CN102659446A - Pure SiC membrane tube support and preparation method thereof - Google Patents
Pure SiC membrane tube support and preparation method thereof Download PDFInfo
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- CN102659446A CN102659446A CN2012100934661A CN201210093466A CN102659446A CN 102659446 A CN102659446 A CN 102659446A CN 2012100934661 A CN2012100934661 A CN 2012100934661A CN 201210093466 A CN201210093466 A CN 201210093466A CN 102659446 A CN102659446 A CN 102659446A
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Abstract
The invention belongs to the technical field of porous ceramic materials and their preparation and especially discloses a pure SiC membrane tube support and a preparation method thereof. The pure SiC membrane tube support comprises pure SiC, is obtained by pile-up and binding of crude SiC particles having sizes of 5 to 400 microns, and has an uniform communicated aperture structure having an average aperture size of 5 to 120 microns and integral porosity of 25 to 50%. The preparation method comprises that crude SiC particles, crude silicon oxide particles or silicon powder as basic materials and one or more polymers as binders are mixed; the mixture is pressed into a support by a cold isostatic pressing sheath; and the support is sintered into the pure SiC membrane tube support. The pure SiC membrane tube support can be used in an oxidation atmosphere and in a reducing atmosphere, has strong acid corrosion and alkaline corrosion resistance, and can be used for various high/low temperature fluid filtering purification fields such as coal gasification chemical engineering, integrated gasification combined cycle (IGCC) and pressurized fluidized bed combustion (PFBC) coal gasification power generation, and high temperature flue gas, automobile exhaust and water purification.
Description
Technical field
The invention belongs to porous ceramic film material and preparing technical field thereof; Be specially a kind of pure matter silicon carbide film pipe supporter and preparation method thereof, this pure matter silicon carbide film pipe supporter has even open pore structure, consists of pure matter silit; There are not combination phases such as oxide compound; Have the advantages that high pass porosity, low pressure drop, intensity are high, thermal shock resistance is good, use temperature is high, the preparation method is easy to realize, can guarantees product performance.
Background technology
The pyroceramic filtering material is generally all worked under various rigorous environment conditions, requires usually with the pyroceramic filtering material to have as gas sweetening: (1) high physical strength, high temperature resistant (300～900 ℃) and good medium corrosion resistance can; (2) high filtering accuracy falls with filtration gas speed and low pressure; (3) be easy to blowback, stable operation, filtration efficiency height; (4) have good thermal stability, can bear the thermal shocking that the blowback of frequent high-voltage pulse cold air causes.Simultaneously, the influence that according to its application scenario requirement, the pyroceramic strainer must be able to bear the influence that influences change of component that the air-flow chemical property changes, vibrate when spraying into superfine grit, and keep higher efficiency of dust collection, keep requirements such as high flow capacity.The stupalith of selecting not only has chemistry, the mechanical stability of heat, also should have wearing quality and high safety; Especially under high-temperature and high-pressure conditions, when having gas phase sulfur, alkali, chlorine element corrosive situation, also require stupalith to have high chemicalstability.
The unfailing performance of the strainability of pyroceramic filtering material, high high-temp stability and roadholding and long-term operation is a pyroceramic filtering material key for design.Pyroceramic 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 the SiC pottery; Because SiC is than the characteristics that oxide ceramics has high thermal conductivity, low-expansion coefficient, thermal shock resistance is good, use temperature is high (more than 1000 ℃), so the preferred material aspect industrial field high temperature fluid filtrations such as vehicle exhaust, Coal Chemical Industry, molten metal.
But be mostly oxide-bonded SiC potteries such as clay at the maximum silit filtering material of application aspect the high temperature air filtration at present, shortcoming is that thermal conductivity is low, causes thermal shock resistance poor, makes ceramic filter material be difficult to bear big thermal load fluctuation; Particularly in high-temperature coal gasification generation technology (like IGCC, PFBC), because of containing water glass, NaCl composition, the Na that changes into behind the coal burning in the coal
2Si
2O
5Meeting heavy corrosion oxide combined silicon carbide filtering material; The damage inactivation that causes strainer; And research shows that purified SiC stupalith does not receive above-mentioned corrosion; Pure matter carbofrax material can use under high temperature oxidation and reducing atmosphere simultaneously; But technology is few aspect the development of pure matter silit filtering material at present, and resulting product intensity is low, pore size distribution is inhomogeneous, filtration efficiency is not high, filter the shortcoming that pressure drop is big, pore texture is not easy to the blowback cleaning, the application process of restriction silit filtering material.
Therefore, use temperature height, anti-various dielectric corrosions, intensity height, HS, low pressure drop, be easy to regenerate, the 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 that the present invention will solve is: avoid existing silit filtering material to form for oxide compound part bonded materials such as clays mostly; A kind of pure matter silit filtering material is provided; Material consists of the above silit of 99wt%, make this kind material can be under various atmospheric conditions the media-resistant corrosive power stronger.
Another technical problem that the present invention will solve is: avoid the weak point in the existing silicon carbide film Manifold technology, provide a kind of and have that porosity is big, the high and low pressure drop of intensity, regeneration easily, the pure matter silicon carbide film of reusable ideal pipe supporter.
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 supporter that is suitable for large-scale production simple, that moulding is easy, with short production cycle, yield rate is high, production cost is low.
For solving the technical problem that exists in the preparation of silit filtering material, the technical scheme that the present invention taked is:
A kind of pure matter silicon carbide film pipe supporter and preparation method thereof, the supporter feed composition is (according to the mass fraction):
| Thick silicon-carbide particle (5～400 μ m) | 8～60 |
| Silica flour or silicon oxide powder (5～10 μ m) | 20～10 |
| Macromolecular material (one or more of epoxy, phenolic aldehyde and furfuryl resin) | 20～10 |
| Solidifying agent (tosic acid, urotropine, oxalic acid or Hydrocerol A) | 1～2 |
| Organic solvent (ethanol or toluene) | 20～30 |
In the constitutive material; At first change carbon source in the organic resin sintering process into; With silicon oxide and the silica flour reaction sintering in the raw material, can guarantee that particularly above-mentioned various raw materials can not generate other thing phase composites such as oxide compound in sintering process for supporter provides intensity; All be that original silicon-carbide particle and reaction generate the silit phase; Play the effect that combines original silicon-carbide particle mutually and generate silit, guaranteed the pure materialization of material, see accompanying drawing 1XRD diffracting spectrum; Make that the coefficient of expansion, the property retention of high temperature resistance atmosphere corrosion of supporter are pure matter silit state, for improving the strength of materials, heat shock resistance, high-temperature stability and playing an important role creep rupture life.
The silicon oxide of different components, different-grain diameter and silica flour addition have guaranteed that supporter has the permeability of controllable porosity and hole; See accompanying drawing 2, Fig. 3 and Fig. 4; Above raw material is formed, granularity is chosen in the material prepn; Can guarantee that pure matter silicon carbide film pipe supporter has high pass porosity and rational pore texture, guarantee the material permeate well, have low filter pressure.
The preparation method of a kind of pure matter silicon carbide film pipe supporter of the present invention; With coarse particles silit, silicon oxide or silica flour is basic material; Utilize macromolecular material as wedding agent, mix utilizes cold isostatic press bag cover compacting supporter; Obtain pure matter silicon carbide film pipe supporter through sintering, mainly may further comprise the steps:
(1) the supporter shaping raw material is prepared
With thick silicon-carbide particle, silica flour or silicon oxide powder, macromolecular material, solidifying agent by mass percentage example be (80wt%～60wt%): (20wt%～10wt%): (20wt%～10wt%): (1wt%～2wt%); The accurately accurate weighing of prescription; Blend is in organic solvent; Organic solvent content is between 20～30wt% of amount of the mixture, and ball milling gets slurry after mechanical stirring, and then drying and crushing gets the raw material composite powder; The ball milling time is 1～2 hour, and drying temperature is 70～90 ℃.
The coarse particles carborundum granularity between 5～400 μ m (being preferably 50～400 μ m), silica flour or silicon oxide granularity be between 5～10 μ m; Macromolecular material is selected from one or more of epoxy resin, resol and furfuryl resin; Solidifying agent is tosic acid, urotropine, oxalic acid or Hydrocerol A; Organic solvent is ethanol or formaldehyde;
(2) supporter moulding
Above-mentioned composite powder is contained in etc. in the static pressure jacket, adopts mechanical ram-jolt in the filling, wait static pressure jacket size, structure by designing and preparing; Pack into then in the cold isostatic press, moulding pressure is 40～150MPa, and the dwell time looks sample size and decides; Between 2～15 minutes; After slough jacket and obtain prefabricated supporter, the external diameter of prefabricated supporter between 10～100mm, wall thickness 2mm～30mm.
(3) sintering
Under the protective atmosphere of vacuum, argon gas or other rare gas element, sintering, temperature rise rate are 5～15 ℃ of PMs with prefabricated supporter, and temperature is: 1500～2400 ℃, be incubated 0.5～5 hour, and get pure matter silicon carbide film pipe supporter.
Among the present invention; Pure matter silicon carbide film pipe supporter consist of pure matter SiC, supporter is piled up be combined into by coarse particles 5～400 μ m silit, has even open pore structure; Mean pore size 5～120 μ m (being preferably 20～80 μ m), whole void content is between 25～50%.
Among the present invention, the length of pure matter silicon carbide film pipe supporter is 100～2000mm, the pipe diameter between 30～100mm, wall thickness between 5～30mm, flexural strength 30～70MPa.
Among the present invention, in the pure matter silicon carbide film pipe supporter, pure matter SiC content is more than 99wt%, and material internal crystal grain combines fully by silicon-carbide particle not have clay or other oxide-bonded phases from sinter bonded.
The technical scheme of a kind of pure matter silicon carbide film pipe supporter of the present invention and preparation method thereof has following outstanding effect:
1. pure matter silicon carbide film pipe supporter of the present invention has single silit and forms; Guaranteed the corrosion resistance of material under various high-temperature mediums; Especially under the unsuitable reducing atmosphere and high-alkali corrosive environment that uses of oxide combined silicon carbide filtering material; Have good stability, guarantee the material long life.
2. the macroporous structure of pure matter silicon carbide film pipe supporter of the present invention has guaranteed that material use mesolow falls, high permeability, and is beneficial to the realization that blowback is cleaned, and regeneration easily, and is reusable.
3. pure matter silicon carbide film pipe supporter crystal grain combination of the present invention combines original silicon-carbide particle for reaction generates silit, and the two is qualitative consistently to guarantee that the intercrystalline combination is firm, guarantees that material has high intensity and thermal shock resistance.
4. pure matter silicon carbide film pipe supporter preparation method technology controlling and process of the present invention is flexible, can design the product of different size as required, and with short production cycle, cost is low, is easy to realize, can ensure product performance.
5. pure matter silicon carbide film pipe support body material Application Areas provided by the invention is wide; Use in the time of under atmosphere such as oxidation, reduction, high chlorine, alkali, sulphur, silicon, can growing; More can under 1000 ℃ high temperature, use, can be used for 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 handle filter tube support body.
Description of drawings
Fig. 1 silicon carbide film pipe XRD diffractogram.
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 texture.
The pure matter silicon carbide film of Fig. 4 pipe supporter pore texture.
Embodiment
The present invention is a basic material with coarse particles silit, silicon oxide or silica flour, utilizes macromolecular material as wedding agent, mix; Utilize cold isostatic press bag cover compacting supporter; Thin silicon-carbide particle, silica flour, pore-forming material additive and organic resin preparation rete raw material are adopted in the back, adopt spraying or dipping method surface preparation rete, after drying; Sintering obtains the finished film pipe, mainly may further comprise the steps:
(1) the supporter shaping raw material is prepared
With thick silicon-carbide particle, silica flour or silicon oxide powder, macromolecular material, solidifying agent by mass percentage example be (80wt%～60wt%): (20wt%～10wt%): (20wt%～10wt%): (1wt%～2wt%); The accurately accurate weighing of prescription; Blend is in organic solvent; Organic solvent content is between 20～30wt% of amount of the mixture, and ball milling gets slurry after mechanical stirring, and then drying and crushing gets the raw material composite powder; The ball milling time is 1～2 hour, and drying temperature is 70～90 ℃.
The coarse particles carborundum granularity between 5～400 μ m, silica flour or silicon oxide granularity be between 5～10 μ m; Macromolecular material is selected from one or more of epoxy resin, resol and furfuryl resin; Solidifying agent is tosic acid, urotropine, oxalic acid or Hydrocerol A; Organic solvent is ethanol or formaldehyde;
(2) supporter moulding
Above-mentioned composite powder is contained in etc. in the static pressure jacket, adopts mechanical ram-jolt in the filling, wait static pressure jacket size, structure by designing and preparing; Pack into then in the cold isostatic press, moulding pressure is 40～150MPa, and the dwell time looks sample size and decides; Between 2～15 minutes; After slough jacket and obtain prefabricated supporter, the external diameter of prefabricated supporter between 10～100mm, wall thickness 2mm～30mm.
(3) the rete raw material is prepared
With silicon carbide powder, silica flour or silicon oxide powder, macromolecular material, pore-forming material additive, solidifying agent by mass percentage example be (80wt%～60wt%): (20wt%～10wt%): (20wt%～10wt%): (20wt%～10wt%): (1wt%～2wt%); The accurately accurate weighing of prescription; Blend is in organic solvent, and organic solvent content is between 50～80wt%, and ball milling gets the rete slurry after mechanical stirring; The ball milling time is 1～2 hour, and is for use.
Carborundum granularity is between 0.5～40 μ m, and silica flour or silicon oxide granularity are between 0.5～20 μ m; Macromolecular material is selected from one or more of epoxy resin, resol and furfuryl resin; Solidifying agent is tosic acid, urotropine, oxalic acid or Hydrocerol A; Organic solvent is ethanol or formaldehyde, and the pore-creating additive is Mierocrystalline cellulose or Z 150PH etc.
(4) superficial film preparation
Superficial film can adopt dipping or spraying method to carry out.
Dipping method: with the prefabricated supporter that obtains in (2) step, immerse in the rete slurry, lift, make supporting body surface apply one deck slurry, and after drying floods again, through dipping number of times control surface thicknesses of layers with 10-50mm/s speed;
Spraying method: utilize gas spray gun slurry to be sprayed on the prefabricated supporter of rotation,, obtain superficial film after the drying through relative displacement speed control thicknesses of layers between adjustable support body and the spray gun.
Measure through dry caudacoria O.D.T., the control surface thicknesses of layers is between 50～1000 μ m.
(5) sintering
With the film pipe precast body behind the coated surface rete under the protective atmosphere of vacuum, argon gas or other rare gas element, sintering, 1～10 ℃ of temperature rise rate PM is warming up to 800～1200 ℃, is incubated 0.5～1 hour and sloughs the pore-creating additive; Back temperature rise rate is 5～15 ℃ of PMs, and temperature is: 1500～2400 ℃, be incubated 0.5～5 hour, and get the pure matter silicon carbide film of gradient-porosity pipe.
Among the present invention, the pure matter silicon carbide film of gradient-porosity pipe consist of pure matter SiC, constitute the gradient filtration by support body layer and superficial film; Wherein, supporter is piled up be combined into by coarse particles silit, mean pore size 5～120 μ m, and superficial film is piled up be combined into by fine particle silit, aperture 0.1～20 μ m, the whole void content of film pipe is between 25～50%.
The length of the pure matter silicon carbide film of said gradient-porosity pipe is 100～2000mm, ultimate compression strength 30～70MPa.
In the pure matter silicon carbide film of the said gradient-porosity pipe, pure matter SiC content is more than 99wt%, and surplus is an impurity element, and material internal crystal grain combines fully by silicon-carbide particle not have clay or other oxide-bonded phases from sinter bonded.
Embodiment 1
With 300 μ m silicon-carbide particles, 5 μ m silica flours, resol, tosic acid by mass percentage example be 80: 20: 15: 1 blend is in ethanol; Ethanol content accounts for the 20wt% of total amount; Ball milling got slurry in 1.5 hours after mechanical stirring, and then 80 ℃ of following drying and crushing get the raw material composite powder.Above-mentioned composite powder is contained in etc. in the static pressure jacket, adopts mechanical ram-jolt in the filling, waiting static pressure jacket design tube blank size is that 2000mm is long; Internal diameter 40mm, external diameter 60mm, after pack in the cold isostatic press; Moulding pressure is 150MPa, pressurize 5 minutes, after slough jacket and obtain prefabricated supporter.
Is 70: 15: 20 with 1.5 μ m silicon carbide powders, 1.5 μ m silica flours, epoxy resin, Mierocrystalline cellulose, tosic acid by mass ratio: blend in 10: 2 is in ethanol, and ethanol content accounts for the 60wt% of total amount, and ball milling gets the rete slurry after mechanical stirring.
The superficial film preparation will be selected two kinds of method validations for use:
Dipping method: the prefabricated supporter that will obtain, immerse in the rete slurry, lift with 20mm/s speed; Make supporting body surface apply one deck slurry, and after drying, dipping again; Flood 3 times, 5 times, 6 times to such an extent that three kinds flood surface film tunic pipes repeatedly, be labeled as a, b, c film pipe respectively.Spraying method: utilize gas spray gun slurry to be sprayed on the prefabricated supporter of rotation,, obtain superficial film after the drying through relative displacement speed control thicknesses of layers between adjustable support body and the spray gun.The spray gun material flow is 20 Grams Per Seconds, and relative displacement speed is 80mm/min, 50mm/min, 30mm/min, gets three kinds of sprayed surface rete film pipes, is respectively d, e, f film pipe.
With the film pipe precast body behind the coated surface rete under the protective atmosphere of argon gas, sintering, 5 ℃ of temperature rise rate PMs are warming up to 1200 ℃, are incubated 0.5 hour; Back temperature rise rate is 10 ℃ of PMs, and temperature is: 2000 ℃, be incubated 1 hour, and get the pure matter silicon carbide film of the gradient-porosity pipe of six kinds of different rete coating methods.
As shown in Figure 1, can find out from silicon carbide film pipe XRD diffractogram: the silicon carbide film pipe is that secondary silit combines original silicon-carbide particle to form, and does not have second phase, realizes the pure materialization purpose of material.Obtaining material three-point bending flexural 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.
Like Fig. 2-shown in Figure 4, filter tube support body and pure matter silit filter gradient pore structured that rete forms: the supporter average pore size is 60 μ m, and porosity is 42%; The superficial film average pore size is 0.8 μ m, and porosity is 40%, 1000 ℃ of material heatproofs.As shown in Figure 4, can find out from pure matter silicon carbide film pipe supporter pore texture: the material internal porous nickel is communicated with, and can guarantee the required low filtration resistance of supporter, the requirement of high permeability, and crystal grain combines closely to have guaranteed the material high-intensity performance simultaneously.
Embodiment 2
Be with embodiment 1 difference:
With 25 μ m silicon-carbide particles, 10 μ m silicon oxide powders, furfuryl resin, tosic acid by mass percentage example be 70: 15: 20: 2 blend are in ethanol; Ethanol content accounts for the 30wt% of total amount; Ball milling got slurry in 2 hours after mechanical stirring, and then 80 ℃ of following drying and crushing get the raw material composite powder.Above-mentioned composite powder is contained in etc. in the static pressure jacket, adopts mechanical ram-jolt in the filling, waiting static pressure jacket design tube blank size is that 1000mm is long; Internal diameter 80mm, external diameter 100mm, after pack in the cold isostatic press; Moulding pressure is 100MPa, pressurize 12 minutes, after slough jacket and obtain prefabricated supporter.
Is 80: 20: 15 with 0.5 μ m silicon carbide powder, 0.5 μ m silica flour, resol, Z 150PH, oxalic acid by mass ratio: blend in 10: 1 is in ethanol, and ethanol content accounts for the 80wt% of total amount, and ball milling gets the rete slurry after mechanical stirring.
With the prefabricated supporter that obtains, immerse in the rete slurry, lift with 30mm/s speed; Make supporting body surface apply one deck slurry, and after drying, dipping again; Flood repeatedly 3 times, with the film pipe precast body behind the coated surface rete under the protective atmosphere of argon gas, sintering; 3 ℃ of temperature rise rate PMs are warming up to 800 ℃, are incubated 1 hour; Back temperature rise rate is 15 ℃ of PMs, and temperature is: 2400 ℃, be incubated 1.5 hours, and get the pure matter silicon carbide film of gradient-porosity pipe.
Obtaining material three-point bending flexural strength is 70MPa, and like Fig. 2-shown in Figure 4, filter tube support body and pure matter silit filter gradient pore structured that rete forms: thicknesses of layers is respectively 150 μ m, the supporter average pore size is 5 μ m, and porosity is 38%; The superficial film average pore size is 0.2 μ m, and porosity is 35%, 900 ℃ of material heatproofs.As shown in Figure 4, can find out from pure matter silicon carbide film pipe supporter pore texture: the material internal porous nickel is communicated with, and can guarantee the required low filtration resistance of supporter, the requirement of high permeability, and crystal grain combines closely to have guaranteed the material high-intensity performance simultaneously.
Embodiment 3
Be with embodiment 1 difference:
With 25 μ m silicon-carbide particles, 5 μ m silica flours, furfuryl resin, tosic acid by mass percentage example be 70: 15: 20: 2 blend are in ethanol; Ethanol content accounts for the 30wt% of total amount; Ball milling got slurry in 2 hours after mechanical stirring, and then 80 ℃ of following drying and crushing get the raw material composite powder.Above-mentioned composite powder is contained in etc. in the static pressure jacket, adopts mechanical ram-jolt in the filling, waiting static pressure jacket design tube blank size is that 1000mm is long; Internal diameter 20mm, external diameter 30mm, after pack in the cold isostatic press; Moulding pressure is 100MPa, pressurize 12 minutes, after slough jacket and obtain prefabricated supporter.
Is 80: 20: 15 with 0.5 μ m silicon carbide powder, 0.5 μ m silica flour, resol, Z 150PH, oxalic acid by mass ratio: blend in 10: 1 is in ethanol, and ethanol content accounts for the 80wt% of total amount, and ball milling gets the rete slurry after mechanical stirring.
With the prefabricated supporter that obtains, immerse in the rete slurry, lift with 30mm/s speed; Make supporting body surface apply one deck slurry, and after drying, dipping again; Flood repeatedly 3 times, with the film pipe precast body behind the coated surface rete under the protective atmosphere of argon gas, sintering; 3 ℃ of temperature rise rate PMs are warming up to 800 ℃, are incubated 1 hour; Back temperature rise rate is 15 ℃ of PMs, and temperature is: 2400 ℃, be incubated 1.5 hours, and get the pure matter silicon carbide film of gradient-porosity pipe.
Obtaining material three-point bending flexural strength is 70MPa, and like Fig. 2-shown in Figure 4, filter tube support body and pure matter silit filter gradient pore structured that rete forms: thicknesses of layers is respectively 150 μ m, the supporter average pore size is 5 μ m, and porosity is 38%; The superficial film average pore size is 0.2 μ m, and porosity is 35%, 900 ℃ of material heatproofs.As shown in Figure 4, can find out from pure matter silicon carbide film pipe supporter pore texture: the material internal porous nickel is communicated with, and can guarantee the required low filtration resistance of supporter, the requirement of high permeability, and crystal grain combines closely to have guaranteed the material high-intensity performance simultaneously.
Embodiment 4
Be with embodiment 1 difference:
With 400 μ m silicon-carbide particles, 10 μ m silicon oxide powders, furfuryl resin, tosic acid by mass percentage example be 80: 10: 10: 1 blend is in ethanol; Ethanol content accounts for the 20wt% of total amount; Ball milling got slurry in 1 hour after mechanical stirring, and then 80 ℃ of following drying and crushing get the raw material composite powder.Above-mentioned composite powder is contained in etc. in the static pressure jacket, adopts mechanical ram-jolt in the filling, waiting static pressure jacket design tube blank size is that 1500mm is long; Internal diameter 40mm, external diameter 100mm, after pack in the cold isostatic press; Moulding pressure is 120MPa, pressurize 5 minutes, after slough jacket and obtain prefabricated supporter.
Is 70: 15: 15 with 5 μ m silicon carbide powders, 5 μ m silica powders, resol, Z 150PH, oxalic acid by mass ratio: blend in 10: 1 is in formaldehyde, and formaldehyde content accounts for the 80wt% of total amount, and ball milling gets the rete slurry after mechanical stirring.
Utilize gas spray gun slurry to be sprayed on the prefabricated supporter of rotation,, obtain superficial film after the drying through relative displacement speed control thicknesses of layers between adjustable support body and the spray gun.The spray gun material flow is 50 Grams Per Seconds, and relative displacement speed is 70mm/min, drying.With the film pipe precast body sintering under vacuum behind the coated surface rete, 10 ℃ of temperature rise rate PMs are warming up to 1000 ℃, are incubated 1 hour; Back temperature rise rate is 5 ℃ of PMs, and temperature is: 1800 ℃, be incubated 1.5 hours, and get the pure matter silicon carbide film of gradient-porosity pipe.
Obtaining material three-point bending flexural strength is 50MPa; Like Fig. 2-shown in Figure 4; Filter tube support body and pure matter silit filter gradient pore structured that rete forms: thicknesses of layers is respectively 500 μ m, the supporter average pore size is 120 μ m, and porosity is 50%; The superficial film average pore size is 1.5 μ m, and porosity is 40%, 1000 ℃ of material heatproofs.As shown in Figure 4, can find out from pure matter silicon carbide film pipe supporter pore texture: the material internal porous nickel is communicated with, and can guarantee the required low filtration resistance of supporter, the requirement of high permeability, and crystal grain combines closely to have guaranteed the material high-intensity performance simultaneously.
Embodiment result shows, the invention provides a kind of pure matter silicon carbide film pipe supporter and preparation method thereof; This pure matter silicon carbide film pipe supporter has even open pore structure; Consist of pure matter silit, do not exist oxide compound etc. to combine phase, have high pass porosity, low pressure drop, intensity is high, thermal shock resistance is good, use temperature is high characteristics; The preparation method is easy to realize, can guarantees product performance.The present invention can use under oxidizing atmosphere; Also can under reducing atmosphere, use; The acid-and base-resisting corrosive nature is strong, can be used for various high and low temperature filtering flows such as gasification chemical industry and IGCC, PFBC coal gasification power generation, high-temperature flue gas, vehicle exhaust, water purification and purifies.
Claims (6)
1. pure matter silicon carbide film pipe supporter; It is characterized in that: pure matter silicon carbide film pipe supporter consist of pure matter SiC; Supporter is piled up be combined into by coarse particles 5～400 μ m silit; Have even open pore structure, mean pore size 5～120 μ m, whole void content is between 25～50%.
2. according to the described pure matter silicon carbide film pipe supporter of claim 1, it is characterized in that: the length of pure matter silicon carbide film pipe supporter is 100～2000mm, the pipe diameter between 30～100mm, wall thickness between 5～30mm, flexural strength 30～70MPa.
3. according to the described pure matter silicon carbide film pipe supporter of claim 1, it is characterized in that: in the pure matter silicon carbide film pipe supporter, pure matter SiC content is more than 99wt%, and material internal crystal grain combines fully by silicon-carbide particle from sinter bonded.
4. according to the preparation method of the described pure matter silicon carbide film pipe supporter of claim 1; It is characterized in that: with coarse particles silit, silicon oxide or silica flour is basic material; Utilize macromolecular material as wedding agent; Mix utilizes cold isostatic press bag cover compacting supporter, obtains pure matter silicon carbide film pipe supporter through sintering.
5. according to the preparation method of the described pure matter silicon carbide film pipe supporter of claim 4, it is characterized in that concrete preparation process is following:
(1) the supporter shaping raw material is prepared
With thick silicon-carbide particle, silica flour or silicon oxide powder, macromolecular material, solidifying agent by mass percentage example be that (80wt%～60wt%): (20wt%～10wt%): (20wt%～10wt%): (blend of 1wt%～2wt%) is in organic solvent; Organic solvent content is between 20～30wt% of amount of the mixture; Ball milling gets slurry after mechanical stirring, and then drying and crushing gets the raw material composite powder;
(2) supporter moulding
Above-mentioned composite powder is contained in etc. in the static pressure jacket, adopts mechanical ram-jolt in the filling, wait static pressure jacket size, structure by designing and preparing; Pack into then in the cold isostatic press; Moulding pressure is 40～150MPa, the dwell time between 2～15 minutes, after slough jacket and obtain prefabricated supporter;
(3) sintering
Under the protective atmosphere of vacuum, argon gas or other rare gas element, sintering, temperature rise rate are 5～15 ℃ of PMs with prefabricated supporter, and temperature is: 1500～2400 ℃, be incubated 0.5～5 hour, and get pure matter silicon carbide film pipe supporter.
6. according to the preparation method of the described pure matter silicon carbide film pipe supporter of claim 5, it is characterized in that in the step (1), the coarse particles carborundum granularity is between 5～400 μ m, silica flour or silicon oxide granularity are between 5～10 μ m; Macromolecular material is selected from one or more of epoxy resin, resol and furfuryl resin; Solidifying agent is tosic acid, urotropine, oxalic acid or Hydrocerol A; Organic solvent is ethanol or formaldehyde.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100934661A CN102659446B (en) | 2012-03-31 | 2012-03-31 | Pure SiC membrane tube support and preparation method thereof |
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| CN2012100934661A CN102659446B (en) | 2012-03-31 | 2012-03-31 | Pure SiC membrane tube support and preparation method thereof |
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| CN102659446A true CN102659446A (en) | 2012-09-12 |
| CN102659446B CN102659446B (en) | 2013-11-20 |
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Cited By (9)
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| CN103387232A (en) * | 2013-07-31 | 2013-11-13 | 苏州纳埃净化科技有限公司 | Synthesis method of silicon carbide porous material |
| CN104261867A (en) * | 2014-09-23 | 2015-01-07 | 武汉工程大学 | Preparation method of pure silicon carbide porous ceramic membrane |
| CN105693276A (en) * | 2014-11-27 | 2016-06-22 | 中国科学院金属研究所 | Silicon carbide filtering film and low temperature preparation method thereof |
| 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 |
| CN108499326A (en) * | 2018-06-13 | 2018-09-07 | 南京圣卡孚科技有限公司 | A kind of flue gas recovery device and recovery method based on silicon carbide film |
| 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 |
| CN109574672A (en) * | 2018-12-20 | 2019-04-05 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of silicon carbide reaction-sintered micro-filtration film layer |
| CN109678522A (en) * | 2018-12-20 | 2019-04-26 | 中国科学院上海硅酸盐研究所 | A kind of normal pressure solid-phase sintered silicon carbide film support and preparation method thereof |
| CN112939606A (en) * | 2021-03-18 | 2021-06-11 | 西安交通大学 | Porous silicon carbide ceramic and preparation method thereof |
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| CN103387232A (en) * | 2013-07-31 | 2013-11-13 | 苏州纳埃净化科技有限公司 | Synthesis method of silicon carbide porous material |
| CN104261867A (en) * | 2014-09-23 | 2015-01-07 | 武汉工程大学 | Preparation method of pure silicon carbide porous ceramic membrane |
| CN104261867B (en) * | 2014-09-23 | 2016-01-20 | 武汉工程大学 | A kind of preparation method of pure carborundum porous ceramics film |
| CN105693276A (en) * | 2014-11-27 | 2016-06-22 | 中国科学院金属研究所 | Silicon carbide filtering film and low temperature preparation method thereof |
| CN105693276B (en) * | 2014-11-27 | 2019-02-19 | 中国科学院金属研究所 | A kind of silicon carbide filter film layer and its low temperature preparation method |
| 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 |
| CN108499326A (en) * | 2018-06-13 | 2018-09-07 | 南京圣卡孚科技有限公司 | A kind of flue gas recovery device and recovery method based on silicon carbide film |
| 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 |
| CN109574672A (en) * | 2018-12-20 | 2019-04-05 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of silicon carbide reaction-sintered micro-filtration film layer |
| CN109678522A (en) * | 2018-12-20 | 2019-04-26 | 中国科学院上海硅酸盐研究所 | A kind of normal pressure solid-phase sintered silicon carbide film support and preparation method thereof |
| CN112939606A (en) * | 2021-03-18 | 2021-06-11 | 西安交通大学 | Porous silicon carbide ceramic and preparation method thereof |
| CN112939606B (en) * | 2021-03-18 | 2022-12-09 | 西安交通大学 | Porous silicon carbide ceramic and preparation method thereof |
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