JP2010253447A - 排ガス浄化用触媒 - Google Patents
排ガス浄化用触媒 Download PDFInfo
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- JP2010253447A JP2010253447A JP2009109850A JP2009109850A JP2010253447A JP 2010253447 A JP2010253447 A JP 2010253447A JP 2009109850 A JP2009109850 A JP 2009109850A JP 2009109850 A JP2009109850 A JP 2009109850A JP 2010253447 A JP2010253447 A JP 2010253447A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 343
- 238000000746 purification Methods 0.000 title claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 80
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 41
- 239000010948 rhodium Substances 0.000 claims abstract description 41
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 41
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 40
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 51
- 239000001301 oxygen Substances 0.000 claims description 51
- 229910052760 oxygen Inorganic materials 0.000 claims description 51
- 239000011232 storage material Substances 0.000 claims description 48
- 229910000510 noble metal Inorganic materials 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 97
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 97
- 239000002002 slurry Substances 0.000 description 84
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 36
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 31
- 229910001928 zirconium oxide Inorganic materials 0.000 description 31
- 239000000758 substrate Substances 0.000 description 16
- 238000011144 upstream manufacturing Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000001603 reducing effect Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- 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 4
- 239000000446 fuel Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003284 rhodium compounds Chemical class 0.000 description 2
- 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 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
- B01D53/9472—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different zones
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
【解決手段】排ガス浄化用触媒1は、排ガスが流れる1つ以上の貫通孔が設けられた基材10と、基材10に支持され且つ酸素貯蔵材を含有した触媒層20とを具備し、排ガスが供給される第1部分100と、第1部分を通過した前記排ガスが供給される第2部分200とを含み、触媒層20は、白金及び/又はパラジウムを含有した第1触媒層20Aとロジウムを含有した第2触媒層20Bとの積層構造を第1部分100に含むと共に、ロジウムを含有した第3触媒層20Cを第2部分200に含み、第2部分200は、第1部分100と比較して単位容積当りの酸素貯蔵材含量がより少ない。
【選択図】 図2
Description
まず、ジニトロジアミン白金硝酸溶液とセリウム酸化物粉末とジルコニウム酸化物粉末とアルミナ粉末とアルミナゾルとを混合して、スラリーを調製した。以下、このスラリーを「スラリーSA」と呼ぶ。
セリウム酸化物粉末及びジルコニウム酸化物粉末の含量をより少なくし、アルミナ含量をより多くしたこと以外は、スラリーSBと同様のスラリーを調製した。以下、このスラリーを「スラリーSC」と呼ぶ。
ロジウム含量をより多くしたこと以外は、スラリーSCと同様のスラリーを調製した。以下、このスラリーを「スラリーSD」と呼ぶ。
ジニトロジアミン白金硝酸溶液と硝酸パラジウム溶液とセリウム酸化物粉末とジルコニウム酸化物粉末とアルミナ粉末とアルミナゾルとを混合して、スラリーを調製した。以下、このスラリーを「スラリーSF」と呼ぶ。
セリウム酸化物含量及びジルコニウム酸化物含量をより少なくすると共に、アルミナ含量をより多くしたこと以外は、スラリーSAと同様のスラリーを調製した。以下、このスラリーを「スラリーSG」と呼ぶ。
セリウム酸化物含量、ジルコニウム酸化物含量及びアルミナ含量をより少なくしたこと以外は、スラリーSGと同様のスラリーを調製した。以下、このスラリーを「スラリーSI」と呼ぶ。
セリウム酸化物含量、ジルコニウム酸化物含量及びアルミナ含量をより多くしたこと以外は、スラリーSBと同様のスラリーを調製した。以下、このスラリーを「スラリーSJ」と呼ぶ。
ジニトロジアミン白金硝酸溶液と硝酸ロジウム溶液とセリウム酸化物粉末とジルコニウム酸化物粉末とアルミナ粉末とアルミナバインダとを混合し、スラリーを調製した。以下、このスラリーを「スラリーSK」と呼ぶ。
触媒C1乃至C8について、排気量4.3Lのエンジンを用いて、950℃で50時間の耐久試験を行った。その後、これら触媒の各々を、直列4気筒2.4Lエンジンを搭載した自動車に設置した。そして、この自動車をLA#4(hot)モードで走行させて、NOx排出量を測定した。
直列4気筒2.4Lエンジンを搭載した自動車の排気系にSC(Start Catalyst)触媒と触媒C1とをエンジン側からこの順に設置した。その後、H2S排出量を測定しながら、以下のようにして自動車の運転条件を変化させた。
Claims (6)
- 排ガスが流れる1つ以上の貫通孔が設けられた基材と、前記基材に支持され且つ酸素貯蔵材を含有した触媒層とを具備し、前記排ガスが供給される第1部分と、前記第1部分を通過した前記排ガスが供給される第2部分とを含んだ排ガス浄化用触媒であって、
前記触媒層は、白金及び/又はパラジウムを含有した第1触媒層とロジウムを含有した第2触媒層との積層構造を前記第1部分に含むと共に、ロジウムを含有した第3触媒層を前記第2部分に含み、
前記第1触媒層の単位容積当りの白金含量とパラジウム含量との和は、前記第2触媒層の単位容積当りの白金含量とパラジウム含量との和及び前記第3触媒層の単位容積当りの白金含量とパラジウム含量との和と比較してより多く、前記第2触媒層の単位容積当りのロジウム含量及び前記第3触媒層の単位容積当りのロジウム含量は、前記第1触媒層の単位容積当りのロジウム含量と比較してより多く、
前記第2部分は、前記第1部分と比較して単位容積当りの前記酸素貯蔵材含量がより少ないことを特徴とする排ガス浄化用触媒。 - 前記第3触媒層の単位容積当りの前記酸素貯蔵材含量は、前記第1触媒層の単位容積当りの前記酸素貯蔵材含量と比較してより少ないことを特徴とする請求項1に記載の排ガス浄化用触媒。
- 前記第2触媒層の単位容積当りの前記酸素貯蔵材含量は、前記第1触媒層の単位容積当りの前記酸素貯蔵材含量と比較してより少ないことを特徴とする請求項1又は2に記載の排ガス浄化用触媒。
- 前記第2触媒層は、前記第1触媒層を間に挟んで前記基材と向き合っていることを特徴とする請求項1乃至3の何れか1項に記載の排ガス浄化用触媒。
- 前記第1触媒層は貴金属として白金及び/又はパラジウムのみを含み、前記第2触媒層は貴金属としてロジウムのみを含んだことを特徴とする請求項1乃至4の何れか1項に記載の排ガス浄化用触媒。
- 前記第3触媒層は貴金属としてロジウムのみを含んだことを特徴とする請求項5に記載の排ガス浄化用触媒。
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