 1~3mm, outer layer selects foam aperture
For 300~500 μm；
Solid powder particle is carborundum powder, silica flour or the two mixed-powder；Organic polymer resin is selected from epoxy resin, phenol
The one or more of urea formaldehyde and furfural resin；Curing agent is：P-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid；Have
Solvent is ethanol or formaldehyde；
（2）Support body formed
The foam that internal layer needs, which is cut into, first needs the hollow cylindrical of size, and outer foam cuts into 1~2mm thin-walled
Hollow cylinder, and cause outer hollow cylinder internal diameter to be equal to inner foam external diameter, then both are nested together, in step（1）
In soak in ready slurry, take out simultaneously pass through centrifugation, the method for air-blowing removes unnecessary slurry, keep foamed open cell, drying
Solidification, then repeatedly said process, the double gradient pore structured pure matter foam silicon carbons for obtaining required solid volume fraction support
Body presoma short tube, wherein solid volume fraction are controlled between 35~65%, and baking and curing temperature is 120~180 DEG C；
（3）Spicing forming type
Will（2）The supporter presoma short tube that step obtains is machined into the structure that can be mutually inserted, and is made using slurry of the same race
For bonding agent, the grafting of supporter presoma short tube is bonded into the foam support body for needing size, is then pyrolyzed, then burnt through infiltration
The composition of knot is remaining Si and SiC foam silicon carbon supporter；
（4）High temperature purification treatment
Will（3）Obtained non-pure matter foam silicon carbon supporter carries out at high temperature, introducing the processing of carbon atmosphere so that remaining Si with
Carbon atmosphere reacts to form carborundum, obtains double gradient pore structured pure matter foam silicon carbon supporters；
During the high temperature purification treatment, technical process and technological parameter are as follows：Carbon atmosphere uses acetylene or methane and argon gas
Or example is 1 to helium by volume:1 composition, temperature are 1800~1950 DEG C, and heating rate is 10~20 DEG C/min, insulation 0.5
~5 hours, obtain double gradient pore structured pure matter foam silicon carbon supporters；
（5）Film layer raw material prepares
By silicon carbide powder, silica flour or silicon oxide powder, organosilane precursor, pore-creating agent addition agent, organic solvent in mass ratio
Example be（8~6）：（2~1）：（2~1）：（2~1）：（5~8）Blending, ball milling obtains membrane layer pulp after mechanical agitation；
（6）It is prepared by superficial film
（4）Double gradient pore structured pure matter foam silicon carbon supporting body surfaces that step obtains carry out film bottom using brushing method
Layer is uniformly after coating, then carried out using spraying coating process；
（7）Film layer sinters
By the membrane tube precast body after coating surface film layer under the protective atmosphere of vacuum, argon gas or other inert gases, sinter, rise
Warm 1~10 DEG C/min of speed, 1000~1400 DEG C are warming up to, are incubated 0.5~1 hour, Temperature fall cooling, obtain having three
Gradient pore structured pure matter foam silicon carbon supporter membrane tube.
6. according to the preparation side with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes described in claim 5
Method, it is characterised in that step（1）In, solid powder particle granularity is between 5~20 μm；Organic polymer resin is selected from epoxy
The one or more of resin, phenolic resin and furfural resin；Curing agent is p-methyl benzenesulfonic acid, methenamine, oxalic acid or lemon
Lemon acid；Organic solvent is ethanol or formaldehyde.
7. the preparation method with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes as described in claim 5,
Characterized in that, step（3）In：
The technical process and technological parameter of pyrolysis are as follows：The protective atmosphere of argon gas, nitrogen or other inert gases, or in vacuum
Under the conditions of, 1~10 DEG C/min of heating rate, 800~1200 DEG C are warming up to, are incubated 0.5~2 hour, generate double gradient-porosity knots
The pure matter foam silicon carbon supporter of structure；
The technical process and technological parameter of melting infiltration sintering are as follows：The raw material selected in infiltration reaction-sintered is silicon, in argon gas, nitrogen
Or siliconising is sintered under the protective atmosphere of other inert gases, and or siliconising is sintered under vacuum, heating rate is 5~
15 DEG C/min, melt temperature is：1600~1900 DEG C, 0.5~5 hour is incubated, obtains non-pure matter foam silicon carbon membrane tube support
Body.
8. according to the preparation side with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes described in claim 5
Method, it is characterised in that step（5）In, silicon carbide powder granularity is between 0.5~100 μm, silica flour or silicon oxide powder granularity
Between 0.5~20 μm；Organosilane precursor is triethyl silicane, tetramethylsilane；Solvent is toluene or dimethylbenzene, pore-creating
Additive is polyvinyl alcohol（PVA）Or methylcellulose.
9. according to the preparation side with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes described in claim 5
Method, it is characterised in that step（6）In, the technical process of spraying is as follows：Slurry is sprayed on the prefabricated of rotation using gas spray gun
On supporter, thicknesses of layers is controlled by adjusting relative displacement between supporter and spray gun, superficial film is obtained after drying.
10. according to the preparation side with three gradient pore structured pure matter foam silicon carbon supporter membrane tubes described in claim 5
Method, it is characterised in that step（7）In, superficial film thickness is between 50~500 μm.
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| CN108395252A (en) * | 2018-01-26 | 2018-08-14 | 山东理工大学 | Liquid-phase sintering multichannel silicon carbide ceramic support body and preparation method thereof |
| CN108947535A (en) * | 2018-09-21 | 2018-12-07 | 北京航空航天大学 | A kind of preparation method of porous carbide film |
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