JP6392024B2 - 排気浄化装置 - Google Patents
排気浄化装置 Download PDFInfo
- Publication number
- JP6392024B2 JP6392024B2 JP2014164171A JP2014164171A JP6392024B2 JP 6392024 B2 JP6392024 B2 JP 6392024B2 JP 2014164171 A JP2014164171 A JP 2014164171A JP 2014164171 A JP2014164171 A JP 2014164171A JP 6392024 B2 JP6392024 B2 JP 6392024B2
- Authority
- JP
- Japan
- Prior art keywords
- exhaust
- catalyst
- metal oxide
- sulfur
- solid acid
- 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.)
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- 238000000746 purification Methods 0.000 title claims description 32
- 239000003054 catalyst Substances 0.000 claims description 159
- 238000001179 sorption measurement Methods 0.000 claims description 67
- 230000009467 reduction Effects 0.000 claims description 65
- 229910044991 metal oxide Inorganic materials 0.000 claims description 59
- 150000004706 metal oxides Chemical class 0.000 claims description 59
- 239000007789 gas Substances 0.000 claims description 54
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 229930195733 hydrocarbon Natural products 0.000 claims description 37
- 150000002430 hydrocarbons Chemical class 0.000 claims description 37
- 239000011973 solid acid Substances 0.000 claims description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052709 silver Inorganic materials 0.000 claims description 28
- 239000004332 silver Substances 0.000 claims description 28
- 239000010457 zeolite Substances 0.000 claims description 27
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910052676 chabazite Inorganic materials 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 description 64
- 229910017840 NH 3 Inorganic materials 0.000 description 43
- 239000000446 fuel Substances 0.000 description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 241000269350 Anura Species 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000002828 fuel tank Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 210000002421 cell wall Anatomy 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- -1 for example Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical group 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004071 soot Substances 0.000 description 5
- 229910052815 sulfur oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/02—Metallic plates or honeycombs, e.g. superposed or rolled-up corrugated or otherwise deformed sheet metal
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
- F01N2370/04—Zeolitic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/067—Surface coverings for exhaust purification, e.g. catalytic reaction usable with sulfurised fuels
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0682—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2610/00—Adding substances to exhaust gases
- F01N2610/03—Adding substances to exhaust gases the substance being hydrocarbons, e.g. engine fuel
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
Description
本開示の技術における排気浄化装置の他の態様は、前記固体酸金属酸化物が、チャバサイトである。
本開示の技術における排気浄化装置の他の態様は、前記排気の流れる方向における前記還元触媒よりも上流に、前記排気を加熱する加熱部をさらに備える。前記吸着層は、前記アンモニアと前記排気に含まれる三酸化硫黄または四酸化硫黄との反応生成物である硫酸アンモニウムを生成し、前記加熱部は、前記硫酸アンモニウムが熱分解する温度まで前記排気の温度を高めて、前記三酸化硫黄または前記四酸化硫黄よりも前記銀との反応性が低い二酸化硫黄を生成する。
図1を参照してエンジンの概略構成を説明する。
図1に示されるように、エンジン10のシリンダブロック11は、一列に並んでいる6つのシリンダ11aを有している。シリンダブロック11の近傍には、シリンダ11aの並ぶ方向に延びるコモンレール12が配置され、コモンレール12は、圧力の高められた燃料である軽油を溜める。コモンレール12は、6つの燃料噴射弁13に接続し、各燃料噴射弁13は、相互に異なるシリンダ11aに向けて軽油を噴射する。
図2および図3を参照して還元触媒22の構成を説明する。なお、図2には、流通方向と直交する面に沿った還元触媒22の断面構造が示されている。また、図3には、図示の便宜上、図2の3−3線に沿った還元触媒22の断面構造のうち、セル壁と、セル壁における流通方向に沿って延びる1つの面に積層された多層触媒52の断面構造とが示されている。
図3に示されるように、多層触媒52は、モノリス担体51のセル壁51aを覆う触媒層61と、触媒層61を覆う吸着層62とを有している。吸着層62は、触媒層61を覆うことによって、還元触媒22における排気Exに接する表面22sを形成している。
触媒層61にて、NOxの還元剤として用いられる軽油中の炭化水素は、排気中に含まれる炭化水素、および、フィルター添加弁23と触媒添加弁24との少なくとも一方が排気に添加した炭化水素を含む。炭化水素は、炭素数が10から20であるアルカンを主に含み、直鎖状のアルカンおよび分岐鎖状のアルカンを含む。
吸着層62を構成する固体酸金属酸化物は、触媒層61を構成する粒子の形成材料と比べて、酸点の量である酸量が大きい。これにより、触媒層61で生成されたNH3が吸着層62の酸点に吸着する確率が高くなる。そのため、触媒層61で生成されたNH3は、吸着層62の酸点に吸着しやすくなる。
(M1,M2 1/2)m(AlmSinO2(m+n))・xH2O…(A)
なお、M1は、例えば、Li+、Na+、および、K+等であり、M2は、例えば、Ca2+、Mg2+、および、Ba2+等である。ゼオライトは、例えば、チャバサイト構造を有するものが好ましく、チャバサイトがさらに好ましい。
ゼオライトおよびSAPOでは、アルミナと同様に、水酸基や電荷を有する原子が酸点として機能するため、NH3が吸着層62に吸着される。
図4から図7を参照して排気浄化装置20の作用を説明する。なお、図4から図7では、多層触媒52が形成されるモノリス担体51の図示が省略されている。
NH3+H+→NH4 +…(1)
図6に示されるように、排気に含まれる硫黄酸化物(SOx)、例えば、三酸化硫黄が吸着層62に到達すると、吸着層62に吸着されたNH3と三酸化硫黄とによる反応、すなわち、以下の反応式2で示される反応が吸着層62にて生じる。
2NH3+SO3+H2O→(NH4)2SO4…(2)
このように、還元触媒22の表面22sがNH3を吸着する吸着層62によって形成されているため、還元触媒22に供給された排気に含まれる硫黄酸化物は、まず、吸着層62に接する。そして、硫黄酸化物、例えば、三酸化硫黄がNH3と反応して反応生成物である硫酸アンモニウムを生成することで、硫黄酸化物が吸着層62に捕らえられる。それゆえに、還元触媒22に供給された硫黄酸化物が吸着層62を通過して触媒層61に到達することが抑えられ、触媒層61に含まれる銀が硫黄酸化物と反応することが抑えられる。
(1)触媒層61を覆う吸着層62が還元触媒22の表面22sを形成するため、排気に含まれる硫黄酸化物が、吸着層62が吸着したアンモニアと反応する。これにより、硫黄酸化物が吸着層62に吸着されるため、硫黄酸化物が触媒層61に接することが抑えられる。結果として、触媒層61の機能が損なわれにくくなるため、排気に含まれるNOxの量が減りにくくなることが抑えられる。
・排気の流通方向における還元触媒22の上流には、加熱部の一例としてフィルター21が配置されている。これに限らず、加熱部は、例えば、バーナーであってもよいし、フィルター21とは別に排気浄化装置20が搭載する酸化触媒でもよい。要は、加熱部は、流通方向における還元触媒22の上流にて、排気の温度を高めることのできるものであればよく、こうした構成によっても、上記(5)に準じた効果を得ることができる。
(付記1)
前記複数の孔の各々の直径が、
前記アンモニアよりも大きく、かつ、前記炭化水素よりも小さい
請求項2に記載の排気浄化装置。
前記加熱部は、
前記排気中の微粒子を捉えるフィルターである
請求項5に記載の排気浄化装置。
Claims (4)
- ディーゼルエンジンに搭載された排気浄化装置であって、
排気通路の途中に位置して排気に含まれる窒素酸化物を還元する還元触媒と、
前記排気の流れる方向において、前記還元触媒よりも上流に位置し、前記排気を加熱する加熱部と、
前記排気の流れる方向において、前記加熱部と前記還元触媒との間に位置し、前記排気に向けて軽油を噴射する触媒添加弁と、を備え、
前記還元触媒は、触媒層と、前記触媒層の全体を覆って前記排気に接する前記還元触媒の表面を形成する吸着層とを備え、
前記触媒層は、触媒としての銀と前記銀を担持する触媒担体とを含み、前記触媒担体がアルミナ、および、ゼオライトのいずれかであり、炭化水素を用いて前記窒素酸化物を還元することで、アンモニアを生成する反応を促し、
前記吸着層は、酸性を有する固体酸金属酸化物を含み、前記触媒層よりも酸量が大きく、前記触媒層にて生成されたアンモニアを吸着し、前記排気に含まれる硫黄酸化物と前記吸着したアンモニアとを接触させる特性を有し、これによって、前記アンモニアと前記排気に含まれる三酸化硫黄または四酸化硫黄との反応生成物である硫酸アンモニウムを生成し、
前記加熱部は、推定された前記排気に含まれる前記硫黄酸化物の量が所定の量よりも大きいとき、前記硫酸アンモニウムが熱分解する温度まで前記排気の温度を高めて、前記三酸化硫黄または前記四酸化硫黄よりも前記銀との反応性が低い二酸化硫黄を生成し、
前記触媒添加弁は、前記加熱部が前記排気の温度を高めると同時に、前記排気に前記軽油を噴射する
排気浄化装置。 - 前記固体酸金属酸化物は多孔質材料であり、
前記吸着層は、前記固体酸金属酸化物で形成された複数の粒子を含み、
前記固体酸金属酸化物の有する複数の孔は、前記孔の直径が、前記炭化水素よりも小さい孔を含む
請求項1に記載の排気浄化装置。 - 前記固体酸金属酸化物が、
アルミナ、シリカアルミナ、シリカチタニア、シリカマグネシア、ゼオライト、および、シリコアルミノフォスフェートから構成される群から選択される少なくとも1つである
請求項1または2に記載の排気浄化装置。 - 前記固体酸金属酸化物がチャバサイトである
請求項3に記載の排気浄化装置。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2014164171A JP6392024B2 (ja) | 2014-08-12 | 2014-08-12 | 排気浄化装置 |
PCT/JP2015/072464 WO2016024535A1 (ja) | 2014-08-12 | 2015-08-07 | 排気浄化装置 |
CN201580042490.4A CN106574534B (zh) | 2014-08-12 | 2015-08-07 | 排气净化装置 |
EP15832569.6A EP3181846B1 (en) | 2014-08-12 | 2015-08-07 | Exhaust purification device |
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JP2014164171A JP6392024B2 (ja) | 2014-08-12 | 2014-08-12 | 排気浄化装置 |
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CN111167274B (zh) * | 2020-01-19 | 2021-11-12 | 中南大学 | 一种从冶炼烟气中脱除三氧化硫的方法及其脱除装置 |
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JPH07289896A (ja) * | 1994-04-26 | 1995-11-07 | Hitachi Ltd | 排ガス浄化触媒およびその製造方法 |
JPH09249414A (ja) * | 1996-03-12 | 1997-09-22 | Mitsui Eng & Shipbuild Co Ltd | アンモニアおよび二酸化硫黄の製造方法 |
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US7585477B2 (en) * | 2003-11-11 | 2009-09-08 | Honda Motor Co., Ltd. | Catalyst and method for catalytic reduction of nitrogen oxides |
US7213395B2 (en) * | 2004-07-14 | 2007-05-08 | Eaton Corporation | Hybrid catalyst system for exhaust emissions reduction |
JP4463248B2 (ja) * | 2006-07-31 | 2010-05-19 | 本田技研工業株式会社 | NOx低減化システムの制御方法 |
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JP5770409B2 (ja) * | 2007-11-01 | 2015-08-26 | 日野自動車株式会社 | 排ガス浄化装置 |
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CN102482971B (zh) * | 2009-08-28 | 2014-10-29 | 尤米科尔股份公司及两合公司 | 在具有相同存储功能的催化转化器上游具有具有存储功能的催化活性壁流式过滤器的尾气后处理体系 |
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JP2013122179A (ja) * | 2011-12-09 | 2013-06-20 | Toyota Motor Corp | 内燃機関の排気浄化装置 |
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