CN102633531B - Gradient-porosity pure silicon carbide membrane tube - Google Patents
Gradient-porosity pure silicon carbide membrane tube Download PDFInfo
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- CN102633531B CN102633531B CN201210094292.0A CN201210094292A CN102633531B CN 102633531 B CN102633531 B CN 102633531B CN 201210094292 A CN201210094292 A CN 201210094292A CN 102633531 B CN102633531 B CN 102633531B
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 117
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000012528 membrane Substances 0.000 title abstract 8
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 230000003068 static effect Effects 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 86
- 239000000463 material Substances 0.000 claims description 85
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000011148 porous material Substances 0.000 claims description 41
- 239000000377 silicon dioxide Substances 0.000 claims description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 31
- 235000013312 flour Nutrition 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 229920005546 furfural resin Polymers 0.000 claims description 11
- 229940116315 oxalic acid Drugs 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 229960004106 citric acid Drugs 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 229960004011 methenamine Drugs 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 6
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- 239000001913 cellulose Substances 0.000 claims description 5
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- 230000001105 regulatory effect Effects 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
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- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 2
- 238000010248 power generation Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
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- 239000002245 particle Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
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- 230000035939 shock Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011214 refractory ceramic Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
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- 238000013001 point bending Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910003978 SiClx Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 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
- 238000007792 addition Methods 0.000 description 2
- 208000016791 bilateral striopallidodentate calcinosis Diseases 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- -1 phenolic aldehyde Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
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- Filtering Materials (AREA)
Abstract
The invention belongs to the technical field of multipore ceramic materials and preparation thereof, and particularly relates to a gradient-porosity pure silicon carbide membrane tube and a preparation method thereof. The gradient-porosity pure silicon carbide membrane tube consists of pure SiC; a gradient filter structure consists of a supporting body layer and a surface membrane layer, wherein the supporting body is formed by stacking and combining roughly granular SiC, and the average aperture is 5-120 mu m; the surface membrane layer is formed by stacking and combining finely granular SiC, and the aperture is 0.1-20 mu m; and the whole porosity of the membrane tube is 25-50%. The preparation method comprises burdening, forming the supporting body, preparing the membrane layer and sintering, wherein forming is performed under equal static pressure; the forming pressure is controlled between 40 and 150MPa; the sintering temperature is controlled between 1,500 and 2,400 DEG C; and heat is preserved for 0.5-5 hours. The method is easy to implement, and the performance of a product can be guaranteed. The gradient-porosity pure silicon carbide membrane tube can be used under an oxidization atmosphere and a reduction atmosphere, is high in acid and alkaline corrosion resistance and can be applied to gas chemical engineering and integrated gasification combined cycle (IGCC) and pressurized fluidized bed combustion (PFBC) power generation and used for filtering and purifying various types of high- and low- temperature fluid, such as high-temperature flue, automobile tail gas, water and the like.
Description
Technical field
The invention belongs to porous ceramic film material and preparing technical field thereof, be specially the pure matter silicon carbide film of a kind of gradient-porosity pipe and preparation method thereof, this kind of pure matter silicon carbide film pipe has gradient pore structured, consist of pure matter carborundum, do not exist oxide etc. in conjunction with phase, have high pass porosity, low pressure drop, intensity is high, thermal shock resistance good, serviceability temperature is high feature, preparation method is easy to realize, and can guarantee properties of product.
Background technology
Refractory ceramics filtering material is generally all worked under the environmental condition of various harshnesses, conventionally requires to have: mechanical strength, high temperature resistant (300～900 ℃) and good medium corrosion resistance energy that (1) is high as gas purification with refractory ceramics filtering material; (2) high filtering accuracy and filtration gas speed and low Pressure Drop; (3) be easy to blowback, stable operation, filter efficiency high; (4) there is good thermal stability, can bear the thermal shock that the blowback of high-voltage pulse cold air causes frequently.Meanwhile, the impact that according to its application scenario requirement, High Temperature Ceramic Filter must be able to bear the impact that affects change of component that air-flow chemical characteristic changes, vibrate while spraying into superfine grit, and keep higher efficiency of dust collection, keep the requirements such as high flow capacity.The ceramic material of selecting not only has hot chemistry, mechanical stability, also should have durability and high reliability; Especially under high-temperature and high-pressure conditions, when there is the situation of gas phase sulfur, alkali, the corrosion of chlorine element, also require ceramic material to there is high chemical stability.
The unfailing performance of the strainability of refractory ceramics filtering material, high high-temp stability and roadholding and long-term operation is the key of refractory ceramics filtering material design.The refractory ceramics filtering material with filtration, desulfurization or denitration multifunctional all will be that gas purification material further develops direction.In all kinds of ceramic filter materials, the most promising with SiC pottery, because SiC is compared with the feature that oxide ceramics has high thermal conductivity, low-expansion coefficient, thermal shock resistance is good, serviceability temperature is high (more than 1000 ℃), so the preferred material aspect the industrial field high temperature fluid filtrations such as vehicle exhaust, Coal Chemical Industry, molten metal.
But apply maximum carborundum filtering materials at present and mostly be the oxides such as clay in conjunction with SiC pottery aspect high temperature air filtration, shortcoming is that thermal conductivity is low, causes thermal shock resistance poor, make ceramic filter material be difficult to bear large thermic load fluctuation; Particularly in high-temperature coal gasification generation technology (as IGCC, PFBC), because containing sodium metasilicate, NaCl composition, the Na changing into after coal burning in coal
2si
2o
5meeting heavy corrosion oxide combined silicon carbide filtering material, the damage inactivation that causes filter, and research shows that pure SiC ceramic material is not subject to above-mentioned corrosion, pure matter carbofrax material can be used under high-temperature oxydation and reducing atmosphere simultaneously, but aspect the development of pure matter carborundum filtering material, technology is few at present, resulting product intensity is low, pore-size distribution is inhomogeneous, filter efficiency is not high, filter the shortcoming that pressure drop is large, pore structure is not easy to blowback cleaning, the application process of restriction carborundum filtering material.
Therefore, high, high strength, low pressure drop of high, the resistance to various dielectric corrosions of serviceability temperature, intensity, be easy to regeneration, preparation method is reliable, cost is low pure matter silicon carbide film pipe filtering material is that people expect.
Summary of the invention
The technical problem to be solved in the present invention is: the material of avoiding existing carborundum filtering material to be mostly the oxide part combinations such as clay forms, a kind of pure matter carborundum filtering material is provided, material consists of the above carborundum of 99wt%, make this kind of material can be under various atmospheric conditions media-resistant corrosive power stronger.
Another technical problem that the present invention will solve is: avoid the weak point in existing silicon carbide film Manifold technology, provide a kind of have gradient pore structured, porosity is large, the high and low pressure drop of intensity, easily regeneration, reusable desirable pure matter carborundum porous ceramics film pipe.
The technical problem that the present invention also will solve is: provide a kind of raw material to be easy to get, to prepare the preparation method of the pure matter silicon carbide film pipe that is suitable for large-scale production simple, moulding is easy, with short production cycle, yield rate is high, production cost is low.
For solving the technical problem existing in the preparation of carborundum filtering material, the technical solution used in the present invention is:
The pure matter carbofrax material of bilayer that the pure matter silicon carbide film of a kind of gradient-porosity of the present invention pipe has a different pore structures is fired and is formed, and comprises support body layer and superficial film.Wherein:
(1) support body layer raw material components is (according to the mass fraction):
| Thick silicon-carbide particle (5～400 μ m) | 80～60 |
| Silica flour or silicon oxide powder (5～10 μ m) | 20～10 |
| Macromolecular material (one or more of epoxy, phenolic aldehyde and furfural resin) | 20～10 |
| Curing agent (p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid) | 1～2 |
| Organic solvent (ethanol or toluene) | 20～30 |
(2) superficial film raw material components is (according to the mass fraction):
| Thin silicon-carbide particle (0.5～40 μ m) | 80～60 |
| Silica flour or silicon oxide powder (0.5～20 μ m) | 20～10 |
| Macromolecular material (one or more of epoxy, phenolic aldehyde and furfural resin) | 20～10 |
| Pore creating material additive (cellulose or polyvinyl alcohol etc.) | 20～10 |
| Curing agent (p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid) | 1～2 |
| Organic solvent (ethanol or formaldehyde) | 50～80 |
In constitutive material, in organic resin sintering process, first change carbon source into, with silica and the silica flour reaction-sintered in raw material, can guarantee for supporter and rete provide intensity, particularly above-mentioned various raw material can not generate other phases compositions such as oxide in sintering process, be all original silicon-carbide particle and reaction Formed SiClx phase, and Formed SiClx plays the effect in conjunction with original silicon-carbide particle mutually, guaranteed the pure materialization of material, see accompanying drawing 1XRD diffracting spectrum, make the coefficient of expansion of material surface rete and supporter, high temperature resistance atmosphere corrosion performance harmoniously, for improving the strength of materials, heat shock resistance, high-temperature stability and creep rupture life play an important role.
Different silica and silica flour addition have guaranteed that supporter has the permeability of controllable porosity and hole, different pore creating material additions can guarantee high porosity and the permeability of superficial film, the support body layer that particularly Silicon Carbide Powder of different material component, different-grain diameter forms and the gradient composite structure of superficial film, see accompanying drawing 2, Fig. 3 and Fig. 4, for gradient pore structured, provide technical support; Above raw material composition, granularity selection are in material preparation, can guarantee that pure matter silicon carbide film pipe has high pass porosity and rational pore structure, guarantee material permeate well, there is low filter pressure, the assurance filtering accuracy that simultaneously meticulous superficial film design can be good.
The preparation method of the pure matter silicon carbide film of a kind of gradient-porosity of the present invention pipe, take coarse granule carborundum, silica or silica flour as stock, utilize macromolecular material as bonding agent, mix, utilizes cold isostatic press bag cover compacting supporter, the thin silicon-carbide particle of rear employing, silica flour, pore creating material additive and organic resin preparation rete raw material, adopt spraying or dipping method surface to prepare rete, after drying, sintering obtains finished film pipe, mainly comprises the following steps:
(1) supporter shaping raw material is prepared
By thick silicon-carbide particle, silica flour or silicon oxide powder, macromolecular material, curing agent by mass percentage example be (80wt%～60wt%): (20wt%～10wt%): (20wt%～10wt%): (1wt%～2wt%), accurately formula accurately weighs, blend is in organic solvent, organic solvent content is between 20～30wt% of amount of the mixture, after mechanical agitation, ball milling obtains slurry, then drying and crushing obtains raw material composite powder, Ball-milling Time is 1～2 hour, and baking temperature is 70～90 ℃.
Coarse granule carborundum granularity is preferably 50～400 μ m at 5～400 μ m() between, silica flour or silica granularity be between 5～10 μ m; Macromolecular material is selected from one or more of epoxy resin, phenolic resins and furfural resin; Curing agent is p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid; Organic solvent is ethanol or formaldehyde;
(2) supporter moulding
Above-mentioned composite powder is contained in etc. in static pressure jacket, in filling, adopt mechanical ram-jolt, on static pressure jacket design size, structure, by design, prepare, then pack in cold isostatic press, moulding pressure is 40～150MPa, and the dwell time is depending on sample size, between 2～15 minutes, after slough jacket and obtain precast support body, the external diameter of precast support body between 10～100mm, wall thickness 2mm～30mm.
(3) rete raw material is prepared
By silicon carbide powder, silica flour or silicon oxide powder, macromolecular material, pore creating material additive, curing agent by mass percentage example be (80wt%～60wt%): (20wt%～10wt%): (20wt%～10wt%): (20wt%～10wt%): (1wt%～2wt%), accurately formula accurately weighs, blend is in organic solvent, organic solvent content is between 50～80wt%, after mechanical agitation, ball milling obtains rete slurry, Ball-milling Time is 1～2 hour, stand-by.
Carborundum granularity is preferably 0.5～5 μ m at 0.5～40 μ m() between, silica flour or silica granularity are preferably 0.5～5 μ m at 0.5～20 μ m() between; Macromolecular material is selected from one or more of epoxy resin, phenolic resins and furfural resin; Curing agent is p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid; Organic solvent is ethanol or formaldehyde, and pore-creating additive is cellulose or polyvinyl alcohol etc.
(4) superficial film preparation
Superficial film can adopt dipping or spraying method to carry out.
Dipping method: by the precast support body obtaining in (2) step, immerse in rete slurry, with 10～50mm/s speed, lift, make supporting body surface apply one deck slurry, then dry, then flood, by dipping number of times control surface thicknesses of layers;
Spraying method: utilize gas spray gun pulp spraying to be coated on the precast support body of rotation, by regulating relative displacement speed 20～100mm/min controlling diaphragm layer thickness between supporter and spray gun, obtain superficial film after being dried.
By dry caudacoria pipe outside diameter measuring, control surface thicknesses of layers is between 50～1000 μ m.
(5) sintering
By the film pipe precast body after coating surface rete under the protective atmosphere of vacuum, argon gas or other inert gas, sintering, 1～10 ℃ per minute of heating rate, is warming up to 800～1200 ℃, is incubated 0.5～1 hour and sloughs pore-creating additive; Rear heating rate is 5～15 ℃ per minute, and temperature is: 1500～2400 ℃, be incubated 0.5～5 hour, and obtain the pure matter silicon carbide film of gradient-porosity pipe.
In the present invention, the pure matter silicon carbide film of gradient-porosity pipe consist of pure matter SiC, by support body layer and superficial film, form gradient filtration structure; Wherein, supporter is piled up and is combined into by coarse granule carborundum, and average pore size 5～120(is preferably 20～80) μ m, superficial film is piled up and is combined into by fine grained carborundum, aperture 0.1～20(is preferably 0.2～5) μ m, the whole porosity of film pipe is between 25～50%.
The length of the pure matter silicon carbide film of described gradient-porosity pipe is 100～2000mm, compression strength 30～70MPa.
In the pure matter silicon carbide film of described gradient-porosity pipe, pure matter SiC content is more than 99wt%, and surplus is impurity element, material internal crystal grain in conjunction with completely by silicon-carbide particle from sinter bonded, do not exist clay or other oxides in conjunction with phase.
The technical scheme of the pure matter silicon carbide film of a kind of gradient-porosity of the present invention pipe and preparation method thereof has following outstanding effect:
1. pure matter silicon carbide film pipe of the present invention has single carborundum composition, guaranteed the corrosion resistance of material under various high-temperature mediums, especially under the reducing atmosphere and high-alkali corrosive environment that is not suitable for using at oxide combined silicon carbide filtering material, have good stability, the unification that rete and supporter form can guarantee both harmonious property, guarantees the material long life.
2. pure matter silicon carbide film pipe of the present invention has abundant gradient pore structured uniformly, the macroporous structure of supporter has guaranteed that materials'use mesolow falls, high permeability, the meticulous pore structure of superficial film guarantees that material has good filtering accuracy and filter efficiency, and be beneficial to the realization that blowback is cleaned, regeneration easily, reusable.
3. pure matter silicon carbide film pipe crystal grain combination of the present invention is for reaction Formed SiClx is in conjunction with original silicon-carbide particle, and the two qualitative consistent assurance intercrystalline, in conjunction with firmly, guarantees that material has high intensity and thermal shock resistance.
4. pure matter silicon carbide film tube preparation method technology controlling and process of the present invention is flexible, can design as required the product of different size, and with short production cycle, cost is low, is easy to realize, and can ensure properties of product.
5. pure matter silicon carbide film tube material application provided by the invention is wide, in the time of can growing under the atmosphere such as oxidation, reduction, high chlorine, alkali, sulphur, silicon, use, more can under the high temperature of 1000 ℃, use, can be used for the various industrial smokes such as Coal Chemical Industry and the filtration of high-temperature coal gasification generation technology raw gas, high-temperature boiler, also can be used for sewage water filtration and process.
Accompanying drawing explanation
Fig. 1 silicon carbide film pipe XRD diffraction pattern.
The pure matter silicon carbide film of Fig. 2 pipe is gradient pore structured.
The pure matter silicon carbide film of Fig. 3 tube-surface rete pore structure.
The pure matter silicon carbide film of Fig. 4 pipe supporter pore structure.
The specific embodiment
The present invention be take coarse granule carborundum, silica or silica flour as stock, utilize macromolecular material as bonding agent, mix, utilize cold isostatic press bag cover compacting supporter, the thin silicon-carbide particle of rear employing, silica flour, pore creating material additive and organic resin preparation rete raw material, adopt spraying or dipping method surface to prepare rete, after drying, sintering obtains finished film pipe, mainly comprises the following steps:
(1) supporter shaping raw material is prepared
By thick silicon-carbide particle, silica flour or silicon oxide powder, macromolecular material, curing agent by mass percentage example be (80wt%～60wt%): (20wt%～10wt%): (20wt%～10wt%): (1wt%～2wt%), accurately formula accurately weighs, blend is in organic solvent, organic solvent content is between 20～30wt% of amount of the mixture, after mechanical agitation, ball milling obtains slurry, then drying and crushing obtains raw material composite powder, Ball-milling Time is 1～2 hour, and baking temperature is 70～90 ℃.
Coarse granule carborundum granularity between 5～400 μ m, silica flour or silica granularity be between 5～10 μ m; Macromolecular material is selected from one or more of epoxy resin, phenolic resins and furfural resin; Curing agent is p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid; Organic solvent is ethanol or formaldehyde;
(2) supporter moulding
Above-mentioned composite powder is contained in etc. in static pressure jacket, in filling, adopt mechanical ram-jolt, on static pressure jacket design size, structure, by design, prepare, then pack in cold isostatic press, moulding pressure is 40～150MPa, and the dwell time is depending on sample size, between 2～15 minutes, after slough jacket and obtain precast support body, the external diameter of precast support body between 10～100mm, wall thickness 2mm～30mm.
(3) rete raw material is prepared
By silicon carbide powder, silica flour or silicon oxide powder, macromolecular material, pore creating material additive, curing agent by mass percentage example be (80wt%～60wt%): (20wt%～10wt%): (20wt%～10wt%): (20wt%～10wt%): (1wt%～2wt%), accurately formula accurately weighs, blend is in organic solvent, organic solvent content is between 50～80wt%, after mechanical agitation, ball milling obtains rete slurry, Ball-milling Time is 1～2 hour, stand-by.
Carborundum granularity is between 0.5～40 μ m, and silica flour or silica granularity are between 0.5～20 μ m; Macromolecular material is selected from one or more of epoxy resin, phenolic resins and furfural resin; Curing agent is p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid; Organic solvent is ethanol or formaldehyde, and pore-creating additive is cellulose or polyvinyl alcohol etc.
(4) superficial film preparation
Superficial film can adopt dipping or spraying method to carry out.
Dipping method: by the precast support body obtaining in (2) step, immerse in rete slurry, with 10-50mm/s speed, lift, make supporting body surface apply one deck slurry, then dry, then flood, by dipping number of times control surface thicknesses of layers;
Spraying method: utilize gas spray gun pulp spraying to be coated on the precast support body of rotation, by regulating relative displacement speed controlling diaphragm layer thickness between supporter and spray gun, obtain superficial film after being dried.
By dry caudacoria pipe outside diameter measuring, control surface thicknesses of layers is between 50～1000 μ m.
(5) sintering
By the film pipe precast body after coating surface rete under the protective atmosphere of vacuum, argon gas or other inert gas, sintering, 1～10 ℃ per minute of heating rate, is warming up to 800～1200 ℃, is incubated 0.5～1 hour and sloughs pore-creating additive; Rear heating rate is 5～15 ℃ per minute, and temperature is: 1500～2400 ℃, be incubated 0.5～5 hour, and obtain the pure matter silicon carbide film of gradient-porosity pipe.
In the present invention, the pure matter silicon carbide film of gradient-porosity pipe consist of pure matter SiC, by support body layer and superficial film, form gradient filtration structure; Wherein, supporter is piled up and is combined into by coarse granule carborundum, average pore size 5～120 μ m, and superficial film is piled up and is combined into by fine grained carborundum, aperture 0.1～20 μ m, the whole porosity of film pipe is between 25～50%.
The length of the pure matter silicon carbide film of described gradient-porosity pipe is 100～2000mm, compression strength 30～70MPa.
In the pure matter silicon carbide film of described gradient-porosity pipe, pure matter SiC content is more than 99wt%, and surplus is impurity element, material internal crystal grain in conjunction with completely by silicon-carbide particle from sinter bonded, do not exist clay or other oxides in conjunction with phase.
Embodiment 1
By 300 μ m silicon-carbide particles, 5 μ m silica flours, phenolic resins, p-methyl benzenesulfonic acid by mass percentage example be that 80:20:15:1 blend is in ethanol, ethanol content accounts for the 20wt% of total amount, after mechanical agitation ball milling 1.5 hours slurry, then drying and crushing obtains raw material composite powder at 80 ℃.Above-mentioned composite powder is contained in etc. in static pressure jacket, adopts mechanical ram-jolt in filling, waiting static pressure jacket design tube blank size is that 2000mm is long, internal diameter 40mm, external diameter 60mm, after pack in cold isostatic press, moulding pressure is 150MPa, pressurize 5 minutes, after slough jacket and obtain precast support body.
By 1.5 μ m silicon carbide powders, 1.5 μ m silica flours, epoxy resin, cellulose, p-methyl benzenesulfonic acid in mass ratio example be 70:15:20:10:2 blend in ethanol, ethanol content accounts for the 60wt% of total amount, after mechanical agitation, ball milling obtains rete slurry.
Superficial film preparation will be selected two kinds of method validations:
Dipping method: by the precast support body obtaining, immerse in rete slurry, lift with 20mm/s speed, make supporting body surface apply one deck slurry, then dry, then flood, repeatedly flood 3 times, 5 times, 6 times to obtain three kinds of dipping skin covering of the surface tunic pipes, be labeled as respectively a, b, c film pipe.Spraying method: utilize gas spray gun pulp spraying to be coated on the precast support body of rotation, by regulating relative displacement speed controlling diaphragm layer thickness between supporter and spray gun, obtain superficial film after being dried.Spray gun material flow is 20 Grams Per Seconds, and relative displacement speed is 80mm/min, 50mm/min, 30mm/min, obtains three kinds of sprayed surface rete film pipes, is respectively d, e, f film pipe.
By the film pipe precast body after coating surface rete under the protective atmosphere of argon gas, sintering, 5 ℃ per minute of heating rate, is warming up to 1200 ℃, is incubated 0.5 hour; Rear heating rate is 10 ℃ per minute, and temperature is: 2000 ℃, be incubated 1 hour, and obtain the pure matter silicon carbide film of the gradient-porosity pipe of six kinds of different rete coating methods.
As shown in Figure 1, from silicon carbide film pipe XRD diffraction pattern, can find out: silicon carbide film pipe is that secondary carborundum forms in conjunction with original silicon-carbide particle, does not have second-phase, realize the pure materialization object of material.Obtaining material three-point bending bending strength is 55MPa, and a, b, c, d, e, f film pipe layer thickness are respectively 100 μ m, 180 μ m, 250 μ m, 200 μ m, 500 μ m, 1000 μ m.
As shown in Fig. 2-Fig. 4, filter tube support body and pure matter carborundum filter gradient pore structured that rete forms: supporter average pore size is 60 μ m, and porosity is 42%; Superficial film average pore size is 0.8 μ m, and porosity is 40%, 1000 ℃ of material heatproofs.As shown in Figure 4, from pure matter silicon carbide film pipe supporter pore structure, can find out: material internal porous nickel is communicated with, and can guarantee the required low filtration resistance of supporter, the requirement of high permeability, crystal grain, in conjunction with closely, has been guaranteed material high-intensity performance simultaneously.
Embodiment 2
Difference from Example 1 is:
By 25 μ m silicon-carbide particles, 10 μ m silicon oxide powders, furfural resin, p-methyl benzenesulfonic acid by mass percentage example be that 70:15:20:2 blend is in ethanol, ethanol content accounts for the 30wt% of total amount, after mechanical agitation ball milling 2 hours slurry, then drying and crushing obtains raw material composite powder at 80 ℃.Above-mentioned composite powder is contained in etc. in static pressure jacket, adopts mechanical ram-jolt in filling, waiting static pressure jacket design tube blank size is that 1000mm is long, internal diameter 80mm, external diameter 100mm, after pack in cold isostatic press, moulding pressure is 100MPa, pressurize 12 minutes, after slough jacket and obtain precast support body.
By 0.5 μ m silicon carbide powder, 0.5 μ m silica flour, phenolic resins, polyvinyl alcohol, oxalic acid in mass ratio example be 80:20:15:10:1 blend in ethanol, ethanol content accounts for the 80wt% of total amount, after mechanical agitation, ball milling obtains rete slurry.
By the precast support body obtaining, immerse in rete slurry, with 30mm/s speed, lift, make supporting body surface apply one deck slurry, then dry, flood again, repeatedly flood 3 times, by the film pipe precast body after coating surface rete under the protective atmosphere of argon gas, sintering, 3 ℃ per minute of heating rate, is warming up to 800 ℃, is incubated 1 hour; Rear heating rate is 15 ℃ per minute, and temperature is: 2400 ℃, be incubated 1.5 hours, and obtain the pure matter silicon carbide film of gradient-porosity pipe.
Obtaining material three-point bending bending strength is 70MPa, as shown in Fig. 2-Fig. 4, filter tube support body and pure matter carborundum filter gradient pore structured that rete forms: thicknesses of layers is respectively 150 μ m, supporter average pore size is 5 μ m, and porosity is 38%; Superficial film average pore size is 0.2 μ m, and porosity is 35%, 900 ℃ of material heatproofs.As shown in Figure 4, from pure matter silicon carbide film pipe supporter pore structure, can find out: material internal porous nickel is communicated with, and can guarantee the required low filtration resistance of supporter, the requirement of high permeability, crystal grain, in conjunction with closely, has been guaranteed material high-intensity performance simultaneously.
Embodiment 3
Difference from Example 1 is:
By 25 μ m silicon-carbide particles, 5 μ m silica flours, furfural resin, p-methyl benzenesulfonic acid by mass percentage example be that 70:15:20:2 blend is in ethanol, ethanol content accounts for the 30wt% of total amount, after mechanical agitation ball milling 2 hours slurry, then drying and crushing obtains raw material composite powder at 80 ℃.Above-mentioned composite powder is contained in etc. in static pressure jacket, adopts mechanical ram-jolt in filling, waiting static pressure jacket design tube blank size is that 1000mm is long, internal diameter 20mm, external diameter 30mm, after pack in cold isostatic press, moulding pressure is 100MPa, pressurize 12 minutes, after slough jacket and obtain precast support body.
By 0.5 μ m silicon carbide powder, 0.5 μ m silica flour, phenolic resins, polyvinyl alcohol, oxalic acid in mass ratio example be 80:20:15:10:1 blend in ethanol, ethanol content accounts for the 80wt% of total amount, after mechanical agitation, ball milling obtains rete slurry.
By the precast support body obtaining, immerse in rete slurry, with 30mm/s speed, lift, make supporting body surface apply one deck slurry, then dry, flood again, repeatedly flood 3 times, by the film pipe precast body after coating surface rete under the protective atmosphere of argon gas, sintering, 3 ℃ per minute of heating rate, is warming up to 800 ℃, is incubated 1 hour; Rear heating rate is 15 ℃ per minute, and temperature is: 2400 ℃, be incubated 1.5 hours, and obtain the pure matter silicon carbide film of gradient-porosity pipe.
Obtaining material three-point bending bending strength is 70MPa, as shown in Fig. 2-Fig. 4, filter tube support body and pure matter carborundum filter gradient pore structured that rete forms: thicknesses of layers is respectively 150 μ m, supporter average pore size is 5 μ m, and porosity is 38%; Superficial film average pore size is 0.2 μ m, and porosity is 35%, 900 ℃ of material heatproofs.As shown in Figure 4, from pure matter silicon carbide film pipe supporter pore structure, can find out: material internal porous nickel is communicated with, and can guarantee the required low filtration resistance of supporter, the requirement of high permeability, crystal grain, in conjunction with closely, has been guaranteed material high-intensity performance simultaneously.
Embodiment 4
Difference from Example 1 is:
By 400 μ m silicon-carbide particles, 10 μ m silicon oxide powders, furfural resin, p-methyl benzenesulfonic acid by mass percentage example be that 80:10:10:1 blend is in ethanol, ethanol content accounts for the 20wt% of total amount, after mechanical agitation ball milling 1 hour slurry, then drying and crushing obtains raw material composite powder at 80 ℃.Above-mentioned composite powder is contained in etc. in static pressure jacket, adopts mechanical ram-jolt in filling, waiting static pressure jacket design tube blank size is that 1500mm is long, internal diameter 40mm, external diameter 100mm, after pack in cold isostatic press, moulding pressure is 120MPa, pressurize 5 minutes, after slough jacket and obtain precast support body.
By 5 μ m silicon carbide powders, 5 μ m silica powders, phenolic resins, polyvinyl alcohol, oxalic acid in mass ratio example be 70:15:15:10:1 blend in formaldehyde, content of formaldehyde accounts for the 80wt% of total amount, after mechanical agitation, ball milling obtains rete slurry.
Utilize gas spray gun pulp spraying to be coated on the precast support body of rotation, by regulating relative displacement speed controlling diaphragm layer thickness between supporter and spray gun, after being dried, obtain superficial film.Spray gun material flow is 50 Grams Per Seconds, and relative displacement speed is 70mm/min, dry.By the film pipe precast body sintering under vacuum after coating surface rete, 10 ℃ per minute of heating rate, is warming up to 1000 ℃, is incubated 1 hour; Rear heating rate is 5 ℃ per minute, and temperature is: 1800 ℃, be incubated 1.5 hours, and obtain the pure matter silicon carbide film of gradient-porosity pipe.
Obtaining material three-point bending bending strength is 50MPa, as shown in Fig. 2-Fig. 4, filter tube support body and pure matter carborundum filter gradient pore structured that rete forms: thicknesses of layers is respectively 500 μ m, supporter average pore size is 120 μ m, and porosity is 50%; Superficial film average pore size is 1.5 μ m, and porosity is 40%, 1000 ℃ of material heatproofs.As shown in Figure 4, from pure matter silicon carbide film pipe supporter pore structure, can find out: material internal porous nickel is communicated with, and can guarantee the required low filtration resistance of supporter, the requirement of high permeability, crystal grain, in conjunction with closely, has been guaranteed material high-intensity performance simultaneously.
Embodiment result shows, the invention provides the pure matter silicon carbide film of a kind of gradient-porosity pipe and preparation method thereof, described pure matter silicon carbide film pipe has gradient pore structured, consist of pure matter carborundum, do not exist oxide etc. in conjunction with phase, there is high pass porosity, low pressure drop, intensity is high, thermal shock resistance is good, the feature that serviceability temperature is high, can under oxidizing atmosphere, use, also can under reducing atmosphere, use, acidproof, caustic corrosion performance is strong, can be used for coal gasification chemical industry and IGCC, PFBC coal gasification power generation, high-temperature flue gas, vehicle exhaust, the various height such as water purification, cryogen filtration, purification, described preparation method comprises successively batching, supporter moulding, Film preparation and burns till, and its technique is simple, and cost is low, is easy to realize, and can guarantee properties of product.
Claims (4)
1. the pure matter silicon carbide film of a gradient-porosity pipe, is characterized in that: the pure matter silicon carbide film of gradient-porosity pipe consist of pure matter SiC, by support body layer and superficial film, form gradient filtration structure; Wherein, supporter is piled up and is combined into by coarse granule carborundum, average pore size 5-120 μ m, and superficial film is piled up and is combined into by fine grained carborundum, aperture 0.1-20 μ m, the whole porosity of film pipe is between 25-50%;
The preparation method of the pure matter silicon carbide film of described gradient-porosity pipe, take coarse granule carborundum, silicon oxide powder or silica flour as stock, utilize macromolecular material as bonding agent, mix, utilize cold isostatic press bag cover compacting supporter, rear employing fine grained carborundum, silica flour or silicon oxide powder, pore creating material additive and organic resin preparation rete raw material, adopt spraying or dipping method surface to prepare rete, after drying, sintering obtains finished film pipe; Concrete preparation process is as follows:
(1) supporter shaping raw material is prepared
By coarse granule carborundum, silica flour or silicon oxide powder, macromolecular material, curing agent by mass percentage example be (80wt%-60wt%): (20wt%-10wt%): (20wt%-10wt%): (1wt%-2wt%) blend is in organic solvent, organic solvent content is between the 20-30wt% of amount of the mixture, after mechanical agitation, ball milling obtains slurry, and then drying and crushing obtains raw material composite powder;
(2) supporter moulding
Above-mentioned composite powder is contained in etc. in static pressure jacket, in filling, adopts mechanical ram-jolt, wait static pressure jacket design size, structure by design preparation, then pack in cold isostatic press, moulding pressure is 40-150MPa, the dwell time between 2-15 minute, after slough jacket and obtain precast support body;
(3) rete raw material is prepared
By fine grained carborundum, silica flour or silicon oxide powder, macromolecular material, pore creating material additive, curing agent by mass percentage example be (80wt%-60wt%): (20wt%-10wt%): (20wt%-10wt%): (20wt%-10wt%): (1wt%-2wt%) blend is in organic solvent, organic solvent content is between 50-80wt%, and after mechanical agitation, ball milling obtains rete slurry;
(4) superficial film preparation
Superficial film adopts dipping or spraying method to carry out;
(5) sintering
By the film pipe precast body after coating surface rete under the protective atmosphere of vacuum, argon gas or other inert gas, sintering, heating rate 1-10 ℃ per minute, is warming up to 800-1200 ℃, is incubated and within 0.5-1 hour, sloughs pore creating material additive; Rear heating rate is 5-15 ℃ per minute, and temperature is: 1500-2400 ℃, and insulation 0.5-5 hour, obtains the pure matter silicon carbide film of gradient-porosity pipe;
In step (1), coarse granule carborundum granularity is between 50-400 μ m, and silica flour or silicon oxide powder granularity are between 5-10 μ m; Macromolecular material is selected from one or more of epoxy resin, phenolic resins and furfural resin; Curing agent is p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid; Organic solvent is ethanol or formaldehyde;
In step (3), fine grained carborundum granularity is between 0.5-5 μ m, and silica flour or silicon oxide powder granularity are between 0.5-20 μ m; Macromolecular material is selected from one or more of epoxy resin, phenolic resins and furfural resin; Curing agent is p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid; Organic solvent is ethanol or formaldehyde, and pore creating material additive is cellulose or polyvinyl alcohol;
In step (4), superficial film thickness is between 50-1000 μ m.
2. according to the pure matter silicon carbide film of gradient-porosity claimed in claim 1 pipe, it is characterized in that, in step (4), dipping method: by the precast support body obtaining in step (2), immerse in rete slurry, lift with 10-50mm/s speed, make supporting body surface apply one deck slurry, then dry, then flood, by dipping number of times control surface thicknesses of layers.
3. according to the pure matter silicon carbide film of gradient-porosity claimed in claim 1 pipe, it is characterized in that, in step (4), spraying method: utilize gas spray gun pulp spraying to be coated on the precast support body of rotation, by regulating relative displacement speed controlling diaphragm layer thickness between supporter and spray gun, after being dried, obtain superficial film.
4. according to the pure matter silicon carbide film of gradient-porosity claimed in claim 1 pipe, it is characterized in that: the length of the pure matter silicon carbide film of gradient-porosity pipe is 100-2000mm, compression strength 30-70MPa.
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| CN103360101A (en) * | 2013-06-25 | 2013-10-23 | 西安交通大学 | Preparation method of gradient composite SiC ceramic filter tube |
| CN104174298B (en) * | 2014-08-20 | 2015-08-19 | 武汉工程大学 | A kind of preparation method of water purification gradient silicon carbide ceramic membrane |
| CN105727755B (en) * | 2014-12-09 | 2018-08-28 | 中国科学院金属研究所 | A kind of gradient-porosity silicon nitride combined silicon carbide membrane tube and preparation method thereof |
| CN105727756B (en) * | 2014-12-09 | 2018-11-06 | 中国科学院金属研究所 | A kind of pair of gradient pore structured Sialon silicon carbide membrane tube and preparation method thereof |
| CN106045571B (en) * | 2016-05-31 | 2018-05-15 | 中钢集团洛阳耐火材料研究院有限公司 | A kind of preparation method of gradient porous silicon carbide ceramic |
| JP7078706B2 (en) * | 2017-07-06 | 2022-05-31 | インテグリス・インコーポレーテッド | Silicon Carbide Filter Membrane and Usage |
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| CN110451980B (en) * | 2019-09-16 | 2021-11-05 | 江苏久朗高科技股份有限公司 | Preparation method of flange neck enhanced ceramic high-temperature flue gas filter pipe |
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