JP2001187344A - Waste gas cleaning material and waste gas cleaning device - Google Patents
Waste gas cleaning material and waste gas cleaning deviceInfo
- Publication number
- JP2001187344A JP2001187344A JP2000000236A JP2000000236A JP2001187344A JP 2001187344 A JP2001187344 A JP 2001187344A JP 2000000236 A JP2000000236 A JP 2000000236A JP 2000000236 A JP2000000236 A JP 2000000236A JP 2001187344 A JP2001187344 A JP 2001187344A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- gas purifying
- filter
- catalyst
- wall
- 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.)
- Granted
Links
- 239000002912 waste gas Substances 0.000 title abstract 7
- 238000004140 cleaning Methods 0.000 title abstract 3
- 239000011538 cleaning material Substances 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 118
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims abstract description 68
- RPYFZMPJOHSVLD-UHFFFAOYSA-N copper vanadium Chemical compound [V][V][Cu] RPYFZMPJOHSVLD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 17
- 238000005192 partition Methods 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 91
- 239000011148 porous material Substances 0.000 claims description 87
- 229910000510 noble metal Inorganic materials 0.000 claims description 33
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 31
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 238000009423 ventilation Methods 0.000 claims description 28
- 229910052878 cordierite Inorganic materials 0.000 claims description 26
- 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 group [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 claims description 26
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 24
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical group C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 24
- 238000001125 extrusion Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000011144 upstream manufacturing Methods 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 abstract description 289
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 229910016383 CuV2O6 Inorganic materials 0.000 abstract 1
- 238000000746 purification Methods 0.000 description 46
- 230000000694 effects Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000009471 action Effects 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005336 cracking Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004071 soot Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- 230000002542 deteriorative effect Effects 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 101100325793 Arabidopsis thaliana BCA2 gene Proteins 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SLPMWOSBXIRBOE-UHFFFAOYSA-N [N+](=O)(O)[O-].[N+](=O)([O-])[Pt](N)(N)[N+](=O)[O-] Chemical compound [N+](=O)(O)[O-].[N+](=O)([O-])[Pt](N)(N)[N+](=O)[O-] SLPMWOSBXIRBOE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- CGPVLUCOFNAVGV-UHFFFAOYSA-N copper;pentahydrate Chemical compound O.O.O.O.O.[Cu] CGPVLUCOFNAVGV-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RBFRVUKIVGOWND-UHFFFAOYSA-L oxygen(2-);vanadium(4+);sulfate Chemical compound [O-2].[V+4].[O-]S([O-])(=O)=O RBFRVUKIVGOWND-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas After Treatment (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Filtering Materials (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、ディーゼルエンジ
ンから排出される排ガス中に含まれるパティキュレート
(固体状炭素微粒子、液体あるいは固体状の高分子量炭
化水素微粒子)を燃焼して浄化する排ガス浄化材及び排
ガス浄化装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying material for purifying by burning particulates (solid carbon fine particles, liquid or solid high molecular weight hydrocarbon fine particles) contained in exhaust gas discharged from a diesel engine. And an exhaust gas purifying apparatus.
【0002】[0002]
【従来の技術】ディーゼルエンジンからの排ガスに含ま
れるパティキュレートは、その粒子径がほぼ1μm以下
で大気中に浮遊しやすく、また発ガン性物質も含んでい
ることから、人体への影響が大きな問題となり、ディー
ゼルエンジンからのパティキュレートの排出規制が強化
されつつある。2. Description of the Related Art Particulates contained in exhaust gas from a diesel engine have a particle diameter of about 1 μm or less, easily float in the atmosphere, and contain carcinogenic substances. It is becoming a problem, and regulations on particulate emissions from diesel engines are being tightened.
【0003】排ガスからのパティキュレートを除去する
方法の一つとして、耐熱性構造体からなる排ガス浄化体
でパティキュレートを捕集した後、バーナーやヒーター
等の加熱手段で排ガス浄化体を加熱して、パティキュレ
ートを燃焼し、炭酸ガスに変えて放出する方法がある。
また、排ガス浄化材としては、前述の排ガス浄化体に金
属酸化物等からなる排ガス浄化用触媒を担持したもので
あり、この場合捕集されたパティキュレートは排ガス浄
化用触媒の触媒作用によって触媒がないときに比べてよ
り低温で燃焼させることができる。As one method of removing particulates from exhaust gas, after collecting the particulates with an exhaust gas purifier composed of a heat-resistant structure, the exhaust gas purifier is heated by heating means such as a burner or a heater. There is a method of burning particulates and converting them into carbon dioxide gas.
Further, as the exhaust gas purifying material, the exhaust gas purifying body described above carries an exhaust gas purifying catalyst made of a metal oxide or the like. In this case, the collected particulates are catalyzed by the catalytic action of the exhaust gas purifying catalyst. It can be burned at a lower temperature than when it is not.
【0004】このような排ガス浄化用触媒を担持した排
ガス浄化材を用いて、パティキュレートを排ガス温度で
燃焼することができれば、加熱手段を排ガス浄化装置内
に配設する必要がなく、排ガス浄化装置の構成を簡単に
することができる。[0004] If the particulates can be burned at the temperature of the exhaust gas using the exhaust gas purifying material carrying such an exhaust gas purifying catalyst, there is no need to arrange a heating means in the exhaust gas purifying apparatus. Can be simplified.
【0005】しかしながら、現状では排ガス浄化用触媒
を担持した排ガス浄化材についても、排ガス温度でパテ
ィキュレートを十分に燃焼させることは困難であり、加
熱手段との併用が不可欠となっている。したがって、よ
り低温でパティキュレートを燃焼できる高い触媒活性を
有する排ガス浄化用触媒の開発が望まれている。However, at present, it is difficult for the exhaust gas purifying material carrying the exhaust gas purifying catalyst to sufficiently burn the particulates at the exhaust gas temperature, and it is indispensable to use it together with a heating means. Therefore, development of an exhaust gas purifying catalyst having a high catalytic activity capable of burning particulates at a lower temperature is desired.
【0006】排ガス浄化用触媒としては、これまでにC
uやV等の金属酸化物を用いたものが比較的高い活性を
有することが知られている。例えば、特開昭58−14
3840号公報(以下、イ号公報と略称する。)には、
CuとVを含む複合金属酸化物からなる排ガス浄化用触
媒が開示されている。また、特開昭58−174236
号公報(以下、ロ号公報と略称する。)には、Cu、
V、Mo等の金属酸化物にアルカリ金属を添加した排ガ
ス浄化用触媒が開示されている。また、特公平4−42
063公報(以下、ハ号公報と略称する。)には、C
u、Mn、Mo等の金属酸化物にアルカリ金属の酸化物
と貴金属を添加した排ガス浄化用触媒が開示されてい
る。As exhaust gas purifying catalysts, C-
It is known that those using metal oxides such as u and V have relatively high activity. For example, JP-A-58-14
No. 3840 (hereinafter abbreviated as “A”) discloses:
An exhaust gas purifying catalyst comprising a composite metal oxide containing Cu and V is disclosed. Also, Japanese Patent Application Laid-Open No. 58-174236
Publication (hereinafter abbreviated as Publication B) includes Cu,
An exhaust gas purifying catalyst in which an alkali metal is added to a metal oxide such as V or Mo is disclosed. In addition, 4-42
No. 063 (hereinafter abbreviated as C), C
There is disclosed an exhaust gas purifying catalyst in which an alkali metal oxide and a noble metal are added to a metal oxide such as u, Mn, and Mo.
【0007】[0007]
【発明が解決しようとする課題】しかしながら、イ号公
報、ロ号公報及びハ号公報に記載の排ガス浄化用触媒を
担持させた排ガス浄化材は、供給される排ガスと排ガス
浄化用触媒とを効率的に接触させ、捕集する構造を有し
ていないために、この排ガス浄化用触媒の触媒活性を十
分に活かすことができず排ガス中のパティキュレートが
捕捉されないまま通過してしまい、排ガス浄化率が低い
という問題点があった。However, the exhaust gas purifying material carrying the exhaust gas purifying catalyst described in Japanese Patent Application Laid-Open Publication Nos. A, B, and C discloses that the supplied exhaust gas and the exhaust gas purifying catalyst are efficiently used. The catalytic activity of the exhaust gas purifying catalyst cannot be fully utilized because it does not have a structure for contacting and collecting the exhaust gas, and the particulates in the exhaust gas pass without being trapped, resulting in an exhaust gas purification rate. Was low.
【0008】さらに、排ガス浄化触媒及びこれの担持す
る排ガス浄化材が、排ガスと良好な接触状態を維持させ
て触媒反応を効率的に起こさせる組織状態を有していな
いので、排ガス浄化材に捕集されたパティキュレートを
排ガス温度で十分に燃焼させることができないという問
題点があった。Further, since the exhaust gas purifying catalyst and the exhaust gas purifying material carried by the exhaust gas purifying catalyst do not have a structural state for maintaining a good contact state with the exhaust gas and efficiently causing a catalytic reaction, the exhaust gas purifying catalyst is trapped by the exhaust gas purifying material. There is a problem that the collected particulates cannot be sufficiently burned at the exhaust gas temperature.
【0009】本発明は上記従来の課題を解決するもので
あり、排ガスと触媒との反応効率及び捕集効率を高めて
パティキュレートを効率的に燃焼させることのできる排
ガス浄化材及び排ガス浄化装置を提供することを目的と
する。The present invention solves the above-mentioned conventional problems, and provides an exhaust gas purifying material and an exhaust gas purifying apparatus capable of increasing the reaction efficiency and trapping efficiency between an exhaust gas and a catalyst and efficiently burning particulates. The purpose is to provide.
【0010】[0010]
【課題を解決するための手段】本発明の排ガス浄化材
は、ガス透過性隔壁で仕切られた通気セルの集合体から
なるウォールスルー型フィルターの各隣接する通気セル
のガス入口側又はガス出口側の一方を交互に目封じして
なり、主たる結晶構造がCuV2O6である銅元素(a)
とバナジウム元素(b)のモル比(a:b)が1:1.
5〜1:3.5の銅バナジウム化合物(c)と、硫酸セ
シウム(d)とのモル比(c:d)が1:3〜1:3.
5である排ガス浄化触媒を前記通気セルの内壁面に被覆
して形成されている。The exhaust gas purifying material of the present invention comprises a gas inlet side or a gas outlet side of each adjacent ventilation cell of a wall-through filter comprising an aggregate of ventilation cells separated by gas-permeable partitions. Are alternately plugged, and a copper element (a) whose main crystal structure is CuV 2 O 6
And the molar ratio (a: b) of the vanadium element (b) is 1: 1.
The molar ratio (c: d) of the copper vanadium compound (c) of 5 to 1: 3.5 and the cesium sulfate (d) is 1: 3 to 1: 3.
5 is formed by coating the exhaust gas purification catalyst on the inner wall surface of the ventilation cell.
【0011】これによって、排ガスと触媒との反応効率
及び捕集効率を高めてパティキュレートを効率的に燃焼
させることのできる排ガス浄化材及び排ガス浄化装置を
提供することができる。As a result, it is possible to provide an exhaust gas purifying material and an exhaust gas purifying apparatus which can increase the reaction efficiency and the trapping efficiency between the exhaust gas and the catalyst and efficiently burn the particulates.
【0012】[0012]
【発明の実施の形態】請求項1に記載の排ガス浄化材
は、ガス透過性隔壁で仕切られた通気セルの集合体から
なるウォールスルー型フィルターの各隣接する通気セル
のガス入口側又はガス出口側の一方を交互に目封じして
なり、主たる結晶構造がCuV2O6である銅元素(a)
とバナジウム元素(b)のモル比(a:b)が1:1.
5〜1:3.5の銅バナジウム化合物(c)と、硫酸セ
シウム(d)とのモル比(c:d)が1:3〜1:3.
5である排ガス浄化触媒を前記通気セルの内壁面に被覆
して形成されている。The exhaust gas purifying material according to the first aspect of the present invention is a gas inlet side or a gas outlet of each adjacent ventilation cell of a wall-through filter comprising an aggregate of ventilation cells separated by gas-permeable partitions. A copper element (a) having a main crystal structure of CuV 2 O 6 with one of the sides alternately plugged
And the molar ratio (a: b) of the vanadium element (b) is 1: 1.
The molar ratio (c: d) of the copper vanadium compound (c) of 5 to 1: 3.5 and the cesium sulfate (d) is 1: 3 to 1: 3.
5 is formed by coating the exhaust gas purification catalyst on the inner wall surface of the ventilation cell.
【0013】これによって以下の作用が得られる。As a result, the following effects can be obtained.
【0014】(a)ウォールスルー型フィルターの各隣
接する通気セルのガス入口側又はガス出口側の一方が交
互に目封じされているので、排ガス浄化材に供給される
排ガスが排ガス浄化触媒で被覆されたガス透過性隔壁を
通過して、排ガスと排ガス浄化触媒とを確実に接触さ
せ、排ガス中の捕捉されたパティキュレートを効率的に
燃焼させることができる。(A) Since the gas inlet side or the gas outlet side of each adjacent ventilation cell of the wall-through type filter is alternately plugged, the exhaust gas supplied to the exhaust gas purifying material is covered with the exhaust gas purifying catalyst. The exhaust gas and the exhaust gas purifying catalyst can be reliably brought into contact with each other through the gas permeable partition wall, so that the trapped particulates in the exhaust gas can be efficiently burned.
【0015】(b)排ガス浄化触媒が主たる結晶構造が
CuV2O6で特定量比の銅バナジウム化合物と硫酸セシ
ウムを特定量比で含有しているので、複数の異なる酸化
状態を取ることのできる銅、バナジウムを混在させるこ
とによる優れた触媒活性を有効に利用して排ガス浄化効
率を向上させることができる。(B) Since the main crystal structure of the exhaust gas purifying catalyst is CuV 2 O 6 and contains a copper vanadium compound and a cesium sulfate at a specific ratio in a specific ratio, a plurality of different oxidation states can be taken. It is possible to improve the exhaust gas purification efficiency by effectively utilizing the excellent catalytic activity by mixing copper and vanadium.
【0016】(c)排ガス浄化触媒には硫酸セシウムが
添加されているので、銅バナジウム化合物を含む混合物
を焼成して形成される排ガス浄化触媒の焼結体強度を高
めて耐用性を向上させることができる。(C) Since cesium sulfate is added to the exhaust gas purifying catalyst, the strength of the sintered body of the exhaust gas purifying catalyst formed by firing a mixture containing a copper vanadium compound is improved to improve the durability. Can be.
【0017】(d)硫酸セシウムを排ガス中の硫化物成
分を酸化又は還元させる触媒として機能させることがで
き、この場合には排ガス浄化作用をさらに向上させるこ
とが可能である。(D) Cesium sulfate can function as a catalyst for oxidizing or reducing the sulfide component in the exhaust gas, and in this case, the action of purifying the exhaust gas can be further improved.
【0018】(e)銅バナジウム化合物と硫酸セシウム
とのモル比が両者の触媒活性を相乗的に最も発揮させる
ことのできる特定範囲に限定されるので、パティキュレ
ート中の固体状炭素微粒子を効果的に燃焼させることが
できる。(E) Since the molar ratio between the copper vanadium compound and the cesium sulfate is limited to a specific range in which the catalytic activities of both can be exhibited most synergistically, the solid carbon fine particles in the particulate can be effectively used. Can be burned.
【0019】(f)主たる結晶構造がCuV2O6である
ので、銅元素とバナジウム元素を燃焼触媒として最も効
率的に機能させる特定範囲に安定に維持できる。(F) Since the main crystal structure is CuV 2 O 6 , the copper element and the vanadium element can be stably maintained in a specific range in which they function most efficiently as a combustion catalyst.
【0020】ここで、ウォールスルー型フィルターは、
例えば、排ガス供給方向の長さが約120〜250m
m、直径が100〜250mmの円柱状や、直方体状で
あり、その円柱の軸方向や直方体の長さ方向に多数の通
気セルを集合して状態で構成されている。この通気セル
は、例えば正方形の流路断面を有して、通気セルの配置
数は2.54cm平方当たり100〜250個であっ
て、排ガスをこの通気セル内に通過させ、その通気セル
の入口側から出口側に向けて流すことができる。Here, the wall-through type filter is
For example, the length in the exhaust gas supply direction is about 120 to 250 m
m, a columnar shape having a diameter of 100 to 250 mm, or a rectangular parallelepiped, and a large number of ventilation cells are assembled in the axial direction of the cylinder or the lengthwise direction of the rectangular parallelepiped. The ventilation cell has, for example, a square flow path cross section. The number of ventilation cells is 100 to 250 per 2.54 cm 2, and the exhaust gas is passed through the ventilation cell. From the side to the exit side.
【0021】ウォールスルー型フィルターは、バインダ
ーを添加した可塑性原料を金型に供給して、通気セルを
多数有した形状に押出し成形したり、あるいは原料を分
散させたスラリーを型に流し込んで硬化させて成形する
ことができる。このウォールスルー型フィルターの材質
には、アルミナ、アルミナ−シリカ、ジルコニア、チタ
ニア、マグネシア、チタン酸アルミニウム、コージェラ
イト、ムライト、炭化ケイ素、炭化ホウ素、窒化ケイ
素、窒化アルミニウム、サイアロン等のセラミックス材
料が使用できる。この通気セルの隔壁部分即ち、ウォー
ルスルー型フィルターの本体部は、供給される排ガスを
透過させることのできるガス透過性を有するように、細
孔径や分布状態等の組織状態が調整されたものである。In the wall-through type filter, a plastic raw material to which a binder is added is supplied to a mold and extruded into a shape having a large number of ventilation cells, or a slurry in which the raw material is dispersed is poured into a mold and cured. Can be molded. Ceramic materials such as alumina, alumina-silica, zirconia, titania, magnesia, aluminum titanate, cordierite, mullite, silicon carbide, boron carbide, silicon nitride, aluminum nitride and sialon are used for the material of this wall-through filter. it can. The partition part of this ventilation cell, that is, the body part of the wall-through type filter has a gas permeability that allows the supplied exhaust gas to pass therethrough, and the tissue state such as pore diameter and distribution state is adjusted. is there.
【0022】このウォールスルー型フィルターの互いに
隣接する各通気セルの排ガス入口側及又は出口側の一方
が、アルミナ、シリカ、マグネシア、あるいはこれらの
複合酸化物成分物からなる結晶質やガラス質等の無機質
粉末と有機結合剤又は無機結合剤との混合物によって充
填されて、封止されている。これによって、ウォールス
ルー型フィルターを構成する各通気セルの通気性の隔壁
に、供給される排ガスを透過させ、排ガス流路を形成す
ることができ、通気セル上の触媒と接触させ、効率的に
触媒反応を起こすことができる。One of the exhaust gas inlet side and the outlet side of each of the ventilation cells adjacent to each other of the wall-through type filter is made of alumina, silica, magnesia, or a crystalline or vitreous material composed of a composite oxide component thereof. It is filled and sealed with a mixture of an inorganic powder and an organic binder or an inorganic binder. This allows the supplied exhaust gas to pass through the gas-permeable partition walls of each of the ventilation cells constituting the wall-through filter, thereby forming an exhaust gas flow path, and allowing the exhaust gas flow path to efficiently contact the catalyst on the ventilation cell, Catalytic reactions can take place.
【0023】銅バナジウム化合物としては、例えば、C
u5V2O10、CuV2O6、Cu3V2O 8が使用でき、ある
いはこれらの中から2種以上を混合した複合酸化物の状
態で用いることもできる。As the copper vanadium compound, for example, C
uFiveVTwoOTen, CuVTwoO6, CuThreeVTwoO 8Can be used
Or the form of a composite oxide in which two or more of these are mixed
It can also be used in a state.
【0024】排ガス浄化触媒は、銅バナジウム化合物及
び硫酸セシウムを含む混合物の層をウォールスルー型フ
ィルターの通気セル内の壁面に形成して、必要により所
定の温度で焼成させて形成した例えば厚みが数〜数十μ
mの触媒層である。The exhaust gas purifying catalyst is formed, for example, by forming a layer of a mixture containing a copper vanadium compound and cesium sulfate on the wall surface in a ventilation cell of a wall-through type filter and firing it at a predetermined temperature if necessary. ~ Several tens of μ
m of the catalyst layer.
【0025】銅バナジウム化合物と硫酸セシウムとのモ
ル比が1:3より小さいと、硫酸セシウムの量が多くな
り、硫酸セシウムが銅バナジウム化合物を覆ってしまう
ために、主触媒となる銅、バナジウムのうちすすに接触
しうる量が不足して、実質的な触媒機能を発揮させるこ
とができなくなる。また、この重量比が1:3.5より
大きくなると、硫酸セシウムの量が不足して、相乗効果
による触媒活性を十分に発揮できなくなるために好まし
くない。If the molar ratio of the copper vanadium compound to the cesium sulfate is less than 1: 3, the amount of cesium sulfate increases, and the cesium sulfate covers the copper vanadium compound. The amount that can be contacted with the soot is insufficient, and a substantial catalytic function cannot be exhibited. On the other hand, if the weight ratio is more than 1: 3.5, the amount of cesium sulfate is insufficient, and the catalytic activity due to the synergistic effect cannot be sufficiently exhibited.
【0026】請求項2に記載の排ガス浄化材は、請求項
1において、前記ウォールスルー型フィルターのガス透
過性隔壁がコージェライトであり、全細孔容積が0.2
cc/g以上、孔径10μm以上の細孔の容積が全細孔
容積に対して40〜60%、平均細孔径が8〜20μ
m、気孔率が40〜60%であるように構成されてい
る。[0026] In the exhaust gas purifying material according to claim 2, the gas permeable partition wall of the wall-through type filter is cordierite and the total pore volume is 0.2.
cc / g or more, the volume of pores having a pore diameter of 10 μm or more is 40 to 60% of the total pore volume, and the average pore diameter is 8 to 20 μm.
m, the porosity is 40-60%.
【0027】これによって、請求項1の作用の他、以下
の作用が得られる。Thus, the following operation can be obtained in addition to the operation of the first aspect.
【0028】(a)ガス透過性材料を熱膨張変化の少な
いコージェライトとして、透過性組織の条件が設定され
るので、排ガスを排ガス浄化材に供給する際の圧損を抑
制して、効率的に排ガス中のパティキュレートを捕捉
し、ガス流路に担持させた触媒を作用させて、パティキ
ュレートを効率的に燃焼させることができる。(A) Since the gas permeable material is cordierite having a small change in thermal expansion and the conditions of the permeable structure are set, the pressure loss at the time of supplying the exhaust gas to the exhaust gas purifying material is suppressed, and the gas is efficiently used. The particulates in the exhaust gas are captured, and the catalyst supported on the gas flow path is acted on, so that the particulates can be efficiently burned.
【0029】(b)コージェライトを用いて、その熱膨
張係数を低くすることができるので、自動車のマニホー
ルド内に装着して使用する際の過酷な温度変動に対して
も、生じる熱膨張差を小さくして亀裂や剥落等が生じる
のを抑制して、長期にわたる耐用性に優れた排ガス浄化
材とすることができる。(B) Since the coefficient of thermal expansion can be reduced by using cordierite, the difference in thermal expansion caused by severe temperature fluctuation at the time of mounting and using in a manifold of an automobile can be reduced. It is possible to make the exhaust gas purifying material excellent in long-term durability by suppressing the occurrence of cracks, spalling and the like by making it small.
【0030】(c)浄化の際のパティキュレート中の固
体状炭素微粒子と触媒との接触性が適正化され、パティ
キュレートが排ガス浄化材の中に蓄積することなく浄化
することができる。(C) The contact between the solid carbon fine particles in the particulates and the catalyst during purification is optimized, and the particulates can be purified without accumulating in the exhaust gas purifying material.
【0031】ここで、コージェライトにおける全細孔容
積が0.2cc/gより少ないと、ガス透過性が不足し
てフィルター内にパティキュレートが堆積しやすくなり
触媒機能を低下させる要因になる。また、孔径10μm
以上の細孔の容積が全細孔容積に対して40%、平均細
孔径が8μm、気孔率が40%よりそれぞれ小さい場合
には、ガスフィルターとして必要なガス透過性を確保す
ることが困難になる。逆に孔径10μm以上の細孔の容
積が全細孔容積に対して60%、平均細孔径が20μ
m、気孔率が60%よりそれぞれ大きい場合には、ガス
フィルターとして必要な構造体としての強度が低下する
等の弊害が強まるので好ましくない。Here, when the total pore volume of cordierite is less than 0.2 cc / g, gas permeability is insufficient, and particulates are easily deposited in the filter, which is a factor of deteriorating the catalytic function. Also, the hole diameter is 10 μm
When the volume of the above pores is smaller than 40% of the total pore volume, the average pore diameter is smaller than 8 μm, and the porosity is smaller than 40%, it is difficult to secure gas permeability necessary for a gas filter. Become. Conversely, the volume of pores having a pore diameter of 10 μm or more is 60% of the total pore volume, and the average pore diameter is 20 μm.
When the m and the porosity are each greater than 60%, adverse effects such as a decrease in the strength of a structure required as a gas filter are undesirably increased.
【0032】請求項3に記載の排ガス浄化材は、請求項
1において、前記ウォールスルー型フィルターのガス透
過性隔壁が押し出し成形により得られるチタン酸アルミ
ニウムであり、その平均細孔径が8〜42μm、気孔率
が29〜63μm、押し出し方向の熱膨張係数αaが−
2.3×10-6℃-1〜0×10-6℃-1、押し出し方向と
垂直な方向の熱膨張係数αbが0×10-6℃-1〜2.4
×10-6℃-1であるように構成されている。According to a third aspect of the present invention, in the exhaust gas purifying material according to the first aspect, the gas permeable partition wall of the wall-through type filter is aluminum titanate obtained by extrusion molding, and has an average pore diameter of 8 to 42 μm. The porosity is 29 to 63 μm, and the coefficient of thermal expansion α a in the extrusion direction is −
2.3 × 10 −6 ° C. −1 to 0 × 10 −6 ° C. −1 , and a thermal expansion coefficient α b in a direction perpendicular to the extrusion direction is 0 × 10 −6 ° C. −1 to 2.4.
It is configured to be × 10 −6 ° C. −1 .
【0033】これによって、請求項1の作用の他、以下
の作用が得られる。Thus, the following operation can be obtained in addition to the operation of the first aspect.
【0034】(a)ウォールスルー型フィルターの本体
が熱膨張係数の小さいチタン酸アルミニウムで構成さ
れ、しかもその特定方向の熱膨張係数、平均細孔径、気
孔率が所定範囲に設定されているので、耐熱衝撃性及び
ガス透過性に優れた排ガス浄化材を提供することができ
る。(A) Since the body of the wall-through type filter is made of aluminum titanate having a small coefficient of thermal expansion, and the coefficient of thermal expansion in a specific direction, the average pore diameter, and the porosity are set in predetermined ranges, An exhaust gas purifying material having excellent thermal shock resistance and gas permeability can be provided.
【0035】(b)浄化の際のパティキュレート中の固
体状炭素微粒子と触媒との接触性が適正化され、パティ
キュレートが排ガス浄化材の中に蓄積することなく浄化
すると共に、排ガス浄化材の耐熱性が向上し、パティキ
ュレート浄化の際の割れや溶損を防止する作用を有す
る。(B) The contact between the solid carbon fine particles in the particulates and the catalyst at the time of purification is optimized, and the particulates are purified without accumulating in the exhaust gas purifying material. Heat resistance is improved, and it has the effect of preventing cracking and melting during particulate purification.
【0036】ここで、平均細孔径が8μm、気孔率が2
9%よりそれぞれ小さいと、十分なガス透過性を確保す
ることが困難になる。逆に平均細孔径が42μm、気孔
率が63%よりそれぞれ大きいと機械的強度が不足し
て、耐用性が劣化する要因となるので好ましくない。Here, the average pore diameter is 8 μm and the porosity is 2
If each is less than 9%, it will be difficult to ensure sufficient gas permeability. Conversely, if the average pore diameter is greater than 42 μm and the porosity is greater than 63%, however, the mechanical strength is insufficient and the durability is deteriorated, which is not preferable.
【0037】押し出し方向の熱膨張係数αaが−2.3
×10-6℃-1より小さく、押し出し方向と垂直な方向の
熱膨張係数αbが0より小さい場合には、温度変動際し
て、両方向の熱膨張が亀裂等の発生し易い状態に作用す
ることもあるので好ましくない。また、押し出し方向の
熱膨張係数αaが0より大きく、押し出し方向と垂直な
方向の熱膨張係数αbが2.4×10-6℃-1より大きく
なる場合にも同様の傾向が現れるので好ましくない。The coefficient of thermal expansion α a in the extrusion direction is -2.3.
If the coefficient of thermal expansion α b in the direction perpendicular to the extrusion direction is smaller than 0 and smaller than × 10 -6 ° C. -1 , the thermal expansion in both directions acts in a state where cracks and the like are likely to occur when the temperature changes. It is not preferable because it may be performed. A similar tendency appears when the thermal expansion coefficient α a in the extrusion direction is larger than 0 and the thermal expansion coefficient α b in the direction perpendicular to the extrusion direction is larger than 2.4 × 10 −6 ° C. −1 . Not preferred.
【0038】請求項4に記載の排ガス浄化材は、請求項
1において、前記ウォールスルー型フィルターのガス透
過性隔壁が炭化ケイ素であり、平均細孔径が6〜15μ
m、気孔率が42〜53%であるように構成されてい
る。According to a fourth aspect of the present invention, in the exhaust gas purifying material according to the first aspect, the gas permeable partition wall of the wall-through type filter is made of silicon carbide and has an average pore diameter of 6 to 15 μm.
m, the porosity is 42 to 53%.
【0039】これによって、請求項1の作用の他、以下
の作用が得られる。Thus, the following operation can be obtained in addition to the operation of the first aspect.
【0040】(a)炭化ケイ素は、長時間高温にされて
もクリープ変形を起こすようなことがなく、高熱伝導性
で温度変動にも強いので、パティキュレート浄化の際の
割れや溶損を防止して耐熱性を向上できる。(A) Since silicon carbide does not undergo creep deformation even when subjected to high temperatures for a long time, has high thermal conductivity and is resistant to temperature fluctuations, it prevents cracking and melting damage during particulate purification. To improve heat resistance.
【0041】(b)炭化ケイ素が酸化されてなるSiO
2の被膜を介在させ、銅バナジウム化合物と硫酸セシウ
ムからなる排ガス浄化触媒とウォールスルー型炭化ケイ
素製フィルター本体との反応を防止できる。(B) SiO formed by oxidizing silicon carbide
The reaction of the exhaust gas purifying catalyst composed of the copper vanadium compound and cesium sulfate with the wall-through type silicon carbide filter body can be prevented by interposing the coating of ( 2 ).
【0042】ここで、炭化ケイ素の平均細孔径が6μ
m、気孔率が42%よりそれぞれ小さいと、十分なガス
透過性を確保することが困難になる。逆に平均細孔径が
15μm、気孔率が53%よりそれぞれ大きいと機械的
強度が不足して、耐用性が劣化する要因となるので好ま
しくない。Here, the average pore diameter of silicon carbide is 6 μm.
When m and the porosity are smaller than 42%, it is difficult to secure sufficient gas permeability. Conversely, if the average pore diameter is greater than 15 μm and the porosity is greater than 53%, however, the mechanical strength is insufficient and the durability is deteriorated, which is not preferable.
【0043】請求項5に記載の排ガス浄化装置は、請求
項1乃至4のいずれか1項に記載の排ガス浄化材を排ガ
ス流の上流側に配置し、貴金属を担持させた排ガス浄化
ハニカム体を排ガス流の下流側に配置して構成されてい
る。According to a fifth aspect of the present invention, there is provided an exhaust gas purifying honeycomb body having the exhaust gas purifying material according to any one of the first to fourth aspects arranged upstream of an exhaust gas flow and carrying a noble metal. It is arranged downstream of the exhaust gas flow.
【0044】これによって、以下の作用が得られる。As a result, the following effects can be obtained.
【0045】(a)担持される触媒の触媒特性と排ガス
流路の特性とが異なる排ガス浄化材と排ガス浄化ハニカ
ム体とをそれぞれ独立に分離して連続して設けることに
より、上流側の排ガス浄化材で排ガス中のパティキュレ
ート中のすすを確実に捕捉し燃焼させ、下流側の排ガス
浄化ハニカム体で効率的にパティキュレートの残りであ
るSOFや一酸化炭素、炭化水素等の有害成分を除去す
ることができる。(A) By providing an exhaust gas purifying material and an exhaust gas purifying honeycomb body having different catalytic characteristics and exhaust gas flow path characteristics from each other independently and continuously, the exhaust gas purifying on the upstream side is performed. The soot in the particulates in the exhaust gas is reliably captured and burned by the material, and the exhaust gas purification honeycomb body on the downstream side efficiently removes harmful components such as SOF, carbon monoxide, and hydrocarbons, which are the remaining particulates. be able to.
【0046】(b)貴金属を含む排ガスハニカム体を下
流側に設けるので、貴金属とパティキュレートが予め除
かれた排ガスを貴金属と接触させ、貴金属触媒の活性を
有効に利用できると共に、貴金属がパティキュレートと
接触することにより触媒特性が劣化するのを防止するこ
とができる。これによって、貴金属の必要量を少なくし
て、低いコストで排ガス浄化装置を製造することができ
る。(B) Since the exhaust gas honeycomb body containing the noble metal is provided on the downstream side, the exhaust gas from which the noble metal and the particulates have been removed in advance is brought into contact with the noble metal, so that the activity of the noble metal catalyst can be effectively used and the noble metal can be used in the particulate form. The catalyst characteristics can be prevented from deteriorating due to contact with. Thereby, the required amount of the noble metal can be reduced, and the exhaust gas purifying apparatus can be manufactured at low cost.
【0047】(c)遷移金属の酸化物を含む排ガス浄化
体と、貴金属を含む排ガス浄化ハニカム体を分離して設
けているために、遷移金属の酸化物と貴金属との結合な
どによる触媒組成の変化を防ぐことができ、それぞれの
耐用性を高められる。(C) Since the exhaust gas purifying body containing the oxide of the transition metal and the honeycomb body for purifying the exhaust gas containing the noble metal are provided separately, the catalyst composition by the combination of the oxide of the transition metal and the noble metal is formed. Changes can be prevented, and the durability of each can be increased.
【0048】ここで、排ガス浄化ハニカム体としては、
フロースルータイプのセラミックハニカム、ウォールス
ルータイプのセラミックハニカム、フロースルータイプ
のメタルハニカム等が挙げられるが、セラミックハニカ
ムが好適に使用される。セラミックハニカムの材質とし
ては、コージェライト、チタン酸アルミニウム、ムライ
ト、α−アルミナ、ジルコニア、チタニア、炭化ケイ素
等が挙げられる。Here, as the exhaust gas purifying honeycomb body,
Examples include a flow-through type ceramic honeycomb, a wall-through type ceramic honeycomb, and a flow-through type metal honeycomb. A ceramic honeycomb is preferably used. Examples of the material of the ceramic honeycomb include cordierite, aluminum titanate, mullite, α-alumina, zirconia, titania, silicon carbide, and the like.
【0049】これらの材料は、少なくともディーゼルエ
ンジンに適用した場合の排気ガス温度(約350〜45
0℃)よりも高温度に耐える耐熱性を有したものがよ
い。These materials are used at least in the exhaust gas temperature (approximately 350 to 45) when applied to a diesel engine.
(0 ° C.).
【0050】貴金属としては、白金、ロジウム、パラジ
ウム等の耐熱温度が高く触媒活性に優れ、しかも腐食し
難い金属が好適に用いられる。As the noble metal, a metal such as platinum, rhodium or palladium, which has a high heat resistance and high catalytic activity and is hardly corroded, is preferably used.
【0051】排ガス浄化ハニカム体の貴金属を担持させ
た触媒層は、耐熱性の高いシリカ、アルミナ、ジルコニ
ア、チタニア等又はこれらの複合物からなる無機酸化物
からなる粉末の粒子表面に貴金属を分散させて形成した
触媒担持体であり、これらの粉末あるいは成形体を所定
温度で焼結させるか、あるいは無機接着剤等を用いて層
状に固定化して形成される。The catalyst layer supporting the noble metal of the exhaust gas purifying honeycomb body is formed by dispersing the noble metal on the particle surface of a powder of an inorganic oxide having high heat resistance such as silica, alumina, zirconia, titania or a composite thereof. This is a catalyst carrier formed by sintering these powders or compacts at a predetermined temperature or fixing them in a layer using an inorganic adhesive or the like.
【0052】排ガス浄化ハニカム体に用いる貴金属は、
上流の排ガス浄化材捕捉できなかった排ガス中の共存成
分である一酸化炭素、炭化水素並びにパティキュレート
の残りであるSOFを浄化する作用を有する。The noble metals used in the exhaust gas purifying honeycomb body are as follows:
It has the function of purifying carbon monoxide and hydrocarbons, which are coexisting components in the exhaust gas that could not be captured in the upstream exhaust gas purifying material, and SOF, which is the remainder of particulates.
【0053】請求項6に記載の排ガス浄化装置は、請求
項5において、前記排ガス浄化ハニカム体が、Pt、P
d、Rhの内少なくとも一種以上をシリカ・アルミナを
コーティングしたアルミナ上に担持させてなる貴金属排
ガス浄化触媒を、コージェライト質又はチタン酸アルミ
ニウム質のハニカム体にコーティングして構成されてい
る。According to a sixth aspect of the present invention, in the exhaust gas purifying apparatus according to the fifth aspect, the exhaust gas purifying honeycomb body comprises Pt, Pt,
A catalyst for purifying a noble metal exhaust gas in which at least one of d and Rh is supported on alumina coated with silica / alumina is coated on a cordierite or aluminum titanate honeycomb body.
【0054】これによって、請求項5の作用の他、以下
の作用が得られる。Thus, in addition to the function of claim 5, the following function can be obtained.
【0055】(a)排ガス浄化ハニカム体が熱膨張率の
小さいコージェライト質又はチタン酸アルミニウム質か
らなるので、熱衝撃に対して優れた破壊抵抗性を有し
て、その耐用性を向上させることができる。(A) Since the exhaust gas purifying honeycomb body is made of cordierite or aluminum titanate having a low coefficient of thermal expansion, it has excellent fracture resistance to thermal shock and improves its durability. Can be.
【0056】(b)貴金属触媒をシリカ・アルミナをコ
ーティングしたアルミナ上に担持させているので、貴金
属触媒とアルミナ粒子と親和性を向上させることがで
き、貴金属触媒がアルミナ粒子から剥離するのを防止し
て、耐用性をさらに向上させることができる。(B) Since the noble metal catalyst is supported on alumina coated with silica / alumina, the affinity between the noble metal catalyst and the alumina particles can be improved, and the noble metal catalyst is prevented from peeling from the alumina particles. Thus, the durability can be further improved.
【0057】(c)シリカ・アルミナの作用によりSO
2との反応を抑制できる。(C) SO by the action of silica / alumina
Reaction with 2 can be suppressed.
【0058】以下に、本発明の実施の形態について図面
を参照しながら説明する。Hereinafter, embodiments of the present invention will be described with reference to the drawings.
【0059】(実施の形態1)図1は本発明の実施の形
態1の排ガス浄化材の断面図である。(Embodiment 1) FIG. 1 is a sectional view of an exhaust gas purifying material according to Embodiment 1 of the present invention.
【0060】図1において、1は実施の形態1の排ガス
浄化材、2は通気セルを多数有して構成されるウォール
スルー型フィルター、3はウォールスルー型フィルター
2の各通気セルの入口側又は出口側を交互に目封じした
目封じ部、4は通気セルの内壁面に層状に形成される排
ガス浄化触媒、5は排ガス浄化材1が装着される排ガス
浄化装置の容器6との間に介挿される無機繊維質材料等
からなるバルク状の断熱材である。In FIG. 1, reference numeral 1 denotes an exhaust gas purifying material according to the first embodiment, 2 denotes a wall-through filter having a large number of ventilation cells, and 3 denotes an inlet side of each ventilation cell of the wall-through filter 2 or A plugging portion in which the outlet side is plugged alternately, 4 is an exhaust gas purifying catalyst formed in layers on the inner wall surface of the ventilation cell, and 5 is an intermediary between a container 6 of the exhaust gas purifying device to which the exhaust gas purifying material 1 is mounted. It is a bulk heat insulator made of an inorganic fiber material or the like to be inserted.
【0061】排ガス浄化材1は通気セルの端部を交互に
目封じ部3で密封シールしたコージェライト質材料から
なるウォールスルー型フィルター2と、その通気セルの
表面に被覆された排ガス浄化触媒4とからなる。交互に
片端を目封じして排ガスの通気路を構成したウォールス
ルー型フィルター2は排ガス浄化材1の骨格をなすもの
であり、その全細孔容積が0.2cc/g以上、10μ
m以上の細孔容積が40〜60%、平均細孔径が8〜2
0μm、気孔率が40〜60%である時に、排ガス中の
パティキュレートをファイルター内に堆積させることな
く有効に燃焼させて排ガスを浄化する作用を有する。The exhaust gas purifying material 1 comprises a wall-through type filter 2 made of a cordierite material in which the ends of the ventilation cells are alternately hermetically sealed with plugging portions 3, and an exhaust gas purification catalyst 4 coated on the surface of the ventilation cell. Consists of The wall-through type filter 2 having an exhaust gas ventilation passage formed by alternately plugging one end forms a skeleton of the exhaust gas purifying material 1, and has a total pore volume of 0.2 cc / g or more and 10 μm or more.
m has a pore volume of 40 to 60% and an average pore diameter of 8 to 2
When the porosity is 0 μm and the porosity is 40 to 60%, it has an action of purifying the exhaust gas by effectively burning the particulates in the exhaust gas without accumulating in the filter.
【0062】ここで、全細孔容積が0.2cc/g以
下、10μm以上の細孔容積が40%未満、平均細孔径
が8μm未満、気孔率が40%未満の時には、パティキ
ュレートがフィルター内に堆積しやすく、又全細孔容積
が0.2cc/g以上で、10μm以上の細孔容積が6
0%よりも多く、平均細孔径が20μmよりも大きく、
気孔率が40%よりも大きくても、かえってフィルター
を通過するパティキュレートが増加して、パティキュレ
ートを十分に燃焼、浄化することができない。Here, when the total pore volume is 0.2 cc / g or less, the pore volume of 10 μm or more is less than 40%, the average pore diameter is less than 8 μm, and the porosity is less than 40%, the particulates are contained in the filter. And a total pore volume of 0.2 cc / g or more and a pore volume of 10 μm or more
More than 0%, the average pore size is greater than 20 μm,
Even if the porosity is larger than 40%, the amount of particulates passing through the filter is increased, and the particulates cannot be sufficiently burned and purified.
【0063】(実施の形態2)図2は本発明の実施の形
態2の排ガス浄化装置の断面図である。(Embodiment 2) FIG. 2 is a sectional view of an exhaust gas purifying apparatus according to Embodiment 2 of the present invention.
【0064】図2において、20は実施の形態2の排ガ
ス浄化装置、21は排ガス浄化装置20の容器6内の排
ガス浄化材1の下流側に設けられる排ガス浄化ハニカム
体、22は排ガス浄化ハニカム体21の排ガス流路の内
面に被覆される貴金属触媒である。なお、前記実施の形
態1と同様の機能を有するものについては、同一の符号
を付してその説明を省略する。In FIG. 2, reference numeral 20 denotes an exhaust gas purifying apparatus according to the second embodiment, 21 denotes an exhaust gas purifying honeycomb body provided downstream of the exhaust gas purifying material 1 in the container 6 of the exhaust gas purifying apparatus 20, and 22 denotes an exhaust gas purifying honeycomb body. Noble metal catalyst coated on the inner surface of the exhaust gas channel No. 21. Components having the same functions as those in the first embodiment are denoted by the same reference numerals, and description thereof is omitted.
【0065】実施の形態2の排ガス浄化装置20は、交
互に通気セルの片端を目封じ部3で封止してガス透過性
の隔壁を通るガス流路を形成し、隔壁面を排ガス浄化触
媒4で被覆したコージェライト質のウォールスルー型フ
ィルター2を排ガス流の上流側に配置し、排ガス流路表
面に被覆された貴金属触媒22を有した排ガス浄化ハニ
カム体21を排ガス流の下流側に配置して構成されてい
る。上流側に配置されたウォールスルー型フィルター2
は触媒フィルターの骨格をなすものであり、その全細孔
容積が0.2cc/g以上、10μm以上の細孔容積が
40〜60%、平均細孔径が8〜20μm、気孔率が4
0〜60%である時に、排ガス中のパティキュレート、
中でも主にSOOT(すす)をファイルター内に堆積さ
せることなく浄化する作用を有する。全細孔容積が0.
2cc/g以下、10μm以上の細孔容積が40%未
満、平均細孔径が8μm未満、気孔率が40%未満の時
には、パティキュレートがフィルター内に堆積しやす
く、又全細孔容積が0.2cc/g以上で、10μm以
上の細孔容積が60%よりも多く、平均細孔径が20μ
mよりも大きく、気孔率が40%よりも大きくても、か
えってフィルターを通過するパティキュレートが増加し
て、パティキュレートを十分に浄化することができな
い。下流側に配置された触媒フィルターの排ガス浄化ハ
ニカム体21は触媒フィルターの骨格をなすものであ
り、排ガス中のパティキュレート、中でもSOF分並び
に一酸化炭素や炭化水素を酸化させて浄化する作用を有
する。In the exhaust gas purifying apparatus 20 of the second embodiment, one end of the ventilation cell is alternately sealed with the plugging portion 3 to form a gas flow path passing through the gas permeable partition wall, and the partition wall surface is formed by the exhaust gas purifying catalyst. A cordierite-type wall-through type filter 2 coated with 4 is disposed on the upstream side of the exhaust gas flow, and an exhaust gas purification honeycomb body 21 having a noble metal catalyst 22 coated on the exhaust gas flow path surface is disposed on the downstream side of the exhaust gas flow. It is configured. Wall-through type filter 2 arranged on the upstream side
Is a skeleton of a catalyst filter, the total pore volume of which is 0.2 cc / g or more, the pore volume of 10 μm or more is 40 to 60%, the average pore diameter is 8 to 20 μm, and the porosity is 4
When it is 0 to 60%, particulates in exhaust gas,
Among them, it mainly has a function of purifying SOOT (soot) without accumulating in the filter. The total pore volume is 0.
When the pore volume is 2 cc / g or less, the pore volume of 10 μm or more is less than 40%, the average pore diameter is less than 8 μm, and the porosity is less than 40%, the particulates are easily deposited in the filter, and the total pore volume is 0.1 μm. At 2 cc / g or more, the pore volume of 10 μm or more is more than 60%, and the average pore diameter is 20 μm.
Even if the porosity is larger than m and the porosity is larger than 40%, the amount of particulates passing through the filter increases, and the particulates cannot be sufficiently purified. The exhaust gas purifying honeycomb body 21 of the catalyst filter disposed on the downstream side forms a skeleton of the catalyst filter, and has an action of oxidizing and purifying particulates, especially SOF, and carbon monoxide and hydrocarbons in the exhaust gas. .
【0066】(実施の形態3)実施の形態3の排ガス浄
化材は、実施の形態1のウォールスルー型フィルター2
の材質をコージェライト質材料からチタン酸アルミニウ
ム質材料に換えたもで、その配置構成は図1の場合と同
様である。(Embodiment 3) The exhaust gas purifying material of Embodiment 3 is the same as the wall-through filter 2 of Embodiment 1.
Is changed from a cordierite-based material to an aluminum titanate-based material, and its arrangement is the same as that of FIG.
【0067】実施の形態3の排ガス浄化材1は交互に片
端を目封じしたウォールスルー型チタン酸アルミニウム
製フィルターと、該チタン酸アルミニウム製フィルター
表面に被覆された排ガス浄化触媒4とからなる。交互に
片端を目封じしたウォールスルー型チタン酸アルミニウ
ム製フィルターは触媒の骨格をなすものであり、その平
均細孔径が8〜42μm、気孔率が29〜63%である
時に、浄化の際のパティキュレートと触媒との接触性が
適正化され、パティキュレートが排ガス浄化材の中に蓄
積することなく浄化すると共に、排ガス浄化材の耐熱性
が向上し、パティキュレート浄化の際の割れや溶損を防
止する作用を有する。平均細孔径が8μm未満、気孔率
が29%未満の時には、パティキュレートがフィルター
内に堆積しやすく、逆に平均細孔径が42μmよりも大
きく、気孔率が63%よりも大きくても、かえってフィ
ルターを通過するパティキュレートが増加して、パティ
キュレートを十分に浄化することができない。The exhaust gas purifying material 1 of the third embodiment comprises a wall-through type aluminum titanate filter whose one end is alternately plugged, and an exhaust gas purifying catalyst 4 coated on the surface of the aluminum titanate filter. The wall-through type aluminum titanate filter in which one end is alternately plugged forms the skeleton of the catalyst. When the average pore diameter is 8 to 42 μm and the porosity is 29 to 63%, the particle size of the filter during purification is reduced. The contact between the curate and the catalyst is optimized, and the particulates are purified without accumulating in the exhaust gas purifying material.The heat resistance of the exhaust gas purifying material is improved, and cracks and erosion during particulate purification are reduced. Has the effect of preventing. When the average pore size is less than 8 μm and the porosity is less than 29%, the particulates tend to accumulate in the filter. Conversely, even if the average pore size is greater than 42 μm and the porosity is greater than 63%, The amount of particulates passing through is increased, and the particulates cannot be sufficiently purified.
【0068】(実施の形態4)実施の形態4の排ガス浄
化装置は、実施の形態2のウォールスルー型フィルター
2の材質をコージェライト質材料からチタン酸アルミニ
ウム質材料に換えたものでその配置構成は図2にしめし
たものと同様である。(Embodiment 4) An exhaust gas purifying apparatus according to Embodiment 4 is obtained by changing the material of the wall-through type filter 2 of Embodiment 2 from a cordierite-based material to an aluminum titanate-based material. Are the same as those shown in FIG.
【0069】実施の形態4の排ガス浄化装置20は排気
ガス流の上流側に交互に片端を目封じしたウォールスル
ー型チタン酸アルミニウム製フィルターと、該チタン酸
アルミニウム製フィルター表面に被覆された触媒層とか
らなる排ガス浄化フィルターを、排ガス流の下流側にハ
ニカム体と、該ハニカム体表面上に被覆された触媒層と
からなる排ガス浄化フィルターとからなる。上流側に配
置された触媒フィルターの交互に片端を目封じしたウォ
ールスルー型チタン酸アルミニウム製フィルターは触媒
フィルターの骨格をなすものであり、その平均細孔径が
8〜42μm、気孔率が29〜63%である時に、排ガ
ス浄化の際のパティキュレートと触媒との接触性が適正
化され、パティキュレートが排ガス浄化材の中に蓄積す
ることなく浄化すると共に、排ガス浄化材の耐熱性が向
上し、パティキュレート浄化の際の割れや溶損を防止す
る作用を有する。平均細孔径が8μm未満、気孔率が2
9%未満の時には、パティキュレートがフィルター内に
堆積しやすく、逆に平均細孔径が42μmよりも大き
く、気孔率が63%よりも大きくても、かえってフィル
ターを通過するパティキュレートが増加して、パティキ
ュレートを十分に浄化することができない。下流側に配
置された触媒フィルターのハニカム体は触媒フィルター
の骨格をなすものであり、排ガス中のパティキュレー
ト、中でもSOF分並びに一酸化炭素や炭化水素を浄化
する作用を有する。The exhaust gas purifying apparatus 20 of the fourth embodiment comprises a wall-through type aluminum titanate filter having one end plugged alternately upstream of the exhaust gas flow, and a catalyst layer coated on the surface of the aluminum titanate filter. And an exhaust gas purification filter comprising a honeycomb body on the downstream side of the exhaust gas flow and a catalyst layer coated on the surface of the honeycomb body. The wall-through type aluminum titanate filter in which one end of the catalyst filter arranged alternately is plugged constitutes the skeleton of the catalyst filter, and has an average pore diameter of 8 to 42 μm and a porosity of 29 to 63. %, The contact between the particulates and the catalyst at the time of exhaust gas purification is optimized, the particulates are purified without accumulating in the exhaust gas purification material, and the heat resistance of the exhaust gas purification material is improved. It has the function of preventing cracking and melting during particulate purification. Average pore diameter of less than 8 μm, porosity of 2
When it is less than 9%, the particulates tend to accumulate in the filter, and conversely, even if the average pore diameter is greater than 42 μm and the porosity is greater than 63%, the particulates passing through the filter will increase, Particulates cannot be sufficiently purified. The honeycomb body of the catalyst filter disposed on the downstream side forms a skeleton of the catalyst filter, and has an action of purifying particulates in exhaust gas, especially SOF, carbon monoxide and hydrocarbons.
【0070】(実施の形態5)実施の形態5の排ガス浄
化材は、実施の形態1のウォールスルー型フィルター2
の材質をコージェライト質材料から炭化ケイ素質材料に
換えたものである。(Embodiment 5) The exhaust gas purifying material of Embodiment 5 is the same as the wall-through filter 2 of Embodiment 1.
Is changed from cordierite material to silicon carbide material.
【0071】実施の形態5の排ガス浄化材1は交互に片
端を目封じしたウォールスルー型炭化ケイ素製フィルタ
ーと、該炭化ケイ素製フィルター表面に被覆された排ガ
ス浄化触媒4の層とからなる。ウォールスルー型炭化ケ
イ素製フィルターは、その平均細孔径が6〜15μm、
気孔率が42〜53%である時に、浄化の際のパティキ
ュレートと触媒との接触性が適正化され、パティキュレ
ートが排ガス浄化材の中に蓄積することなく浄化すると
共に、排ガス浄化材の耐熱性が向上し、パティキュレー
ト浄化の際の割れや溶損を防止すると共に、ウォールス
ルー型炭化ケイ素製フィルターの表面に存在するSiO
2により銅バナジウム化合物と硫酸セシウムからなる排
ガス浄化触媒とウォールスルー型炭化ケイ素製フィルタ
ーとの反応を防止する作用を有する。平均細孔径が6μ
m未満、気孔率が42%未満の時には、パティキュレー
トがフィルター内に堆積しやすく、逆に平均細孔径が1
0μmよりも大きく、気孔率が53%よりも大きくて
も、かえってフィルターを通過するパティキュレートが
増加して、パティキュレートを十分に浄化することがで
きない。The exhaust gas purifying material 1 of the fifth embodiment comprises a wall-through type silicon carbide filter whose one end is alternately plugged, and a layer of the exhaust gas purifying catalyst 4 coated on the surface of the silicon carbide filter. The wall-through type silicon carbide filter has an average pore diameter of 6 to 15 μm,
When the porosity is 42 to 53%, the contact between the particulates and the catalyst during purification is optimized, the particulates are purified without accumulating in the exhaust gas purification material, and the heat resistance of the exhaust gas purification material is reduced. To prevent cracking and erosion during particulate purification, and to prevent the presence of SiO present on the surface of the wall-through type silicon carbide filter.
2 has the effect of preventing the reaction between the exhaust gas purification catalyst comprising a copper vanadium compound and cesium sulfate and the wall-through type silicon carbide filter. Average pore size is 6μ
When the porosity is less than 42% and the porosity is less than 42%, particulates tend to accumulate in the filter.
Even if it is larger than 0 μm and the porosity is larger than 53%, the amount of particulates passing through the filter increases, and the particulates cannot be sufficiently purified.
【0072】(実施の形態6)実施の形態6の排ガス浄
化装置は、実施の形態2のウォールスルー型フィルター
2の材質をコージェライト質から炭化ケイ素質に換えた
ものである。(Embodiment 6) In an exhaust gas purifying apparatus according to Embodiment 6, the material of the wall-through type filter 2 of Embodiment 2 is changed from cordierite to silicon carbide.
【0073】実施の形態6の排ガス浄化装置20は排ガ
ス流の上流側に交互に片端を目封じしたウォールスルー
型炭化ケイ素製フィルターと、該炭化ケイ素製フィルタ
ー表面に被覆された触媒層とからなる排ガス浄化フィル
ターを、排ガス流の下流側にハニカム体と、該ハニカム
体表面上に被覆された触媒層とからなる排ガス浄化フィ
ルターとからなる。上流側に配置された触媒フィルター
の交互に片端を目封じしたウォールスルー型炭化ケイ素
製フィルターは触媒フィルターの骨格をなすものであ
り、その平均細孔径が6〜15μm、気孔率が42〜5
3%である時に、浄化の際のパティキュレートと触媒と
の接触性が適正化され、パティキュレートが排ガス浄化
材の中に蓄積することなく浄化すると共に、排ガス浄化
材の耐熱性が向上し、パティキュレート浄化の際の割れ
や溶損を防止すると共にウォールスルー型炭化ケイ素製
フィルターの表面に存在するSiO2により銅バナジウ
ム化合物と硫酸セシウムからなる排ガス浄化触媒とウォ
ールスルー型炭化ケイ素製フィルターとの反応を防止す
る作用を有する。平均細孔径が6μm未満、気孔率が4
2%未満の時には、パティキュレートがフィルター内に
堆積しやすく、逆に平均細孔径が10μmよりも大き
く、気孔率が53%よりも大きくても、かえってフィル
ターを通過するパティキュレートが増加して、パティキ
ュレートを十分に浄化することができない。下流側に配
置された触媒フィルターのハニカム体は触媒フィルター
の骨格をなすものであり、排ガス中のパティキュレー
ト、中でもSOF分並びに一酸化炭素や炭化水素を浄化
する作用を有する。The exhaust gas purifying apparatus 20 of the sixth embodiment comprises a wall-through type silicon carbide filter whose one end is alternately plugged on the upstream side of the exhaust gas flow, and a catalyst layer coated on the surface of the silicon carbide filter. The exhaust gas purification filter includes an exhaust gas purification filter including a honeycomb body downstream of the exhaust gas flow and a catalyst layer coated on the surface of the honeycomb body. The wall-through type silicon carbide filter in which one end of the catalyst filter arranged alternately is plugged constitutes a skeleton of the catalyst filter, and has an average pore diameter of 6 to 15 μm and a porosity of 42 to 5 μm.
At 3%, the contact between the particulates and the catalyst during purification is optimized, and the particulates are purified without accumulating in the exhaust gas purifying material, and the heat resistance of the exhaust gas purifying material is improved. the wall-through type exhaust emission control catalyst and wall-through type silicon carbide filter made by carbonization SiO 2 existing on the surface of silicon made filter copper vanadium compound and a cesium sulfate as to prevent cracking or melting during purifying the particulates Has the effect of preventing reactions. Average pore diameter less than 6 μm, porosity of 4
When it is less than 2%, the particulates easily accumulate in the filter, and conversely, even if the average pore diameter is greater than 10 μm and the porosity is greater than 53%, the particulates passing through the filter increase, Particulates cannot be sufficiently purified. The honeycomb body of the catalyst filter disposed on the downstream side forms a skeleton of the catalyst filter, and has an action of purifying particulates in exhaust gas, especially SOF, carbon monoxide and hydrocarbons.
【0074】[0074]
【実施例】次に、本発明の実施の形態をさらに具体化し
た実施例について説明する。EXAMPLES Next, examples which further embody the embodiments of the present invention will be described.
【0075】(実施例1)それぞれ239.4g、48
9g及び705.6gの硫酸銅五水和物(ナカライテス
ク製)、酸化硫酸バナジウム(和光純薬工業製)及び硫
酸セシウム(添川理化学製)を2000gの精製水に溶
かした溶液に、全細孔容積が0.2cc/g、10μm
以上の細孔容積が45%、平均細孔径が13μm、気孔
率が48%、1インチ当たりのセル数が100個である
交互に片端を目封じしたウォールスルー型コージェライ
ト製フィルターを含浸し、余分な溶液をエアーブローに
より除去した後に、乾燥、焼成して排ガス浄化フィルタ
ーを得る。該排ガス浄化フィルターに断熱材を巻き付
け、所定の容器に固定する事で排ガス浄化材を得る。Example 1 239.4 g, 48 respectively
9 g and 705.6 g of copper sulfate pentahydrate (manufactured by Nacalai Tesque), vanadium oxide sulfate (manufactured by Wako Pure Chemical Industries) and cesium sulfate (manufactured by Soegawa Rikagaku) were dissolved in 2000 g of purified water. Volume is 0.2cc / g, 10μm
Impregnated with a filter made of a wall-through type cordierite having a pore volume of 45%, an average pore diameter of 13 μm, a porosity of 48%, and a cell number of 100 cells per inch alternately plugged at one end, After removing excess solution by air blow, drying and firing are performed to obtain an exhaust gas purification filter. An exhaust gas purifying material is obtained by winding a heat insulating material around the exhaust gas purifying filter and fixing it to a predetermined container.
【0076】(実施例2)最初に排ガス流の上流側に設
置する排ガス浄化フィルターの作製方法について説明す
る。それぞれ239.4g、489g及び705.6g
の硫酸銅五水和物(ナカライテスク製)、酸化硫酸バナ
ジウム(和光純薬工業製)及び硫酸セシウム(添川理化
学製)を2000gの精製水に溶かした溶液に、全細孔
容積が0.2cc/g、10μm以上の細孔容積が45
%、平均細孔径が13μm、気孔率が48%、1インチ
当たりのセル数が100個である交互に片端を目封じし
たウォールスルー型コージェライト製フィルターを含浸
し、余分な溶液をエアーブローにより除去した後に、乾
燥、焼成して排ガス浄化フィルターを得る。次に排ガス
流の下流側に設置する排ガス浄化フィルターの作製方法
について説明すると、375gの硝酸アルミニウム(和
光純薬工業製)を精製水5Lに加えて撹拌後、前記溶液
中に活性アルミナ(住友化学工業製)1400gを加え
て一昼夜撹拌する。次に、ケイ酸ナトリウム90gと水
酸化ナトリウム99.5gを加えて、活性アルミナ表面
上にシリカ・アルミナの前駆体を析出させる。前記溶液
を十分に洗浄後乾燥し、空気中で焼成する。次に、純水
2.5Lに分散剤(花王製)720gを加えた混合溶液
に、前記シリカ・アルミナを被覆した活性アルミナ14
00gを加えて20hr混合して、スラリーを作製す
る。このスラリーを前記混合溶液と同じ溶液で粉体濃度
が1/3になるように希釈して、この希釈スラリー中に
直径5.66インチ、長さ6インチ、セル数400セル
/平方インチのコージェライト製ハニカム構造体を浸漬
し、引き上げた後に余分なスラリーをエアブローにより
除去した後、300℃で乾燥する。この作業を数回繰り
返して所定量をコートした後、空気中で焼成する。次い
で、純水5Lに所定量の硝酸パラジウム、クエン酸を加
えた液中に前記ハニカム構造体を浸漬し、引き上げた後
に余分な溶液をエアブローにより除去した後、凍結乾燥
法により乾燥後、空気中で焼成する。最後に、純水5L
に所定量のジニトロジアミノ白金硝酸溶液、クエン酸を
溶解した液中に前記パラジウムを担持したハニカム構造
体を浸漬し、引き上げた後に余分な溶液をエアブローに
より除去した後、凍結乾燥法により乾燥後、還元雰囲気
中で焼成することで排ガス浄化フィルターを得る。(Example 2) First, a method of manufacturing an exhaust gas purifying filter installed upstream of an exhaust gas flow will be described. 239.4 g, 489 g and 705.6 g respectively
Of copper pentahydrate (manufactured by Nacalai Tesque), vanadium oxide (manufactured by Wako Pure Chemical Industries) and cesium sulfate (manufactured by Soegawa Rikagaku) in 2,000 g of purified water had a total pore volume of 0.2 cc. / G, pore volume of 10 μm or more is 45
%, An average pore diameter of 13 μm, a porosity of 48%, and a filter made of a wall-through type cordierite alternately plugged at one end with 100 cells per inch. After removal, drying and firing are performed to obtain an exhaust gas purification filter. Next, a method of manufacturing an exhaust gas purifying filter installed on the downstream side of the exhaust gas flow will be described. 375 g of aluminum nitrate (manufactured by Wako Pure Chemical Industries) is added to 5 L of purified water, stirred, and activated alumina (Sumitomo Chemical) is added to the solution. (Manufactured by Kogyo Co., Ltd.) and stirred for 24 hours. Next, 90 g of sodium silicate and 99.5 g of sodium hydroxide are added to precipitate a silica-alumina precursor on the surface of the activated alumina. The solution is thoroughly washed, dried and fired in air. Next, activated alumina 14 coated with the silica-alumina was added to a mixed solution obtained by adding 720 g of a dispersant (manufactured by Kao) to 2.5 L of pure water.
Add 00g and mix for 20hrs to make a slurry. This slurry was diluted with the same solution as the above-mentioned mixed solution so that the powder concentration became 1/3, and a cordier having a diameter of 5.66 inches, a length of 6 inches and a cell number of 400 cells / square inch was added to the diluted slurry. After dipping and lifting the honeycomb structure made of light, excess slurry is removed by air blow, and then dried at 300 ° C. This operation is repeated several times to coat a predetermined amount, and then fired in the air. Next, the honeycomb structure was immersed in a solution obtained by adding a predetermined amount of palladium nitrate and citric acid to 5 L of pure water, and after being pulled up, an excess solution was removed by air blow, followed by drying by a freeze-drying method, followed by drying in air. Baking. Finally, 5L of pure water
A predetermined amount of dinitrodiaminoplatinum nitric acid solution, the honeycomb structure carrying palladium is immersed in a solution of citric acid, and after pulling up, an excess solution is removed by air blow and then dried by a freeze-drying method. By firing in a reducing atmosphere, an exhaust gas purification filter is obtained.
【0077】それぞれの該排ガス浄化フィルターに断熱
材を巻き付け、所定容器の所定位置に固定する事で排ガ
ス浄化材を得る。An exhaust gas purifying material is obtained by wrapping a heat insulating material around each of the exhaust gas purifying filters and fixing it at a predetermined position in a predetermined container.
【0078】(実施例3)排ガス浄化触媒を担持するフ
ィルターが、平均細孔径が15μm、気孔率が50%、
押し出し方向の熱膨張係数αaが−2.3×10-6〜0
℃-1、押し出し方向と垂直な方向の熱膨張係数αaが0
〜2.4×10-6℃-1である交互に片端を目封じしたウ
ォールスルー型チタン酸アルミニウム製フィルターであ
ること以外は、実施例1と同様である。Example 3 A filter supporting an exhaust gas purifying catalyst has an average pore diameter of 15 μm, a porosity of 50%,
The coefficient of thermal expansion α a in the extrusion direction is −2.3 × 10 −6 to 0
℃ -1 , thermal expansion coefficient α a in the direction perpendicular to the extrusion direction is 0
It is the same as Example 1 except that it is a wall-through type aluminum titanate filter in which one end is alternately plugged at a temperature of up to 2.4 × 10 −6 ° C. −1 .
【0079】(実施例4)排ガス流の上流側に配置する
排ガス浄化触媒を担持するフィルターが、平均細孔径が
15μm、気孔率が50%、押し出し方向の熱膨張係数
αaが−2.3×10-6〜0℃-1、押し出し方向と垂直
な方向の熱膨張係数αaが0〜2.4×10-6℃-1であ
る交互に片端を目封じしたウォールスルー型チタン酸ア
ルミニウム製フィルターであること以外は、実施例2と
同様である。(Example 4) A filter carrying an exhaust gas purifying catalyst disposed on the upstream side of an exhaust gas flow has an average pore diameter of 15 µm, a porosity of 50%, and a thermal expansion coefficient α a in the extrusion direction of -2.3. × 10 -6 ~0 ℃ -1, extrusion direction and wall-through type aluminum titanate thermal expansion coefficient alpha a perpendicular direction is plugged alternately at one end is 0~2.4 × 10 -6 ℃ -1 It is the same as Example 2 except that it is a filter made.
【0080】(実施例5)排ガス浄化触媒を担持するフ
ィルターが、平均細孔径が9μm、気孔率が47%であ
る交互に片端を目封じしたウォールスルー型炭化ケイ素
製フィルターであること以外は、実施例1と同様であ
る。Example 5 A filter carrying an exhaust gas purifying catalyst was a wall-through type silicon carbide filter having an average pore diameter of 9 μm and a porosity of 47%, and alternately plugged at one end. This is similar to the first embodiment.
【0081】(実施例6)排ガス流の上流側に配置する
排ガス浄化触媒を担持するフィルターが、平均細孔径が
9μm、気孔率が47%である交互に片端を目封じした
ウォールスルー型炭化ケイ素製フィルターであること以
外は、実施例2と同様である。(Example 6) A wall-through type silicon carbide filter having an average pore diameter of 9 µm and a porosity of 47% was alternately plugged, with a filter carrying an exhaust gas purifying catalyst disposed upstream of the exhaust gas flow. It is the same as Example 2 except that it is a filter made.
【0082】(実施例A1)それぞれ239.4g、4
89g及び705.6gの硫酸銅五水和物(ナカライテ
スク製)、酸化硫酸バナジウム(和光純薬工業製)及び
硫酸セシウム(添川理化学製)を2000gの精製水に
溶かした溶液に、全細孔容積が0.2cc/gより小さ
く、10μm以上の細孔容積が40〜60%の範囲外、
平均細孔径が8〜20μmの範囲外、気孔率が40〜6
0%の範囲外で、1インチ当たりのセル数が100個で
ある交互に片端を目封じしたウォールスルー型コージェ
ライト製フィルターを含浸し、余分な溶液をエアーブロ
ーにより除去した後に、乾燥、焼成して排ガス浄化フィ
ルターを得る。該排ガス浄化フィルターに断熱材を巻き
付け、所定の容器に固定する事で排ガス浄化材を得た。(Example A1) 239.4 g each, 4
89 g and 705.6 g of copper sulfate pentahydrate (manufactured by Nacalai Tesque), vanadium oxide (manufactured by Wako Pure Chemical Industries) and cesium sulfate (manufactured by Soegawa Rikagaku) were dissolved in 2000 g of purified water. The volume is smaller than 0.2 cc / g and the pore volume of 10 μm or more is out of the range of 40 to 60%,
The average pore diameter is out of the range of 8 to 20 μm, and the porosity is 40 to 6.
Out of the range of 0%, the filter is impregnated with a wall-through type cordierite filter alternately plugged at one end with 100 cells per inch, excess solution is removed by air blow, and then dried and fired. To obtain an exhaust gas purification filter. An exhaust gas purifying material was obtained by winding a heat insulating material around the exhaust gas purifying filter and fixing it to a predetermined container.
【0083】(実施例A2)最初に排ガス流の上流側に
設置する排ガス浄化フィルターの作製方法について説明
すると、それぞれ239.4g、489g及び705.
6gの硫酸銅五水和物(ナカライテスク製)、酸化硫酸
バナジウム(和光純薬工業製)及び硫酸セシウム(添川
理化学製)を2000gの精製水に溶かした溶液に、全
細孔容積が0.2cc/gより小さく、10μm以上の
細孔容積が40〜60%の範囲外、平均細孔径が8〜2
0μmの範囲外、気孔率が40〜60%の範囲外で、1
インチ当たりのセル数が100個である交互に片端を目
封じしたウォールスルー型コージェライト製フィルター
を含浸し、余分な溶液をエアーブローにより除去した後
に、乾燥、焼成して排ガス浄化フィルターを得た。(Example A2) First, a method of manufacturing an exhaust gas purifying filter installed on the upstream side of an exhaust gas flow will be described. 239.4 g, 489 g and 705.
A solution prepared by dissolving 6 g of copper sulfate pentahydrate (manufactured by Nacalai Tesque), vanadium oxide (manufactured by Wako Pure Chemical Industries) and cesium sulfate (manufactured by Soegawa Rikagaku) in 2000 g of purified water has a total pore volume of 0. Smaller than 2 cc / g, pore volume of 10 μm or more is out of the range of 40 to 60%, and average pore size is 8 to 2
0 μm, porosity outside the range of 40-60%, 1
Impregnated with a filter made of a wall-through type cordierite alternately plugged at one end with 100 cells per inch, removing excess solution by air blow, drying and firing to obtain an exhaust gas purification filter. .
【0084】次に排ガス流の下流側に設置する排ガス浄
化ハニカム体の作製方法について説明する。375gの
硝酸アルミニウム(和光純薬工業製)を精製水5Lに加
えて撹拌後、前記溶液中に活性アルミナ(住友化学工業
製)1400gを加えて一昼夜撹拌する。次に、ケイ酸
ナトリウム90gと水酸化ナトリウム99.5gを加え
て、活性アルミナ表面上にシリカ・アルミナの前駆体を
析出させる。前記溶液を十分に洗浄後乾燥し、空気中で
焼成する。次に、純水2.5Lに分散剤(花王製)72
0gを加えた混合溶液に、前記シリカ・アルミナを被覆
した活性アルミナ1400gを加えて20hr混合し
て、スラリーを作製する。Next, a method for manufacturing an exhaust gas purifying honeycomb body installed on the downstream side of the exhaust gas flow will be described. 375 g of aluminum nitrate (manufactured by Wako Pure Chemical Industries) is added to 5 L of purified water, and the mixture is stirred. Then, 1400 g of activated alumina (manufactured by Sumitomo Chemical) is added to the solution, and the mixture is stirred for 24 hours. Next, 90 g of sodium silicate and 99.5 g of sodium hydroxide are added to precipitate a silica-alumina precursor on the surface of the activated alumina. The solution is thoroughly washed, dried and fired in air. Next, a dispersant (manufactured by Kao) 72 was added to 2.5 L of pure water.
To a mixed solution containing 0 g, 1400 g of activated alumina coated with the silica / alumina was added and mixed for 20 hours to prepare a slurry.
【0085】このスラリーを前記混合溶液と同じ溶液で
粉体濃度が1/3になるように希釈して、この希釈スラ
リー中に直径5.66インチ、長さ6インチ、セル数4
00セル/平方インチのコージェライト製ハニカム構造
体を浸漬し、引き上げた後に余分なスラリーをエアブロ
ーにより除去した後、300℃で乾燥する。This slurry was diluted with the same solution as the above-mentioned mixed solution so that the powder concentration was reduced to 1/3. The diluted slurry was 5.66 inches in diameter, 6 inches in length, and 4 cells in number.
A honeycomb structure made of cordierite of 00 cells / square inch is immersed and pulled up, and after removing excess slurry by air blow, drying is performed at 300 ° C.
【0086】この作業を数回繰り返して所定量をコート
した後、空気中で焼成する。次いで、純水5Lに所定量
の硝酸パラジウム、クエン酸を加えた液中に前記ハニカ
ム構造体を浸漬し、引き上げた後に余分な溶液をエアブ
ローにより除去した後、凍結乾燥法により乾燥後、空気
中で焼成する。This operation is repeated several times to coat a predetermined amount, followed by firing in air. Next, the honeycomb structure was immersed in a solution obtained by adding a predetermined amount of palladium nitrate and citric acid to 5 L of pure water, and after being pulled up, an excess solution was removed by air blow, followed by drying by a freeze-drying method and drying in air. Baking.
【0087】最後に、純水5Lに所定量のジニトロジア
ミノ白金硝酸溶液、クエン酸を溶解した液中に前記パラ
ジウムを担持させたハニカム構造体を浸漬し、引き上げ
た後に余分な溶液をエアブローにより除去した後、凍結
乾燥法により乾燥後、還元雰囲気中で焼成することで排
ガス浄化ハニカム体を得る。Lastly, the honeycomb structure carrying palladium was immersed in a predetermined amount of dinitrodiaminoplatinic nitric acid solution and a solution of citric acid dissolved in 5 liters of pure water, pulled up, and the excess solution was removed by air blowing. Then, after drying by a freeze-drying method, it is fired in a reducing atmosphere to obtain an exhaust gas purifying honeycomb body.
【0088】それぞれの該排ガス浄化材及び排ガス浄化
ハニカム体に断熱材を巻き付け、所定容器の所定位置に
固定する事で排ガス浄化装置を構成した。A heat insulating material was wound around each of the exhaust gas purifying material and the exhaust gas purifying honeycomb body, and was fixed at a predetermined position in a predetermined container to constitute an exhaust gas purifying apparatus.
【0089】(実施例A3)排ガス浄化触媒を担持する
フィルターが、平均細孔径が8〜42μmの範囲外、気
孔率が29〜63%の範囲外、押し出し方向の熱膨張係
数αaが−2.3×10-6〜0℃-1の範囲外、押し出し
方向と垂直な方向の熱膨張係数αaが0〜2.4×10
-6℃-1の範囲外である交互に片端を目封じしたウォール
スルー型チタン酸アルミニウム製フィルターであること
以外は、実施例1と同様である。(Example A3) A filter carrying an exhaust gas purifying catalyst has an average pore diameter outside the range of 8 to 42 μm, a porosity outside the range of 29 to 63%, and a thermal expansion coefficient α a in the extrusion direction of −2. Outside the range of 3 × 10 −6 to 0 ° C. −1, the coefficient of thermal expansion α a in the direction perpendicular to the extrusion direction is 0 to 2.4 × 10
It is the same as Example 1 except that it is a wall-through type aluminum titanate filter alternately plugged at one end outside the range of -6 ° C- 1 .
【0090】(実施例A4)排ガス流の上流側に配置す
る排ガス浄化触媒を担持するフィルターが、平均細孔径
が8〜42μmの範囲外、気孔率が29〜63%の範囲
外、押し出し方向の熱膨張係数αaが−2.3×10-6
〜0℃-1の範囲外、押し出し方向と垂直な方向の熱膨張
係数αaが0〜2.4×10-6℃-1の範囲外である交互
に片端を目封じしたウォールスルー型チタン酸アルミニ
ウム製フィルターであること以外は、実施例2と同様で
ある。(Example A4) A filter carrying an exhaust gas purifying catalyst disposed on the upstream side of an exhaust gas flow has an average pore diameter outside the range of 8 to 42 μm, a porosity outside the range of 29 to 63%, and Thermal expansion coefficient α a is -2.3 × 10 -6
A wall-through type titanium having one end alternately plugged out of the range of 0 ° C. -1 and a coefficient of thermal expansion α a in the direction perpendicular to the extrusion direction of 0 to 2.4 × 10 -6 ° C. -1 It is the same as Example 2 except that it is a filter made of aluminum acid.
【0091】(実施例A5)排ガス浄化触媒を担持する
フィルターが、平均細孔径が6〜15μmの範囲外、気
孔率が42〜53%の範囲外である交互に片端を目封じ
したウォールスルー型炭化ケイ素製フィルターであるこ
と以外は、実施例1と同様である。(Example A5) A filter carrying an exhaust gas purifying catalyst was a wall-through type filter having an average pore diameter outside the range of 6 to 15 μm and a porosity outside the range of 42 to 53%, and alternately plugged at one end. It is the same as Example 1 except that the filter is made of silicon carbide.
【0092】(実施例A6)排ガス流の上流側に配置す
る排ガス浄化触媒を担持するフィルターが、平均細孔径
が6〜15μmの範囲外、気孔率が42〜53%の範囲
外である交互に片端を目封じしたウォールスルー型炭化
ケイ素製フィルターであること以外は、実施例2と同様
である。(Example A6) Filters carrying an exhaust gas purifying catalyst arranged upstream of an exhaust gas flow alternately have an average pore diameter outside the range of 6 to 15 μm and a porosity outside the range of 42 to 53%. It is the same as Example 2 except that the filter is a wall-through type silicon carbide filter with one end plugged.
【0093】(評価実験1):触媒活性を評価する試験 前記(実施例1)〜(実施例6)及び(実施例A1)〜
(実施例A6)で作製したフィルター上へ均一に活性炭
をのせた後、固定床流通系反応装置にセットした。反応
ガスとして、酸素、二酸化硫黄を所定濃度含有する(バ
ランスガス=窒素)を流通させながら、温度を室温から
500℃まで昇温しながら活性炭の燃焼状況を、CO/
CO2センサーを用いて追跡し、活性炭が5%燃焼した
ときの温度で触媒性能(活性:単位℃)を比較した。ま
た、耐久試験として、500℃で所定時間加熱処理を行
った後、前記と同様の試験方法で触媒性能を評価した。(Evaluation Experiment 1): Test for Evaluating Catalyst Activity The above (Example 1) to (Example 6) and (Example A1) to
After the activated carbon was uniformly placed on the filter prepared in (Example A6), the filter was set in a fixed bed flow reactor. While flowing oxygen and sulfur dioxide containing predetermined concentrations (balance gas = nitrogen) as the reaction gas, the temperature of the activated carbon was increased from room temperature to 500 ° C. while the combustion state of the activated carbon was changed to CO /
Tracking was performed using a CO 2 sensor, and the catalyst performance (activity: unit ° C) was compared at the temperature at which activated carbon burned 5%. Further, as a durability test, after performing a heat treatment at 500 ° C. for a predetermined time, the catalyst performance was evaluated by the same test method as described above.
【0094】なお、(表1)〜(表3)はそれぞれコー
ジェライト、チタン酸アルミニウム、炭化ケイ素を素材
に用いたときの評価実験1の結果を、以降に示すリーク
率を求めた評価実験2の結果と合わせて示している。Tables 1 to 3 show the results of evaluation experiment 1 when cordierite, aluminum titanate and silicon carbide were used as materials, respectively, and evaluation experiment 2 in which the leak rate was determined. The results are shown together with the results.
【0095】[0095]
【表1】 [Table 1]
【0096】[0096]
【表2】 [Table 2]
【0097】[0097]
【表3】 [Table 3]
【0098】(評価実験2):リーク率を求める試験 (実施例1)〜(実施例6)及び(実施例A1)〜(実
施例A6)で作製したフィルターから直径70mm×厚
み1mmの試験片を切り出してこれをホルダーに固定し
た。ホルダーを、エンジン排気量3400cc、4気筒
のディーゼルエンジンの配管から分取したマイクロダイ
リューショントンネルの後流側に設置し、ホルダーの前
後の圧力差によりリーク率を求め、この結果を(表2)
に示した。(Evaluation Experiment 2): Test for Determining the Leakage Rate A test piece having a diameter of 70 mm and a thickness of 1 mm was obtained from the filters prepared in Examples 1 to 6 and A1 to A6. Was cut out and fixed to a holder. The holder was installed on the downstream side of the micro-dilution tunnel, which was separated from the pipe of a diesel engine with a displacement of 3400 cc and four cylinders, and the leak rate was calculated from the pressure difference between before and after the holder. )
It was shown to.
【0099】以上(表1)に示した結果より明らかなよ
うに、実施例1及び実施例2で示される排ガス浄化触媒
を有した排ガス浄化材は、実施例A1及び実施例A2に
示すものに比べてパティキュレートの燃焼浄化作用が良
好でパティキュレートのリーク率が低いことが分かる。As is clear from the results shown in Table 1 above, the exhaust gas purifying materials having the exhaust gas purifying catalysts shown in Examples 1 and 2 were the same as those shown in Examples A1 and A2. In comparison, it can be seen that the combustion purification action of the particulates is good and the leak rate of the particulates is low.
【0100】即ち、実施例1及び実施例2の排ガス浄化
材は、銅元素とバナジウム元素のモル比が1:1.5〜
1:3.5であり、その主たる結晶構造がCuV2O
6で、且つその存在比が25mol%以上である銅バナ
ジウム化合物と硫酸セシウムの比が1:3〜1:3.5
である排ガス浄化触媒を有し、その排ガス浄化触媒を、
全細孔容積が0.2cc/g以上、10μm以上の細孔
容積が40〜60%、平均細孔径が8〜20μm、気孔
率が40〜60%である交互に片端を目封じしたウォー
ルスルー型コージェライト製フィルターに担持させたも
のである。That is, the exhaust gas purifying materials of Example 1 and Example 2 had a molar ratio of copper element and vanadium element of 1: 1.5 to 1.5.
1: 3.5, and its main crystal structure is CuV 2 O
6 , and the ratio of the copper vanadium compound and the cesium sulfate whose abundance is 25 mol% or more is 1: 3 to 1: 3.5.
Having an exhaust gas purifying catalyst,
A wall through having one end sealed alternately having a total pore volume of 0.2 cc / g or more, a pore volume of 10 μm or more of 40 to 60%, an average pore diameter of 8 to 20 μm, and a porosity of 40 to 60%. It was carried on a cordierite filter.
【0101】一方、実施例A1及び実施例A2の排ガス
浄化材は、銅元素とバナジウム元素のモル比が1:1.
5〜1:3.5であり、その主たる結晶構造がCuV2
O6で、且つその存在比が25mol%以上である銅バ
ナジウム化合物と硫酸セシウムの比が1:3〜1:3.
5の特性を有する排ガス浄化触媒を有し、全細孔容積が
0.2cc/gより小さく、10μm以上の細孔容積が
40〜60%の範囲外、平均細孔径が8〜20μmの範
囲外、気孔率が40〜60%の範囲外である交互に片端
を目封じしたウォールスルー型コージェライト製フィル
ターに担持させたものである。On the other hand, in the exhaust gas purifying materials of Examples A1 and A2, the molar ratio of copper element to vanadium element was 1: 1.
5-1: 3.5, and its main crystal structure is CuV 2
O 6 , and the ratio of the copper vanadium compound having an abundance of 25 mol% or more to cesium sulfate is 1: 3 to 1: 3.
Exhaust gas purifying catalyst having the characteristic of No. 5, the total pore volume is smaller than 0.2 cc / g, the pore volume of 10 μm or more is outside the range of 40 to 60%, and the average pore diameter is outside the range of 8 to 20 μm. The filter is supported on a wall-through type cordierite filter having a porosity outside the range of 40 to 60% and having one end plugged alternately.
【0102】(表2)に示される結果より明らかなよう
に、実施例3及び実施例4で示される排ガス浄化触媒を
有した排ガス浄化材は、実施例A3及び実施例A4に示
すものに比べて、パティキュレートの浄化作用が良好で
リーク率が低いと共に、排ガス浄化材の耐熱性が向上
し、パティキュレート浄化の際の割れや溶損を防止でき
ることが判った。As is clear from the results shown in Table 2, the exhaust gas purifying materials having the exhaust gas purifying catalysts shown in Examples 3 and 4 were different from those shown in Examples A3 and A4. As a result, it has been found that the particulates have a good purifying action and a low leak rate, and the heat resistance of the exhaust gas purifying material is improved, so that cracking and melting damage during particulate purification can be prevented.
【0103】この実施例3及び4で示される排ガス浄化
材は、銅元素とバナジウム元素のモル比が1:1.5〜
1:3.5であり、その主たる結晶構造がCuV2O
6で、且つその存在比が25mol%以上である銅バナ
ジウム化合物と硫酸セシウムの比が1:3〜1:3.5
の排ガス浄化触媒を有し、その平均細孔径が8〜42μ
m、気孔率が29〜63%、押し出し方向の熱膨張係数
αaが−2.3×10-6〜0℃-1、押し出し方向と垂直
な方向の熱膨張係数αaが0〜2.4×10-6℃-1であ
る交互に片端を目封じしたウォールスルー型チタン酸ア
ルミニウム製フィルターに担持されて形成されている。The exhaust gas purifying materials shown in Examples 3 and 4 had a molar ratio of copper element to vanadium element of 1: 1.5 to 1.5.
1: 3.5, and its main crystal structure is CuV 2 O
6 , and the ratio of the copper vanadium compound and the cesium sulfate whose abundance is 25 mol% or more is 1: 3 to 1: 3.5.
Exhaust gas purification catalyst having an average pore diameter of 8 to 42 μm
m, the porosity is 29 to 63%, the coefficient of thermal expansion α a in the extrusion direction is −2.3 × 10 −6 to 0 ° C. −1 , and the coefficient of thermal expansion α a in the direction perpendicular to the extrusion direction is 0 to 2. 4 is carried to one end alternately is × 10 -6 ° C. -1 to plugging the wall-through type aluminum titanate filter is formed.
【0104】これに対して実施例A3及び実施例A4の
排ガス浄化材は、銅元素とバナジウム元素のモル比が
1:1.5〜1:3.5であり、その主たる結晶構造が
CuV 2O6で、且つその存在比が25mol%以上であ
る銅バナジウム化合物と硫酸セシウムの比が1:3〜
1:3.5である排ガス浄化触媒を有し、その排ガス浄
化触媒を、平均細孔径が8〜42μmの範囲外、気孔率
が29〜63%の範囲外、押し出し方向の熱膨張係数α
aが−2.3×10-6〜0℃-1の範囲外、押し出し方向
と垂直な方向の熱膨張係数αaが0〜2.4×10-6℃
-1の範囲外である交互に片端を目封じしたウォールスル
ー型チタン酸アルミニウム製フィルターに担持して形成
されたものである。On the other hand, in Examples A3 and A4,
Exhaust gas purifying materials have a molar ratio of copper to vanadium
1: 1.5 to 1: 3.5, whose main crystal structure is
CuV TwoO6And the abundance ratio is 25 mol% or more.
The ratio of copper vanadium compound to cesium sulfate is 1: 3 to
1: 3.5 Exhaust gas purification catalyst
The catalyst is converted to an average pore size outside the range of 8 to 42 μm, the porosity.
Is outside the range of 29 to 63%, and the thermal expansion coefficient α in the extrusion direction is α.
aIs -2.3 × 10-6~ 0 ° C-1Out of range, extrusion direction
Coefficient of thermal expansion α perpendicular toaIs 0 to 2.4 × 10-6° C
-1Alternately plugged at one end outside the range
-Formed supported on aluminum titanate filter
It was done.
【0105】(表3)に示される結果より明らかなよう
に、実施例5及び実施例6で示される排ガス浄化触媒を
有した排ガス浄化材は、実施例A5及び実施例A6に示
すものに比べて、パティキュレートの浄化作用が良好で
リーク率が低い共に、排ガス浄化材の耐熱性が向上し、
パティキュレート浄化の際の割れや溶損を防止でき、さ
らにウォールスルー型炭化ケイ素製フィルターの表面に
存在するSiO2により銅バナジウム化合物と硫酸セシ
ウムからなる排ガス浄化触媒とウォールスルー型炭化ケ
イ素製フィルターとの反応を防止する作用が良好なこと
が判った。As is clear from the results shown in Table 3, the exhaust gas purifying materials having the exhaust gas purifying catalysts shown in Examples 5 and 6 were different from those shown in Examples A5 and A6. Therefore, the purification action of particulates is good and the leak rate is low, and the heat resistance of the exhaust gas purification material is improved,
It can prevent cracking and erosion during particulate purification, and furthermore, an exhaust gas purification catalyst comprising a copper vanadium compound and cesium sulfate by SiO 2 present on the surface of the wall-through type silicon carbide filter and a wall-through type silicon carbide filter. It was found that the action of preventing the reaction was good.
【0106】この実施例5及び6で示される排ガス浄化
材は銅元素とバナジウム元素のモル比が1:1.5〜
1:3.5であり、その主たる結晶構造がCuV2O
6で、且つその存在比が25mol%以上である銅バナ
ジウム化合物と硫酸セシウムの比が1:3〜1:3.5
である排ガス浄化触媒を有し、その排ガス浄化触媒を、
平均細孔径が6〜15μm、気孔率が42〜53%であ
る交互に片端を目封じしたウォールスルー型炭化ケイ素
製フィルターに担持して形成されている。The exhaust gas purifying materials shown in Examples 5 and 6 had a molar ratio of copper element to vanadium element of 1: 1.5 to 1.5.
1: 3.5, and its main crystal structure is CuV 2 O
6 , and the ratio of the copper vanadium compound and the cesium sulfate whose abundance is 25 mol% or more is 1: 3 to 1: 3.5.
Having an exhaust gas purifying catalyst,
The filter is supported on a wall-through type silicon carbide filter having an average pore diameter of 6 to 15 μm and a porosity of 42 to 53% alternately plugged at one end.
【0107】また、実施例A5及び実施例A6で示した
排ガス浄化材は、銅元素とバナジウム元素のモル比が
1:1.5〜1:3.5であり、その主たる結晶構造が
CuV 2O6で、且つその存在比が25mol%以上であ
る銅バナジウム化合物と硫酸セシウムの比が1:3〜
1:3.5である排ガス浄化触媒を有し、その排ガス浄
化触媒を、平均細孔径が6〜15μmの範囲外、気孔率
が42〜53%の範囲外である交互に片端を目封じした
ウォールスルー型炭化ケイ素製フィルターに担持させて
形成したものである。Further, it was shown in Examples A5 and A6.
Exhaust gas purifying materials have a molar ratio of copper to vanadium
1: 1.5 to 1: 3.5, whose main crystal structure is
CuV TwoO6And the abundance ratio is 25 mol% or more.
The ratio of copper vanadium compound to cesium sulfate is 1: 3 to
1: 3.5 Exhaust gas purification catalyst
The average pore diameter of the activated catalyst is out of the range of 6 to 15 μm, and the porosity is
Is outside the range of 42-53%, and one end is plugged alternately
Supported on wall-through type silicon carbide filter
It was formed.
【0108】[0108]
【発明の効果】請求項1に記載の発明によれば、これに
よって以下の効果が得られる。According to the first aspect of the present invention, the following effects can be obtained.
【0109】(a)ウォールスルー型フィルターの各隣
接する通気セルのガス入口側又はガス出口側の一方が交
互に目封じされているので、排ガス浄化材に供給される
排ガスが排ガス浄化触媒で被覆されたガス透過性隔壁を
通過して、排ガスと排ガス浄化触媒とを確実に接触さ
せ、排ガス中の捕捉されたパティキュレートを効率的に
燃焼させることができる。(A) Since the gas inlet side or the gas outlet side of each adjacent ventilation cell of the wall-through type filter is alternately plugged, the exhaust gas supplied to the exhaust gas purifying material is covered with the exhaust gas purifying catalyst. The exhaust gas and the exhaust gas purifying catalyst can be reliably brought into contact with each other through the gas permeable partition wall, so that the trapped particulates in the exhaust gas can be efficiently burned.
【0110】(b)排ガス浄化触媒が主たる結晶構造が
CuV2O6で特定量比の銅バナジウム化合物と硫酸セシ
ウムを特定量比で含有しているので、複数の異なる酸化
状態を取ることのできる銅、バナジウムを混在させるこ
とによる優れた触媒活性を有効に利用して排ガス浄化効
率を向上させることができる。(B) Since the main crystal structure of the exhaust gas purifying catalyst is CuV 2 O 6 and contains a copper vanadium compound and a cesium sulfate at a specific ratio in a specific ratio, a plurality of different oxidation states can be taken. It is possible to improve the exhaust gas purification efficiency by effectively utilizing the excellent catalytic activity by mixing copper and vanadium.
【0111】(c)排ガス浄化触媒には硫酸セシウムが
添加されているので、銅バナジウム化合物を含む混合物
を焼成して形成される排ガス浄化触媒の焼結体強度を高
めて耐用性を向上させることができる。(C) Since cesium sulfate is added to the exhaust gas purifying catalyst, the strength of the sintered body of the exhaust gas purifying catalyst formed by firing the mixture containing the copper vanadium compound is improved to improve the durability. Can be.
【0112】(d)硫酸セシウムを排ガス中の硫化物成
分を酸化又は還元させる触媒として機能させることがで
き、この場合には排ガス浄化作用をさらに向上させるこ
とがも可能である。(D) Cesium sulfate can function as a catalyst for oxidizing or reducing sulfide components in exhaust gas, and in this case, the action of purifying exhaust gas can be further improved.
【0113】(e)銅バナジウム化合物と硫酸セシウム
とのモル比が両者の触媒活性を相乗的に最も発揮させる
ことのできる特定範囲に限定されるので、パティキュレ
ート中の固体状炭素微粒子を効果的に燃焼させることが
できる。(E) Since the molar ratio of the copper vanadium compound and the cesium sulfate is limited to a specific range capable of synergistically exhibiting the catalytic activities of both, the solid carbon fine particles in the particulates are effectively removed. Can be burned.
【0114】(f)主たる結晶構造がCuV2O6である
ので、銅元素とバナジウム元素を燃焼触媒として最も効
率的に機能させる特定範囲に安定に維持できる。(F) Since the main crystal structure is CuV 2 O 6 , the copper element and the vanadium element can be stably maintained in a specific range in which they function most efficiently as a combustion catalyst.
【0115】請求項2に記載の発明によれば、これによ
って、請求項1の効果の他、以下の効果が得られる。According to the second aspect of the present invention, the following effects can be obtained in addition to the effects of the first aspect.
【0116】(a)ガス透過性材料を熱膨張変化の少な
いコージェライトとして、透過性組織の条件が設定され
るので、排ガスを排ガス浄化材に供給する際の圧損を抑
制して、効率的に排ガス中のパティキュレートを捕捉
し、ガス流路に担持させた触媒を作用させて、パティキ
ュレートを効率的に燃焼させることができる。(A) Since the gas permeable material is cordierite with a small change in thermal expansion and the conditions of the permeable structure are set, the pressure loss when the exhaust gas is supplied to the exhaust gas purifying material is suppressed, and the gas is efficiently used. The particulates in the exhaust gas are captured, and the catalyst supported on the gas flow path is acted on, so that the particulates can be efficiently burned.
【0117】(b)コージェライトを用いて、その熱膨
張係数を低くすることができるので、自動車のマニホー
ルド内に装着して使用する際の過酷な温度変動に対して
も、生じる熱膨張差を小さくして亀裂や剥落等が生じる
のを抑制して、長期にわたる耐用性に優れた排ガス浄化
材とすることができる。(B) Since the coefficient of thermal expansion can be reduced by using cordierite, the difference in thermal expansion that occurs even when subjected to severe temperature fluctuations when used in a manifold of an automobile is used. It is possible to make the exhaust gas purifying material excellent in long-term durability by suppressing the occurrence of cracks, spalling and the like by making it small.
【0118】(c)浄化の際のパティキュレート中の固
体状炭素微粒子と触媒との接触性が適正化され、パティ
キュレートが排ガス浄化材の中に蓄積することなく浄化
することができる。(C) The contact between the solid carbon fine particles in the particulates and the catalyst during purification is optimized, and the particulates can be purified without accumulating in the exhaust gas purifying material.
【0119】請求項3に記載の発明によれば、これによ
って、請求項1の効果の他、以下の効果が得られる。According to the third aspect of the present invention, the following effects can be obtained in addition to the effects of the first aspect.
【0120】(a)ウォールスルー型フィルターの本体
が熱膨張係数の小さいチタン酸アルミニウムで構成さ
れ、しかもその特定方向の熱膨張係数、平均細孔径、気
孔率が所定範囲に設定されているので、耐熱衝撃性及び
ガス透過性に優れた排ガス浄化材を提供することができ
る。(A) Since the main body of the wall-through type filter is made of aluminum titanate having a small coefficient of thermal expansion, and the coefficient of thermal expansion in a specific direction, the average pore diameter, and the porosity are set within predetermined ranges, An exhaust gas purifying material having excellent thermal shock resistance and gas permeability can be provided.
【0121】(b)浄化の際のパティキュレート中の固
体状炭素微粒子と触媒との接触性が適正化され、パティ
キュレートが排ガス浄化材の中に蓄積することなく浄化
すると共に、排ガス浄化材の耐熱性が向上し、パティキ
ュレート浄化の際の割れや溶損を防止する作用を有す
る。(B) The contact between the solid carbon fine particles in the particulates and the catalyst during purification is optimized, and the particulates are purified without accumulating in the exhaust gas purifying material. Heat resistance is improved, and it has the effect of preventing cracking and melting during particulate purification.
【0122】請求項4に記載の発明によれば、これによ
って、請求項1の効果の他、以下の効果が得られる。According to the fourth aspect of the present invention, the following effects can be obtained in addition to the effects of the first aspect.
【0123】(a)炭化ケイ素は、長時間高温にされて
もクリープ変形を起こすようなことがなく、高熱伝導性
で温度変動にも強いので、パティキュレート浄化の際の
割れや溶損を防止して耐熱性を向上できる。(A) Since silicon carbide does not undergo creep deformation even when subjected to a high temperature for a long time, has high thermal conductivity and is resistant to temperature fluctuation, it prevents cracking and melting damage during particulate purification. To improve heat resistance.
【0124】(b)炭化ケイ素が酸化されてなるSiO
2の被膜を介在させ、銅バナジウム化合物と硫酸セシウ
ムからなる排ガス浄化触媒とウォールスルー型炭化ケイ
素製フィルター本体との反応を防止できる。(B) SiO formed by oxidizing silicon carbide
The reaction of the exhaust gas purifying catalyst composed of the copper vanadium compound and cesium sulfate with the wall-through type silicon carbide filter body can be prevented by interposing the coating of ( 2 ).
【0125】請求項5に記載の発明によれば、これによ
って、以下の効果が得られる。According to the fifth aspect of the present invention, the following effects can be obtained.
【0126】(a)担持される触媒の触媒特性と排ガス
流路の特性とが異なる排ガス浄化材と排ガス浄化ハニカ
ム体とをそれぞれ独立に分離して連続して設けることに
より、上流側の排ガス浄化材で排ガス中のパティキュレ
ート中のすすを確実に捕捉し燃焼させ、下流側の排ガス
浄化ハニカム体で効率的にパティキュレートの残りであ
るSOFや一酸化炭素、炭化水素等の有害成分を除去す
ることができる。(A) By providing an exhaust gas purifying material and an exhaust gas purifying honeycomb body which are different from each other in the catalytic characteristics of the supported catalyst and the characteristics of the exhaust gas flow path independently and continuously, the exhaust gas purifying material on the upstream side is provided. The soot in the particulates in the exhaust gas is reliably captured and burned by the material, and the exhaust gas purification honeycomb body on the downstream side efficiently removes harmful components such as SOF, carbon monoxide, and hydrocarbons, which are the remaining particulates. be able to.
【0127】(b)貴金属を含む排ガスハニカム体を下
流側に設けるので、貴金属とパティキュレートが予め除
かれた排ガスを貴金属と接触させ、貴金属触媒の活性を
有効に利用できると共に、貴金属がパティキュレートと
接触することにより触媒特性が劣化するのを防止するこ
とができる。これによって、貴金属の必要量を少なくし
て、低いコストで排ガス浄化装置を製造することができ
る。(B) Since the exhaust gas honeycomb body containing the noble metal is provided on the downstream side, the exhaust gas from which the noble metal and the particulates have been removed in advance is brought into contact with the noble metal, so that the activity of the noble metal catalyst can be effectively used and the noble metal can be used in the particulate form. The catalyst characteristics can be prevented from deteriorating due to contact with. Thereby, the required amount of the noble metal can be reduced, and the exhaust gas purifying apparatus can be manufactured at low cost.
【0128】(c)遷移金属の酸化物を含む排ガス浄化
体と、貴金属を含む排ガス浄化ハニカム体を分離して設
けているために、遷移金属の酸化物と貴金属との結合な
どによる触媒組成の変化を防ぐことができ、それぞれの
耐用性を高められる。(C) Since the exhaust gas purifying body containing the oxide of the transition metal and the honeycomb body for purifying the exhaust gas containing the noble metal are provided separately, the catalyst composition by the combination of the oxide of the transition metal and the noble metal is formed. Changes can be prevented, and the durability of each can be increased.
【0129】請求項6に記載の発明によれば、これによ
って、請求項5の効果の他、以下の効果が得られる。According to the sixth aspect of the present invention, the following effects can be obtained in addition to the effects of the fifth aspect.
【0130】(a)排ガス浄化ハニカム体が熱膨張率の
小さいコージェライト質又はチタン酸アルミニウム質か
らなるので、熱衝撃に対して優れた破壊抵抗性を有し
て、その耐用性を向上させることができる。(A) Since the exhaust gas purifying honeycomb body is made of cordierite or aluminum titanate having a small coefficient of thermal expansion, it has excellent fracture resistance to thermal shock and improves its durability. Can be.
【0131】(b)貴金属触媒をシリカ・アルミナをコ
ーティングしたアルミナ上に担持させているので、貴金
属触媒とアルミナ粒子と親和性を向上させることがで
き、貴金属触媒がアルミナ粒子から剥離するのを防止し
て、耐用性をさらに向上させることができる。(B) Since the noble metal catalyst is supported on alumina coated with silica / alumina, the affinity between the noble metal catalyst and the alumina particles can be improved, and the noble metal catalyst is prevented from peeling from the alumina particles. Thus, the durability can be further improved.
【0132】(c)シリカ・アルミナの作用によりSO
2との反応を抑制できる。(C) By the action of silica / alumina, SO
Reaction with 2 can be suppressed.
【図1】本発明の実施の形態1における排ガス浄化材の
断面図FIG. 1 is a sectional view of an exhaust gas purifying material according to a first embodiment of the present invention.
【図2】本発明の実施の形態2における排ガス浄化装置
の断面図FIG. 2 is a sectional view of an exhaust gas purifying apparatus according to Embodiment 2 of the present invention.
1 排ガス浄化材 2 ウォールスルー型フィルター 3 目封じ部 4 排ガス浄化触媒 5 断熱材 6 容器 20 排ガス浄化装置 21 排ガス浄化ハニカム体 22 貴金属触媒 DESCRIPTION OF SYMBOLS 1 Exhaust gas purifying material 2 Wall-through type filter 3 Sealing part 4 Exhaust gas purifying catalyst 5 Insulating material 6 Container 20 Exhaust gas purifying device 21 Exhaust gas purifying honeycomb body 22 Precious metal catalyst
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) B01J 27/224 B01J 35/04 301E 35/04 301 301P 35/10 301F 35/10 301 F01N 3/02 301B F01N 3/02 301 301E 3/10 A 3/10 3/24 N 3/24 E 3/28 301P 3/28 301 B01D 53/36 104B (72)発明者 徳渕 信行 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 井上 雅博 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Fターム(参考) 3G090 AA02 BA01 EA02 3G091 AA18 AB02 BA01 CA04 GA09 GA23 GB06W GB07W GB10W GB14W HA08 HA29 4D019 AA01 BA05 BB06 BC07 CA01 CB04 4D048 AA14 AB01 BA03X BA06X BA07X BA10X BA14X BA23X BA30X BA31X BA33Y BA35X BA42X BA45X BA46X BB02 BB12 BB14 CA01 CC04 CC34 CC46 CC63 CD05 EA07 4G069 AA03 AA08 BA01A BA01B BA03A BA03B BA13A BA13B BB02A BB02B BB06A BB06B BB10A BB10B BB15A BB15B BC06A BC06B BC16A BC16B BC31A BC31B BC50A BC50B BC54A BC54B BC71A BC72A BC72B BC75A BC75B BD05A BD05B CA07 CA18 EA19 EA25 EA27 EB10 EB12Y EB14Y EB15Y EC06X EC07X EC08X EC17X EC18X EC27 ED06 EE09 FA03 FA06 FB23 FC08 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 27/224 B01J 35/04 301E 35/04 301 301P 35/10 301F 35/10 301 F01N 3/02 301B F01N 3/02 301 301E 3/10 A 3/10 3/24 N 3/24 E 3/28 301P 3/28 301 B01D 53/36 104B (72) Inventor Nobuyuki Tokubuchi 1006 Kadoma Odama, Kadoma City, Osaka Matsushita Inside Electric Industrial Co., Ltd. (72) Inventor Masahiro Inoue 1006 Odakadoma, Kadoma City, Osaka Pref. Matsushita Electric Industrial Co., Ltd. F-term (reference) BA05 BB06 BC07 CA01 CB04 4D048 AA14 AB01 BA03X BA06X BA07X BA10X BA14X BA23X BA30X BA31X BA33Y BA35X BA42X BA45X BA46X BB02 BB 12 BB14 CA01 CC04 CC34 CC46 CC63 CD05 EA07 4G069 AA03 AA08 BA01A BA01B BA03A BA03B BA13A BA13B BB02A BB02B BB06A BB06B BB10A BB10B BB15A BB15B BC06A BC06B BC16A BC16B BC31A BC31B BC50A BC50B BC54A BC54B BC71A BC72A BC72B BC75A BC75B BD05A BD05B CA07 CA18 EA19 EA25 EA27 EB10 EB12Y EB14Y EB15Y EC06X EC07X EC08X EC17X EC18X EC27 ED06 EE09 FA03 FA06 FB23 FC08
Claims (6)
合体からなるウォールスルー型フィルターの各隣接する
通気セルのガス入口側又はガス出口側の一方を交互に目
封じしてなり、主たる結晶構造がCuV2O6である銅元
素(a)とバナジウム元素(b)のモル比(a:b)が
1:1.5〜1:3.5の銅バナジウム化合物(c)
と、硫酸セシウム(d)とのモル比(c:d)が1:3
〜1:3.5である排ガス浄化触媒を前記通気セルの内
壁面に被覆して形成されたことを特徴とする排ガス浄化
材。1. A wall-through filter comprising a collection of ventilation cells separated by gas-permeable partitions, wherein one of the gas inlet side and the gas outlet side of each adjacent ventilation cell is alternately plugged, and is mainly used. Copper vanadium compound (c) having a crystal structure of CuV 2 O 6 and a molar ratio (a: b) of copper element (a) to vanadium element (b) of 1: 1.5 to 1: 3.5.
And the molar ratio (c: d) of cesium sulfate (d) is 1: 3
An exhaust gas purifying material formed by coating an inner wall surface of the ventilation cell with an exhaust gas purifying catalyst of 〜1: 3.5.
過性隔壁がコージェライトであり、全細孔容積が0.2
cc/g以上、孔径10μm以上の細孔の容積が全細孔
容積に対して40〜60%、平均細孔径が8〜20μ
m、気孔率が40〜60%であることを特徴とする請求
項1に記載の排ガス浄化材。2. The gas permeable partition wall of the wall-through type filter is cordierite, and the total pore volume is 0.2.
cc / g or more, the volume of pores having a pore diameter of 10 μm or more is 40 to 60% of the total pore volume, and the average pore diameter is 8 to 20 μm.
The exhaust gas purifying material according to claim 1, wherein m and the porosity are 40 to 60%.
過性隔壁が押し出し成形により得られるチタン酸アルミ
ニウムであり、その平均細孔径が8〜42μm、気孔率
が29〜63μm、押し出し方向の熱膨張係数αaが−
2.3×10-6℃-1〜0×10-6℃-1、押し出し方向と
垂直な方向の熱膨張係数αbが0×10- 6℃-1〜2.4
×10-6℃-1であることを特徴とする請求項1に記載の
排ガス浄化材。3. The gas permeable partition wall of the wall-through type filter is aluminum titanate obtained by extrusion molding, the average pore diameter is 8 to 42 μm, the porosity is 29 to 63 μm, and the coefficient of thermal expansion α in the extrusion direction is α. a is-
2.3 × 10 -6 ℃ -1 ~0 × 10 -6 ℃ -1, extrusion direction perpendicular to the direction of the thermal expansion coefficient alpha b is 0 × 10 - 6 ℃ -1 ~2.4
The exhaust gas purifying material according to claim 1 , wherein the temperature is × 10 -6 ° C -1 .
過性隔壁が炭化ケイ素であり、平均細孔径が6〜15μ
m、気孔率が42〜53%であることを特徴とする請求
項1に記載の排ガス浄化材。4. A gas permeable partition wall of the wall-through type filter is made of silicon carbide, and has an average pore diameter of 6 to 15 μm.
The exhaust gas purifying material according to claim 1, wherein m and the porosity are 42 to 53%.
ガス浄化材を排ガス流の上流側に配置し、貴金属を担持
させた排ガス浄化ハニカム体を排ガス流の下流側に配置
したことを特徴とする排ガス浄化装置。5. The exhaust gas purifying material according to any one of claims 1 to 4, wherein the exhaust gas purifying material is disposed upstream of the exhaust gas flow, and the exhaust gas purifying honeycomb body supporting the noble metal is disposed downstream of the exhaust gas flow. An exhaust gas purifying device characterized by the above-mentioned.
d、Rhの内少なくとも一種以上をシリカ・アルミナを
コーティングしたアルミナ上に担持させてなる貴金属排
ガス浄化触媒を、コージェライト質又はチタン酸アルミ
ニウム質のハニカム体にコーティングして構成されてい
ることを特徴とする請求項5に記載の排ガス浄化装置。6. An exhaust gas purifying honeycomb body comprising Pt, Pt,
Noble metal exhaust gas purifying catalyst comprising at least one of d and Rh supported on alumina coated with silica / alumina is coated on a cordierite or aluminum titanate honeycomb body. The exhaust gas purifying apparatus according to claim 5, wherein
Priority Applications (1)
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JP2000000236A JP5106716B2 (en) | 2000-01-05 | 2000-01-05 | Exhaust gas purification material and exhaust gas purification device |
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Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000000236A JP5106716B2 (en) | 2000-01-05 | 2000-01-05 | Exhaust gas purification material and exhaust gas purification device |
Publications (2)
Publication Number | Publication Date |
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JP2001187344A true JP2001187344A (en) | 2001-07-10 |
JP5106716B2 JP5106716B2 (en) | 2012-12-26 |
Family
ID=18529614
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