CN107847915A - Exhaust-gas purifying filter - Google Patents
Exhaust-gas purifying filter Download PDFInfo
- Publication number
- CN107847915A CN107847915A CN201680044690.8A CN201680044690A CN107847915A CN 107847915 A CN107847915 A CN 107847915A CN 201680044690 A CN201680044690 A CN 201680044690A CN 107847915 A CN107847915 A CN 107847915A
- Authority
- CN
- China
- Prior art keywords
- exhaust
- gas purifying
- ceramic layer
- porous mass
- filter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000919 ceramic Substances 0.000 claims abstract description 94
- 239000013078 crystal Substances 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000002485 combustion reaction Methods 0.000 claims abstract description 15
- 239000013618 particulate matter Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 43
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 7
- 239000006104 solid solution Substances 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 description 49
- 239000005022 packaging material Substances 0.000 description 40
- 239000000523 sample Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 17
- 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 16
- 229910052878 cordierite Inorganic materials 0.000 description 15
- 238000009792 diffusion process Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 yittrium oxide Chemical compound 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000003137 locomotive effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
-
- 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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/30—
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/915—Catalyst supported on particulate filters
- B01D2255/9155—Wall flow filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/065—Surface coverings for exhaust purification, e.g. catalytic reaction for reducing soot ignition temperature
Abstract
Exhaust-gas purifying filter (1) has the porous mass filter (2) that can trap contained particulate matter from the exhaust of internal combustion engine discharge and supported in the catalyst containing Ag (3) of the porous mass filter (2).Porous mass filter (2) is made up of ceramic crystalline grain (21), and the ceramic crystalline grain (21) contains crystal boundary (211).At least surface hole portion (212) in the crystal boundary (211) is filled by heat-stable ceramic layer (25).
Description
Technical field
The present invention relates to the porous mass filter that can trap particulate matter and be supported on the Porous filtering
The exhaust-gas purifying filter of the catalyst containing Ag of device, more particularly to being captured in the exhaust of diesel engine or petrol engine
Contained particulate matter and make the exhaust-gas purifying filter of its reduction.
Background technology
It is known to discharge carbon fine grained equigranular material (particulate matter from diesel engine or petrol engine：PM).In recent years,
Limitation for PM discharge rate is in increasingly tighter trend, is not only diesel engine locomotive, from the discharge of gasoline engine locomotive
PM also turns into important problem.Trapping for PM, such as use the Porous with the ojosa being made up of cordierite etc.
Filter and be supported on the porous mass filter catalyst exhaust-gas purifying filter.It is net that catalyst is used for exhaust
The burning for changing the PM that filter is trapped removes.As such catalyst, such as use Ag etc. (with reference to patent document 1).
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2007-296518 publications
The content of the invention
Invent problem to be solved
However, easily spread under hot environment as use environment temperature of the Ag in exhaust-gas purifying filter.If also,
It is more then to play being present in for function in the diffusion inside for the ceramic grain boundary for forming porous mass filter as catalyst by Ag
The Ag quantitative changes on the surface of hole mass filter are few, and catalyst performance reduces.So supporting the conventional of the catalyst containing Ag
In exhaust-gas purifying filter, the problem that PM combustibilities are easily reduced in high temperature environments be present.
The present invention is made under background context, be intended to provide it is a kind of in high temperature environments, for PM combustion characteristics reduction
The exhaust-gas purifying filter that degree reduces.
The means to solve the problem
The mode of the present invention is exhaust-gas purifying filter, and it has：Porous mass filter, it can trap and be arranged from internal combustion engine
Contained particulate matter in the exhaust gone out；And catalyst containing Ag, support in the porous mass filter, above-mentioned porous mass filter
With heat-stable ceramic layer, at least table in the crystal boundary for the ceramic crystalline grain that above-mentioned heat-stable ceramic layer landfill forms the porous mass filter
Face opening portion.
Invention effect
In above-mentioned exhaust-gas purifying filter, at least table of the crystal boundary for the ceramic crystalline grain for forming above-mentioned porous mass filter
Face opening portion is formed with heat-stable ceramic layer.That is, can be as the surface hole portion quilt of the entrance into crystal boundary by heat-stable ceramic layer
Blocking.Therefore, it is possible to make the diffusion of from the Ag to crystal boundary physically be blocked.So under hot environment into crystal boundary
Ag diffusion can be suppressed, and can suppress the reduction of the Ag amounts in the surface of porous mass filter.As a result, above-mentioned exhaust
Even if polishing filter is in high temperature environments, also reduce for the degree of the reduction of PM combustion characteristics.Also, urged Ag will be contained
Heated though agent supports when porous mass filter, can also prevent diffusions of the Ag during heating into crystal boundary,
Therefore the combustion characteristics for PM at initial stage after manufacturing can be improved.
Brief description of the drawings
In the accompanying drawing of apposition：
Fig. 1 is the skeleton diagram of the exhaust-gas purifying filter being arranged in the exhaust flow path of internal combustion engine in embodiment 1.
Fig. 2 is the stereogram of the exhaust-gas purifying filter in embodiment 1.
Fig. 3 is the amplification profile in the axial direction of the exhaust-gas purifying filter in embodiment 1.
Fig. 4 is the amplification profile in the next door of the porous mass filter in embodiment 1.
Fig. 5 is the enlarged drawing of the region V in Fig. 4.
Fig. 6 in embodiment 1, (a) represent form heat-stable ceramic layer before porous mass filter surface in times
The figure of the sweep electron microscope photo of 10000 times of rate, (b) represent the porous mass filter formed after heat-stable ceramic layer
The figure of the sweep electron microscope photo of 10000 times of multiplying power in surface.
Fig. 7 in embodiment 1, (a) represent form heat-stable ceramic layer before porous mass filter surface in times
The figure of the sweep electron microscope photo of 20000 times of rate, (b) represent the porous mass filter formed after heat-stable ceramic layer
The figure of the sweep electron microscope photo of 20000 times of multiplying power in surface.
Fig. 8 is the Ag on the surface of the embodiment sample and comparative sample that represent the exhaust-gas purifying filter in experimental example 1
The figure of the change of concentration.
Fig. 9 is the PM burning speed of the embodiment sample and comparative sample that represent the exhaust-gas purifying filter in experimental example 1
The figure of the change of degree.
Figure 10 is the amplification profile near the ceramic crystal boundary of the comparative sample of the exhaust-gas purifying filter in experimental example 1
Figure.
For Figure 11 in experimental example 1, (a) represents the scanning of the comparative sample for the exhaust-gas purifying filter being embedded in resin
The figure of the reflection electronic picture of formula electron microscope, (b) represent the comparative sample for the exhaust-gas purifying filter being embedded in resin
EPMA mapping figure.
Figure 12 is that the Ag on the surface of the firing temperature and exhaust-gas purifying filter that represent the heat-stable ceramic layer in experimental example 2 is dense
The figure of the relation of the change of degree.
Figure 13 is to represent the firing temperature of heat-stable ceramic layer and the PM burning velocities of exhaust-gas purifying filter in experimental example 2
Change relation figure.
Embodiment
(the 1st embodiment)
Next, 1~Fig. 7 of reference picture illustrates the embodiment involved by exhaust-gas purifying filter.As shown in figure 1, this reality
The exhaust-gas purifying filter 1 for applying mode is used to remove particulate matter (that is, particle contained in the exhaust discharged from internal combustion engine 5
Material：PM), it is arranged in the blast pipe 51 as the stream of exhaust.Exhaust-gas purifying filter 1 can for example be applied to diesel oil
Engine, it can also be applied to petrol engine.
As shown in FIG. 2 and 3, exhaust-gas purifying filter 1 possesses the porous mass filter 2 that can trap PM.As more
Hole mass filter 2 can use honeycomb structure.Specifically, porous mass filter 2 is for example, cylindric, internally have with
The next door 22 and multiple units 23 of the extensions of X vertically to be fenced up by next door 22 that clathrate is set.Porous mass filter
Shape both can be the polygon prism shape of cylindric as the present embodiment or quadrangular etc..In addition, next door 22 can
With the shape such as this reality of the unit 23 in the radial section (that is, the section on the direction vertical with axial X) of porous mass filter 2
Apply mode and formed like that as the mode of quadrangle.In addition, next door 22 can also be with the radial section of porous mass filter 2
The mode that the shape of unit 23 turns into the polygons such as triangle, hexagon, octagon is formed, and can also be with said units 23
Shape turn into circular mode and formed.
In addition, the end 27,28 of the one party in both ends of each unit 23 on axial X is sealed by spigot 29.It is specific and
Speech, as shown in figure 3, in multiple units 23 of porous mass filter 2, the downstream of inflow unit 231 that supply and discharge gas flows into
The end 27 of end 28 and the upstream side for the deliverying unit 232 for discharging exhaust is closed by spigot 29.Also, flow into unit
The end 27 of 231 upstream side, the end 28 in the downstream of deliverying unit 232 are open.In addition, the rock mechanism of spigot 29 is unlimited
In the present embodiment shown in Fig. 2 and Fig. 3.For example, can partly have end of the end 27 with downstream of upstream side
The unit 23 that 28 this two side are closed by spigot 29, can also partly end 27 and downstream with upstream side end 28 this
The unit 23 that two Fang Wei are closed by spigot 29.
As shown in FIG. 4 and 5, porous mass filter 2 is the porous body being made up of ceramic crystalline grain 21, internally with gas
Hole 26.Cordierite, SiC, aluminium titanates etc. can be used as ceramics.Exist between crystal grain 21 and be used as Nano grade (example
Such as 1nm~200nm) gap crystal boundary 211, in crystal boundary 211 formed with being for example made up of the sintered body of alpha aluminium oxide particle
Heat-stable ceramic layer 25.As long as heat-stable ceramic layer 25 is formed as at least filling the surface hole portion 212 of crystal boundary 211.Such as Fig. 5 institutes
Show, can also be formed as the inside that not only landfill surface opening portion 212 also fills crystal boundary 211 at least in part, and then can be with
Be formed as covering the surface of porous mass filter 2.Surface hole portion 212 refers to the crystal boundary 211 of crystal grain 21 and porous mass filter 2
The part of connection in interior stomata 26 or unit 23, crystal boundary 211 could also say that and catalyst containing Ag 3 or oxide particle 4
Support the part of face connection.
In addition, the catalyst containing Ag 3 that PM is removed for burning is supported with the next door 22 of porous mass filter 2.As containing
Ag catalyst 3, such as Ag, Ag alloy can be used, Ag and/or Ag alloys are configured between multiple alumina wafers
Catalyst etc..The catalyst containing Ag 3 of present embodiment is made up of Ag.Catalyst containing Ag 3 via ceria-zirconia particulate 41,
The grade of alumina particle 42 oxide particle 4 and support in porous mass filter 2.Catalyst containing Ag 3 is supported in the surface in next door 22
The inside in (specifically, the face exposed into unit 23 in next door 22) and next door 22 is (specifically, in next door 22
The face exposed to stomata 26).In addition, catalyst containing Ag 3 is supported in the next door of porous mass filter 2 via oxide particle 4
22.As shown in figure 5, as the oxide particle 4 in present embodiment, ceria-zirconia particulate 41 and aluminum oxide be present
Particle 42.That is, supported ceria-zirconia particles 41 of catalyst containing Ag 3 respectively and alumina particle 42 support in
The next door 22 of porous mass filter 2.
Next, the manufacture method of the exhaust-gas purifying filter of present embodiment is illustrated.
First, the cordierite raw material of the raw material of the porous mass filter as ojosa is prepared.Cordierite raw material contains
Silica, talcum, kaolin, aluminum oxide, aluminium hydroxide etc., contain carbon as improving the burning material of the porosity.
Also, carry out adjusting so that the final composition after firing is SiO for raw material composition2：47~55 mass %, Al2O3：33~42
Quality %, MgO：12~18 mass %.The porosity of porous mass filter can be controlled by adjusting carbon amounts.Cordierite raw material
By making water equal solvent, thickener, dispersant etc. mix jointly to be adjusted to clayey.The cordierite raw material of clayey passes through
It is extruded using mould, it is dried so as to obtain the formed body of honeycomb shape afterwards.
Next, preparing the cordierite raw material (hereinafter referred to as " spigot formation material ") of spigot formation, the raw material is existed
Disperse in water or oily equal solvent together with thickener, dispersant etc., to adjust slurry.The slurry is carried out by using mixer
Stir so as to obtain.
Next, the both ends of the surface in the formed body of honeycomb shape paste masking tape.Afterwards, with the phase in honeycomb formed article
The mode that adjacent unit is alternately open in both ends of the surface partly removes masking tape.Thus, the two of the unit for answering bolt seal
End face forms opening portion.The removal of masking tape such as can by the irradiation of laser carry out.Then, by honeycomb formed article
The above-mentioned spigot of both ends of the surface difference dipping form the slurry of material.Thus, immersed in from opening portion to the unit for answering bolt seal appropriate
Spigot formed material.
Then, after formed body is dried, the firing of formed body is carried out.Thus, formed body forms material sintering with spigot.
So, as shown in FIG. 2 and 3, it can obtain the ojosa that the opening portion of adjacent unit 23 is alternately closed by spigot 29
Porous mass filter 2.Porous mass filter 2 is cylindric, and the thickness in next door 22 for example can be in 0.1mm~0.4mm model
Enclose and interior suitably changed.In addition, the porosity of porous mass filter 2 can for example be carried out in the range of 40%~70%
Suitably change.
Next, by porous mass filter dipping in alumina sol.Thus, alumina sol is sucked into Porous mistake
In filter.Thereafter, porous mass filter is taken out from alumina sol, and winged unnecessary alumina sol is blown by air blast.Connect
, after porous mass filter is dried with 150 DEG C of temperature, with 800~1200 DEG C burn within 1~5 hour in baking furnace
System.Thus, as shown in figure 5, the crystal boundary 211 in the crystal grain 21 of cordierite forms the heat-stable ceramic layer 25 that is made up of aluminum oxide.
In addition, as alumina sol, the alumina sol 520 of Nissan Chemical Ind Ltd has been used.On the aluminum oxide
Colloidal sol, its average 1 particle diameter is 10~20nm, and pH is adjusted to 3~5, and crystalline form is boehmite.By using with crystal grain 21
Crystal boundary 211 gap compared to ceramic molecules such as average 1 less alumina sols of particle diameter, can be more reliably
Form the heat-stable ceramic layer 25 of the surface hole portion 212 of closure crystal boundary 211.In addition, average 1 particle diameter means to utilize laser
Diffraction/scattering method and particle diameter that the volume aggregate-value in the size distribution tried to achieve is 50%.
Next, the catalyst containing Ag that function is played as PM combustion catalysts is supported in honeycomb structure.First, such as with
Under the catalyst containing Ag for making oxidized composition granule like that and supporting.Specifically, 10 are turned into Al and Ag mol ratio：1
Mode weigh θ aluminum oxide and silver oxide, and put it into the closed vessel of Hydrothermal Synthesiss.Then, with closed vessel
Solid component add pure water into closed vessel as below 5 mass % mode, and inject and Al same molars
Nitric acid.Into the solution, add Ceria-zirconia solid solution pellet and mixed.Stir the content in closed vessel
Afterwards, make to close with keeping air atmosphere in closed vessel, kept for 24 hours under conditions of 175 DEG C of temperature, 10 air pressure.Thus,
The colloidal sol of Ag salic particle is supported.Catalyst colloidal sol has been obtained like this.
Next, by porous mass filter dipping in catalyst colloidal sol.Afterwards, Porous mistake is taken out from catalyst colloidal sol
Filter, blown by air blast and fly the unnecessary colloidal sol for being attached to porous mass filter.Then, with temperature 150 DEG C filter Porous
After device is dried, with the firing 1~5 hour of 400~1000 DEG C of temperature in baking furnace.Thus, porous mass filter 2 is made via by oxygen
Change the oxide particle 4 that cerium-zirconia particles 41 are formed with alumina particle and support catalyst containing Ag 3.Like this, schemed
Exhaust-gas purifying filter 1 shown in 2~Fig. 5.
Pair next, the action effect of present embodiment illustrates.
As shown in Fig. 2~Fig. 5, in exhaust-gas purifying filter 1, being made up of cordierite for porous mass filter 2 is being formed
Crystal grain 21 crystal boundary 211 at least surface hole portion 212, formed with heat-stable ceramic layer 25.That is, can turn into crystal boundary 211
The surface hole portion 212 of entrance blocked by heat-stable ceramic layer 25.Therefore, diffusions of the Ag into crystal boundary 211 is physically hidden
Gear, thus diffusions of the Ag in high temperature environments into crystal boundary 211 are suppressed, the Ag amounts in the surface of porous mass filter 2
The degree of reduction reduces.As a result, even if exhaust-gas purifying filter 1 is in high temperature environments, for the reduction of PM combustion characteristics
Degree also reduce.Also, Ag is into crystal boundary 211 during due to that can also prevent the heating when catalyst containing Ag 3 is supported
Diffusion, therefore the combustion characteristics for PM at initial stage after manufacture can be improved.
Shown in Fig. 6 and Fig. 7, the scan-type electricity on the surface of the porous mass filter before and after the formation of heat-stable ceramic layer
Sub- microscope (SEM) photo.Specifically, by cutting off each porous mass filter on axial X so that next door is exposed, and
The surface in next door is observed by SEM.As shown in Fig. 6 (a) and Fig. 7 (a), the Porous filtering before heat-stable ceramic layer is formed
In device, gap be present in the crystal boundary of crystal grain.On the other hand, as shown in Fig. 6 (b) and Fig. 7 (b), after heat-stable ceramic layer is formed,
The gap of crystal boundary is filled by heat-stable ceramic layer, and the surface hole portion of crystal boundary is blocked.
In addition, as in the present embodiment, preferably heat-stable ceramic layer 25 is not made only in surface hole portion 212, is also formed
In the inside of crystal boundary 211 and/or the surface of porous mass filter 2 (reference picture 5).Now, can further prevent from containing
Ag of diffusion from the Ag catalyst 3 to crystal boundary 211.In addition, now, the formation of heat-stable ceramic layer 25 becomes easy.That is, for example on
Alumina sol stated etc. is such, and porous mass filter dipping is being included into the slurry of the material for forming heat-stable ceramic layer
In, after air blast, heated, thus, it is possible to be readily derived in the surface hole portion 212 of crystal boundary 211 and inside, more
The surface of hole mass filter 2 forms the porous mass filter of heat-stable ceramic layer 25.In addition, heat-stable ceramic layer 25 both can be by crystalline substance
The inside on boundary all fills, and can also have the region not filled by heat-stable ceramic layer in the inside of crystal boundary.
Heat-stable ceramic layer 25 can use above-mentioned alumina sol etc. as, have average particulate diameter more than composition
The small ceramic molecule of the width of the crystal boundary 211 of the ceramic crystalline grain 21 of hole mass filter 2 and formed.By the way that Porous is filtered
Device 2 is impregnated in the slurry or colloidal sol containing such ceramic molecule, and the less ceramics of average particulate diameter can be made micro-
Little particle invades the crystal boundary of crystal grain.Then, as described above, can be in crystal boundary 211 by sintering ceramic molecule
And/or surface forms heat-stable ceramic layer 25.On the other hand, if porous mass filter is immersed in into the slurry containing ceramic molecule
In material or colloidal sol, then slurry or colloidal sol containing ceramic molecule not only invade the crystal boundary of the crystal grain 21 of porous mass filter 2
211st, also invaded into the stomata 26 of micron order (such as 0.2 μm~500 μm) present in porous mass filter 2.However,
Slurry or colloidal sol in stomata 26 remove easily by air blast.Therefore, it is possible to prevent in stomata 26 by ceramic molecule
Sintered body fills.And, it is suppressed that the increase of the pressure loss.
Preferably, the sintering for the ceramic molecule that heat-stable ceramic layer 25 is below 100nm by average 1 particle diameter
Body is formed.In this case, when forming heat-stable ceramic layer 25, form more reliably ceramic molecule intrusion porous
In the crystal boundary 211 of the ceramic crystalline grain 21 of mass filter 2.It is further preferred that heat-stable ceramic layer 25 is by average 1 particle diameter
The sintered body of below 50nm ceramic molecule is formed, it is further preferred that, it is below 30nm by average 1 particle diameter
Ceramic molecule sintered body form.In addition, average 1 particle diameter energy of the ceramic molecule in heat-stable ceramic layer
It is enough to be tried to achieve by using the analysis of the SEM photograph of image analysis software (such as WinROOF of three paddy business (strain)).
In the present embodiment, the heat-stable ceramic layer 25 being made up of Alpha-alumina is formd.Now, due to forming compactness
Higher heat-stable ceramic layer 25, therefore can further suppress diffusions of the Ag into crystal boundary 211.In addition, except above-mentioned α-oxygen
Change beyond aluminium, heat-stable ceramic layer 25 can also be by the temperature in use (such as 100~950 DEG C of temperature) in exhaust-gas purifying filter 1
Or stable ceramic material is formed under the hot environment (such as 300~1000 DEG C of temperature) during manufacture.Specifically, can be formed
By from aluminum oxide, cerium oxide, zirconium oxide, titanium oxide, silica, yittrium oxide, lanthana, neodymia, magnesia, iron oxide,
And at least one kind of and composition the heat-stable ceramic layer 25 selected in Ceria-zirconia solid solution.By from cerium oxide, oxygen
Change zirconium, titanium oxide, silica, yittrium oxide, lanthana, neodymia, magnesia, iron oxide and Ceria-zirconia solid solution
In the case of at least one kind of formation heat-stable ceramic layer 25 selected in body, heat-stable ceramic layer 25 can play co-catalyst performance.By
This, can realize the promotion of the PM burnings based on catalyst containing Ag 3.In addition, heat-stable ceramic layer 25 also can by Alpha-alumina with
Outer aluminum oxide (such as gama-alumina, δ-aluminum oxide, θ-aluminum oxide) and formed, from the excellent heat-stable ceramic of compactness can be formed
25 this viewpoint of layer are set out, preferably Alpha-alumina.In addition, Alpha-alumina, δ-aluminum oxide, θ-aluminum oxide, gama-alumina etc. are each
The crystal structure of aluminum oxide can be controlled by heating-up temperature after being impregnated in alumina sol etc..For example, by 600
Heating-up temperature is adjusted between~1200 DEG C, adjusted the heat time between 1~5 hour, can be formed by desired crystallization structure
The heat-stable ceramic layer 25 that the aluminum oxide made is formed.
In addition, catalyst containing Ag 3 is via the oxide being made up of ceria-zirconia particulate 41 and alumina particle 42
Particle 4 and support in porous mass filter 2 (reference picture 5).In this case, by being played by ceria-zirconia particulate 41
For the co-catalyst function of catalyst containing Ag 3 and the increase effect of the specific surface area played by alumina particle 42, energy
It is enough further to improve PM combustion activities.In addition, in this case, from the viewpoint of the mutual condensations of Ag are suppressed, it can also enter
One step improves PM combustion activities.As the oxide particle 4 for supporting catalyst containing Ag 3, except above-mentioned aluminum oxide can be used
Beyond particle, ceria-zirconia particulate, additionally it is possible to use cerium oxide particles, zirconia particles, titan oxide particles, dioxy
Silicon carbide particle, yttria particles, lanthanum oxide particles, neodymia particle, magnesium oxide particle, ferric oxide particles etc., additionally it is possible to will be several
These particles of kind are mixed and used.
(experimental example 1)
This example is to the various assays of manufactured exhaust-gas purifying filter (embodiment sample) progress in embodiment 1
Example.Embodiment sample has the porous mass filter 2 of ojosa being made up of cordierite and to be supported on this porous
The catalyst containing Ag being made up of Ag 3 (2~Fig. 5 of reference picture) in mass filter 2.Also, the violet for forming porous mass filter 2 is blue or green
At least surface hole portion 212 of the crystal boundary 211 of the crystal grain 21 of stone, filled by the heat-stable ceramic layer 25 being made up of Alpha-alumina.Separately
Outside, in this experimental example, use as comparing, also the exhaust-gas purifying filter (comparative sample) for not forming heat-stable ceramic layer is entered
Assay is gone.The comparative sample be not by porous mass filter be impregnated in alumina sol and be made this point with
Outside, exhaust-gas purifying filter made of ground identical with embodiment sample.In addition, in experimental example 1 and experimental example described later 2,
On being marked with the reference identical used in already described embodiment 1, as long as not particularly shown, then it represents that with embodiment party
Inscape identical inscape in formula 1 etc..
(change of surface A g concentration)
Each exhaust-gas purifying filter (embodiment sample and comparative sample) before and after engine endurance test is investigated
Surface Ag concentration change.Engine endurance test in the pipe arrangement of petrol engine by setting each exhaust purification filter
Device simultaneously makes the atmosphere of air-fuel ratio (i.e. A/F ratios) 13 and air atmosphere alternately changes and keeps 5 under conditions of 850 DEG C of temperature
Hour is carried out.Then, expose next door by cutting off each exhaust-gas purifying filter before and after engine endurance test, and lead to
Cross electron probe microanalyzer (EPMA) analysis determine at any 10 point on next door surface each element concentration (at least Ag with
Al concentration of element).As EPMA analytical equipments, the EPMA-1720 for using (strain) Shimadzu Seisakusho Ltd. to make, applying voltage
Each element concentration is determined under 1 μm of 15kV, beam dimensions this analysis condition.It is catalyzed to eliminate the Ag that contains supported
The uneven influence of agent, is evaluated using the relative concentration of the Ag relative to alumina concentration.Ag relative concentration (%)
Calculated by following formulas (1).In addition, the change (%) of Ag concentration is calculated by following formulas (2).Its result such as Fig. 8
It is shown.
With respect to Ag concentration=100 × Ag concentration/Al concentration (1)
Change=100 of Ag concentration × (the relative Ag concentration before relative Ag concentration-long duration test after long duration test)/resistance to
Relative Ag concentration (2) before experiment long
(change of PM burning velocities)
Each exhaust-gas purifying filter (embodiment sample and comparative sample) before and after engine endurance test is investigated
PM burning velocities change.Long duration test is carried out identically with the change of above-mentioned surface A g concentration.Then, it is piled up in PM
Each exhaust-gas purifying filter before and after engine endurance test.Then, being divided with flow velocity 20L/ makes nitrogen in exhaust-gas purifying filter
Middle circulation and with programming rate 50 DEG C/minute exhaust-gas purifying filter is heated to 500 DEG C of temperature, protected at 500 DEG C of the temperature
Hold between 5 points.Thereafter, circulated by making oxygen-containing 10 volume % nitrogen with flow velocity 20L/ points in exhaust-gas purifying filter, so as to
The PM accumulated in exhaust-gas purifying filter is set to burn.Then, by determining by PM burning and caused CO2With CO amount 8
Minute, so as to try to achieve the PM amounts burnt within the stipulated time.Then, the PM quantity combusteds based on the stipulated time, are calculated from oxygen
The average PM burning velocities (mg/ seconds) of 5 seconds are played after importing.In addition, (strain) hole field is used to make made gas analyser
" MEXA-1600D " determines CO2With CO amount.Also, the PM before and after engine endurance test is calculated by following formulas (3)
The change of burning velocity.Its result is as shown in Figure 9.
Change=100 of PM burning velocities × (the PM burning speed before PM burning velocities-long duration test after long duration test
Degree) PM burning velocities (3) before/long duration test
It can be seen from Fig. 8, the Ag concentration on exhaust-gas purifying filter its surface after long duration test of embodiment sample is almost
Do not change.Because in embodiment sample, the ceramics (specifically cordierite) of porous mass filter 2 are being formed
At least surface hole portion 212 of the crystal boundary 211 of crystal grain 21 is formed with heat-stable ceramic layer 25 (reference picture 4 and Fig. 5).That is, pass through
The heat-stable ceramic layer 25 can suppress to be supported containing in the surface of porous mass filter 2 present at least at surface hole portion 212
Ag catalyst 3 (specifically Ag) spreads into crystal boundary, inhibits the reduction of the Ag concentration on surface as described above.As a result,
As being understood according to Fig. 9, the reduction of PM burning velocities is also inhibits after long duration test.
On the other hand, it can be seen from Fig. 8, the Ag on exhaust-gas purifying filter its surface after long duration test of comparative sample
Concentration is greatly reduced.Because in comparative sample, in the crystal boundary of the crystal grain 21 for the cordierite for forming porous mass filter 9
211 be formed without embodiment sample as heat-stable ceramic layer (reference picture 10).That is, due to the surface hole portion in crystal boundary 211
212, in the absence of the material for the diffusion for hindering catalyst containing Ag 3, support the catalyst containing Ag 3 in the surface of porous mass filter 9
Easily to the diffusion inside of crystal boundary 211.Therefore, as described above, the Ag concentration on surface reduces.As a result, such as it can be seen from Fig. 9
Like that, after long duration test, PM burning velocities are greatly lowered.In addition, Figure 10 be for comparative sample show with it is above-mentioned
The figure in Fig. 5 identicals region of embodiment 1.
In addition, the map analysis based on EPMA are carried out for the section of comparative sample.Specifically, adjustment resin
The sample that the section of landfill comparative sample forms, obtain the SEM photograph (wherein, reflection electronic picture) of the sample.Also, pair with
The SEM photograph identical region, has carried out EPMA map analysis.Its result is as shown in figure 11.Shone in the SEM shown in Figure 11 (a)
In piece, region A light gray zones domain representation cordierite, region B denseer gray area represents the resin for sample adjustment,
The region representation air layer of region C black.In addition, the white portion present in the region A being made up of cordierite represents Ag.
In Figure 11 (a), surrounded with ellipse to show main Ag domain of the existence.In addition, in Figure 11 (b), violet is shown with black
Green stone, resin, air phase, Ag domain of the existence is shown with white.In Figure 11 (b), also surrounded with ellipse main to show
Ag domain of the existence.Understood according to Figure 11 (a) and Figure 11 (b), in comparative sample, as described above due to the table of crystal boundary
Face opening portion is not blocked, and actually Ag is diffused into crystal boundary.In addition, EPMA passes through in device and condition same as described above
Under map analysis and carry out.
So, the embodiment sample for the porous mass filter that the surface hole portion with crystal boundary has been blocked by heat-stable ceramic layer
Compared with the comparative sample that surface hole portion is not blocked, diffusions of the Ag into crystal boundary is suppressed.Therefore, in embodiment sample
Exhaust-gas purifying filter in, the reduction degree of the combustion characteristics for PM under hot environment diminishes.
(experimental example 2)
In this example, heating-up temperature during formation by changing heat-stable ceramic layer, is formed by the different oxygen of crystal structure
Change the heat-stable ceramic layer that aluminium is formed, and shadow caused by the inhibition that is spread to Ag of the crystal structure that have studied heat-stable ceramic layer
Ring.
Specifically, first, alternately close the opening portion for adjacent unit being obtained in the same manner as above-mentioned embodiment 1
, the porous mass filter of the ojosa being made up of cordierite.Also, in the same manner as embodiment 1, by porous mass filter
After being immersed in alumina sol, porous mass filter is taken out from alumina sol, and winged unnecessary oxidation is blown by air blast
Alumina gel.
Then, after drying porous mass filter with 150 DEG C of temperature, with 600 DEG C, 800 DEG C or 1000 in baking furnace
Fire 5 hours DEG C respectively.Thus, the heat-stable ceramic layer that is made up of aluminum oxide is formd in the crystal boundary of the crystal grain of cordierite.In addition,
As alumina sol, using with the above-mentioned identical alumina sol of embodiment 1.Thereafter, in the same manner as embodiment 1,
It is used as the catalyst containing Ag of PM combustion catalysts performance function by supporting it, so as to obtain exhaust-gas purifying filter.
For with the exhaust gas purification of the heat-stable ceramic layer of (600 DEG C, 800 DEG C, 1000 DEG C) formation of each firing temperature
Filter, the change of Ag concentration and the change of PM burning velocities are determined identically with above-mentioned experimental example 1.Its result such as Figure 12
And shown in Figure 13.
It can be seen from Figure 12, have net with the exhaust of 1000 DEG C of heat-stable ceramic layers fired alumina sol and formed of temperature
Change filter, after long duration test, the Ag concentration on its surface does not almost change.Because lead under 1000 DEG C of this high temperature
Cross and fire and form the heat-stable ceramic layer being made up of Alpha-alumina of densification.I.e., by fine and close heat-stable ceramic layer fully
Inhibit diffusions of the Ag into crystal boundary.As a result, it can be seen from Figure 13, PM burning velocities are also inhibits after long duration test
Reduction.
On the other hand, for with 600 DEG C and 800 DEG C heat-stable ceramic layers fired alumina sol and formed of temperature
Exhaust-gas purifying filter, compared with 1000 DEG C of situations about being fired of temperature, the Ag concentration on the surface after long duration test drop
It is low.Because the heat-stable ceramic layer using gama-alumina as principal component is formd in the firing at 600 DEG C of temperature, in temperature
Formd in firing at 800 DEG C using δ-aluminum oxide and/or θ-aluminum oxide as the heat-stable ceramic layer of principal component, these oxidations
Aluminium compactness compared with Alpha-alumina is relatively low.Even with the heat-resisting pottery being made up of gama-alumina, δ-aluminum oxide, θ-aluminum oxide
Enamel coating, compared with the absence of the situation of heat-stable ceramic layer (specifically above-mentioned comparative sample), it can also suppress Ag diffusion,
But compared with Alpha-alumina, Ag diffusion inhibition reduces.As a result, it can be seen from Figure 13, carried out with 1000 DEG C with temperature
The situation of firing is compared, the reduction amplitude increase of the PM burning velocities after long duration test.Therefore, heat-stable ceramic layer is preferably by α-oxygen
Change aluminium to form.
As previously discussed, though understanding embodiments of the present invention, the present invention is not limited to above-mentioned embodiment,
Various deformations can be carried out in the range of its main idea by not departing from.
Description of reference numerals
1 exhaust-gas purifying filter
2 porous mass filters
21 crystal grain
211 crystal boundaries
212 surface hole portions
25 heat-stable ceramic layers
3 catalyst containing Ag
Claims (6)
1. a kind of exhaust-gas purifying filter (1), has：
Porous mass filter (2), contained particulate matter from the exhaust of internal combustion engine (5) discharge can be trapped；And
Catalyst containing Ag (3), support in the porous mass filter (2),
Above-mentioned porous mass filter (2) has heat-stable ceramic layer (25), and above-mentioned heat-stable ceramic layer (25) landfill forms the Porous
At least surface hole portion (212) in the crystal boundary (211) of the ceramic crystalline grain (21) of filter (2).
2. exhaust-gas purifying filter (1) as claimed in claim 1, wherein,
Above-mentioned heat-stable ceramic layer (25) is not only formed at above-mentioned surface hole portion (212), is also formed into the interior of above-mentioned crystal boundary (211)
Portion and at least one party on the surface of above-mentioned porous mass filter (2).
3. exhaust-gas purifying filter (1) as claimed in claim 1 or 2, wherein,
Above-mentioned heat-stable ceramic layer (25) is made up of the sintered body of average 1 below particle diameter 100nm ceramic molecule.
4. such as exhaust-gas purifying filter according to any one of claims 1 to 3 (1), wherein,
Above-mentioned heat-stable ceramic layer (25) from aluminum oxide, ceria, zirconium oxide and Ceria-zirconia solid solution by selecting
At least one kind of composition gone out.
5. such as exhaust-gas purifying filter according to any one of claims 1 to 4 (1), wherein,
Above-mentioned heat-stable ceramic layer (25) is made up of Alpha-alumina.
6. such as exhaust-gas purifying filter according to any one of claims 1 to 5 (1), wherein,
Above-mentioned catalyst containing Ag (3) is via from alumina particle, cerium oxide particles, zirconia particles and cerium oxide-oxidation
At least one kind of oxide particle (4) for being selected in zirconium solid solution particle and support in above-mentioned porous mass filter (2).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015151990A JP2017029916A (en) | 2015-07-31 | 2015-07-31 | Exhaust gas purification filter |
| JP2015-151990 | 2015-07-31 | ||
| PCT/JP2016/070240 WO2017022407A1 (en) | 2015-07-31 | 2016-07-08 | Exhaust gas purifying filter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107847915A true CN107847915A (en) | 2018-03-27 |
Family
ID=57942915
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680044690.8A Withdrawn CN107847915A (en) | 2015-07-31 | 2016-07-08 | Exhaust-gas purifying filter |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2017029916A (en) |
| CN (1) | CN107847915A (en) |
| DE (1) | DE112016003478T5 (en) |
| WO (1) | WO2017022407A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110617122A (en) * | 2018-06-20 | 2019-12-27 | 日本碍子株式会社 | Honeycomb filter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110617122A (en) * | 2018-06-20 | 2019-12-27 | 日本碍子株式会社 | Honeycomb filter |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112016003478T5 (en) | 2018-04-12 |
| JP2017029916A (en) | 2017-02-09 |
| WO2017022407A1 (en) | 2017-02-09 |
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Application publication date: 20180327 |