WO2010146954A1 - Filtre céramique permettant de supporter un catalyseur et son procédé de fabrication - Google Patents

Filtre céramique permettant de supporter un catalyseur et son procédé de fabrication Download PDF

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Publication number
WO2010146954A1
WO2010146954A1 PCT/JP2010/058271 JP2010058271W WO2010146954A1 WO 2010146954 A1 WO2010146954 A1 WO 2010146954A1 JP 2010058271 W JP2010058271 W JP 2010058271W WO 2010146954 A1 WO2010146954 A1 WO 2010146954A1
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Prior art keywords
ceramic filter
catalyst
supporting
aluminum titanate
sintered body
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PCT/JP2010/058271
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English (en)
Japanese (ja)
Inventor
伸樹 糸井
宏仁 森
隆寛 三島
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大塚化学株式会社
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Publication of WO2010146954A1 publication Critical patent/WO2010146954A1/fr

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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
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24494—Thermal expansion coefficient, heat capacity or thermal conductivity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • B01D39/2072—Other inorganic materials, e.g. ceramics the material being particulate or granular
    • B01D39/2075—Other inorganic materials, e.g. ceramics the material being particulate or granular sintered or bonded by inorganic agents
    • 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
    • B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/2429—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
    • 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
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2455—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the whole honeycomb or segments
    • 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
    • B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2482—Thickness, height, width, length or diameter
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/478—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on aluminium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0006—Honeycomb structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0471—Surface coating material
    • B01D2239/0478—Surface coating material on a layer of the filter
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
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    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • 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
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
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    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
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Definitions

  • the present invention relates to a catalyst-supporting ceramic filter using aluminum titanate and a method for producing the same.
  • Aluminum titanate is expected to be a porous material used in automobile exhaust gas treatment catalyst carriers, diesel particulate filters (DPFs), etc. because of its low thermal expansion, excellent thermal shock resistance, and high melting point. Development is underway.
  • Patent Document 1 an aluminum titanate sintered body having high strength and less mechanical strength deterioration with respect to repeated thermal history is obtained without impairing the high melting point and low thermal expansion property of aluminum titanate. Therefore, it has been proposed to sinter aluminum titanate added with magnesium oxide and silicon oxide.
  • Patent Document 2 discloses that an exhaust gas filter is manufactured using columnar aluminum titanate, and when the longitudinal direction of the columnar particles has a negative thermal expansion coefficient, the direction perpendicular to the longitudinal direction is positive thermal expansion. It has been proposed to manufacture an exhaust gas filter that has a coefficient or a negative thermal expansion coefficient in the direction perpendicular to the longitudinal direction when the longitudinal direction of the columnar particles has a positive thermal expansion coefficient.
  • a film made of inorganic fine particles such as alumina is provided on the surface of the ceramic filter in order to increase the specific surface area.
  • the inorganic fine particle film is generally formed by applying a solution containing inorganic fine particles.
  • the inorganic fine particles enter the structural minute cracks of aluminum titanate. There was a problem.
  • the microcrack contributes to the low thermal expansibility of aluminum titanate. When inorganic fine particles enter the microcrack, there is a problem that the low thermal expansibility of aluminum titanate cannot be obtained.
  • Patent Document 3 in order to solve the above-described problem, before the inorganic fine particle film is provided, a precoat treatment is performed, and the precoat is filled in the minute cracks of the aluminum titanate, so that the inorganic fine particles are formed. It has been proposed to prevent entry into microcracks.
  • An object of the present invention is to provide a ceramic filter for supporting a catalyst that can obtain a low thermal expansion coefficient without requiring a pre-coating treatment before forming an inorganic fine particle film, and a method for producing the same.
  • the ceramic filter body is formed using aluminum titanate having an average aspect ratio of 1.3 or more.
  • aluminum titanate having an average aspect ratio of 1.3 or more it has a low thermal expansion coefficient even when an inorganic fine particle film is directly provided on the surface of the ceramic filter body without forming a precoat film.
  • a ceramic filter for supporting a catalyst can be obtained.
  • the aluminum titanate used for forming the ceramic filter body is a columnar aluminum titanate having an average aspect ratio of 1.3 or more.
  • the average aspect ratio of the aluminum titanate used in the present invention is more preferably 1.5 or more, and the upper limit value of the average aspect ratio is not particularly limited, but is generally 5 or less.
  • the inorganic fine particle film provided on the surface of the ceramic filter body is preferably in the range of 5 to 50 parts by weight, more preferably in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the ceramic filter body. .
  • Examples of the inorganic fine particles forming the inorganic fine particle film include alumina and zirconia.
  • the average particle size of the inorganic fine particles is preferably in the range of 0.1 to 5 ⁇ m.
  • the inorganic fine particle film can be formed by applying a solution such as a sol containing inorganic fine particles.
  • the catalyst-supporting ceramic filter of the present invention can be used with a catalyst such as silver supported on the surface thereof.
  • the number average minor axis diameter of the columnar aluminum titanate is preferably 10 ⁇ m or less.
  • the number average minor axis diameter is more preferably in the range of 5 to 10 ⁇ m.
  • the number average major axis diameter is preferably in the range of 7 to 17 ⁇ m.
  • the number average major axis diameter and the number average minor axis diameter of the columnar aluminum titanate can be measured by, for example, a flow type particle image analyzer.
  • a method for producing the columnar aluminum titanate of the present invention there is a method comprising a step of mixing a raw material containing a titanium source, an aluminum source and a magnesium source while pulverizing them into mechanochemicals, and a step of firing the pulverized mixture.
  • a method for producing the columnar aluminum titanate of the present invention there is a method comprising a step of mixing a raw material containing a titanium source, an aluminum source and a magnesium source while pulverizing them into mechanochemicals, and a step of firing the pulverized mixture.
  • the temperature for firing the pulverized mixture is preferably a temperature in the range of 1300 to 1600 ° C. By firing within such a temperature range, the columnar aluminum titanate of the present invention can be produced more efficiently.
  • Calcination time is not particularly limited, but it is preferably performed within a range of 0.5 hours to 20 hours.
  • Mechanochemical crushing includes a method of crushing while giving a physical impact. Specifically, pulverization by a vibration mill can be mentioned. By pulverizing with a vibration mill, the disruption of atomic arrangement and the decrease in interatomic distance occur simultaneously due to the shear stress caused by the grinding of the mixed powder, resulting in atomic movement of the contact part of different particles, resulting in a metastable phase. Can be obtained. Thereby, a pulverized mixture with high reaction activity is obtained, and the columnar aluminum titanate of the present invention can be produced by firing the pulverized mixture with high reaction activity.
  • the mechanochemical pulverization in the present invention is generally performed as a dry process without using water or a solvent.
  • the mixing treatment time by mechanochemical pulverization is not particularly limited, but generally it is preferably within the range of 0.1 to 6 hours.
  • the raw materials used in the present invention include a titanium source, an aluminum source, and a magnesium source.
  • a titanium source a compound containing titanium oxide can be used. Specific examples include titanium oxide, rutile ore, titanium hydroxide wet cake, and hydrous titania.
  • the aluminum source a compound that generates aluminum oxide by heating can be used.
  • Specific examples include aluminum oxide, aluminum hydroxide, and aluminum sulfate. Among these, aluminum oxide is particularly preferably used.
  • magnesium source a compound that generates magnesium oxide by heating can be used, and specific examples include magnesium hydroxide, magnesium oxide, and magnesium carbonate. Among these, magnesium hydroxide and magnesium oxide are particularly preferably used.
  • the magnesium source is preferably contained in the raw material so as to be within the range of 0.5 to 2.0% by weight in terms of the respective oxides with respect to the total of the titanium source and the aluminum source. If it is less than 0.5% by weight, a sintered body having a low coefficient of thermal expansion and high mechanical strength may not be obtained. On the other hand, if it exceeds 2.0% by weight, columnar aluminum titanate having an average aspect ratio of 1.3 or more may not be obtained.
  • the raw material may further contain a silicon source.
  • Examples of the silicon source include silicon oxide and silicon. Among these, silicon oxide is particularly preferably used.
  • the content of the silicon source in the raw material is preferably in the range of 0.5 to 10% by weight in terms of the respective oxides with respect to the total of the titanium source and the aluminum source. By setting it within such a range, columnar aluminum titanate can be more stably produced.
  • the thermal expansion coefficient between 30 and 800 ° C. in the extrusion direction of the ceramic filter body is 0.5 ⁇ 10 ⁇ 6 / ° C. or less, and the C-axis crystal orientation ratio with respect to the extrusion direction is 0.75.
  • the above is preferable.
  • the thermal expansion coefficient is 0.5 ⁇ 10 ⁇ 6 / ° C. or less, it is possible to obtain characteristics excellent in thermal shock resistance.
  • the lower limit value of the thermal expansion coefficient is not particularly limited, but is generally at least ⁇ 1.0 ⁇ 10 ⁇ 6 / ° C.
  • the thermal expansion coefficient in the extrusion direction can be reduced.
  • the crystal orientation ratio of the C axis with respect to the filter body extrusion direction in the present invention can be obtained from the following equation.
  • C-axis crystal orientation ratio in the filter body extrusion direction A / (A + B)
  • A: C-axis orientation in the filter body extrusion direction I 002 / (I 002 + I 230 )
  • B: Degree of C-axis orientation in the vertical direction of the filter body I 002 / (I 002 + I 230 )
  • I 002 and I 230 are the extrusion surface for extrusion direction, the peak intensity of the (002) plane when the X-ray diffraction vertical plane in the vertical direction (I 002) and (230) plane peak intensity (I 230 ).
  • the C axis extends along the longitudinal direction of the columnar body. For this reason, when the filter body is extruded, the C-axis is aligned in the extrusion direction, so that the thermal expansion coefficient in the extrusion direction can be lowered.
  • the method for producing a ceramic filter for supporting a catalyst comprises a step of producing a ceramic filter body by extruding and then firing the raw material containing the columnar aluminum titanate, and an inorganic material on the surface of the ceramic filter body. And a step of forming a fine particle film.
  • the raw material containing aluminum titanate can be prepared by adding, for example, a pore-forming agent, a binder, a dispersant, and water to aluminum titanate.
  • This raw material is molded into a honeycomb structure using, for example, an extrusion molding machine, plugged on one side so that the cell openings have a checkered pattern, and then dried to obtain a molded body obtained.
  • the ceramic filter body can be manufactured by firing. Examples of the firing temperature include 1400 to 1600 ° C.
  • Examples of pore-forming agents include graphite, graphite, wood powder, and polyethylene.
  • Examples of the binder include methyl cellulose, ethyl cellulose, and polyvinyl alcohol.
  • Examples of the dispersant include fatty acid soap and ethylene glycol. The amount of pore-forming agent, binder, dispersant, and water can be adjusted as appropriate.
  • an inorganic fine particle film is formed on the surface of the ceramic filter body.
  • the inorganic fine particle film can be formed by applying a solution containing inorganic fine particles.
  • the film containing inorganic fine particles include a sol solution.
  • a ceramic filter for supporting a catalyst having a low coefficient of thermal expansion can be obtained without requiring a precoat treatment before forming an inorganic fine particle film.
  • FIG. 1 is a scanning electron micrograph showing columnar aluminum titanate obtained in an example according to the present invention.
  • FIG. 2 is a perspective view showing the honeycomb sintered body.
  • FIG. 3 is a perspective view showing a measurement sample cut out from the honeycomb sintered body.
  • FIG. 4 is a schematic diagram for explaining a method for measuring the bending strength of a honeycomb sintered body.
  • FIG. 5 is a perspective view showing a measurement sample cut out from the honeycomb sintered body.
  • FIG. 6 is a perspective view showing a honeycomb sintered body.
  • FIG. 7 is a perspective view showing a measurement sample for measuring the X-ray diffraction of the extruded surface cut out from the honeycomb sintered body.
  • FIG. 8 is a perspective view showing a honeycomb sintered body.
  • FIG. 9 is a perspective view showing a measurement sample for measuring X-ray diffraction of a vertical plane cut out from the honeycomb sintered body.
  • FIG. 10 is an X-ray diffraction chart of the columnar aluminum titanate obtained in Example 1 according to the present invention.
  • Example 1 [Production of aluminum titanate] 360.0 g of titanium oxide, 411.1 g of aluminum oxide, 9.7 g of magnesium hydroxide, and 19.0 g of silicon oxide were mixed for 2.0 hours while being pulverized with a vibration mill.
  • FIG. 1 is an SEM photograph showing the aluminum titanate obtained in this example. As shown in FIG. 1, it can be seen that the aluminum titanate obtained in this example has a columnar shape.
  • FIG. 10 is a view showing an X-ray diffraction chart of aluminum titanate obtained in this example.
  • honeycomb sintered body Using the aluminum titanate obtained in the above example, a honeycomb sintered body was manufactured as follows.
  • the obtained clay is extruded to form a honeycomb structure with an extrusion molding machine, and then dried with a hot air dryer, and then the resulting molded body is fired at 1500 ° C. to form a ceramic filter body.
  • a honeycomb sintered body was obtained.
  • FIG. 2 is a perspective view showing the honeycomb sintered body. As shown in FIG. 2, the honeycomb sintered body 1 has 8 ⁇ 8 cells, and the end surface 1a has a size of 1.8 cm in length and 1.8 cm in width. An arrow A indicates the extrusion direction, and an arrow B indicates a direction perpendicular to the extrusion direction A.
  • the porosity was measured by cutting a portion corresponding to 2 ⁇ 2 cells from the center portion 2 of the above 8 ⁇ 8 cell honeycomb sintered body 1 so that the length along the extrusion direction A was about 2 cm. It was.
  • FIG. 3 is a perspective view showing the measurement sample 3. Using the measurement sample 3 shown in FIG. 3, the porosity was measured according to JIS R1634.
  • the length along the extrusion direction A from the central portion 2 of the 8 ⁇ 8 cell honeycomb sintered body 1 is about 2 cm. It cut out so that it might become, and it was set as the measurement sample 3. As shown in FIG. 5, the linear expansion coefficient in the extrusion direction A of the measurement sample 3 was measured according to JIS R1618.
  • Crystal orientation ratio The C-axis crystal orientation ratio of the obtained honeycomb sintered body was measured as the crystal orientation ratio.
  • the crystal orientation ratio was calculated from the crystal orientation degree in the extrusion direction and the crystal orientation degree in the direction perpendicular to the extrusion direction (vertical crystal orientation degree) as shown in the following formula.
  • Crystal orientation ratio Crystal orientation in extrusion direction / (Crystal orientation in extrusion direction + Crystal orientation in vertical direction)
  • the degree of crystal orientation was determined by X-ray diffraction.
  • the crystal orientation degree in the vertical direction was calculated by measuring X-ray diffraction of the vertical surface of the honeycomb sintered body and obtaining I (002) and I (230) in the same manner as described above.
  • 6 and 7 are perspective views showing the production of a measurement sample for measuring the X-ray diffraction of the extruded surface.
  • the region 4 including the end face 1a of the honeycomb sintered body 1 was cut out to prepare a measurement sample shown in Fig. 7.
  • the measurement sample 5 shown in FIG. 7 the X-ray diffraction of the extruded surface 5a of the measurement sample 5 was measured.
  • FIG 8 and 9 are perspective views showing the production of a sample for measuring X-ray diffraction on a vertical plane, that is, a plane perpendicular to the extrusion plane.
  • a region 6 corresponding to 8 ⁇ 2 cells of the honeycomb sintered body 1 was cut out along the extrusion direction A to obtain a measurement sample 7 shown in FIG.
  • the measurement of the X-ray diffraction of the surface (extruded surface) 7a along the extrusion direction A of the measurement sample 7 was performed.
  • the (002) plane is a plane perpendicular to the C axis, and the high strength of the (002) plane means that the C axis is oriented.
  • honeycomb sintered body (ceramic filter main body) was dipped in alumina sol, then pulled up and dried at 110 ° C. for 3 hours. Then, it baked at 500 degreeC with the electric furnace for 1 hour, and formed the alumina coating film on the surface of a honeycomb sintered compact.
  • the formed alumina coating film was 15 parts by weight with respect to 100 parts by weight of the honeycomb sintered body in terms of Al 2 O 3 . Therefore, the alumina coating amount was 15% by weight.
  • the alumina sol was prepared by stirring a slurry of 25% by weight of alumina, 10% by weight of water-soluble cellulose and 65% by weight of deionized water for 1 hour.
  • the average particle size of alumina was 0.15 ⁇ m.
  • the thermal expansion coefficient of the catalyst-supporting ceramic filter obtained as described above was measured in the same manner as described above. The measurement results are shown in Table 1.
  • Example 2 [Production of aluminum titanate] 354.7 g of titanium oxide, 405.0 g of aluminum oxide, 21.3 g of magnesium hydroxide, and 19.0 g of silicon oxide were mixed for 2.0 hours while being pulverized with a vibration mill.
  • honeycomb sintered bodies Using the aluminum titanate obtained in the above example, a honeycomb sintered body was produced in the same manner as in Example 1, and the obtained honeycomb sintered body was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
  • Example 1 [Production of aluminum titanate and honeycomb sintered body] A honeycomb sintered body (ceramic filter body) was manufactured in the same manner as in Example 1 by using aluminum titanate obtained in the same manner as in Example 1.
  • honeycomb sintered body (ceramic filter main body) was immersed in a 10% by weight polyvinyl alcohol aqueous solution, taken out, dried at 110 ° C. for 3 hours, and precoated.
  • the polymer coating film was formed so that the amount of the polymer coating film as the precoat treatment was 5 parts by weight with respect to 100 parts by weight of the honeycomb sintered body. Therefore, the polymer coating amount is 5% by weight.
  • the honeycomb sintered body subjected to the pre-coating treatment was immersed in alumina sol in the same manner as in Example 1 to form an alumina coating, and a catalyst-supporting ceramic filter was produced.
  • the coefficient of thermal expansion of the obtained catalyst-carrying ceramic filter was measured in the same manner as described above, and the measurement results are shown in Table 1.
  • Example 2 The honeycomb sintered body obtained in Example 2 was pre-coated in the same manner as in Comparative Example 1, and then an alumina coating film was formed to produce a catalyst-supporting ceramic filter.
  • honeycomb sintered bodies A honeycomb sintered body was manufactured and evaluated in the same manner as in Example 1 except that the aluminum titanate obtained in this comparative example was used.
  • the thermal expansion coefficient of the catalyst-supporting ceramic filter was measured, and the measurement results are shown in Table 1.
  • Comparative Example 4 A honeycomb sintered body was manufactured in the same manner as in Comparative Example 3. The resulting honeycomb sintered body was pre-coated in the same manner as in Comparative Example 1, and then an alumina coating film was formed to produce a catalyst-supporting ceramic filter.
  • Table 1 shows the coefficient of thermal expansion of the ceramic filter for catalyst support.
  • the catalyst-supporting ceramic filters of Examples 1 and 2 according to the present invention have a thermal expansion coefficient close to 0, which is a preferable thermal expansion coefficient as a catalyst-supporting ceramic filter, without performing pre-coating treatment. Is shown. This is because, by using columnar aluminum titanate having an aspect ratio of 1.3 or more, the thermal expansion coefficient in the extrusion direction of the ceramic filter body can be lowered, so that micro cracks of the aluminum titanate (microcracks) This is because even if alumina enters, a low thermal expansion coefficient close to 0 can be obtained.
  • Honeycomb sintered body (ceramic filter body) DESCRIPTION OF SYMBOLS 1a ... End face of honeycomb sintered body 2 ... Center part of honeycomb sintered body 3 ... Measurement sample cut out from honeycomb sintered body 4 ... Area near end face of honeycomb sintered body 5 ... Extruded surface of honeycomb sintered body X Sample for measuring line diffraction 5a ... extruded surface 6 ... 8 ⁇ 2 cell region of honeycomb sintered body 7 ... Sample for measuring X-ray diffraction of vertical surface of honeycomb sintered body 7a ... vertical surface 10 ... pressing bar 11,12 ... support point

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Geometry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Filtering Materials (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Catalysts (AREA)

Abstract

L'invention porte sur un filtre céramique permettant de supporter un catalyseur, permettant d'obtenir un faible coefficient de dilatation thermique sans avoir besoin d'un enrobage préalable avant la formation d'un film particulaire inorganique. L'invention porte également sur un procédé permettant de fabriquer ledit filtre céramique. Le filtre céramique de l'invention permettant de supporter un catalyseur sur la surface de filtre est caractérisé par l'obtention : d'un corps de filtre céramique formé à partir d'un titanate d'aluminium ayant un rapport de forme moyen (la longueur moyenne en nombre du grand axe divisée par la longueur moyenne en nombre du petit axe) d'au moins 1,3 ; et un film particulaire inorganique formé directement sur la surface du corps de filtre céramique afin d'augmenter sa surface spécifique.
PCT/JP2010/058271 2009-06-19 2010-05-17 Filtre céramique permettant de supporter un catalyseur et son procédé de fabrication WO2010146954A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010285295A (ja) * 2009-06-09 2010-12-24 Otsuka Chem Co Ltd 柱状チタン酸アルミニウム及びその製造方法並びにハニカム構造体
JP2010285294A (ja) * 2009-06-09 2010-12-24 Otsuka Chem Co Ltd 柱状チタン酸アルミニウム及びその製造方法並びにハニカム構造体
WO2012046577A1 (fr) * 2010-10-04 2012-04-12 大塚化学株式会社 Filtre d'épuration de gaz d'échappement, et son procédé de production
WO2018061958A1 (fr) * 2016-09-30 2018-04-05 住友理工株式会社 Procédé de développement et dispositif de développement de plaque d'impression

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014014059A1 (fr) * 2012-07-20 2014-01-23 住友化学株式会社 Filtre en nid-d'abeilles

Citations (2)

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Publication number Priority date Publication date Assignee Title
JP2008043852A (ja) * 2006-08-11 2008-02-28 Tokyo Yogyo Co Ltd セラミックスフィルタ
JP2008272737A (ja) * 2007-03-30 2008-11-13 Ibiden Co Ltd ハニカムフィルタ

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008043852A (ja) * 2006-08-11 2008-02-28 Tokyo Yogyo Co Ltd セラミックスフィルタ
JP2008272737A (ja) * 2007-03-30 2008-11-13 Ibiden Co Ltd ハニカムフィルタ

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010285295A (ja) * 2009-06-09 2010-12-24 Otsuka Chem Co Ltd 柱状チタン酸アルミニウム及びその製造方法並びにハニカム構造体
JP2010285294A (ja) * 2009-06-09 2010-12-24 Otsuka Chem Co Ltd 柱状チタン酸アルミニウム及びその製造方法並びにハニカム構造体
WO2012046577A1 (fr) * 2010-10-04 2012-04-12 大塚化学株式会社 Filtre d'épuration de gaz d'échappement, et son procédé de production
WO2018061958A1 (fr) * 2016-09-30 2018-04-05 住友理工株式会社 Procédé de développement et dispositif de développement de plaque d'impression

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