WO2017061382A1 - Honeycomb filter - Google Patents
Honeycomb filter Download PDFInfo
- Publication number
- WO2017061382A1 WO2017061382A1 PCT/JP2016/079316 JP2016079316W WO2017061382A1 WO 2017061382 A1 WO2017061382 A1 WO 2017061382A1 JP 2016079316 W JP2016079316 W JP 2016079316W WO 2017061382 A1 WO2017061382 A1 WO 2017061382A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ceramic
- coat layer
- ceramic coat
- honeycomb structure
- honeycomb filter
- Prior art date
Links
- 239000000919 ceramic Substances 0.000 claims abstract description 139
- 230000002093 peripheral effect Effects 0.000 claims abstract description 13
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 45
- 239000011148 porous material Substances 0.000 claims description 21
- 239000011247 coating layer Substances 0.000 abstract description 7
- 238000005524 ceramic coating Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 64
- 238000000034 method Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000005350 fused silica glass Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
Definitions
- the present invention relates to a honeycomb filter.
- a honeycomb filter comprising a porous ceramic honeycomb structure and a columnar core portion having a sealing portion, and a porous ceramic coat layer provided on the outer peripheral surface of the core portion It has been known. When the ceramic coat layer is provided, the strength of the honeycomb filter can be improved.
- a honeycomb filter there is a case of loading a catalyst on pore surfaces of the porous ceramic honeycomb structural body for the purpose of reduction of promoting or NO x soot combustion.
- the filter When a catalyst is supported, the filter is often dipped in an aqueous slurry containing a catalyst component (including a precursor) and a catalyst support, and then the slurry is dried.
- the catalyst is also supported on the ceramic coat layer. Since the ceramic coat layer does not function as a filter, it is not necessary to support a catalyst from the beginning, and the catalyst often contains relatively expensive raw materials such as noble metals and zeolite, which causes an increase in cost.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a honeycomb filter capable of suppressing catalyst loading on a ceramic coat layer.
- the honeycomb filter according to the present invention includes a columnar core portion and a porous ceramic coat layer provided on the outer peripheral surface of the core portion.
- the core portion includes a porous ceramic honeycomb structure having a plurality of channels, one end of a part of the plurality of channels, and the remaining channel in the plurality of channels. And a plurality of sealing portions for closing the other end.
- the loss on ignition Lc means the amount of mass reduction after the ignition test per unit mass of the ceramic coat layer
- the specific surface area Sc means the surface area per unit mass of the ceramic coat layer
- Lc / Sc is the surface area per unit area of the ceramic coat layer. This means the amount of mass reduction after the ignition test.
- the amount of loss on ignition of the ceramic coat layer has a correlation with the amount of surface hydroxyl groups of the ceramic before the ignition test, and the amount of hydroxyl groups has a correlation with high hydrophilicity.
- the expression (1) is satisfied, that is, the loss on ignition per surface area of the ceramic coat layer is sufficiently small, so that the amount of surface hydroxyl groups per surface area of the ceramic coat layer is sufficiently small as compared with the prior art. Therefore, the liquid absorption amount of the aqueous slurry of the ceramic coat layer can be reduced.
- the ceramic coat layer can contain fused ceramic particles such as fused silica particles and fused alumina particles.
- the ceramic coat layer may include fibrous ceramic particles.
- honeycomb filter can further include a catalyst supported on the ceramic honeycomb structure.
- FIG. 1 is a schematic cross-sectional view of a honeycomb filter according to an embodiment of the present invention.
- the honeycomb filter 300 includes a core part 100 and a ceramic coat layer 200.
- the core part 100 has a column shape and has an inlet end face (one end face) 100a and an outlet end face (the other end face) 100b.
- the core part 100 has a porous ceramic honeycomb structure 120 and a plurality of sealing parts 130.
- the ceramic honeycomb structure 120 includes a plurality of inlet channels (a plurality of first channels) 110a and a plurality of outlet channels (a plurality of second channels) 110b.
- the cross-sectional shapes of the inlet channel 110a and the outlet channel 110b can be, for example, a circle, an ellipse, a quadrangle, a hexagon, and an octagon.
- the ceramic honeycomb structure 120 functions as a partition wall that separates the inlet channel 110a and the outlet channel 110b adjacent to each other.
- Each inlet channel 110a is opened at the inlet end surface 100a and sealed by the sealing portion 130 at the outlet end surface 100b.
- Each outlet channel 110b is opened at the outlet end surface 100b and sealed by the sealing portion 130 at the inlet end surface 100a.
- the sealing portion 130 has a plug shape, but the sealing portion 130 may be formed by deforming a part of the ceramic honeycomb structure 120 (for example, a conical shape portion).
- Examples of the ceramic of the core part are an aluminum titanate ceramic, a silicon carbide ceramic, and a cordierite ceramic.
- the aluminum titanate-based ceramic can contain magnesium, silicon, and the like.
- the ceramic may contain trace components derived from raw materials or trace components inevitably contained in the production process.
- the porosity of the ceramic honeycomb structure 120 can be 50 to 75%.
- the porosity is preferably 55 to 70%, more preferably 55 to 65% in order to maintain the pressure loss performance and improve the catalyst activity. If the porosity exceeds 75%, the strength of the ceramic honeycomb structure 120 may decrease.
- the porosity can be measured by mercury porosimetry.
- the cell density can be, for example, 35 to 80 cells / cm 2 .
- the ceramic coat layer 200 is provided on the outer peripheral surface of the core part 100.
- the ceramic coat layer 200 can be provided over the entire circumference on the outer peripheral surface.
- the thickness of the ceramic coat layer 200 can be set to 0.2 to 2.0 mm, for example.
- the ceramic coat layer 200 may have ceramic particles and an inorganic binder that binds them.
- the ceramic coat layer can be porous.
- the porosity of the ceramic coat layer 200 is smaller than that of the ceramic honeycomb structure and can be 10 to 40%.
- Examples of the ceramic of the ceramic coat layer 200 are, for example, alumina, silica, aluminum titanate, cordierite, and the like. It may be the same as or different from the ceramic of the core part 100.
- Ceramic particles examples include non-fibrous particles (ratio of major axis to minor axis (aspect ratio) of less than 3 times) and fibrous particles (ratio of major axis to minor axis (aspect ratio) of 3 times). Above). When fibrous ceramic particles are included, mechanical strength (Young's modulus) can be improved.
- An example of the particle size of the non-fibrous particles (D50 of the volume-based particle size distribution by a laser diffraction particle size distribution measuring device) can be 2 to 30 ⁇ m.
- the major axis of the fibrous particles can be 10 to 200 ⁇ m, and the minor axis can be 2 to 10 ⁇ m.
- the aspect ratio of the fibrous particles can be 3-100.
- the ratio of the mass of fibrous particles to the mass of all ceramic particles can be 5 to 25%.
- the ceramic particles can include, for example, fused ceramic particles such as fused alumina and fused silica as non-fibrous particles. Since the molten ceramic particles are melted at, for example, 2000 ° C. or higher, the amount of surface hydroxyl groups is small.
- Examples of the inorganic binder are colloidal silica, alumina sol, titania sol, water glass, hydraulic alumina, ⁇ -alumina, boehmite alumina, alumina cement, and Portland cement.
- the amount of the inorganic binder can be 3 to 30 parts by weight with respect to 100 parts by weight of the ceramic particles.
- the ceramic coat layer when the specific surface area and the loss on ignition of the ceramic coat layer are Sc (m 2 / g) and Lc ( ⁇ ), respectively, the ceramic coat layer satisfies the formula (1).
- the loss on ignition is the rate of decrease in mass before and after the heat treatment of the object, and in this embodiment, there is a correlation with the amount of hydroxyl groups in the object.
- the conditions for the heat treatment are 2 hours at 1100 ° C. in an air atmosphere.
- the specific surface area can be measured by a mercury intrusion method.
- the measurement conditions can be a maximum pressure of 414 Mpa (60,000 psia).
- Lc means the amount of mass reduction after the ignition test per unit mass of the ceramic coat layer
- specific surface area Sc means the surface area per unit mass of the ceramic coat layer
- Lc / Sc is the surface area per unit area of the ceramic coat layer. This means the amount of mass reduction after the ignition test.
- the magnitude of the loss on ignition of the ceramic coat layer is correlated with the amount of surface hydroxyl groups of the ceramic before the ignition test, and the amount of hydroxyl groups is considered to correlate with the hydrophilicity.
- the expression (1) is satisfied, that is, the loss on ignition per surface area of the ceramic coat layer is sufficiently small, so that the amount of surface hydroxyl groups per surface area of the ceramic coat layer is sufficiently small. Therefore, the hydrophilicity of the ceramic coat layer can be reduced, absorption of the aqueous slurry can be suppressed, and catalyst loading on the ceramic coat layer can be suppressed.
- Lc / Sc can be 100 ⁇ 10 ⁇ 5 g / m 2 or less. Further, Lc / Sc can be 1 ⁇ 10 ⁇ 5 g / m 2 or more.
- the expression (2) can be satisfied.
- Dc 0.05 ⁇ m
- the average pore diameter in the range of 0.0018 to 100 ⁇ m of the object is measured by the mercury intrusion method, and the cumulative volume fraction of the pore diameter is 50% in the pore diameter distribution. Obtained by obtaining the pore size. Dc can also be 0.10 ⁇ m or more. When the average pore diameter Dc of the ceramic coat layer 200 is large to some extent, the capillary force may be reduced, which may contribute to a reduction in the suction force of the aqueous slurry.
- Dc can satisfy the formula (2A). Dc ⁇ 5 ⁇ m (2A)
- the specific surface area, loss on ignition, and average pore diameter of the ceramic honeycomb structure 120 can be appropriately set according to desired filtration characteristics and the like.
- the specific surface area and the loss on ignition of the ceramic honeycomb structure 120 are Sh (m 2 / g) and Lh ( ⁇ ), respectively, the ceramic honeycomb structure 120 can satisfy the expression (3).
- the ignition loss Lh means the mass reduction amount after the ignition test per unit mass of the ceramic honeycomb structure 120
- the specific surface area Sh means the surface area per unit mass of the ceramic honeycomb structure 120
- Lh / Sh is It means the amount of mass reduction after the ignition test per surface area of the ceramic honeycomb structure 120. It is preferable that the ceramic honeycomb structure satisfies the formula (3), that is, if the loss of ignition per surface area of the ceramic honeycomb structure 120 is sufficiently large, the ceramic honeycomb structure can easily absorb the aqueous slurry.
- Lh / Sh can be 500 ⁇ 10 ⁇ 5 g / m 2 or more, can be 600 ⁇ 10 ⁇ 5 g / m 2 or more, and can be 700 ⁇ 10 ⁇ 5 g / m 2 or more. And can be 1000 ⁇ 10 ⁇ 5 g / m 2 or less.
- the expression (4) can also be satisfied.
- the water Krem absorbency of the ceramic honeycomb structure 120 defined in JIS P8141: 2004 is As and the water Klem absorbency defined in JIS P8141: 2004 of the ceramic coat layer 200 is Ac
- Ac / As can be 0.3 or less, can be 0.25 or less, and can be 0.2 or less.
- a food red solution was used, and the manufacturer was Ogura Food Chemical Co., Ltd.
- the product name is a red preparation, which is used by dissolving 0.5 g in 100 g of water.
- a green raw material containing a ceramic source, a pore former, an organic binder, a solvent, and an additive added as necessary is prepared to obtain a green ceramic honeycomb structure 120.
- one end of the flow path is blocked by a known method using the same raw material as the green raw material to form the green sealing portion 130 to obtain the green core portion.
- the core part 100 made of ceramic is obtained by firing the green core part. Thereafter, if necessary, processing such as cutting and polishing of the outer peripheral surface of the core portion 100 may be performed.
- a ceramic coat layer 200 is formed on the outer peripheral surface of the core portion 100. Specifically, first, a coating paste containing ceramic particles, an inorganic binder, and a solvent such as water is prepared.
- the raw material of the ceramic coat layer is adjusted so that Lc / Sc of the ceramic coat layer 200 satisfies the formula (1).
- the weight ratio of the binder to the inorganic substance and the particle size of the binder may be adjusted.
- the weight ratio of the binder is increased.
- the loss on ignition for example, a raw material having a small surface hydroxyl group can be used as the ceramic particles of the ceramic coat layer.
- the ceramic particles whose hydroxyl groups are reduced by passing through a high-temperature process are preferable to use at least a part of the ceramic particles whose hydroxyl groups are reduced by passing through a high-temperature process as ceramic particles, but other raw materials having a small amount of hydroxyl groups on the surface can also be used. Further, it is also suitable to further subject the ceramic coat layer using the raw material having a small surface hydroxyl group to a high temperature treatment as described later, and the temperature at that time is usually 400 ° C. or higher, preferably 600 ° C. or higher. More preferably, it is 800 ° C. or higher, and usually 1000 ° C. or lower.
- the average pore diameter Dc of the ceramic coat layer 200 can be adjusted by the particle diameter of the raw material.
- the application method is not particularly limited, and examples thereof include a brush coating method, a roller brush method, and a doctor blade method.
- the coating film is dried and fired as necessary. Drying can be performed by evaporating the solvent in the coating solution at a relatively low temperature of 40 to 200 ° C. In firing, solvent molecules adsorbed on the surface can be removed by treatment at a relatively high temperature of 400 to 1000 ° C. Thereby, a honeycomb filter provided with a core part and a ceramic coat layer is completed.
- One method is a method in which a catalyst support material is supported on the surface of the core portion 100 and then a catalyst is supported on the catalyst support material.
- Another method is a method in which a catalyst support material on which a catalyst is supported is supported on the surface of the core portion 100.
- Still another method is a method of directly supporting the catalyst on the surface of the core portion without supporting the catalyst support material.
- the catalyst support material examples include oxides such as alumina, silica, magnesia, titania, zirconia, ceria, La 2 O 3 , BaO, and zeolite, or composite oxides containing one or more of these.
- the particle size D50 of the catalyst support can be 2 to 5 ⁇ m.
- the catalyst are particles of at least one metal element selected from the group consisting of Pt, Pd, Rh, silver, vanadium, chromium, manganese, iron, cobalt, nickel, and copper, or zeolite catalyst.
- the catalyst support particles may previously carry the catalyst thereon.
- an aqueous slurry containing the catalyst support material and / or the catalyst is prepared, the honeycomb filter is immersed in the aqueous slurry, and then the filter is heated.
- the aqueous slurry may be dried.
- a honeycomb filter carrying a catalyst can be manufactured.
- the honeycomb filter according to the present embodiment since the expression (1) is satisfied, the amount of the catalyst supported on the ceramic coat layer 200 can be reduced. Therefore, the waste of the catalyst can be reduced.
- the present invention is not limited to the above embodiment, and various modifications can be made.
- the ceramic honeycomb structure may not be a cylinder but may be a prism such as a quadrangular prism or a hexagonal prism.
- the arrangement of the flow paths can take various forms such as a triangular arrangement and a square arrangement.
- Example 1 A core portion made of aluminum titanate was prepared. The cross section of each flow path was hexagonal, and the cell density was 380 cpsi. The outer diameter was 25.4 mm and the height was 25.4 mm. The porosity of the ceramic honeycomb structure is 59%, the average pore diameter Dh is 18.12 ⁇ m, the specific surface area Sh is 0.145 m 2 / g, the loss on ignition Lh is 0.12%, and Lh / Sh is 827.6 ⁇ 10 ⁇ It was 5 g / m 2 .
- fused silica particles having a D50 of 5 ⁇ m 170 g of fused silica particles having a D50 of 5 ⁇ m, 30 g of aluminum titanate particles having a D50 of 25 ⁇ m, 20 g of alumina fibers having a major axis of 20 ⁇ m and a minor axis of 4-6 ⁇ m, 22.5 g of colloidal silica having a particle diameter of 12 nm, and 52.5 g of water Were mixed to obtain a coat paste.
- the fused silica particles and aluminum titanate particles are non-fibrous particles.
- This coat paste was applied to the entire outer peripheral surface of the honeycomb structure by a doctor blade method. Thereafter, the coat paste was dried at 150 ° C. and further dried at 1000 ° C. to obtain a honeycomb filter having a core portion and a ceramic coat layer. The weight of the ceramic coat layer adhering to the core portion was 1.46 g.
- the catalyst was supported on the honeycomb filter. Specifically, after stirring 300 g of commercially available ⁇ zeolite into 700 g of pure water, this was pulverized to a mean particle size of 3 ⁇ m with a ball mill to obtain an aqueous slurry, and then a honeycomb filter was dipped in the slurry, Further, it was dried at 500 ° C.
- Example 2 The procedure was the same as Example 1 except that the amount of colloidal silica as an inorganic binder was 33.75 g, the amount of water was 78.75 g, and the drying temperature at the second stage was changed from 1000 ° C. to 700 ° C. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 1.54 g.
- Example 3 Example 2 was the same as Example 1 except that the drying temperature in the second stage was changed from 1000 ° C to 700 ° C.
- the weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.95 g.
- Example 4 The same procedure as in Example 1 was performed except that the drying temperature of the second stage was changed from 1000 ° C. to 450 ° C. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 1.55 g.
- Example 4 was the same as Example 4 except that the thickness of the coat paste applied to the outer peripheral surface of the ceramic honeycomb structure was reduced and the weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.69 g.
- Example 5 Example 5 was repeated except that ⁇ -alumina particles having a D50 of 5 ⁇ m were used instead of fused silica.
- the weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.81 g.
- the ⁇ -alumina particles are neither fibrous particles nor fused ceramic particles.
- Table 1 shows the composition, coating amount, and final drying temperature of the coating paste for forming the ceramic coating layer.
- SYMBOLS 100 ... Core part, 100a ... Inlet end surface (one end surface), 100b ... Outlet end surface (other end surface), 110a ... Inlet flow path (1st flow path), 110b ... Outlet flow path (2nd flow path), 120 ... Ceramic Honeycomb structure, 200 ... ceramic coat layer, 300 ... honeycomb filter.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Structural Engineering (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Filtering Materials (AREA)
Abstract
A honeycomb filter 300 is provided with: a columnar, porous core part 100; and a porous ceramic coating layer 200 provided on the outer peripheral surface of the core part 100. The core part 100 has: a porous ceramic honeycomb structure 120 having a plurality of flow paths; and a plurality of sealing parts 130 for closing one end of some of the plurality of flow paths and the other end of the remaining flow paths of the plurality of flow paths. Letting Sc (m2/g) and Lc (−) be the specific surface area and ignition loss of the ceramic coating layer 200, respectively, Equation (1) is satisfied.
Lc/Sc ≤ 100 × 10-5 g/m2 (1)
Description
本発明は、ハニカムフィルタに関する。
The present invention relates to a honeycomb filter.
従来より、エンジン排ガスのフィルタとして、多孔質のセラミックハニカム構造体及び封口部を有する柱状のコア部と、このコア部の外周面上に設けられた多孔質のセラミックコート層と、を備えるハニカムフィルタが知られている。セラミックコート層を有すると、ハニカムフィルタの強度向上が可能となる。
Conventionally, as a filter for engine exhaust gas, a honeycomb filter comprising a porous ceramic honeycomb structure and a columnar core portion having a sealing portion, and a porous ceramic coat layer provided on the outer peripheral surface of the core portion It has been known. When the ceramic coat layer is provided, the strength of the honeycomb filter can be improved.
このようなハニカムフィルタにおいて、煤燃焼の促進あるいはNOxの低減等を目的として多孔質のセラミックハニカム構造体の細孔表面に触媒を担持する場合がある。触媒を担持する場合には、触媒成分(前駆体含む)及び触媒支持材を含む水系スラリー中にフィルタをディップし、その後スラリーを乾燥させることが多い。
In such a honeycomb filter, there is a case of loading a catalyst on pore surfaces of the porous ceramic honeycomb structural body for the purpose of reduction of promoting or NO x soot combustion. When a catalyst is supported, the filter is often dipped in an aqueous slurry containing a catalyst component (including a precursor) and a catalyst support, and then the slurry is dried.
しかしながら、従来のハニカムフィルタを用いた場合、セラミックコート層にも触媒が担持されてしまう。セラミックコート層はフィルタとして機能しないので触媒を担持する必要が元来無く、さらに、触媒は貴金属やゼオライトなどの比較的高価な原料を含むことが多いのでコスト増の原因となる。
However, when a conventional honeycomb filter is used, the catalyst is also supported on the ceramic coat layer. Since the ceramic coat layer does not function as a filter, it is not necessary to support a catalyst from the beginning, and the catalyst often contains relatively expensive raw materials such as noble metals and zeolite, which causes an increase in cost.
本発明は上記課題に鑑みてなされたものであり、セラミックコート層への触媒の担持を抑制可能なハニカムフィルタを提供することを目的とする。
The present invention has been made in view of the above problems, and an object of the present invention is to provide a honeycomb filter capable of suppressing catalyst loading on a ceramic coat layer.
本発明に係るハニカムフィルタは、柱状のコア部と、前記コア部の外周面上に設けられた多孔質のセラミックコート層と、を備える。前記コア部は、複数の流路を有する多孔質のセラミックハニカム構造体と、前記複数の流路の内の一部の流路の一端、及び、前記複数の流路の内の残部の流路の他端を閉じる複数の封口部と、を有する。
前記セラミックコート層の比表面積、灼熱減量をそれぞれSc(m2/g)、Lc(-)とした時に(1)式を満たす。
Lc/Sc≦100×10-5g/m2 (1) The honeycomb filter according to the present invention includes a columnar core portion and a porous ceramic coat layer provided on the outer peripheral surface of the core portion. The core portion includes a porous ceramic honeycomb structure having a plurality of channels, one end of a part of the plurality of channels, and the remaining channel in the plurality of channels. And a plurality of sealing portions for closing the other end.
When the specific surface area and the loss on ignition of the ceramic coat layer are Sc (m 2 / g) and Lc (−), the formula (1) is satisfied.
Lc / Sc ≦ 100 × 10 −5 g / m 2 (1)
前記セラミックコート層の比表面積、灼熱減量をそれぞれSc(m2/g)、Lc(-)とした時に(1)式を満たす。
Lc/Sc≦100×10-5g/m2 (1) The honeycomb filter according to the present invention includes a columnar core portion and a porous ceramic coat layer provided on the outer peripheral surface of the core portion. The core portion includes a porous ceramic honeycomb structure having a plurality of channels, one end of a part of the plurality of channels, and the remaining channel in the plurality of channels. And a plurality of sealing portions for closing the other end.
When the specific surface area and the loss on ignition of the ceramic coat layer are Sc (m 2 / g) and Lc (−), the formula (1) is satisfied.
Lc / Sc ≦ 100 × 10 −5 g / m 2 (1)
灼熱減量Lcはセラミックコート層単位質量当たりの灼熱試験後の質量減少量を意味し、比表面積Scはセラミックコート層単位質量当たりの表面積を意味するので、Lc/Scは、セラミックコート層の表面積当たりの灼熱試験後の質量減少量を意味する。また、セラミックコート層の灼熱減量の大きさは灼熱試験前のセラミックの表面水酸基の量と相関があり、水酸基の量は親水性の高さと相関があると考えられる。本発明によれば、(1)式を満たす、すなわち、セラミックコート層の表面積当たりの灼熱減量が十分小さいので、セラミックコート層の表面積当たりの表面水酸基の量が従来に比べて十分に小さくなる。したがって、セラミックコート層の水系スラリーの吸液量を低減できる。
Since the loss on ignition Lc means the amount of mass reduction after the ignition test per unit mass of the ceramic coat layer, and the specific surface area Sc means the surface area per unit mass of the ceramic coat layer, Lc / Sc is the surface area per unit area of the ceramic coat layer. This means the amount of mass reduction after the ignition test. In addition, it is considered that the amount of loss on ignition of the ceramic coat layer has a correlation with the amount of surface hydroxyl groups of the ceramic before the ignition test, and the amount of hydroxyl groups has a correlation with high hydrophilicity. According to the present invention, the expression (1) is satisfied, that is, the loss on ignition per surface area of the ceramic coat layer is sufficiently small, so that the amount of surface hydroxyl groups per surface area of the ceramic coat layer is sufficiently small as compared with the prior art. Therefore, the liquid absorption amount of the aqueous slurry of the ceramic coat layer can be reduced.
ここで、前記セラミックコート層の平均気孔径をDc(μm)とした時に(2)式を満たすこともできる。
Dc≧0.05μm (2) Here, when the average pore diameter of the ceramic coat layer is Dc (μm), the expression (2) can also be satisfied.
Dc ≧ 0.05 μm (2)
Dc≧0.05μm (2) Here, when the average pore diameter of the ceramic coat layer is Dc (μm), the expression (2) can also be satisfied.
Dc ≧ 0.05 μm (2)
さらに、前記セラミックコート層は、溶融シリカ粒子や溶融アルミナ粒子などの溶融セラミック粒子を含むことができる。
Furthermore, the ceramic coat layer can contain fused ceramic particles such as fused silica particles and fused alumina particles.
さらに、前記セラミックコート層は、繊維状セラミック粒子を含むことができる。
Furthermore, the ceramic coat layer may include fibrous ceramic particles.
さらに、前記ハニカムフィルタは、前記セラミックハニカム構造体に担持された触媒を更に備えることができる。
Furthermore, the honeycomb filter can further include a catalyst supported on the ceramic honeycomb structure.
本発明によれば、セラミックコート層への触媒の担持を抑制することが可能となる。
According to the present invention, it is possible to suppress the catalyst loading on the ceramic coat layer.
図面を参照して本発明の1実施形態に係るハニカムフィルタ300を説明する。ハニカムフィルタ300は、コア部100、及び、セラミックコート層200を備える。
A honeycomb filter 300 according to an embodiment of the present invention will be described with reference to the drawings. The honeycomb filter 300 includes a core part 100 and a ceramic coat layer 200.
コア部100は、柱形状を有し、入口端面(一端面)100a及び出口端面(他端面)100bを有する。コア部100は、多孔質のセラミックハニカム構造体120及び複数の封口部130を有する。セラミックハニカム構造体120は、複数の入口流路(複数の第1流路)110a及び複数の出口流路(複数の第2流路)110bを有する。入口流路110a及び出口流路110bの断面形状は、例えば、円形、楕円形、四角形、六角形、八角形であることができる。セラミックハニカム構造体120は、互いに隣接する入口流路110a及び出口流路110bをそれぞれ隔てる隔壁として機能する。
The core part 100 has a column shape and has an inlet end face (one end face) 100a and an outlet end face (the other end face) 100b. The core part 100 has a porous ceramic honeycomb structure 120 and a plurality of sealing parts 130. The ceramic honeycomb structure 120 includes a plurality of inlet channels (a plurality of first channels) 110a and a plurality of outlet channels (a plurality of second channels) 110b. The cross-sectional shapes of the inlet channel 110a and the outlet channel 110b can be, for example, a circle, an ellipse, a quadrangle, a hexagon, and an octagon. The ceramic honeycomb structure 120 functions as a partition wall that separates the inlet channel 110a and the outlet channel 110b adjacent to each other.
各入口流路110aは、入口端面100aにおいて開口され、出口端面100bにおいて封口部130により封口されている。また、各出口流路110bは、出口端面100bにおいて開口され、入口端面100aにおいて封口部130により封口されている。なお、図1では、封口部130はプラグ形状であるが、封口部130は、セラミックハニカム構造体120の一部を変形することによって形成したもの(例えば円錐形状部)であってもよい。
Each inlet channel 110a is opened at the inlet end surface 100a and sealed by the sealing portion 130 at the outlet end surface 100b. Each outlet channel 110b is opened at the outlet end surface 100b and sealed by the sealing portion 130 at the inlet end surface 100a. In FIG. 1, the sealing portion 130 has a plug shape, but the sealing portion 130 may be formed by deforming a part of the ceramic honeycomb structure 120 (for example, a conical shape portion).
コア部(セラミックハニカム構造体120及び封口部130)のセラミックの例は、チタン酸アルミニウム系セラミック、炭化ケイ素系セラミック、コージェライト系セラミックである。チタン酸アルミニウム系セラミックは、マグネシウムやケイ素などを含むことができる。セラミックは、原料由来の微量成分又は製造工程において不可避的に含まれる微量成分を含有し得る。
Examples of the ceramic of the core part (the ceramic honeycomb structure 120 and the sealing part 130) are an aluminum titanate ceramic, a silicon carbide ceramic, and a cordierite ceramic. The aluminum titanate-based ceramic can contain magnesium, silicon, and the like. The ceramic may contain trace components derived from raw materials or trace components inevitably contained in the production process.
セラミックハニカム構造体120の気孔率は、50~75%であることができる。圧損性能の保持および触媒活性を向上させる上で、気孔率は55~70%であることが好ましく、55~65%であることがより好ましい。気孔率が75%を超えるとセラミックハニカム構造体120の強度が低下する場合がある。気孔率は水銀圧入法により測定できる。
The porosity of the ceramic honeycomb structure 120 can be 50 to 75%. The porosity is preferably 55 to 70%, more preferably 55 to 65% in order to maintain the pressure loss performance and improve the catalyst activity. If the porosity exceeds 75%, the strength of the ceramic honeycomb structure 120 may decrease. The porosity can be measured by mercury porosimetry.
セル密度は、例えば、35~80cell/cm2とすることができる。
The cell density can be, for example, 35 to 80 cells / cm 2 .
セラミックコート層200は、コア部100の外周面上に設けられている。セラミックコート層200は、外周面上に全周にわたって設けられることができる。セラミックコート層200の厚みは、例えば、0.2~2.0mmとすることができる。
The ceramic coat layer 200 is provided on the outer peripheral surface of the core part 100. The ceramic coat layer 200 can be provided over the entire circumference on the outer peripheral surface. The thickness of the ceramic coat layer 200 can be set to 0.2 to 2.0 mm, for example.
セラミックコート層200は、セラミック粒子、及び、これらを結合する無機バインダを有することができる。セラミックコート層は多孔質であることができる。セラミックコート層200の気孔率は、セラミックハニカム構造体よりも小さく、10~40%であることができる。
The ceramic coat layer 200 may have ceramic particles and an inorganic binder that binds them. The ceramic coat layer can be porous. The porosity of the ceramic coat layer 200 is smaller than that of the ceramic honeycomb structure and can be 10 to 40%.
セラミックコート層200のセラミックの例は、例えば、アルミナ、シリカ、チタン酸アルミニウム、コージェライト等である。コア部100のセラミックと同じでもよいが異なってもよい。
Examples of the ceramic of the ceramic coat layer 200 are, for example, alumina, silica, aluminum titanate, cordierite, and the like. It may be the same as or different from the ceramic of the core part 100.
セラミック粒子の形状の例は、非繊維状粒子(長径と短径との比(アスペクト比)が3倍未満)、及び、繊維状粒子(長径と短径との比(アスペクト比)が3倍以上)である。繊維状のセラミック粒子を含むと、機械的強度(ヤング率)の向上が可能となる。
Examples of the shape of ceramic particles are non-fibrous particles (ratio of major axis to minor axis (aspect ratio) of less than 3 times) and fibrous particles (ratio of major axis to minor axis (aspect ratio) of 3 times). Above). When fibrous ceramic particles are included, mechanical strength (Young's modulus) can be improved.
非繊維状粒子の粒径(レーザ回折式粒度分布測定装置による体積基準の粒度分布のD50)の例は、2~30μmとすることができる。
An example of the particle size of the non-fibrous particles (D50 of the volume-based particle size distribution by a laser diffraction particle size distribution measuring device) can be 2 to 30 μm.
また、繊維状粒子の長径は10~200μmであることができ、短径は2~10μmであることができる。繊維状粒子のアスペクト比は3~100であることができる。
The major axis of the fibrous particles can be 10 to 200 μm, and the minor axis can be 2 to 10 μm. The aspect ratio of the fibrous particles can be 3-100.
全セラミック粒子の質量に対する、繊維状粒子の質量の割合は、5~25%とすることができる。
The ratio of the mass of fibrous particles to the mass of all ceramic particles can be 5 to 25%.
また、セラミック粒子は、例えば、非繊維状粒子として、溶融アルミナ、溶融シリカ等の溶融セラミック粒子を含むことができる。溶融セラミック粒子は例えば2000℃以上で溶融されているので、表面水酸基の量が少ない。
Also, the ceramic particles can include, for example, fused ceramic particles such as fused alumina and fused silica as non-fibrous particles. Since the molten ceramic particles are melted at, for example, 2000 ° C. or higher, the amount of surface hydroxyl groups is small.
無機バインダの例は、コロイダルシリカ、アルミナゾル、チタニアゾル、水ガラス、水硬性アルミナ、ρ-アルミナ、ベーマイトアルミナ、アルミナセメント、ポルトランドセメントである。無機バインダの量は、セラミック粒子100重量部に対して3~30重量部であることができる。
Examples of the inorganic binder are colloidal silica, alumina sol, titania sol, water glass, hydraulic alumina, ρ-alumina, boehmite alumina, alumina cement, and Portland cement. The amount of the inorganic binder can be 3 to 30 parts by weight with respect to 100 parts by weight of the ceramic particles.
そして、本実施形態において、セラミックコート層の比表面積、灼熱減量をそれぞれSc(m2/g)、Lc(-)とした時に、セラミックコート層は(1)式を満たす。
Lc/Sc≦100×10-5g/m2 (1) In this embodiment, when the specific surface area and the loss on ignition of the ceramic coat layer are Sc (m 2 / g) and Lc (−), respectively, the ceramic coat layer satisfies the formula (1).
Lc / Sc ≦ 100 × 10 −5 g / m 2 (1)
Lc/Sc≦100×10-5g/m2 (1) In this embodiment, when the specific surface area and the loss on ignition of the ceramic coat layer are Sc (m 2 / g) and Lc (−), respectively, the ceramic coat layer satisfies the formula (1).
Lc / Sc ≦ 100 × 10 −5 g / m 2 (1)
灼熱減量とは、対象物の加熱処理前後の質量の減少割合のことであり、本実施形態において、対象物の水酸基の量と相関がある。加熱処理の条件は、大気雰囲気において1100℃で2時間である。
比表面積は、水銀圧入法により測定することができる。測定条件は、最高圧力414Mpa(60,000psia)とすることができる。 The loss on ignition is the rate of decrease in mass before and after the heat treatment of the object, and in this embodiment, there is a correlation with the amount of hydroxyl groups in the object. The conditions for the heat treatment are 2 hours at 1100 ° C. in an air atmosphere.
The specific surface area can be measured by a mercury intrusion method. The measurement conditions can be a maximum pressure of 414 Mpa (60,000 psia).
比表面積は、水銀圧入法により測定することができる。測定条件は、最高圧力414Mpa(60,000psia)とすることができる。 The loss on ignition is the rate of decrease in mass before and after the heat treatment of the object, and in this embodiment, there is a correlation with the amount of hydroxyl groups in the object. The conditions for the heat treatment are 2 hours at 1100 ° C. in an air atmosphere.
The specific surface area can be measured by a mercury intrusion method. The measurement conditions can be a maximum pressure of 414 Mpa (60,000 psia).
灼熱減量Lcはセラミックコート層単位質量当たりの灼熱試験後の質量減少量を意味し、比表面積Scはセラミックコート層単位質量当たりの表面積を意味するので、Lc/Scは、セラミックコート層の表面積当たりの灼熱試験後の質量減少量を意味する。また、セラミックコート層の灼熱減量の大きさは灼熱試験前のセラミックの表面水酸基の量と相関があり、水酸基の量は親水性の高さと相関すると考えられる。
Since the loss on ignition Lc means the amount of mass reduction after the ignition test per unit mass of the ceramic coat layer, and the specific surface area Sc means the surface area per unit mass of the ceramic coat layer, Lc / Sc is the surface area per unit area of the ceramic coat layer. This means the amount of mass reduction after the ignition test. The magnitude of the loss on ignition of the ceramic coat layer is correlated with the amount of surface hydroxyl groups of the ceramic before the ignition test, and the amount of hydroxyl groups is considered to correlate with the hydrophilicity.
本実施形態によれば、(1)式を満たす、すなわち、セラミックコート層の表面積当たりの灼熱減量が十分小さいので、セラミックコート層の表面積当たりの表面水酸基の量が十分に小さくなる。したがって、セラミックコート層の親水性を低減できて水系スラリーの吸収を抑制でき、セラミックコート層への触媒の担持を抑制できる。
According to the present embodiment, the expression (1) is satisfied, that is, the loss on ignition per surface area of the ceramic coat layer is sufficiently small, so that the amount of surface hydroxyl groups per surface area of the ceramic coat layer is sufficiently small. Therefore, the hydrophilicity of the ceramic coat layer can be reduced, absorption of the aqueous slurry can be suppressed, and catalyst loading on the ceramic coat layer can be suppressed.
Lc/Scは100×10-5g/m2以下であることができる。また、Lc/Scは1×10-5g/m2以上であることができる。
Lc / Sc can be 100 × 10 −5 g / m 2 or less. Further, Lc / Sc can be 1 × 10 −5 g / m 2 or more.
また、セラミックコート層200の平均気孔径をDc(μm)とした時に(2)式を満たすことができる。
Dc≧0.05μm (2) Further, when the average pore diameter of theceramic coat layer 200 is Dc (μm), the expression (2) can be satisfied.
Dc ≧ 0.05 μm (2)
Dc≧0.05μm (2) Further, when the average pore diameter of the
Dc ≧ 0.05 μm (2)
ここで、平均気孔径は、まず水銀圧入法により対象物の0.0018~100μmの範囲での気孔径分布を測定し、当該気孔径分布において気孔径の累積体積分率が50%となる気孔径を取得することにより得られる。Dcは0.10μm以上であることもできる。
セラミックコート層200の平均気孔径Dcがある程度大きいと、毛細管力が低減して水系スラリーの吸い上げ力の低減に寄与する場合がある。 Here, as for the average pore diameter, first, the pore diameter distribution in the range of 0.0018 to 100 μm of the object is measured by the mercury intrusion method, and the cumulative volume fraction of the pore diameter is 50% in the pore diameter distribution. Obtained by obtaining the pore size. Dc can also be 0.10 μm or more.
When the average pore diameter Dc of theceramic coat layer 200 is large to some extent, the capillary force may be reduced, which may contribute to a reduction in the suction force of the aqueous slurry.
セラミックコート層200の平均気孔径Dcがある程度大きいと、毛細管力が低減して水系スラリーの吸い上げ力の低減に寄与する場合がある。 Here, as for the average pore diameter, first, the pore diameter distribution in the range of 0.0018 to 100 μm of the object is measured by the mercury intrusion method, and the cumulative volume fraction of the pore diameter is 50% in the pore diameter distribution. Obtained by obtaining the pore size. Dc can also be 0.10 μm or more.
When the average pore diameter Dc of the
また、セラミックコート層200の強度を維持する観点から、Dcは(2A)式を満たすことができる。
Dc≦5μm (2A) Further, from the viewpoint of maintaining the strength of theceramic coat layer 200, Dc can satisfy the formula (2A).
Dc ≦ 5μm (2A)
Dc≦5μm (2A) Further, from the viewpoint of maintaining the strength of the
Dc ≦ 5μm (2A)
また、セラミックハニカム構造体120の比表面積、灼熱減量、平均気孔径は、所望のろ過特性等に応じて適宜設定することができる。
セラミックハニカム構造体120の比表面積、灼熱減量、をそれぞれSh(m2/g)、Lh(-)とした時に、セラミックハニカム構造体120は(3)式を満たすことができる。
Lh/Sh≧400×10-5g/m2 (3) In addition, the specific surface area, loss on ignition, and average pore diameter of theceramic honeycomb structure 120 can be appropriately set according to desired filtration characteristics and the like.
When the specific surface area and the loss on ignition of theceramic honeycomb structure 120 are Sh (m 2 / g) and Lh (−), respectively, the ceramic honeycomb structure 120 can satisfy the expression (3).
Lh / Sh ≧ 400 × 10 −5 g / m 2 (3)
セラミックハニカム構造体120の比表面積、灼熱減量、をそれぞれSh(m2/g)、Lh(-)とした時に、セラミックハニカム構造体120は(3)式を満たすことができる。
Lh/Sh≧400×10-5g/m2 (3) In addition, the specific surface area, loss on ignition, and average pore diameter of the
When the specific surface area and the loss on ignition of the
Lh / Sh ≧ 400 × 10 −5 g / m 2 (3)
灼熱減量Lhはセラミックハニカム構造体120の単位質量当たりの灼熱試験後の質量減少量を意味し、比表面積Shはセラミックハニカム構造体120の単位質量当たりの表面積を意味するので、Lh/Shは、セラミックハニカム構造体120の表面積当たりの灼熱試験後の質量減少量を意味する。セラミックハニカム構造体が(3)式を満たす、すなわち、セラミックハニカム構造体120の表面積当たりの灼熱減量が十分大きいと、セラミックハニカム構造体に水系スラリーを吸液させ易くて好適である。
Lh/Shは500×10-5g/m2以上であることができ、600×10-5g/m2以上であることができ、700×10-5g/m2以上であることができ、1000×10-5g/m2以下であることができる。 The ignition loss Lh means the mass reduction amount after the ignition test per unit mass of theceramic honeycomb structure 120, and the specific surface area Sh means the surface area per unit mass of the ceramic honeycomb structure 120, so Lh / Sh is It means the amount of mass reduction after the ignition test per surface area of the ceramic honeycomb structure 120. It is preferable that the ceramic honeycomb structure satisfies the formula (3), that is, if the loss of ignition per surface area of the ceramic honeycomb structure 120 is sufficiently large, the ceramic honeycomb structure can easily absorb the aqueous slurry.
Lh / Sh can be 500 × 10 −5 g / m 2 or more, can be 600 × 10 −5 g / m 2 or more, and can be 700 × 10 −5 g / m 2 or more. And can be 1000 × 10 −5 g / m 2 or less.
Lh/Shは500×10-5g/m2以上であることができ、600×10-5g/m2以上であることができ、700×10-5g/m2以上であることができ、1000×10-5g/m2以下であることができる。 The ignition loss Lh means the mass reduction amount after the ignition test per unit mass of the
Lh / Sh can be 500 × 10 −5 g / m 2 or more, can be 600 × 10 −5 g / m 2 or more, and can be 700 × 10 −5 g / m 2 or more. And can be 1000 × 10 −5 g / m 2 or less.
また、セラミックハニカム構造体120の平均気孔径をDh(μm)とした時に(4)式を満たすこともできる。
Dh≧10μm (4)
Dhがある程度大きいことにより圧力損失が低減でき、高出力・低燃費というメリットがある。
セラミックハニカム構造体120のスス溜め効果向上による環境性能向上の観点から、Dhは(4A)式を満たすことができる。
Dh≦30μm (4A) Further, when the average pore diameter of theceramic honeycomb structure 120 is Dh (μm), the expression (4) can also be satisfied.
Dh ≧ 10 μm (4)
Since Dh is large to some extent, pressure loss can be reduced, and there are advantages of high output and low fuel consumption.
From the viewpoint of improving environmental performance by improving the soot accumulation effect of theceramic honeycomb structure 120, Dh can satisfy the formula (4A).
Dh ≦ 30μm (4A)
Dh≧10μm (4)
Dhがある程度大きいことにより圧力損失が低減でき、高出力・低燃費というメリットがある。
セラミックハニカム構造体120のスス溜め効果向上による環境性能向上の観点から、Dhは(4A)式を満たすことができる。
Dh≦30μm (4A) Further, when the average pore diameter of the
Dh ≧ 10 μm (4)
Since Dh is large to some extent, pressure loss can be reduced, and there are advantages of high output and low fuel consumption.
From the viewpoint of improving environmental performance by improving the soot accumulation effect of the
Dh ≦ 30μm (4A)
本実施形態では、セラミックハニカム構造体120のJIS P8141:2004に定められる水のクレム吸水度をAs、セラミックコート層200のJIS P8141:2004に定められる水のクレム吸水度をAcとしたときに、Ac/Asが0.3以下であることができ、0.25以下であることができ、0.2以下であることができる。
なお、実験に際しては食紅の溶液を使用し、そのメーカー名は小倉食品化工株式会社。品名は、紅色製剤であり、これを100gの水に0.5g溶かして使用した。 In the present embodiment, when the water Krem absorbency of theceramic honeycomb structure 120 defined in JIS P8141: 2004 is As and the water Klem absorbency defined in JIS P8141: 2004 of the ceramic coat layer 200 is Ac, Ac / As can be 0.3 or less, can be 0.25 or less, and can be 0.2 or less.
In the experiment, a food red solution was used, and the manufacturer was Ogura Food Chemical Co., Ltd. The product name is a red preparation, which is used by dissolving 0.5 g in 100 g of water.
なお、実験に際しては食紅の溶液を使用し、そのメーカー名は小倉食品化工株式会社。品名は、紅色製剤であり、これを100gの水に0.5g溶かして使用した。 In the present embodiment, when the water Krem absorbency of the
In the experiment, a food red solution was used, and the manufacturer was Ogura Food Chemical Co., Ltd. The product name is a red preparation, which is used by dissolving 0.5 g in 100 g of water.
続いて、上記のようなハニカムフィルタの製造方法の一例を説明する。
まず、セラミック源、造孔材、有機バインダ、溶媒、及び、必要に応じて添加される添加物を含むグリーン原料を用意し、グリーンのセラミックハニカム構造体120を得る。続いて、グリーン原料と同様の原料を用いて公知の方法により流路の一端を封鎖してグリーンの封口部130を形成し、グリーンのコア部を得る。続いて、グリーンのコア部を焼成することによりセラミック製のコア部100を得る。その後必要に応じて、コア部100の外周面の切削や研磨等の加工を行ってもよい。 Then, an example of the manufacturing method of the above honeycomb filters is demonstrated.
First, a green raw material containing a ceramic source, a pore former, an organic binder, a solvent, and an additive added as necessary is prepared to obtain a greenceramic honeycomb structure 120. Subsequently, one end of the flow path is blocked by a known method using the same raw material as the green raw material to form the green sealing portion 130 to obtain the green core portion. Subsequently, the core part 100 made of ceramic is obtained by firing the green core part. Thereafter, if necessary, processing such as cutting and polishing of the outer peripheral surface of the core portion 100 may be performed.
まず、セラミック源、造孔材、有機バインダ、溶媒、及び、必要に応じて添加される添加物を含むグリーン原料を用意し、グリーンのセラミックハニカム構造体120を得る。続いて、グリーン原料と同様の原料を用いて公知の方法により流路の一端を封鎖してグリーンの封口部130を形成し、グリーンのコア部を得る。続いて、グリーンのコア部を焼成することによりセラミック製のコア部100を得る。その後必要に応じて、コア部100の外周面の切削や研磨等の加工を行ってもよい。 Then, an example of the manufacturing method of the above honeycomb filters is demonstrated.
First, a green raw material containing a ceramic source, a pore former, an organic binder, a solvent, and an additive added as necessary is prepared to obtain a green
続いて、コア部100の外周面上にセラミックコート層200を形成する。具体的には、まず、セラミック粒子、無機バインダ、及び、水などの溶媒を含むコートペーストを用意する。
Subsequently, a ceramic coat layer 200 is formed on the outer peripheral surface of the core portion 100. Specifically, first, a coating paste containing ceramic particles, an inorganic binder, and a solvent such as water is prepared.
ここで、セラミックコート層200のLc/Scが(1)式を満たすように、セラミックコート層の原料を調整する。具体的には、比表面積Scを調節するには、無機物質に対するバインダの重量比率およびバインダの粒径を調節すればよい。例えば比表面積を大きくするには、バインダの重量比率を大きくする。あるいは、バインダの粒径を小さくすればよい。また、灼熱減量を調節するには、例えば、セラミックコート層のセラミック粒子として、表面水酸基の少ない原料を用いることができる。特に、セラミック粒子として高温過程を経ることにより水酸基が少なくされた溶融セラミック粒子を少なくとも一部用いることが好適であるが、他の表面水酸基の少ない原料を用いることもできる。また、表面水酸基の少ない原料を用いたセラミックコート層を、さらに、後述するように高温で焼成処理することも好適であり、その際の温度として通常は400℃以上であり、好ましくは600℃以上であり、更に好ましくは800℃以上であり、通常は1000℃以下である。
Here, the raw material of the ceramic coat layer is adjusted so that Lc / Sc of the ceramic coat layer 200 satisfies the formula (1). Specifically, in order to adjust the specific surface area Sc, the weight ratio of the binder to the inorganic substance and the particle size of the binder may be adjusted. For example, to increase the specific surface area, the weight ratio of the binder is increased. Or what is necessary is just to make the particle size of a binder small. In order to adjust the loss on ignition, for example, a raw material having a small surface hydroxyl group can be used as the ceramic particles of the ceramic coat layer. In particular, it is preferable to use at least a part of the ceramic particles whose hydroxyl groups are reduced by passing through a high-temperature process as ceramic particles, but other raw materials having a small amount of hydroxyl groups on the surface can also be used. Further, it is also suitable to further subject the ceramic coat layer using the raw material having a small surface hydroxyl group to a high temperature treatment as described later, and the temperature at that time is usually 400 ° C. or higher, preferably 600 ° C. or higher. More preferably, it is 800 ° C. or higher, and usually 1000 ° C. or lower.
また、セラミックコート層200の平均気孔径Dcは、原料の粒径等により調節できる。
Further, the average pore diameter Dc of the ceramic coat layer 200 can be adjusted by the particle diameter of the raw material.
つづいて、得られたコートペーストをコア部100の外周面上に全周にわたって塗布する。塗布法は特に限定されず、刷毛塗り法、ローラーブラシ法、ドクターブレード法などが挙げられる。
Subsequently, the obtained coating paste is applied to the outer peripheral surface of the core part 100 over the entire circumference. The application method is not particularly limited, and examples thereof include a brush coating method, a roller brush method, and a doctor blade method.
その後、塗膜を乾燥し、必要に応じて焼成させる。乾燥は、40~200℃の比較的低温でコート液中の溶媒を蒸発させて行うことができる。焼成においては、400~1000℃の比較的高温で処理することにより表面に吸着する溶媒分子の除去を行うことができる。これにより、コア部及びセラミックコート層を備えるハニカムフィルタが完成する。
Then, the coating film is dried and fired as necessary. Drying can be performed by evaporating the solvent in the coating solution at a relatively low temperature of 40 to 200 ° C. In firing, solvent molecules adsorbed on the surface can be removed by treatment at a relatively high temperature of 400 to 1000 ° C. Thereby, a honeycomb filter provided with a core part and a ceramic coat layer is completed.
続いて、本実施形態のハニカムフィルタに対して触媒を担持する方法について説明する。
1つの方法は、コア部100の表面に触媒支持材を担持させ、その後、触媒支持材上に触媒を担持させる方法である。また、他の方法は、触媒が支持された触媒支持材をコア部100の表面に担持させる方法である。さらに他の方法は、触媒支持材を担持させずに、直接コア部の表面に触媒を担持させる方法である。 Next, a method for supporting a catalyst on the honeycomb filter of the present embodiment will be described.
One method is a method in which a catalyst support material is supported on the surface of thecore portion 100 and then a catalyst is supported on the catalyst support material. Another method is a method in which a catalyst support material on which a catalyst is supported is supported on the surface of the core portion 100. Still another method is a method of directly supporting the catalyst on the surface of the core portion without supporting the catalyst support material.
1つの方法は、コア部100の表面に触媒支持材を担持させ、その後、触媒支持材上に触媒を担持させる方法である。また、他の方法は、触媒が支持された触媒支持材をコア部100の表面に担持させる方法である。さらに他の方法は、触媒支持材を担持させずに、直接コア部の表面に触媒を担持させる方法である。 Next, a method for supporting a catalyst on the honeycomb filter of the present embodiment will be described.
One method is a method in which a catalyst support material is supported on the surface of the
触媒支持材の例は、アルミナ、シリカ、マグネシア、チタニア、ジルコニア、セリア、La2O3、BaO、ゼオライト等の酸化物、あるいは、これらの内の1種以上を含む複合酸化物である。触媒支持材の粒径D50は2~5μmとすることができる。
Examples of the catalyst support material are oxides such as alumina, silica, magnesia, titania, zirconia, ceria, La 2 O 3 , BaO, and zeolite, or composite oxides containing one or more of these. The particle size D50 of the catalyst support can be 2 to 5 μm.
触媒の例は、Pt、Pd、Rh、銀、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅からなる群より選択される少なくとも1つの金属元素、又は、ゼオライト触媒の粒子である。上述のように、触媒支持材の粒子は予め触媒をその上に担持していてもよい。
Examples of the catalyst are particles of at least one metal element selected from the group consisting of Pt, Pd, Rh, silver, vanadium, chromium, manganese, iron, cobalt, nickel, and copper, or zeolite catalyst. As described above, the catalyst support particles may previously carry the catalyst thereon.
触媒支持材及び/又は触媒をコア部100の表面に担持させるには、触媒支持材及び/又は触媒を含む水系スラリーを準備し、当該水系スラリー中にハニカムフィルタを浸漬させ、その後フィルタを加熱して水系スラリーを乾燥させればよい。以上のようにして、触媒を担持したハニカムフィルタを製造することができる。
In order to support the catalyst support material and / or the catalyst on the surface of the core part 100, an aqueous slurry containing the catalyst support material and / or the catalyst is prepared, the honeycomb filter is immersed in the aqueous slurry, and then the filter is heated. The aqueous slurry may be dried. As described above, a honeycomb filter carrying a catalyst can be manufactured.
本実施形態に係るハニカムフィルタを用いた場合、(1)式を満たしているので、セラミックコート層200への触媒の担持量を低減できる。したがって、触媒の無駄を削減できる。
When the honeycomb filter according to the present embodiment is used, since the expression (1) is satisfied, the amount of the catalyst supported on the ceramic coat layer 200 can be reduced. Therefore, the waste of the catalyst can be reduced.
本発明は上記実施形態に限定されず様々な変形態様が可能である。
例えば、セラミックハニカム構造体の外形形状、流路の配置について特段の限定はない。たとえば、セラミックハニカム構造体は、円柱でなくても、四角柱、六角柱等の角柱でもよい。流路の配置も三角形配置、正方形配置等種々の態様を取り得る。 The present invention is not limited to the above embodiment, and various modifications can be made.
For example, there are no particular limitations on the outer shape of the ceramic honeycomb structure and the arrangement of the flow paths. For example, the ceramic honeycomb structure may not be a cylinder but may be a prism such as a quadrangular prism or a hexagonal prism. The arrangement of the flow paths can take various forms such as a triangular arrangement and a square arrangement.
例えば、セラミックハニカム構造体の外形形状、流路の配置について特段の限定はない。たとえば、セラミックハニカム構造体は、円柱でなくても、四角柱、六角柱等の角柱でもよい。流路の配置も三角形配置、正方形配置等種々の態様を取り得る。 The present invention is not limited to the above embodiment, and various modifications can be made.
For example, there are no particular limitations on the outer shape of the ceramic honeycomb structure and the arrangement of the flow paths. For example, the ceramic honeycomb structure may not be a cylinder but may be a prism such as a quadrangular prism or a hexagonal prism. The arrangement of the flow paths can take various forms such as a triangular arrangement and a square arrangement.
(実施例1)
チタン酸アルミニウム製のコア部を用意した。各流路の断面は六角形であり、セル密度は380cpsiであった。外径は25.4mmであり、高さは25.4mmであった。セラミックハニカム構造体の気孔率は59%、平均気孔径Dhは18.12μm、比表面積Shは0.145m2/g、灼熱減量Lhは0.12%、Lh/Shは827.6×10-5g/m2であった。 Example 1
A core portion made of aluminum titanate was prepared. The cross section of each flow path was hexagonal, and the cell density was 380 cpsi. The outer diameter was 25.4 mm and the height was 25.4 mm. The porosity of the ceramic honeycomb structure is 59%, the average pore diameter Dh is 18.12 μm, the specific surface area Sh is 0.145 m 2 / g, the loss on ignition Lh is 0.12%, and Lh / Sh is 827.6 × 10 − It was 5 g / m 2 .
チタン酸アルミニウム製のコア部を用意した。各流路の断面は六角形であり、セル密度は380cpsiであった。外径は25.4mmであり、高さは25.4mmであった。セラミックハニカム構造体の気孔率は59%、平均気孔径Dhは18.12μm、比表面積Shは0.145m2/g、灼熱減量Lhは0.12%、Lh/Shは827.6×10-5g/m2であった。 Example 1
A core portion made of aluminum titanate was prepared. The cross section of each flow path was hexagonal, and the cell density was 380 cpsi. The outer diameter was 25.4 mm and the height was 25.4 mm. The porosity of the ceramic honeycomb structure is 59%, the average pore diameter Dh is 18.12 μm, the specific surface area Sh is 0.145 m 2 / g, the loss on ignition Lh is 0.12%, and Lh / Sh is 827.6 × 10 − It was 5 g / m 2 .
5μmのD50を有する溶融シリカ粒子170g、25μmのD50を有するチタン酸アルミニウム粒子30g、長径20μmかつ短径4~6μmのアルミナ繊維20g、粒径12nmのコロイダルシリカ22.5g、及び、水52.5gを混合してコートペーストを得た。溶融シリカ粒子及びチタン酸アルミニウム粒子は非繊維状粒子である。配合を表1に示す。
170 g of fused silica particles having a D50 of 5 μm, 30 g of aluminum titanate particles having a D50 of 25 μm, 20 g of alumina fibers having a major axis of 20 μm and a minor axis of 4-6 μm, 22.5 g of colloidal silica having a particle diameter of 12 nm, and 52.5 g of water Were mixed to obtain a coat paste. The fused silica particles and aluminum titanate particles are non-fibrous particles. The formulation is shown in Table 1.
このコートペーストを、ドクターブレード法によりハニカム構造体の外周面全体に塗布した。その後、150℃でコートペーストを乾燥させ、1000℃でさらに乾燥して、コア部及びセラミックコート層を備えるハニカムフィルタを得た。コア部に付着したセラミックコート層の重量は1.46gであった。
This coat paste was applied to the entire outer peripheral surface of the honeycomb structure by a doctor blade method. Thereafter, the coat paste was dried at 150 ° C. and further dried at 1000 ° C. to obtain a honeycomb filter having a core portion and a ceramic coat layer. The weight of the ceramic coat layer adhering to the core portion was 1.46 g.
続いて、ハニカムフィルタに触媒を担持した。具体的には、市販のβゼオライト300gを700gの純水に撹拌した後、これをボールミルにて平均粒径3μmに粉砕して水系スラリーを得て、その後ハニカムフィルタを当該スラリー中にディップし、さらにその後500℃で乾燥させた。
Subsequently, the catalyst was supported on the honeycomb filter. Specifically, after stirring 300 g of commercially available β zeolite into 700 g of pure water, this was pulverized to a mean particle size of 3 μm with a ball mill to obtain an aqueous slurry, and then a honeycomb filter was dipped in the slurry, Further, it was dried at 500 ° C.
(実施例2)
無機バインダであるコロイダルシリカの量を33.75gとし、水の量を78.75gとし、2段目の乾燥温度を1000℃から700℃に変更する以外は、実施例1と同様とした。セラミックハニカム構造体に形成されたセラミックコート層の重量は1.54gであった。 (Example 2)
The procedure was the same as Example 1 except that the amount of colloidal silica as an inorganic binder was 33.75 g, the amount of water was 78.75 g, and the drying temperature at the second stage was changed from 1000 ° C. to 700 ° C. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 1.54 g.
無機バインダであるコロイダルシリカの量を33.75gとし、水の量を78.75gとし、2段目の乾燥温度を1000℃から700℃に変更する以外は、実施例1と同様とした。セラミックハニカム構造体に形成されたセラミックコート層の重量は1.54gであった。 (Example 2)
The procedure was the same as Example 1 except that the amount of colloidal silica as an inorganic binder was 33.75 g, the amount of water was 78.75 g, and the drying temperature at the second stage was changed from 1000 ° C. to 700 ° C. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 1.54 g.
(実施例3)
2段目の乾燥温度を1000℃から700℃に変更する以外は、実施例1と同様とした。セラミックハニカム構造体に形成されたセラミックコート層の重量は0.95gであった。 (Example 3)
Example 2 was the same as Example 1 except that the drying temperature in the second stage was changed from 1000 ° C to 700 ° C. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.95 g.
2段目の乾燥温度を1000℃から700℃に変更する以外は、実施例1と同様とした。セラミックハニカム構造体に形成されたセラミックコート層の重量は0.95gであった。 (Example 3)
Example 2 was the same as Example 1 except that the drying temperature in the second stage was changed from 1000 ° C to 700 ° C. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.95 g.
(実施例4)
2段目の乾燥温度を1000℃から450℃に変更する以外は、実施例1と同様とした。セラミックハニカム構造体に形成されたセラミックコート層の重量は1.55gであった。 Example 4
The same procedure as in Example 1 was performed except that the drying temperature of the second stage was changed from 1000 ° C. to 450 ° C. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 1.55 g.
2段目の乾燥温度を1000℃から450℃に変更する以外は、実施例1と同様とした。セラミックハニカム構造体に形成されたセラミックコート層の重量は1.55gであった。 Example 4
The same procedure as in Example 1 was performed except that the drying temperature of the second stage was changed from 1000 ° C. to 450 ° C. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 1.55 g.
(実施例5)
セラミックハニカム構造体の外周面に塗布するコートペーストの厚みを薄くして、セラミックハニカム構造体に形成されたセラミックコート層の重量を0.69gとする以外は、実施例4と同様とした。 (Example 5)
Example 4 was the same as Example 4 except that the thickness of the coat paste applied to the outer peripheral surface of the ceramic honeycomb structure was reduced and the weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.69 g.
セラミックハニカム構造体の外周面に塗布するコートペーストの厚みを薄くして、セラミックハニカム構造体に形成されたセラミックコート層の重量を0.69gとする以外は、実施例4と同様とした。 (Example 5)
Example 4 was the same as Example 4 except that the thickness of the coat paste applied to the outer peripheral surface of the ceramic honeycomb structure was reduced and the weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.69 g.
(比較例1)
溶融シリカに代えて、5μmのD50を有するγアルミナ粒子を用いた以外は、実施例5と同様とした。セラミックハニカム構造体に形成されたセラミックコート層の重量は0.81gであった。γアルミナ粒子は繊維状粒子でなく溶融セラミック粒子でもない。
セラミックコート層形成用コートペーストの配合、コート量、最終乾燥温度を表1に示す。 (Comparative Example 1)
Example 5 was repeated except that γ-alumina particles having a D50 of 5 μm were used instead of fused silica. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.81 g. The γ-alumina particles are neither fibrous particles nor fused ceramic particles.
Table 1 shows the composition, coating amount, and final drying temperature of the coating paste for forming the ceramic coating layer.
溶融シリカに代えて、5μmのD50を有するγアルミナ粒子を用いた以外は、実施例5と同様とした。セラミックハニカム構造体に形成されたセラミックコート層の重量は0.81gであった。γアルミナ粒子は繊維状粒子でなく溶融セラミック粒子でもない。
セラミックコート層形成用コートペーストの配合、コート量、最終乾燥温度を表1に示す。 (Comparative Example 1)
Example 5 was repeated except that γ-alumina particles having a D50 of 5 μm were used instead of fused silica. The weight of the ceramic coat layer formed on the ceramic honeycomb structure was 0.81 g. The γ-alumina particles are neither fibrous particles nor fused ceramic particles.
Table 1 shows the composition, coating amount, and final drying temperature of the coating paste for forming the ceramic coating layer.
(評価)
(セラミックコート層形成容易性)
セラミックコート形成用のコートペーストをセラミックハニカム構造体の外周面に塗布する際の外周面に塗布する際の塗工性を評価した。具体的には、セラミックハニカム構造体の外周面にコートペーストを一周塗布した後の、コート層のハニカム構造体に対する接着状態を判定し、均一かつ浮き上がりが無い場合を〇とし、不均一または浮き上がりが有る場合を×とした。 (Evaluation)
(Ease of forming a ceramic coating layer)
The coating property when applying a coating paste for forming a ceramic coat on the outer peripheral surface of the ceramic honeycomb structure was evaluated. Specifically, after the coating paste is applied to the outer peripheral surface of the ceramic honeycomb structure once, the adhesion state of the coating layer to the honeycomb structure is determined. When it exists, it was set as x.
(セラミックコート層形成容易性)
セラミックコート形成用のコートペーストをセラミックハニカム構造体の外周面に塗布する際の外周面に塗布する際の塗工性を評価した。具体的には、セラミックハニカム構造体の外周面にコートペーストを一周塗布した後の、コート層のハニカム構造体に対する接着状態を判定し、均一かつ浮き上がりが無い場合を〇とし、不均一または浮き上がりが有る場合を×とした。 (Evaluation)
(Ease of forming a ceramic coating layer)
The coating property when applying a coating paste for forming a ceramic coat on the outer peripheral surface of the ceramic honeycomb structure was evaluated. Specifically, after the coating paste is applied to the outer peripheral surface of the ceramic honeycomb structure once, the adhesion state of the coating layer to the honeycomb structure is determined. When it exists, it was set as x.
(触媒担持前のセラミックコート層の気孔径)
水銀圧入法を用いて0.0018~100μmの範囲での触媒担持前のセラミックコート層の気孔径分布を測定し、当該気孔径分布において気孔径の累積体積分率が50%となる気孔径を取得することにより平均気孔径を得た。 (Pore diameter of ceramic coat layer before catalyst loading)
Using the mercury intrusion method, the pore size distribution of the ceramic coat layer before catalyst loading in the range of 0.0018 to 100 μm is measured, and the pore size at which the cumulative volume fraction of the pore size is 50% in the pore size distribution is determined. The average pore diameter was obtained by acquisition.
水銀圧入法を用いて0.0018~100μmの範囲での触媒担持前のセラミックコート層の気孔径分布を測定し、当該気孔径分布において気孔径の累積体積分率が50%となる気孔径を取得することにより平均気孔径を得た。 (Pore diameter of ceramic coat layer before catalyst loading)
Using the mercury intrusion method, the pore size distribution of the ceramic coat layer before catalyst loading in the range of 0.0018 to 100 μm is measured, and the pore size at which the cumulative volume fraction of the pore size is 50% in the pore size distribution is determined. The average pore diameter was obtained by acquisition.
(触媒担持前のセラミックコート層の灼熱減量)
切り出した触媒担持前のセラミックコート層のサンプルの質量を測定し、大気雰囲気中で1100℃で2時間熱処理した後に再度質量を測定し、質量減少率を求めた。 (Loss loss of the ceramic coat layer before catalyst loading)
The mass of the sample of the cut ceramic coat layer before supporting the catalyst was measured. After heat treatment at 1100 ° C. for 2 hours in the air atmosphere, the mass was measured again to obtain the mass reduction rate.
切り出した触媒担持前のセラミックコート層のサンプルの質量を測定し、大気雰囲気中で1100℃で2時間熱処理した後に再度質量を測定し、質量減少率を求めた。 (Loss loss of the ceramic coat layer before catalyst loading)
The mass of the sample of the cut ceramic coat layer before supporting the catalyst was measured. After heat treatment at 1100 ° C. for 2 hours in the air atmosphere, the mass was measured again to obtain the mass reduction rate.
(触媒担持前のセラミックコート層及びハニカム構造体のクレム吸水度の比)
触媒担持前のハニカムフィルタからそれぞれのサンプルを切り出して、下端を鉛直に水の中に浸せきし10分後に水が上昇した高さをそれぞれ測定し、比を求めた。 (Ratio of Krem water absorption of ceramic coating layer and honeycomb structure before catalyst loading)
Each sample was cut out from the honeycomb filter before supporting the catalyst, the lower end was immersed in water vertically, the height at which the water rose after 10 minutes was measured, and the ratio was determined.
触媒担持前のハニカムフィルタからそれぞれのサンプルを切り出して、下端を鉛直に水の中に浸せきし10分後に水が上昇した高さをそれぞれ測定し、比を求めた。 (Ratio of Krem water absorption of ceramic coating layer and honeycomb structure before catalyst loading)
Each sample was cut out from the honeycomb filter before supporting the catalyst, the lower end was immersed in water vertically, the height at which the water rose after 10 minutes was measured, and the ratio was determined.
(触媒担持前のセラミックコート層の強度)
JIS K 5600-5-4に基づいて、触媒担持前のセラミックコート層の鉛筆硬度を測定した。鉛筆硬度がB以下の場合を×とし、鉛筆硬度が5H以上の場合を○とした。 (Strength of ceramic coating layer before catalyst loading)
Based on JIS K 5600-5-4, the pencil hardness of the ceramic coat layer before catalyst loading was measured. The case where the pencil hardness was B or less was evaluated as x, and the case where the pencil hardness was 5H or more was evaluated as ◯.
JIS K 5600-5-4に基づいて、触媒担持前のセラミックコート層の鉛筆硬度を測定した。鉛筆硬度がB以下の場合を×とし、鉛筆硬度が5H以上の場合を○とした。 (Strength of ceramic coating layer before catalyst loading)
Based on JIS K 5600-5-4, the pencil hardness of the ceramic coat layer before catalyst loading was measured. The case where the pencil hardness was B or less was evaluated as x, and the case where the pencil hardness was 5H or more was evaluated as ◯.
(セラミックコート層への触媒の担持量)
SEMにより、セラミックコート層に担持された触媒の量を取得した。
セラミックコート層の評価結果を表2に示す。 (Amount of catalyst supported on the ceramic coat layer)
The amount of catalyst supported on the ceramic coat layer was obtained by SEM.
Table 2 shows the evaluation results of the ceramic coat layer.
SEMにより、セラミックコート層に担持された触媒の量を取得した。
セラミックコート層の評価結果を表2に示す。 (Amount of catalyst supported on the ceramic coat layer)
The amount of catalyst supported on the ceramic coat layer was obtained by SEM.
Table 2 shows the evaluation results of the ceramic coat layer.
100…コア部、100a…入口端面(一端面)、100b…出口端面(他端面)、110a…入口流路(第1流路)、110b…出口流路(第2流路)、120…セラミックハニカム構造体、200…セラミックコート層、300…ハニカムフィルタ。
DESCRIPTION OF SYMBOLS 100 ... Core part, 100a ... Inlet end surface (one end surface), 100b ... Outlet end surface (other end surface), 110a ... Inlet flow path (1st flow path), 110b ... Outlet flow path (2nd flow path), 120 ... Ceramic Honeycomb structure, 200 ... ceramic coat layer, 300 ... honeycomb filter.
Claims (5)
- 柱状のコア部と、前記コア部の外周面上に設けられた多孔質のセラミックコート層と、を備え、
前記コア部は、複数の流路を有する多孔質のセラミックハニカム構造体と、
前記複数の流路の内の一部の流路の一端、及び、前記複数の流路の内の残部の流路の他端を閉じる複数の封口部と、を有し、
前記セラミックコート層の比表面積、灼熱減量をそれぞれSc(m2/g)、Lc(-)とした時に(1)式を満たす、ハニカムフィルタ。
Lc/Sc≦100×10-5g/m2 (1) A columnar core part, and a porous ceramic coat layer provided on the outer peripheral surface of the core part,
The core portion is a porous ceramic honeycomb structure having a plurality of flow paths;
One end of a part of the plurality of channels, and a plurality of sealing portions for closing the other end of the remaining channel among the plurality of channels,
A honeycomb filter satisfying the formula (1) when the specific surface area and the loss on ignition of the ceramic coat layer are Sc (m 2 / g) and Lc (−), respectively.
Lc / Sc ≦ 100 × 10 −5 g / m 2 (1) - 前記セラミックコート層の平均気孔径をDc(μm)とした時に(2)式を満たす、請求項1に記載のハニカムフィルタ。
Dc≧0.05μm (2) The honeycomb filter according to claim 1, which satisfies the formula (2) when an average pore diameter of the ceramic coat layer is Dc (µm).
Dc ≧ 0.05 μm (2) - 前記セラミックコート層は、溶融セラミック粒子を含む、請求項1又は2に記載のハニカムフィルタ。 The honeycomb filter according to claim 1 or 2, wherein the ceramic coat layer includes molten ceramic particles.
- 前記セラミックコート層は、繊維状セラミック粒子を含む、請求項1~3のいずれか1項に記載のハニカムフィルタ。 The honeycomb filter according to any one of claims 1 to 3, wherein the ceramic coat layer includes fibrous ceramic particles.
- 前記セラミックハニカム構造体に担持された触媒を更に備える、請求項1~4のいずれか1項に記載のハニカムフィルタ。
The honeycomb filter according to any one of claims 1 to 4, further comprising a catalyst supported on the ceramic honeycomb structure.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015201438A JP2018192377A (en) | 2015-10-09 | 2015-10-09 | Honeycomb filter |
JP2015-201438 | 2015-10-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017061382A1 true WO2017061382A1 (en) | 2017-04-13 |
Family
ID=58487639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/079316 WO2017061382A1 (en) | 2015-10-09 | 2016-10-03 | Honeycomb filter |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP2018192377A (en) |
WO (1) | WO2017061382A1 (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4971217A (en) * | 1972-11-15 | 1974-07-10 | ||
JPS56133036A (en) * | 1980-03-25 | 1981-10-17 | Asahi Glass Co Ltd | Deposition of catalyst onto ceramic honeycomb |
JPH1043603A (en) * | 1996-08-02 | 1998-02-17 | Nissan Motor Co Ltd | Catalytic structure for purifying automotive exhaust gas and its manufacture |
JPH10225642A (en) * | 1997-02-14 | 1998-08-25 | Hitachi Ltd | Exhaust gas purifying catalyst of internal combustion engine |
JP2003012303A (en) * | 2001-06-28 | 2003-01-15 | Sumitomo Chem Co Ltd | Hydrogen refining unit, hydrogen refining catalyst and its carrier, and production method of the carrier |
JP2007522919A (en) * | 2003-12-31 | 2007-08-16 | コーニング インコーポレイテッド | Ceramic structure with hydrophobic coating |
JP2016055282A (en) * | 2014-09-11 | 2016-04-21 | 日本碍子株式会社 | Honeycomb structure |
-
2015
- 2015-10-09 JP JP2015201438A patent/JP2018192377A/en active Pending
-
2016
- 2016-10-03 WO PCT/JP2016/079316 patent/WO2017061382A1/en active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4971217A (en) * | 1972-11-15 | 1974-07-10 | ||
JPS56133036A (en) * | 1980-03-25 | 1981-10-17 | Asahi Glass Co Ltd | Deposition of catalyst onto ceramic honeycomb |
JPH1043603A (en) * | 1996-08-02 | 1998-02-17 | Nissan Motor Co Ltd | Catalytic structure for purifying automotive exhaust gas and its manufacture |
JPH10225642A (en) * | 1997-02-14 | 1998-08-25 | Hitachi Ltd | Exhaust gas purifying catalyst of internal combustion engine |
JP2003012303A (en) * | 2001-06-28 | 2003-01-15 | Sumitomo Chem Co Ltd | Hydrogen refining unit, hydrogen refining catalyst and its carrier, and production method of the carrier |
JP2007522919A (en) * | 2003-12-31 | 2007-08-16 | コーニング インコーポレイテッド | Ceramic structure with hydrophobic coating |
JP2016055282A (en) * | 2014-09-11 | 2016-04-21 | 日本碍子株式会社 | Honeycomb structure |
Also Published As
Publication number | Publication date |
---|---|
JP2018192377A (en) | 2018-12-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5142532B2 (en) | Honeycomb structure | |
EP2937143B1 (en) | Ceramic honeycomb structure and method for producing same | |
JP5017230B2 (en) | Porous film forming paint for automobile exhaust gas purification filter, porous membrane for automobile exhaust gas purification filter, automobile exhaust gas purification filter, and automobile exhaust gas purification filter manufacturing method. | |
JP2011201115A (en) | Zeolite honeycomb molding and zeolite honeycomb sintered compact | |
JP6788515B2 (en) | Sealed honeycomb structure | |
JP5580090B2 (en) | Zeolite structure and method for producing the same | |
JPWO2018012565A1 (en) | Honeycomb structure and method for manufacturing the honeycomb structure | |
WO2015046242A1 (en) | Cordierite ceramic honeycomb structure and production method therefor | |
WO2004076027A1 (en) | Ceramic honeycomb structure | |
WO2013027531A1 (en) | Catalyst support and manufacturing method therefor | |
JPWO2006041174A1 (en) | Ceramic honeycomb structure | |
JP2018149510A (en) | Plugged Honeycomb Structure | |
KR20130138186A (en) | Method for applying discriminating layer onto porous ceramic filters | |
WO2004063125A1 (en) | Coating material, ceramic honeycomb structure and method for production thereof | |
EP2727640A1 (en) | Particle filter | |
JP2015182062A (en) | honeycomb structure | |
WO2019065805A1 (en) | Honeycomb catalyst | |
WO2015025890A1 (en) | Particulate filter | |
JP5616256B2 (en) | Zeolite structure and method for producing the same | |
WO2012131917A1 (en) | Honeycomb structure and method for producing honeycomb structure | |
WO2013145323A1 (en) | Honeycomb filter | |
JP6231908B2 (en) | Plugged honeycomb structure | |
JP2010269268A (en) | Honeycomb structure type filter | |
JP2011098337A (en) | Honeycomb filter | |
WO2011042991A1 (en) | Honeycomb filter |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16853536 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16853536 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: JP |