CN115155187A - Honeycomb structure, preparation method thereof and particle catcher - Google Patents
Honeycomb structure, preparation method thereof and particle catcher Download PDFInfo
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- CN115155187A CN115155187A CN202210524742.9A CN202210524742A CN115155187A CN 115155187 A CN115155187 A CN 115155187A CN 202210524742 A CN202210524742 A CN 202210524742A CN 115155187 A CN115155187 A CN 115155187A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Abstract
The invention relates to a honeycomb structure, a preparation method thereof and a particle catcher. The porosity of the honeycomb structure body is more than or equal to 36%, the pores are divided into through holes and isolated holes, and the volume of the through holes accounts for more than 72% of the total pore volume. The preparation method comprises the following steps: mixing the raw materials, kneading, pugging, ageing, extruding and drying the obtained mixed material to obtain cell unit strips, degreasing and sintering the cell unit strips, then carrying out oxidation treatment at 1250 +/-10 ℃, and splicing the obtained cell unit strips to obtain the honeycomb structure. The invention controls the volume of the through holes to be more than 72 percent of the total pore volume, thereby having high mechanical property, heat conduction property and excellent carbon loading capacity without reducing the back pressure property and the trapping efficiency of the honeycomb structure body.
Description
Technical Field
The invention relates to the field of particle traps, in particular to a honeycomb structure, a preparation method thereof and a particle trap.
Background
Porous honeycomb structures are widely used as filters for trapping and removing particulate matter in a dust-containing fluid such as gasoline and diesel engine exhaust gas, or as catalyst carriers on which catalyst components for purifying harmful substances in exhaust gas are supported. When such a honeycomb structure is applied to an automobile engine, it is necessary that a porous material having a plurality of pores, which is obtained by bonding aggregate such as silicon carbide particles (SiC particles) with a binder such as cordierite, oxide, or silicon metal powder, has excellent characteristics such as thermal shock resistance, while always facing a high-temperature environment. The cellular structure body with a plurality of cells formed by dividing the cellular material can be applied to a particulate filter (GPF, DPF) of an internal combustion engine, and further filters solid particulate matters in exhaust gas through cell walls to reach the emission standard.
The particle trap needs to meet the characteristics of high trapping efficiency, low back pressure, high mechanical strength, high durability and the like, and particularly, the particle trap needs to meet the high trapping efficiency and reach the specified emission standard of tail gas; the pressure drop of tail gas passing through is also reduced, and the oil consumption of the engine is saved; meanwhile, the particle catcher needs to meet the requirements of complicated road conditions and vehicle conditions, so that the particle catcher has excellent mechanical strength and durability. However, high capture efficiency and low back pressure require products characterized by high porosity, while high mechanical strength and high durability require products characterized by low porosity and high product density.
Most of the current processes and products only regulate and control the porosity to try to find the balance between the two, but with the increasing environmental protection requirements, the regulation means can not meet the requirements of both the porosity and the durability.
Chinese patent CN 110759746A adopts adding fibrous pore-forming agent to penetrate isolated pores into through pores to reduce the back pressure characteristic of the particle trap, but adding fibrous pore-forming agent will cause the change of pore size distribution, affect the trapping efficiency, and need to additionally control the particle size consistency and mixing consistency of the pore-forming agent, increase the cost and technical difficulty of the production process.
Therefore, there is a need in the art to develop a product that combines mechanical strength and back pressure characteristics, and combines the difficulty of the production process to improve the usability of the particle catcher.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a honeycomb structure, a preparation method thereof and a particle catcher.
In a first aspect, the present invention provides a honeycomb structure having a porosity of 36% or more, the pores being divided into through holes and isolated holes, wherein the through holes account for 72% or more of the total pore volume.
Because the through holes are used for trapping, the isolated holes not only can not trap particles and reduce the backpressure, but also can reduce the heat conduction characteristic, the pressure resistance characteristic and the carbon loading capacity of the honeycomb ceramic structure. The invention controls the volume of the through holes to occupy more than 72 percent of the total pore volume, thereby having high mechanical property, heat conduction property and excellent carbon loading capacity without reducing the backpressure property and the trapping efficiency of the honeycomb structure body.
The through holes in the present invention are holes that are included in the honeycomb structure and communicate with the outside by having at least one hole. Isolated cells are holes contained in the honeycomb structure body which are not communicated with the outside without any one hole. The through holes and the isolated holes are both in micron order.
According to the honeycomb structure provided by the invention, raw materials of the honeycomb structure comprise metal silicon powder and silicon carbide, wherein the mass of the metal silicon powder is 10-30% of the mass of the silicon carbide, the particle size of the silicon carbide raw material is 21-48 mu m, the sphericity of the silicon carbide raw material is more than 0.78, the particle size of the metal silicon powder is 5-12 mu m, and the sphericity of the metal silicon powder raw material is more than 0.65.
The invention fully considers the relationship of particle size, surface appearance and component content, and finds out the matching characteristic of key binder (metal silicon powder) and silicon carbide aggregate in the aspect of raw materials. Wherein, the undersize or oversize of the silicon carbide particle size can cause the undersize or oversize of the pore size distribution; the too small particle size of the metal silicon powder can cause the cost of the preparation process to rise, and the too large particle size can block small gaps formed by silicon carbide particles with low sphericity in the sintering stage; the sphericity of the silicon carbide raw material is more than 0.78, so that small pores supported by the silicon carbide aggregate protruding part with poor sphericity are prevented from being blocked by large-particle metal silicon powder; the sphericity of the metal silicon powder raw material is more than 0.65, the metal silicon powder with high sphericity is more uniformly dispersed with the silicon carbide aggregate in the mixing process, and the blockage of small gaps of the silicon carbide particles caused by the fusion agglomeration of the metal silicon powder with high content due to uneven distribution of the metal silicon powder is avoided. In short, the volume of the through-holes can be controlled to 72% or more of the total pore volume by controlling the conditions of the raw materials within the above-mentioned ranges.
According to the honeycomb structure provided by the invention, the mass of the metal silicon powder is 18-21% of the mass of the silicon carbide, and the particle size of the silicon carbide raw material is 28-40 μm.
According to the honeycomb structure provided by the invention, the raw material is subjected to oxidation treatment at 1250 +/-10 ℃ after being sintered.
During sintering, the molten metal silicon powder is enriched on the surface due to capillary phenomenon, and the oxidized metal silicon powder is oxidized to generate a silicon dioxide protective film, so that the pore size distribution can be regulated and controlled, the trapping efficiency is enhanced, the mechanical strength of the metal silicon powder can be increased, and the durability of the metal silicon powder is improved.
According to the honeycomb structure provided by the invention, the raw materials further comprise bentonite, a sintering aid, a lubricant, a binder and water.
According to the honeycomb structure provided by the invention, the sintering aid is one or more of aluminum hydroxide, strontium oxide and magnesium carbonate.
According to the honeycomb structure provided by the invention, the lubricant is one or more of glycerol, lauric acid and tall oil.
According to the honeycomb structure provided by the present invention, the binder is one or more of methyl cellulose and polyvinyl alcohol.
In some embodiments of the invention, the silicon metal powder, silicon carbide, bentonite, sintering aid, lubricant, binder, and water are mixed in a ratio of 15:70:1:1.2:1.4:4.8: 6.6.
According to the honeycomb structure provided by the present invention, the median pore diameter of the through holes is 10 to 13 μm.
According to the honeycomb structure provided by the invention, the B-axis bending strength of the honeycomb structure is not less than 15MPa.
According to the honeycomb structure provided by the invention, the thermal conductivity of the honeycomb structure is more than or equal to 20W/mK.
In a second aspect, the present invention provides a method for producing the above honeycomb structure.
The preparation method provided by the invention comprises the following steps:
mixing the raw materials, processing the obtained mixed material to obtain cell unit strips, degreasing and sintering the cell unit strips, then carrying out oxidation treatment at 1250 +/-10 ℃, and splicing the obtained cell unit strips to obtain the honeycomb structure.
Further, the processing includes kneading, pugging, staling, extruding, and drying.
In a third aspect, the present invention provides a particulate trap comprising the above honeycomb structure.
The invention provides a honeycomb structure body, a preparation method thereof and a particle trap, wherein the volume of through holes accounts for more than 72% of the total pore volume, so that the honeycomb structure body has high mechanical property, heat conduction property and excellent carbon carrying capacity while the backpressure property and the trapping efficiency of the honeycomb structure body are not reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it should be noted that the sizes of the parts in the drawings are not drawn according to actual scale. The figures in the following description are some embodiments of the invention.
Fig. 1 is a schematic view of the microstructure of a honeycomb structure obtained in example 1 of the present invention, in which 1, 2, and 3 are through holes, and 4 and 5 are isolated holes;
FIG. 2 is a microscope photograph of a honeycomb structure obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Unless otherwise specified, the starting materials for the examples of the present invention are commercially available.
Example 1
The present embodiment provides a honeycomb structure, and a method for manufacturing the honeycomb structure includes the steps of:
(I) Mixing silicon metal powder, silicon carbide, bentonite, a sintering aid (aluminum hydroxide and strontium oxide mass ratio of 1: 70:1:1.2:1.4:4.8:6.6 were mixed.
(II) kneading the mixture in the step I, pugging, ageing, extruding and drying.
(III) degreasing and sintering (1450 ℃) the unit strip in the step (II).
(IV) carrying out 1250 ℃ oxidation treatment on the sintered unit strip.
And (V) splicing, grinding, skin grafting and coding the unit strips in the step (IV).
The microstructure of the obtained honeycomb structure is schematically shown in fig. 1, and its microscopic view is shown in fig. 2.
Examples 2 to 11
Honeycomb structures were obtained according to the raw materials of table 1 (raw materials and amounts not mentioned in table 1 were the same as those of example 1) and the same production method as that of example 1.
Comparative examples 1 to 4
Honeycomb structures were obtained according to the raw materials of table 1 (raw materials and amounts not mentioned in table 1 were the same as those of example 1) and the same production method as that of example 1.
Comparative example 5
This comparative example provides a honeycomb structure, which was prepared from the same raw materials as in example 1 by the following method:
mixing the raw materials, kneading, pugging, ageing, extruding and drying;
and (3) degreasing and sintering the unit strip obtained in the previous step, then oxidizing at 800 ℃, and finally splicing, grinding, skin grafting and code printing.
TABLE 1
Performance testing
The honeycomb structures obtained in examples 1 to 11 and comparative examples 1 to 5 were subjected to the following performance tests, and the results are shown in table 2.
(1) Three-point bending strength (i.e., B-axis bending strength): the test method is GB-T6569-2006;
(2) Porosity: JC/T2396-2017 diesel particulate trap is specified by wall-flow honeycomb ceramics;
the test of the ceramic tile test method No. 3 of GB/T3810.3-2006 tests the determination of water absorption, apparent porosity, apparent relative density and volume weight;
(3) Median pore diameter: JC/T2396-2017 specification of the diesel engine particle collector by wall-flow honeycomb ceramics;
GB/T21650.1-2008 mercury porosimetry and gas adsorption methods determine solid material pore size distribution and porosity part 1: mercury intrusion method' detection;
(4) Isolated pore volume: drying, grinding and crushing the sample used in the porosity test in the step (2); the measurement was carried out again in accordance with the same standards (stipulated in JC/T2396-2017 wall-flow honeycomb ceramics for diesel particulate traps; "measurement of Water absorption, apparent porosity, apparent relative density and volume weight in section 3 of the GB/T3810.3-2006 ceramic tile test method"). Volume V of powder obtained at this stage 1 Except (2) the unit strip volume V obtained by the porosity test 2 Obtaining the solid rate; isolated pore volume = V 2 * (1-porosity-solid content).
(5) Ratio of through holes to total pore volume: hole(s)Void fraction by volume of cell bar V 2 V (porosity. Cell bar volume V) 2 + isolated pore volume).
(6) Back pressure: back pressure tester with test flow rate of 800m 3 /h。
TABLE 2
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (10)
1. A honeycomb structure characterized by having a porosity of 36% or more and being divided into through holes and isolated holes, wherein the volume of the through holes accounts for 72% or more of the total pore volume.
2. The honeycomb structure according to claim 1, wherein the raw materials of the honeycomb structure comprise metal silicon powder and silicon carbide, wherein the mass of the metal silicon powder is 10-30% of the mass of the silicon carbide, the particle size of the silicon carbide raw material is 21-48 μm, the sphericity of the silicon carbide raw material is greater than 0.78, the particle size of the metal silicon powder is 5-12 μm, and the sphericity of the silicon carbide raw material is greater than 0.65.
3. The honeycomb structure according to claim 2, wherein the mass of the metal silicon powder is 18 to 21% of the mass of the silicon carbide, and the particle size of the silicon carbide raw material is 28 to 40 μm.
4. The honeycomb structure according to claim 2 or 3, wherein the raw material is sintered and then subjected to oxidation treatment at 1250 ± 10 ℃.
5. The honeycomb structure of claim 2 or 3, wherein the raw materials further comprise bentonite, a sintering aid, a lubricant, a binder, and water.
6. The honeycomb structure according to claim 5, wherein the sintering aid is one or more of aluminum hydroxide, strontium oxide, and magnesium carbonate;
and/or the lubricant is one or more of glycerol, lauric acid and tall oil;
and/or the adhesive is one or more of methyl cellulose and polyvinyl alcohol.
7. The honeycomb structure according to claim 1, wherein the median pore diameter of the through holes is 10 to 13 μm.
8. The honeycomb structure according to claim 1, wherein the B-axis bending strength of the honeycomb structure is not less than 15MPa;
and/or the thermal conductivity of the honeycomb structure is more than or equal to 20W/mK.
9. The method for producing the honeycomb structure according to any one of claims 1 to 8, characterized by comprising the steps of:
mixing the raw materials, processing the obtained mixed material to obtain cell unit strips, degreasing and sintering the cell unit strips, then carrying out oxidation treatment at 1250 +/-10 ℃, and splicing the obtained cell unit strips to obtain the honeycomb structure.
10. A particle trap comprising the honeycomb structure of any one of claims 1-8.
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Cited By (1)
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CN117720334A (en) * | 2024-01-30 | 2024-03-19 | 山东奥福环保科技股份有限公司 | High-porosity, thin-wall and high-strength honeycomb ceramic and preparation method and application thereof |
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CN111747751A (en) * | 2019-03-28 | 2020-10-09 | 日本碍子株式会社 | Ceramic porous body, method for producing same, and filter for dust collection |
CN113443914A (en) * | 2020-03-25 | 2021-09-28 | 日本碍子株式会社 | Method for producing silicon carbide-containing honeycomb structure |
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JP2005262831A (en) * | 2004-03-22 | 2005-09-29 | Ngk Insulators Ltd | Honeycomb structure and its manufacturing method |
CN101274293A (en) * | 2007-02-09 | 2008-10-01 | 揖斐电株式会社 | Honeycomb structure and exhaust gas treatment device |
CN101538147A (en) * | 2008-03-19 | 2009-09-23 | 日本碍子株式会社 | Drying method of formed ceramic article |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN117720334A (en) * | 2024-01-30 | 2024-03-19 | 山东奥福环保科技股份有限公司 | High-porosity, thin-wall and high-strength honeycomb ceramic and preparation method and application thereof |
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