JP4057811B2 - Engine exhaust gas purification catalyst - Google Patents
Engine exhaust gas purification catalyst Download PDFInfo
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- JP4057811B2 JP4057811B2 JP2001399571A JP2001399571A JP4057811B2 JP 4057811 B2 JP4057811 B2 JP 4057811B2 JP 2001399571 A JP2001399571 A JP 2001399571A JP 2001399571 A JP2001399571 A JP 2001399571A JP 4057811 B2 JP4057811 B2 JP 4057811B2
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- Prior art keywords
- catalyst
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- aqueous solution
- solution containing
- calcined
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- 239000003054 catalyst Substances 0.000 title claims description 139
- 238000000746 purification Methods 0.000 title claims description 7
- 239000007789 gas Substances 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 55
- 238000002156 mixing Methods 0.000 description 44
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 30
- 239000013618 particulate matter Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 19
- 239000010948 rhodium Substances 0.000 description 19
- 229910001961 silver nitrate Inorganic materials 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 229910052703 rhodium Inorganic materials 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- -1 calcium aluminate compound Chemical class 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-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
- 238000007599 discharging Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 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
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は、エンジンの排ガス中に含まれる有害成分を浄化する触媒に関するものである。
【０００２】
【従来の技術】
近年、ディーゼルエンジンから排出される微粒子物質（ＰＭ：particulate matter）が環境衛生上の大きな問題となっている。ＰＭは主に固体状の炭素微粒子（ＳＯＯＴ）と液体状の炭化水素微粒子（ＳＯＦ：soluble organic fraction）からなっている。
ＰＭの浄化方法の代表的なものとして、交互再生方式と呼ばれ、耐熱性のハニカムフィルタ（以下、フィルタという。）を２個使用し、一方のフィルタでＰＭを捕集しながら、圧力損失が上昇した他方のフィルタをバーナーや電気ヒーター等で６００℃以上に加熱しＰＭを燃焼させることによってフィルタを再生し、繰り返し使用する方法や、逆洗方式と呼ばれ、フィルタに堆積したＰＭをエアーで吹き飛ばしてフィルタから放出した後、バーナーや電気ヒーター等で６００℃以上に加熱しＰＭを燃焼させる方法等が検討されてきた。
しかしながら、これらの方法では、ＰＭの燃焼によりフィルタの温度が急激に上昇するとフィルタが割れたり溶損したりする問題や、装置が大がかりになり車に容易に装着出来ない等の問題があった。
そのため、Ｐｔ系酸化触媒により低温で定常的にＰＭを燃焼させる技術が開発されている。例えば、排ガス中のＮＯをＮＯ2に酸化し、このＮＯ2がＰＭを酸化燃焼させる技術（特開平１０−１５９５５２号公報）や、白金族金属とアルカリ土類金属酸化物の混合物を燃焼触媒とする技術（特公平７−１０６２９０号公報）等が提案されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、従来のＰｔ系の酸化触媒は、何れも排ガス温度が高温でなければＰＭ特にＳＯＯＴ成分が燃焼し難く、ディーゼルエンジン車が低速走行やアイドリング時の排ガス温度ではＰＭがフィルタ内に堆積し、この間にフィルタの圧力損失の上昇が避けられなかった。
【０００４】
【課題を解決するための手段】
本発明者らは、この点について鋭意検討を重ねたところ、特定の酸化物を使用することにより前記課題を解消できるとの知見を得て発明を完成するに至った。すなわち、１２ＣａＯ・７Ａｌ２Ｏ３を主成分とし、酸素ラジカルを４ｘ１０ ２０ ／ｃｍ ３ 以上含有してなることを特徴とするエンジン排ガス浄化用触媒であり、金属成分を担持した該エンジン排ガス浄化用触媒であり、金属成分が金、銀、銅、鉄、亜鉛、マンガン、セリウム及び白金族元素の中から選ばれた１種又は２種以上である該エンジン排ガス浄化用触媒である。また、ガソリンエンジン車の排ガスには、軽油を使用するディーゼルエンジン車の排ガスと同種の未燃焼有害物が含まれており、それらの除去にも本発明の触媒は有効である。
【０００５】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の１２ＣａＯ・７Ａｌ2Ｏ3（以下、Ｃ12Ａ7という。）は、カルシウムアルミネート化合物の一種であり、１２ＣａＯ・７Ａｌ2Ｏ3の他に、３ＣａＯ・Ａｌ2Ｏ3（Ｃ3Ａ）ＣａＯ・Ａｌ2Ｏ3（ＣＡ）、ＣａＯ・２Ａｌ2Ｏ3（ＣＡ2）、ＣａＯ・６Ａｌ2 Ｏ3（ＣＡ6）等が知られている。これらはアルミナセメントの成分である。本発明のエンジン排ガス浄化用触媒としては、Ｃ12Ａ7を主成分とするものが好ましい。
【０００６】
Ｃ12Ａ7は、アルカリ金属、アルカリ土類金属やその他の元素を不純物として含有する場合があるが、本発明の効果を妨げない範囲であれば特に問題はない。
また、Ｃ12Ａ7はセメント鉱物であり、水分が存在すると水和反応を起こしカルシウムアルミネート水和物を生成するが、本発明の効果を妨げない範囲であれば特に問題はない。
しかしながら、Ｃ12Ａ7作製中に、水を用いたり、合成・焼成雰囲気中に水分が存在すると、ＯＨ-イオンがＣ12Ａ7中に包接され、フリー酸素イオン（Ｏ2-）が減少し、酸素ラジカルが有効に生成しないため、可能な限り水分を除くことが好ましい。
【０００７】
Ｃ12Ａ7は、一般にＣａＯ原料（炭酸カルシウム、水酸化カルシウム等）とＡｌ2Ｏ3原料（アルミナ、水酸化アルミナ等）を混合した後、大気中で１２００〜１３５０℃程度の温度で焼成することにより合成され、酸素ラジカルの含有量は１０18／ｃｍ3 程度である。
一方、雰囲気中に乾燥酸素ガスをフローしながら合成すると酸素ラジカルの含有量は、１０19／ｃｍ3 以上と、通常の条件と比べ顕著に増やすことができる。
酸素ラジカルとは、（Ｏ-、Ｏ2-及びＯ3-）で表される原子状及び分子状の酸素ラジカルであり、その含有量はＥＳＲ、ラマンスペクトル測定から定量される。
本発明では、エンジンから排出される微粒子物質であるＰＭの燃焼にＣ12Ａ7に含有される酸素ラジカル、特にＯ- が多いほど好ましい。
【０００８】
Ｃ12Ａ7の粒度は、特に限定されるものではないが、ＰＭの燃焼を効率的に行うため比表面積が１ｍ2／ｇ以上であることが好ましく、３ｍ2／ｇ以上であることがさらに好ましい。
【０００９】
本発明では、Ｃ12Ａ7に金属成分を担持すると、エンジンから排出される微粒子物質であるＰＭの燃焼にさらに有効である。その作用機構については充分解明されていないが、ＰＭと酸素ラジカルの酸化反応を促進する役割を果たしていると推察される。
金属成分としては、特に限定されるものではないが、金、銀、銅、鉄、亜鉛、マンガン、セリウム及び白金、並びにイリジウム、オスミウム、パラジウム、ロジウム、ルテニウム等の白金族元素の中から選ばれた１種又は２種以上であることが好ましい。
また、金属成分の存在形態は、特に限定されるものではない。
【００１０】
本発明の触媒担体としては、特に限定されるものではないが、セラミックフォーム、金属発泡体、ワイヤーメッシュ、セラミック又は金属のハニカム、目封じタイプのセラミックハニカム（以下、セラミックフィルタという。）等が挙げられる。中でも、ディーゼルエンジンの排ガス中のＰＭを捕集・燃焼する点でセラミックフィルタが好ましい。
セラミックフィルタとしては、炭化珪素、コーディエライト、ムライト、アルミナ、ジルコニア、チタニア、リン酸チタン、アルミニウムチタネート、アルミノシリケート等が挙げられる。中でも、ディーゼルエンジンの排ガス中のＰＭを捕集・燃焼する点で炭化珪素やコーディエライトが好ましい。
【００１１】
【発明の実施の形態】
以下、実施例に基づき本発明を詳細に説明する。
【００１２】
【実施例】
実験例１
ディーゼルエンジンの排ガスから捕集したＰＭと表１に示す各種触媒を質量比で１：１０に物理混合したものを、大気雰囲気中で熱重量示差熱分析装置（ＴＧ−ＤＴＡ）を用いＰＭの燃焼試験を行った。結果を表１に併記する。
【００１３】
＜使用材料＞
触媒Ａ：試薬の炭酸カルシウムと試薬の酸化アルミニウムを所定のモル比＝１２：７で混合し、ペレット状に加圧して成形したものをアルミナ管を使用した管状炉内に置き、大気中で１３５０℃、２時間加熱した後ボールミルで粉砕し、Ｃ12Ａ7 の粉末を得た。酸素ラジカルの含有量は１０18／ｃｍ3 、比表面積は３ｍ2 ／ｇであった。
触媒Ｂ：試薬の炭酸カルシウムと試薬の酸化アルミニウムを所定のモル比で混合し、ペレット状に加圧して成形したものをアルミナ管を使用した管状炉内に置き、酸素ガスをフローしながら１３５０℃、２時間加熱した後ボールミルで粉砕し、Ｃ12Ａ7 の粉末を得た。酸素ラジカルの含有量は４×１０20／ｃｍ3 、比表面積は３ｍ2 ／ｇであった。
触媒Ｃ：比表面積１００ｍ2／ｇのγ−Ａｌ2Ｏ3１０ｇにＰｔに換算して０．５ｇの塩化白金酸を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＰｔ担持触媒を得た。
【００１４】
＜測定方法＞
ＴＧ−ＤＴＡ：サンプル量２０ｍｇ、空気流量１００ｍｌ／分、昇温速度１０℃／分、測定温度範囲は室温〜７００℃、ＰＭの燃焼温度は発熱ピーク温度とした。
【００１５】
【表１】
表１より、本発明のＣ12Ａ7は、ＰＭの燃焼温度を顕著に低下させる効果を奏することが判る。
【００１７】
実験例２
表２に示すように、Ｃ12Ａ7 、γ−Ａｌ2Ｏ3に金属成分を担持した触媒について、実験例１と同様にＰＭの燃焼試験を行った。結果を表２に併記する。
【００１８】
＜使用材料＞
触媒Ｄ１：触媒Ａ１０ｇにＡｕに換算して０．５ｇの塩化金酸を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｕ担持触媒を得た。
触媒Ｄ２：触媒Ｂ１０ｇにＡｕに換算して０．５ｇの塩化金酸を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で８時間焼成してＡｕ担持触媒を得た。
触媒Ｄ３：γ−Ａｌ2Ｏ3１０ｇにＡｕに換算して０．５ｇの塩化金酸を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｕ担持触媒を得た。
【００１９】
触媒Ｅ１：触媒Ａ１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ担持触媒を得た。
触媒Ｅ２：触媒Ｂ１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ担持触媒を得た。
触媒Ｅ３：γ−Ａｌ2Ｏ3１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ担持触媒を得た。
【００２０】
触媒Ｆ１：触媒Ａ１０ｇにＣｕに換算して０．５ｇの硝酸銅を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｕ担持触媒を得た。
触媒Ｆ２：触媒Ｂ１０ｇにＣｕに換算して０．５ｇの硝酸銅を含む水溶液１０ｍ１を加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｕ担持触媒を得た。
触媒Ｆ３：γ−Ａｌ2Ｏ3１０ｇにＣｕに換算して０．５ｇの硝酸銅を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｕ担持触媒を得た。
【００２１】
触媒Ｇ１：触媒Ａ１０ｇにＦｅに換算して０．５ｇの硝酸第二鉄を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＦｅ担持触媒を得た。
触媒Ｇ２：触媒Ｂ１０ｇにＦｅに換算して０．５ｇの硝酸第二鉄を含む水溶液１ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＦｅ担持触媒を得た。
触媒Ｇ３：γ−Ａｌ2Ｏ3１０ｇにＦｅに換算して０．５ｇの硝酸第二鉄を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＦｅ担持触媒を得た。
【００２２】
触媒Ｈ１：触媒Ａ１０ｇにＺｎに換算して０．５ｇの酢酸亜鉛を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＺｎ担持触媒を得た。
触媒Ｈ２：触媒Ｂ１０ｇにＺｎに換算して０．５ｇの酢酸亜鉛を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＺｎ担持触媒を得た。
触媒Ｈ３：γ−Ａｌ2Ｏ3１０ｇにＺｎに換算して０．５ｇの酢酸亜鉛を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＺｎ担持触媒を得た。
【００２３】
触媒Ｉ１：触媒Ａ１０ｇにＭｎに換算して０．５ｇの酢酸マンガンを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＭｎ担持触媒を得た。
触媒Ｉ２：触媒Ｂ１０ｇにＭｎに換算して０．５ｇの酢酸マンガンを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＭｎ担持触媒を得た。
触媒Ｉ３：γ−Ａｌ2Ｏ3１０ｇにＭｎに換算して０．５ｇの酢酸マンガンを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＭｎ担持触媒を得た。
【００２４】
触媒Ｊ１：触媒Ａ１０ｇにＣｅに換算して０．５ｇの酢酸セリウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｅ担持触媒を得た。
触媒Ｊ２：触媒Ｂ１０ｇにＣｅに換算して０．５ｇの酢酸セリウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｅ担持触媒を得た。
触媒Ｊ３：γ−Ａｌ2Ｏ3１０ｇにＣｅに換算して０．５ｇの酢酸セリウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｅ担持触媒を得た。
【００２５】
触媒Ｋ１：触媒Ａ１０ｇにＰｔに換算して０．５ｇの塩化白金酸を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＰｔ担持触媒を得た。
触媒Ｋ２：触媒Ｂ１０ｇにＰｔに換算して０．５ｇの塩化白金酸を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＰｔ担持触媒を得た。
触媒Ｋ３（触媒Ｃ）：γ−Ａｌ2Ｏ3１０ｇにＰｔに換算して０．５ｇの塩化白金酸を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＰｔ担持触媒を得た。
【００２６】
触媒Ｌ１：触媒Ａ１０ｇにＰｄに換算して０．５ｇの硝酸パラジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＰｄ担持触媒を得た。
触媒Ｌ２：触媒Ｂ１０ｇにＰｄに換算して０．５ｇの硝酸パラジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＰｄ担持触媒を得た。
触媒Ｌ３：γ−Ａｌ2Ｏ3１０ｇにＰｄに換算して０．５ｇの硝酸パラジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＰｄ担持触媒を得た。
【００２７】
触媒Ｍ１：触媒Ａ１０ｇにＲｈに換算して０．５ｇの硝酸ロジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＰｄ担持触媒を得た。
触媒Ｍ２：触媒Ｂ１０ｇにＲｈに換算して０．５ｇの硝酸ロジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＲｈ担持触媒を得た。
触媒Ｍ３：γ−Ａｌ2Ｏ3１０ｇにＲｈに換算して０．５ｇの硝酸ロジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＲｈ担持触媒を得た。
【００２８】
触媒Ｎ１：触媒Ａ１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．００５ｇの硝酸ロジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｈ担持触媒を得た。
触媒Ｎ２：触媒Ｂ１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．００５ｇの硝酸ロジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｈ担持触媒を得た。
触媒Ｎ３：γ−Ａｌ2Ｏ3１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．５ｇの硝酸ロジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｈ担持触媒を得た。
【００２９】
触媒Ｏ１：触媒Ａ１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．００５ｇの硝酸ルテニウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｕ担持触媒を得た。
触媒Ｏ２：触媒Ｂ１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．００５ｇの硝酸ルテニウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｕ担持触媒を得た。
触媒Ｏ３：γ−Ａｌ2Ｏ3１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．５ｇの硝酸ルテニウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｕ担持触媒を得た。
【００３０】
触媒Ｐ１：触媒Ａ１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．００５ｇの硝酸パラジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｈ担持触媒を得た。
触媒Ｐ２：触媒Ｂ１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．００５ｇの硝酸パラジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｈ担持触媒を得た。
触媒Ｐ３：γ−Ａｌ2Ｏ3１０ｇにＡｇに換算して０．５ｇの硝酸銀を含む水溶液１０ｍｌと、Ｒｈに換算して０．５ｇの硝酸パラジウムを含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＡｇ、Ｒｈ担持触媒を得た。
【００３１】
触媒Ｑ１：触媒Ａ１０ｇにＣｕに換算して０．５ｇの硝酸銅を含む水溶液１０ｍｌと、Ａｇに換算して０．０５ｇの硝酸銀を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｕ、Ａｇ担持触媒を得た。
触媒Ｑ２：触媒Ｂ１０ｇにＣｕに換算して０．５ｇの硝酸銅を含む水溶液１０ｍｌと、Ａｇに換算して０．０５ｇの硝酸銀を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｕ、Ａｇ担持触媒を得た。
触媒Ｑ３：γ−Ａｌ2Ｏ3１０ｇにＣｕに換算して０．５ｇの硝酸銅を含む水溶液１０ｍｌと、Ａｇに換算して０．０５ｇの硝酸銀を含む水溶液１０ｍｌを加えた。十分混合した後蒸発乾固し、６００℃で３時間焼成してＣｕ、Ａｇ担持触媒を得た。
【００３２】
【表２】
表２より、本発明のＣ12Ａ7に金属成分を担持した触媒は、何れもＰＭの燃焼温度を顕著に低下させる効果を奏することが判る。
【００３４】
実験例３
実験例２と同様な条件で調製した種々の触媒２ｋｇを水と湿式粉砕してスラリーを調製し、平均気孔径１５μｍ、気孔率５８％、外形寸法１００ｍｍφ×１４０ｍｍＬ、セル数１６０ｃｐｉ２の炭化珪素製フィルタをスラリーに浸漬して、フィルタに４０ｇ／Ｌ担持した。
これらのフィルタをエンジンベンチ試験装置で１．５Ｌのディーゼルエンジンを使用し、排ガスのフィルタ入り口温度２００℃の条件で、捕集開始から９０分後のフィルタの圧力損失の変化を表３に示した。
【００３５】
【表３】
表３より、本発明のＣ12Ａ7及びそれに金属成分を担持した触媒は、フィルタの圧力損失の上昇が少なく、排ガス中のＰＭを燃焼させていることが判る。
【００３７】
【発明の効果】
本発明のＣ12Ａ7を主成分とするエンジン排ガス浄化用触媒は、従来のものと比ベエンジンの排ガス中のＰＭを低温で燃焼させる優れた効果を奏する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a catalyst for purifying harmful components contained in engine exhaust gas.
[0002]
[Prior art]
In recent years, particulate matter (PM) discharged from diesel engines has become a major environmental health problem. PM is mainly composed of solid carbon fine particles (SOOT) and liquid hydrocarbon fine particles (SOF: soluble organic fraction).
A typical method for purifying PM is called an alternate regeneration system, which uses two heat-resistant honeycomb filters (hereinafter referred to as filters), and collects PM with one filter while reducing pressure loss. The other filter that has risen is heated to 600 ° C or higher with a burner or electric heater to burn the PM, and the filter is regenerated and used repeatedly. After blowing and discharging from a filter, the method etc. which are heated to 600 degreeC or more with a burner, an electric heater, etc. and burn PM are examined.
However, these methods have a problem that the filter is cracked or melted when the temperature of the filter is suddenly increased due to combustion of PM, and that the apparatus becomes large and cannot be easily attached to a car.
Therefore, a technique for constantly burning PM at a low temperature using a Pt-based oxidation catalyst has been developed. For example, NO in exhaust gas is oxidized to NO 2 , and this NO 2 oxidizes and burns PM (Japanese Patent Laid-Open No. 10-159552), or a mixture of a platinum group metal and an alkaline earth metal oxide as a combustion catalyst. A technique (Japanese Patent Publication No. 7-106290) or the like has been proposed.
[0003]
[Problems to be solved by the invention]
However, in the conventional Pt-based oxidation catalysts, PM, especially the SOOT component, is difficult to burn unless the exhaust gas temperature is high, and PM accumulates in the filter at the exhaust gas temperature when the diesel engine vehicle is running at low speed or idling. During this time, an increase in the pressure loss of the filter was inevitable.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies on this point, and have obtained the knowledge that the above-mentioned problems can be solved by using a specific oxide, and have completed the invention. That is, the main component 12CaO · 7Al 2 O 3, oxygen radical is a catalyst for engine exhaust gas purification, characterized by containing 4x10 20 / cm 3 or more, for the engine exhaust gas purifying carrying a metal component It is a catalyst for exhaust gas purification of an engine which is a catalyst and the metal component is one or more selected from gold, silver, copper, iron, zinc, manganese, cerium and platinum group elements. Further, the exhaust gas of gasoline engine vehicles contains unburned harmful substances of the same type as the exhaust gas of diesel engine vehicles that use light oil, and the catalyst of the present invention is also effective in removing them.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
12CaO · 7Al 2 O 3 (hereinafter referred to as C 12 A 7 ) of the present invention is a kind of calcium aluminate compound, and in addition to 12CaO · 7Al 2 O 3 , 3CaO · Al 2 O 3 (C 3 A ) CaO · Al 2 O 3 ( CA), CaO · 2Al 2 O 3 (CA 2), CaO · 6Al 2 O 3 (CA 6) and the like are known. These are components of alumina cement. The engine exhaust gas purification catalyst of the present invention is preferably a catalyst containing C 12 A 7 as a main component.
[0006]
C 12 A 7 may contain an alkali metal, an alkaline earth metal or other element as an impurity, but there is no particular problem as long as it does not hinder the effects of the present invention.
C 12 A 7 is a cement mineral. When water is present, it causes a hydration reaction to produce calcium aluminate hydrate, but there is no particular problem as long as it does not hinder the effects of the present invention.
However, if water is used during the production of C 12 A 7 or if moisture is present in the synthesis / firing atmosphere, OH − ions are included in C 12 A 7 and free oxygen ions (O 2− ) are reduced. However, since oxygen radicals are not effectively generated, it is preferable to remove moisture as much as possible.
[0007]
C 12 A 7 is generally calcined in the atmosphere at a temperature of about 1200 to 1350 ° C. after mixing a CaO raw material (calcium carbonate, calcium hydroxide, etc.) and an Al 2 O 3 raw material (alumina, alumina hydroxide, etc.). The oxygen radical content is about 10 18 / cm 3 .
On the other hand, when synthesis is performed while flowing dry oxygen gas in the atmosphere, the content of oxygen radicals can be remarkably increased to 10 19 / cm 3 or more compared to normal conditions.
The oxygen radicals are atomic and molecular oxygen radicals represented by (O − , O 2− and O 3− ), and their contents are quantified from ESR and Raman spectrum measurements.
In the present invention, it is preferable that oxygen radicals contained in C 12 A 7 , particularly O 2 −, increase in the combustion of PM, which is a particulate material discharged from the engine.
[0008]
The particle size of the C 12 A 7 is not particularly limited, it is preferable that the specific surface area for causing combustion of the PM efficiently is 1 m 2 / g or more, still be at 3m 2 / g or more preferable.
[0009]
In the present invention, when a metal component is supported on C 12 A 7 , it is more effective for combustion of PM which is a particulate material discharged from the engine. Although its mechanism of action has not been fully elucidated, it is presumed that it plays a role in promoting the oxidation reaction of PM and oxygen radicals.
The metal component is not particularly limited, but is selected from gold, silver, copper, iron, zinc, manganese, cerium and platinum, and platinum group elements such as iridium, osmium, palladium, rhodium and ruthenium. It is preferable that it is 1 type or 2 types or more.
Moreover, the presence form of a metal component is not specifically limited.
[0010]
The catalyst carrier of the present invention is not particularly limited, and examples thereof include ceramic foam, metal foam, wire mesh, ceramic or metal honeycomb, plug-type ceramic honeycomb (hereinafter referred to as ceramic filter), and the like. It is done. Among these, a ceramic filter is preferable in terms of collecting and burning PM in exhaust gas from a diesel engine.
Examples of the ceramic filter include silicon carbide, cordierite, mullite, alumina, zirconia, titania, titanium phosphate, aluminum titanate, and aluminosilicate. Among these, silicon carbide and cordierite are preferable in terms of collecting and burning PM in the exhaust gas of the diesel engine.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail based on examples.
[0012]
【Example】
Experimental example 1
Combustion of PM using a thermogravimetric differential thermal analyzer (TG-DTA) in which PM collected from exhaust gas from a diesel engine and various catalysts shown in Table 1 are physically mixed at a mass ratio of 1:10 A test was conducted. The results are also shown in Table 1.
[0013]
<Materials used>
Catalyst A: Reagent calcium carbonate and reagent aluminum oxide were mixed at a predetermined molar ratio = 12: 7, pressed into a pellet and molded in a tubular furnace using an alumina tube, and 1350 in the atmosphere. After heating at 0 ° C. for 2 hours, the mixture was pulverized with a ball mill to obtain C 12 A 7 powder. The oxygen radical content was 10 18 / cm 3 and the specific surface area was 3 m 2 / g.
Catalyst B: Calcium carbonate as a reagent and aluminum oxide as a reagent are mixed at a predetermined molar ratio, pressed into a pellet shape, placed in a tubular furnace using an alumina tube, and 1350 ° C. while flowing oxygen gas. After heating for 2 hours, the mixture was pulverized with a ball mill to obtain C 12 A 7 powder. The oxygen radical content was 4 × 10 20 / cm 3 and the specific surface area was 3 m 2 / g.
Catalyst C: 10 g of an aqueous solution containing 0.5 g of chloroplatinic acid in terms of Pt was added to 10 g of γ-Al 2 O 3 having a specific surface area of 100 m 2 / g. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Pt-supported catalyst.
[0014]
<Measurement method>
TG-DTA: sample amount 20 mg, air flow rate 100 ml / min, heating rate 10 ° C./min, measurement temperature range was room temperature to 700 ° C., and PM combustion temperature was exothermic peak temperature.
[0015]
[Table 1]
From Table 1, it can be seen that C 12 A 7 of the present invention has the effect of significantly reducing the combustion temperature of PM.
[0017]
Experimental example 2
As shown in Table 2, a PM combustion test was conducted in the same manner as in Experimental Example 1 for a catalyst in which a metal component was supported on C 12 A 7 and γ-Al 2 O 3 . The results are also shown in Table 2.
[0018]
<Materials used>
Catalyst D1: 10 ml of an aqueous solution containing 0.5 g of chloroauric acid in terms of Au was added to 10 g of catalyst A. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Au-supported catalyst.
Catalyst D2: 10 ml of an aqueous solution containing 0.5 g of chloroauric acid in terms of Au was added to 10 g of catalyst B. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 8 hours to obtain an Au-supported catalyst.
Catalyst D3: 10 ml of an aqueous solution containing 0.5 g of chloroauric acid in terms of Au was added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Au-supported catalyst.
[0019]
Catalyst E1: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag was added to 10 g of catalyst A. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag-supported catalyst.
Catalyst E2: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag was added to 10 g of catalyst B. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag-supported catalyst.
Catalyst E3: adding an aqueous solution 10ml containing silver nitrate 0.5g in terms of γ-Al 2 O 3 10g to Ag. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag-supported catalyst.
[0020]
Catalyst F1: 10 ml of an aqueous solution containing 0.5 g of copper nitrate in terms of Cu was added to 10 g of catalyst A. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Cu-supported catalyst.
Catalyst F2: 10 ml of an aqueous solution containing 0.5 g of copper nitrate in terms of Cu was added to 10 g of catalyst B. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Cu-supported catalyst.
Catalyst F3: 10 ml of an aqueous solution containing 0.5 g of copper nitrate in terms of Cu was added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Cu-supported catalyst.
[0021]
Catalyst G1: 10 ml of an aqueous solution containing 0.5 g of ferric nitrate in terms of Fe was added to 10 g of catalyst A. After thoroughly mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Fe-supported catalyst.
Catalyst G2: 1 ml of an aqueous solution containing 0.5 g of ferric nitrate in terms of Fe was added to 10 g of catalyst B. After thoroughly mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Fe-supported catalyst.
Catalyst G3: 10 ml of an aqueous solution containing 0.5 g of ferric nitrate in terms of Fe was added to 10 g of γ-Al 2 O 3 . After thoroughly mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Fe-supported catalyst.
[0022]
Catalyst H1: 10 ml of an aqueous solution containing 0.5 g of zinc acetate in terms of Zn was added to 10 g of catalyst A. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Zn-supported catalyst.
Catalyst H2: 10 ml of an aqueous solution containing 0.5 g of zinc acetate in terms of Zn was added to 10 g of catalyst B. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Zn-supported catalyst.
Catalyst H3: 10 ml of an aqueous solution containing 0.5 g of zinc acetate in terms of Zn was added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Zn-supported catalyst.
[0023]
Catalyst I1: 10 ml of an aqueous solution containing 0.5 g of manganese acetate in terms of Mn was added to 10 g of catalyst A. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Mn-supported catalyst.
Catalyst I2: 10 ml of an aqueous solution containing 0.5 g of manganese acetate in terms of Mn was added to 10 g of catalyst B. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Mn-supported catalyst.
Catalyst 13: 10 ml of an aqueous solution containing 0.5 g of manganese acetate in terms of Mn was added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Mn-supported catalyst.
[0024]
Catalyst J1: 10 ml of an aqueous solution containing 0.5 g of cerium acetate in terms of Ce was added to 10 g of catalyst A. After thoroughly mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Ce-supported catalyst.
Catalyst J2: 10 ml of an aqueous solution containing 0.5 g of cerium acetate in terms of Ce was added to 10 g of catalyst B. After thoroughly mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Ce-supported catalyst.
Catalyst J3: 10 ml of an aqueous solution containing 0.5 g of cerium acetate in terms of Ce was added to 10 g of γ-Al 2 O 3 . After thoroughly mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Ce-supported catalyst.
[0025]
Catalyst K1: To 10 g of catalyst A, 10 ml of an aqueous solution containing 0.5 g of chloroplatinic acid in terms of Pt was added. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Pt-supported catalyst.
Catalyst K2: 10 ml of an aqueous solution containing 0.5 g of chloroplatinic acid in terms of Pt was added to 10 g of catalyst B. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Pt-supported catalyst.
Catalyst K3 (Catalyst C): 10 g of an aqueous solution containing 0.5 g of chloroplatinic acid in terms of Pt was added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Pt-supported catalyst.
[0026]
Catalyst L1: 10 ml of an aqueous solution containing 0.5 g of palladium nitrate in terms of Pd was added to 10 g of catalyst A. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Pd-supported catalyst.
Catalyst L2: 10 ml of an aqueous solution containing 0.5 g of palladium nitrate in terms of Pd was added to 10 g of catalyst B. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Pd-supported catalyst.
Catalyst L3: 10 ml of an aqueous solution containing 0.5 g of palladium nitrate in terms of Pd was added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Pd-supported catalyst.
[0027]
Catalyst M1: 10 ml of an aqueous solution containing 0.5 g of rhodium nitrate in terms of Rh was added to 10 g of catalyst A. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Pd-supported catalyst.
Catalyst M2: 10 ml of an aqueous solution containing 0.5 g of rhodium nitrate in terms of Rh was added to 10 g of catalyst B. After thoroughly mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Rh-supported catalyst.
Catalyst M3: 10 ml of an aqueous solution containing 0.5 g of rhodium nitrate in terms of Rh was added to 10 g of γ-Al 2 O 3 . After thoroughly mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Rh-supported catalyst.
[0028]
Catalyst N1: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag and 10 ml of an aqueous solution containing 0.005 g of rhodium nitrate in terms of Rh were added to 10 g of catalyst A. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Rh supported catalyst.
Catalyst N2: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag and 10 ml of an aqueous solution containing 0.005 g of rhodium nitrate in terms of Rh were added to 10 g of catalyst B. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Rh supported catalyst.
Catalyst N3: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag and 10 ml of an aqueous solution containing 0.5 g of rhodium nitrate in terms of Rh were added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Rh supported catalyst.
[0029]
Catalyst O1: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag and 10 ml of an aqueous solution containing 0.005 g of ruthenium nitrate in terms of Rh were added to 10 g of catalyst A. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Ru supported catalyst.
Catalyst O2: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag and 10 ml of an aqueous solution containing 0.005 g of ruthenium nitrate in terms of Rh were added to 10 g of catalyst B. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Ru supported catalyst.
Catalyst O3: an aqueous solution 10ml containing silver nitrate 0.5g in terms of Ag on γ-Al 2 O 3 10g, was added an aqueous solution 10ml containing ruthenium nitrate of 0.5g in terms of Rh. After sufficiently mixing, the mixture was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Ru supported catalyst.
[0030]
Catalyst P1: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag and 10 ml of an aqueous solution containing 0.005 g of palladium nitrate in terms of Rh were added to 10 g of catalyst A. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Rh supported catalyst.
Catalyst P2: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag and 10 ml of an aqueous solution containing 0.005 g of palladium nitrate in terms of Rh were added to 10 g of catalyst B. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Rh supported catalyst.
Catalyst P3: 10 ml of an aqueous solution containing 0.5 g of silver nitrate in terms of Ag and 10 ml of an aqueous solution containing 0.5 g of palladium nitrate in terms of Rh were added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain an Ag and Rh supported catalyst.
[0031]
Catalyst Q1: 10 ml of an aqueous solution containing 0.5 g of copper nitrate in terms of Cu and 10 ml of an aqueous solution containing 0.05 g of silver nitrate in terms of Ag were added to 10 g of catalyst A. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Cu / Ag supported catalyst.
Catalyst Q2: 10 ml of an aqueous solution containing 0.5 g of copper nitrate in terms of Cu and 10 ml of an aqueous solution containing 0.05 g of silver nitrate in terms of Ag were added to 10 g of catalyst B. After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Cu / Ag supported catalyst.
Catalyst Q3: 10 ml of an aqueous solution containing 0.5 g of copper nitrate in terms of Cu and 10 ml of an aqueous solution containing 0.05 g of silver nitrate in terms of Ag were added to 10 g of γ-Al 2 O 3 . After sufficiently mixing, it was evaporated to dryness and calcined at 600 ° C. for 3 hours to obtain a Cu / Ag supported catalyst.
[0032]
[Table 2]
From Table 2, it can be seen that any of the catalysts having a metal component supported on C 12 A 7 of the present invention has an effect of significantly reducing the combustion temperature of PM.
[0034]
Experimental example 3
2 kg of various catalysts prepared under the same conditions as in Experimental Example 2 were wet pulverized with water to prepare a slurry. The slurry was made of silicon carbide having an average pore diameter of 15 μm, a porosity of 58%, an external dimension of 100 mmφ × 140 mmL, and a cell number of 160 cpi 2 The filter was immersed in the slurry, and 40 g / L was supported on the filter.
Table 3 shows changes in the pressure loss of the filter 90 minutes after the start of collection under the condition that the exhaust gas filter inlet temperature is 200 ° C. using a 1.5 L diesel engine with an engine bench test device. .
[0035]
[Table 3]
From Table 3, it can be seen that the catalyst supporting C 12 A 7 and the metal component of the present invention has little increase in the pressure loss of the filter and burns PM in the exhaust gas.
[0037]
【The invention's effect】
The catalyst for purifying engine exhaust gas containing C 12 A 7 as a main component of the present invention has an excellent effect of burning PM in exhaust gas of a conventional engine and a comparative engine at a low temperature.
Claims (3)
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| JP2001399571A JP4057811B2 (en) | 2001-12-28 | 2001-12-28 | Engine exhaust gas purification catalyst |
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| JP4525909B2 (en) * | 2004-10-28 | 2010-08-18 | 戸田工業株式会社 | Water gas shift reaction catalyst, method for producing the same, and method for producing water gas |
| JP5024917B2 (en) * | 2005-10-26 | 2012-09-12 | 三井金属鉱業株式会社 | Exhaust gas purification catalyst for gasoline engine and method for producing the same |
| JP5154890B2 (en) * | 2007-11-02 | 2013-02-27 | Ｄｏｗａエレクトロニクス株式会社 | Complex oxide for exhaust gas purification and exhaust gas purification filter for diesel engine |
| JP4901938B2 (en) * | 2009-10-23 | 2012-03-21 | トヨタ自動車株式会社 | NOx purification catalyst |
| US9150423B2 (en) | 2010-12-07 | 2015-10-06 | Tokyo Institute Of Technology | Ammonia synthesis catalyst and ammonia synthesis method |
| US9084988B2 (en) | 2011-02-07 | 2015-07-21 | Toyota Jidosha Kabushiki Kaisha | NOX purification catalyst |
| EP2680952B1 (en) | 2011-02-07 | 2018-07-11 | Toyota Jidosha Kabushiki Kaisha | Nox purification catalyst |
| US9079167B2 (en) | 2011-02-07 | 2015-07-14 | Toyota Jidosha Kabushiki Kaisha | NOx purification catalyst |
| WO2012108060A1 (en) | 2011-02-07 | 2012-08-16 | Toyota Jidosha Kabushiki Kaisha | NOx PURIFICATION CATALYST |
| KR101940777B1 (en) * | 2012-08-30 | 2019-01-22 | 고쿠리츠다이가쿠호진 토쿄고교 다이가꾸 | Method for producing conductive mayenite compound powder |
| JP7269562B2 (en) * | 2019-03-07 | 2023-05-09 | 太平洋マテリアル株式会社 | Catalyst carrier and catalyst manufacturing method |
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