JP2011104485A - Catalyst for purifying exhaust gas - Google Patents
Catalyst for purifying exhaust gas Download PDFInfo
- Publication number
- JP2011104485A JP2011104485A JP2009260298A JP2009260298A JP2011104485A JP 2011104485 A JP2011104485 A JP 2011104485A JP 2009260298 A JP2009260298 A JP 2009260298A JP 2009260298 A JP2009260298 A JP 2009260298A JP 2011104485 A JP2011104485 A JP 2011104485A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- exhaust gas
- oxide material
- phosphorus
- surface area
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 34
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims description 54
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 42
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 41
- 239000011574 phosphorus Substances 0.000 abstract description 41
- 231100000572 poisoning Toxicity 0.000 abstract description 31
- 230000000607 poisoning effect Effects 0.000 abstract description 31
- 239000011247 coating layer Substances 0.000 abstract description 21
- 239000007789 gas Substances 0.000 description 71
- 239000010410 layer Substances 0.000 description 28
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000011144 upstream manufacturing Methods 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 231100000614 poison Toxicity 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000002574 poison Substances 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 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
- 238000011156 evaluation Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 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
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
本発明は、排ガス浄化用触媒に関し、さらに詳しくは三元触媒の触媒コート層表面に酸化物材料をコートした排ガス浄化用触媒であって酸化物材料の比表面積およびコート量を特定の範囲にすることによって触媒コート層のリン被毒を回避乃至は抑制し得る排ガス浄化用触媒に関するものである。 The present invention relates to an exhaust gas purification catalyst, and more particularly, an exhaust gas purification catalyst in which an oxide material is coated on the surface of a catalyst coat layer of a three-way catalyst, and the specific surface area and the coating amount of the oxide material are in a specific range. The present invention relates to an exhaust gas purifying catalyst capable of avoiding or suppressing phosphorus poisoning of a catalyst coat layer.
自動車等の内燃機関から排出される排ガス中には炭化水素（ＨＣ）、一酸化炭素（ＣＯ）及び酸化窒素（ＮＯＸ）が含まれている。これらの物質は、各国で強化されている排ガス規制を満たし且つ埋蔵量が少なく資源リスクの高い貴金属の使用を最小限に抑えことを目的に開発された排ガス浄化用触媒によって浄化されてから大気中に放出されている。ガソリンエンジン用触媒の代表的なものとしては、アルミナ（Ａｌ２Ｏ３）、シリカ（ＳｉＯ２）、ジルコニア（ＺｒＯ２）、チタニア（ＴｉＯ２）などの多孔質酸化物担体に、貴金属の中でも白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）などを主たる活性種として胆持した三元触媒が広く用いられている。 The exhaust gas discharged from an internal combustion engine such as an automobile contains hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxide (NO x ). These substances are exhausted into the atmosphere after being purified by an exhaust gas purifying catalyst that has been developed with the aim of minimizing the use of precious metals with low reserves and high resource risks that meet the strict exhaust gas regulations in each country. Has been released. Typical gasoline engine catalysts include porous oxide carriers such as alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), titania (TiO 2 ), platinum among noble metals. A three-way catalyst having a main active species of (Pt), palladium (Pd), rhodium (Rh) and the like is widely used.
この三元触媒は、排ガス中のＨＣ及びＣＯを酸化して浄化するとともに、ＨＣ及びＣＯを還元種としてＮＯＸを還元して浄化するものであり、前記の貴金属が最も高活性に作用し得てＨＣ、ＣＯおよびＮＯＸが均一に浄化できるように触媒中を理論空燃比近傍に保つ酸化セリウムを主成分とする酸素吸蔵材（ＯＳＣ材）が含まれている。
一方、触媒を使用するにあたり、触媒被毒は避けられない課題である。被毒は、主にガソリンなどの燃料中に含まれる硫黄分によるものと、エンジンオイル中に含まれるジアルキルジチオリン酸亜鉛（ＺＤＤＰと略記される）によるもの、そしてオクタン価向上剤としてガソリン中に添加されるメチルシクロペンタジエニルマンガントリカルボニル（ＭＭＴと略記される）によるものが挙げられる。
This three-way catalyst oxidizes and purifies HC and CO in exhaust gas, and reduces and purifies NO X using HC and CO as reducing species, and the above-mentioned noble metals can act most highly. Te HC, the oxygen storage material composed mainly of cerium oxide to keep the catalyst in near stoichiometric air-fuel ratio so that it can purify CO and NO X are uniformly (OSC material) is included.
On the other hand, when a catalyst is used, catalyst poisoning is an unavoidable problem. Poisoning is mainly caused by sulfur contained in fuels such as gasoline, zinc dialkyldithiophosphate (abbreviated as ZDDP) contained in engine oil, and added to gasoline as an octane improver. And methylcyclopentadienyl manganese tricarbonyl (abbreviated as MMT).
これらの被毒のうち、硫黄分による被毒物質は、エンジンの空燃比制御や温度制御によりＳＯ２若しくはＨ２Ｓとして気化させて脱離させることも可能であるが、リン(Ｐ)およびＭｎを含む被毒物質は、触媒コート層に付着しガラス質を形成して蓄積するため被毒からの回復は困難となる。
このため、触媒のリンによる被毒を抑制する技術が提案されており、その１つに触媒中にリンと反応しやすい物質を添加する方法が提案されたが、リン付着量が飽和になると触媒層への被毒が始まるため、さらなる解決策が求められている。
Among these poisons, poisonous substances due to sulfur can be vaporized as SO 2 or H 2 S by the air-fuel ratio control or temperature control of the engine and desorbed, but phosphorus (P) and Mn Since the poisoning substance containing, which adheres to the catalyst coat layer and forms a glassy substance, it is difficult to recover from poisoning.
For this reason, a technique for suppressing poisoning of the catalyst by phosphorus has been proposed, and a method for adding a substance that easily reacts with phosphorus into the catalyst has been proposed. As the poisoning of the layers begins, further solutions are needed.
その１つとして、特許文献１には、担体上に貴金属触媒成分を被覆した排ガス浄化用触媒において、触媒表面にＴｉＯ２を被覆したＰ被毒防止処理を施した排ガス浄化用触媒が記載されている。しかし、特許文献１には、排ガス浄化用触媒による浄化作用を定性的に示されているに過ぎず、具体例では排ガス浄化用触媒で一般的に使用されるＯＳＣ材を用いていないため、ＯＳＣ材中に含まれる酸化セリウム（セリア）がＴｉＯ２と反応しやすく却って酸素吸蔵量を低下させて触媒性能に悪影響を及ぼすとの認識はない。 As one of them, Patent Document 1 describes an exhaust gas purification catalyst in which a noble metal catalyst component is coated on a carrier, and an exhaust gas purification catalyst having a catalyst surface coated with TiO 2 and subjected to P poisoning prevention treatment. Yes. However, Patent Document 1 only qualitatively shows the purifying action by the exhaust gas purifying catalyst, and the specific example does not use the OSC material generally used in the exhaust gas purifying catalyst. There is no recognition that cerium oxide (ceria) contained in the material is likely to react with TiO 2 , thereby reducing the oxygen storage amount and adversely affecting the catalyst performance.
特許文献２には、ハニカム形状の担体基材と、該担体基材のセル壁表面に形成された触媒金属を担持した第１コート層と、該第１コート層の表面に形成された触媒金属を担持しない第２コート層とよりなり、該第１コート層の層厚を該第１コート層と該第２コート層の合計層厚の１／１０〜１／５としたディーゼル排ガス浄化用触媒が記載されている。そして、具体例として６５０℃で５０時間の耐久試験後でＨＣ浄化率が７５〜８０％の浄化活性を示す排ガス浄化用触媒が示されている。しかし、特許文献２にはリンによる被毒について記載されてなく、被毒物質がガラス質化して蓄積し得る厳しい条件、すなわちリンを含む運転条件でより高温そして長時間の耐久試験後でも触媒が同様の浄化活性を示すか不明である。 Patent Document 2 discloses a honeycomb-shaped carrier substrate, a first coat layer carrying a catalyst metal formed on the cell wall surface of the carrier substrate, and a catalyst metal formed on the surface of the first coat layer. A diesel exhaust gas purification catalyst comprising: a second coat layer that does not support the first coating layer, wherein the thickness of the first coating layer is 1/10 to 1/5 of the total thickness of the first coating layer and the second coating layer Is described. As a specific example, an exhaust gas purifying catalyst showing a purifying activity with an HC purification rate of 75 to 80% after an endurance test at 650 ° C. for 50 hours is shown. However, Patent Document 2 does not describe the poisoning by phosphorus, and the catalyst can be used even under severe conditions where poisonous substances can vitrify and accumulate, that is, operating conditions including phosphorus, even at higher temperatures and for a long time. It is unknown whether the same purification activity is exhibited.
さらに、特許文献３には、オイル及び／又は燃料に由来する添加剤による毒に対して優れた耐性を有する自動車排ガス処理触媒であって、排ガスと最初に接触する上流端を有する基材、例えばハニカム基材、貴金属を全くか少ししか含まない耐熱性金属酸化物および場合により希土類酸化物からなるベースコート、高濃度の貴金属を含む貴金属含有第１触媒層および上流端から０．５〜５ｃｍ又は３〜７０％の長さを有する毒捕捉領域を有する自動車排ガス処理触媒が記載されている。しかし、特許文献３に記載の自動車排ガス処理触媒によれば、触媒層の表面は毒捕捉領域によって全く保護されないため毒補足領域の性質によっては三元触媒の性能が著しく低下し得る。 Further, Patent Document 3 discloses an automobile exhaust gas treatment catalyst having excellent resistance to poisons caused by additives derived from oil and / or fuel, and a base material having an upstream end that first comes into contact with exhaust gas, for example, Honeycomb substrate, base coat consisting of refractory metal oxide and optionally rare earth oxide with little or no noble metal, first catalyst layer containing noble metal with high concentration of noble metal and 0.5-5 cm or 3 from upstream end An automobile exhaust gas treatment catalyst having a poison capture zone having a length of ˜70% is described. However, according to the automobile exhaust gas treatment catalyst described in Patent Document 3, the surface of the catalyst layer is not protected at all by the poison trapping region, so that the performance of the three-way catalyst can be remarkably lowered depending on the nature of the poison capturing region.
このように、従来公知の技術によっては、リンの存在下に運転されるエンジンに適用される触媒コート層のリン被毒を充分満足のいくレベルまで抑制することができない。
従って、本発明の目的は、リンの存在下に運転されるエンジンに適用される触媒コート層のリン被毒を充分満足のいくレベルまで抑制し得る排ガス浄化用触媒を提供することである。
As described above, it is impossible to suppress phosphor poisoning of the catalyst coat layer applied to the engine operated in the presence of phosphorus to a sufficiently satisfactory level by a conventionally known technique.
Accordingly, an object of the present invention is to provide an exhaust gas purifying catalyst capable of suppressing phosphorus poisoning of a catalyst coat layer applied to an engine operated in the presence of phosphorus to a sufficiently satisfactory level.
本発明は、三元触媒の触媒コート層表面に酸化物材料をコートした排ガス浄化用触媒であって、前記酸化物材料の比表面積が９ｍ２／ｇ以下で且つコート量が１０ｇ／Ｌ以上４０ｇ／Ｌ以下であることを特徴とする排ガス浄化用触媒に関する。
本願発明における酸化物材料の比表面積とは、コートする前の原料として用いる酸化物の比表面積を示す。
また、本明細書において、リン被毒を充分満足のいくレベルまで抑制し得るとは、後述の実施例の欄に詳述される方法で測定したＴＨＣ浄化率が７５％以上であることを意味する。
The present invention is an exhaust gas purifying catalyst in which an oxide material is coated on the surface of a catalyst coat layer of a three-way catalyst, wherein the oxide material has a specific surface area of 9 m 2 / g or less and a coating amount of 10 g / L or more and 40 g. The present invention relates to an exhaust gas purifying catalyst characterized by being / L or less.
The specific surface area of the oxide material in the present invention refers to the specific surface area of the oxide used as a raw material before coating.
Further, in this specification, being able to suppress phosphorus poisoning to a sufficiently satisfactory level means that the THC purification rate measured by the method described in detail in the Examples section below is 75% or more. To do.
本発明によれば、リンの存在下に運転されるエンジンに適用される触媒コート層のリン被毒を充分満足のいくレベルまで抑制し得る排ガス浄化用触媒が得られる。 According to the present invention, it is possible to obtain an exhaust gas purifying catalyst capable of suppressing phosphorus poisoning of a catalyst coat layer applied to an engine operated in the presence of phosphorus to a sufficiently satisfactory level.
本発明によれば、三元触媒の触媒コート層表面に酸化物材料をコートした排ガス浄化用触媒であって、前記酸化物材料の比表面積が９ｍ２／ｇ以下、例えば０．２〜９ｍ２／ｇで且つコート量が１０ｇ／Ｌ以上４０ｇ／Ｌ以下である排ガス浄化用触媒により、経時劣化を受けることが少なく酸素吸蔵量に悪影響を及ぼさずないため、触媒コート層のリン被毒を回避して良好な浄化性能を得ることが可能となる。 According to the present invention, an exhaust gas-purifying catalyst having an oxide material coated on the surface of a catalyst coat layer of a three-way catalyst, the specific surface area of the oxide material is 9 m 2 / g or less, for example, 0.2 to 9 m 2. / G and a coating amount of 10 g / L or more and 40 g / L or less, the catalyst for the catalyst coating layer avoids phosphorous poisoning because it does not deteriorate with time and does not adversely affect the oxygen storage amount. Thus, it is possible to obtain a good purification performance.
以下、本発明の排ガス浄化用触媒について、図１を用いて説明する。
本発明の排ガス浄化用触媒１は、基材２、例えばハニカム基材と、該基材２にコートした三元触媒の触媒コート層３と、その表面に酸化物材料をコートした酸化物材料コート層４からなり、前記酸化物材料の比表面積が９ｍ２／ｇ以下で且つコート量が１０ｇ／Ｌ以上４０ｇ／Ｌ以下であることが必要である。
Hereinafter, the exhaust gas purifying catalyst of the present invention will be described with reference to FIG.
The exhaust gas-purifying catalyst 1 of the present invention comprises a substrate 2, for example, a honeycomb substrate, a catalyst coat layer 3 of a three-way catalyst coated on the substrate 2, and an oxide material coat in which an oxide material is coated on the surface. It is required that the oxide material has a specific surface area of 9 m 2 / g or less and a coating amount of 10 g / L or more and 40 g / L or less.
前記のハニカム基材としてはコージェライトなどのセラミックス材料やステンレス鋼などにより形成され得る。また、本発明の排ガス浄化用触媒は任意の形状に成形して用いることができる。
前記の三元触媒成分としては、貴金属および遷移金属のうちの少なくとも１種の金属が挙げられる。貴金属として、Ｐｔ、Ｐｄ、Ｒｈ、Ｉｒからなる群から選ばれる少なくとも１種の元素、特にＰｄおよびＲｈが挙げられる。三元触媒成分として遷移金属を用いる場合には、例えばＮｉなどが用いられ得る。
The honeycomb substrate can be formed of a ceramic material such as cordierite or stainless steel. Further, the exhaust gas purifying catalyst of the present invention can be used after being molded into an arbitrary shape.
Examples of the three-way catalyst component include at least one of a noble metal and a transition metal. Examples of the noble metal include at least one element selected from the group consisting of Pt, Pd, Rh, and Ir, particularly Pd and Rh. When a transition metal is used as the three-way catalyst component, for example, Ni can be used.
前記の三元触媒の触媒コート層３は、金属酸化物、例えばセリア−ジルコニア複合酸化物に貴金属触媒、例えばＰｄおよびＲｈを担持させた粉末と水とからコート用スラリーを得て、スラリーを基材、例えばハニカム基材に投入し、下部を吸引することによってコートし、乾燥、焼成することによって基材に形成し得る。前記の触媒コート層のコート量はスラリーの粘度や固形分量、スラリー投入量を調整することによって行い得る。 The catalyst coat layer 3 of the three-way catalyst is obtained by obtaining a slurry for coating from a powder in which a metal oxide, for example, a ceria-zirconia composite oxide is loaded with a noble metal catalyst, for example, Pd and Rh, and water. It can be formed into a base material by putting it into a material, for example, a honeycomb base material, coating by sucking the lower part, drying and firing. The coating amount of the catalyst coating layer can be performed by adjusting the viscosity, solid content, and slurry input amount of the slurry.
本発明における触媒コート層にコートする酸化物材料としては、アルミナ、ジルコニア、シリカ、セリアやこれらの少なくとも２種類を組み合わせた複合酸化物が挙げられ、好適にはセリア、ジルコニアおよびアルミナのうちの少なくとも１種類を含むもの、例えばセリア−ジルコニア複合酸化物が挙げられる。また、前記の酸化物材料はさらに１種類以上の希土類元素、例えばセリウム、ランタン、ネオジウム、プラセオジウムを含み得る。これらの希土類元素は酸化物として含有され得る。 Examples of the oxide material to be coated on the catalyst coating layer in the present invention include alumina, zirconia, silica, ceria and a composite oxide in which at least two of these are combined, and preferably at least of ceria, zirconia and alumina. One containing one kind, for example, ceria-zirconia composite oxide can be mentioned. The oxide material may further include one or more rare earth elements such as cerium, lanthanum, neodymium, and praseodymium. These rare earth elements can be contained as oxides.
本発明においては、前記酸化物材料の比表面積およびコート量が重要であり、比表面積は９ｍ２／ｇ以下、例えば０．２〜９ｍ２／ｇ、その中でも１〜９ｍ２／ｇであることが必要である。また、コート量は１０ｇ／Ｌ以上４０ｇ／Ｌ以下、特に１０ｇ／Ｌ以上３０ｇ／Ｌ以下であることが必要である。酸化物材料の比表面積が過度に大きいと酸化物材料のリン被毒抑制効果がかえって低く、コート量が前記下限より少ないと酸化物材料のリン被毒抑制効果が低く、コート量が前記上限より多いと三元触媒の性能が低下する。このように、本発明における酸化物材料層は、直接的には排ガスの浄化反応に寄与しないため、リン被毒が抑制される範囲で最小限とすることが望ましい。 It In the present invention, the important specific surface area and coating weight of the oxide material, the specific surface area 9m 2 / g or less, for example 0.2~9m 2 / g, 1~9m 2 / g among them is required. Further, the coating amount needs to be 10 g / L or more and 40 g / L or less, particularly 10 g / L or more and 30 g / L or less. If the specific surface area of the oxide material is excessively large, the phosphorous poisoning suppression effect of the oxide material is rather low. If the coating amount is less than the lower limit, the phosphorous poisoning suppression effect of the oxide material is low, and the coating amount exceeds the upper limit. If the amount is too large, the performance of the three-way catalyst will deteriorate. Thus, since the oxide material layer in the present invention does not directly contribute to the exhaust gas purification reaction, it is desirable to minimize the oxide material layer within a range in which phosphorus poisoning is suppressed.
本発明の排ガス浄化用触媒は、触媒コート層のリン被毒を充分満足のいくレベルまで抑制しえるため、リンの存在下に運転されるエンジンに適用されても安定した排ガス浄化性能を達成することが可能である。 The exhaust gas purifying catalyst of the present invention can suppress phosphorus poisoning of the catalyst coat layer to a sufficiently satisfactory level, and thus achieves stable exhaust gas purifying performance even when applied to an engine operated in the presence of phosphorus. It is possible.
以下、本発明の実施例を示す。
以下の実施例は単に説明するためのものであり、本発明を限定するものではない。
以下の各例で、触媒の物性および浄化性能の評価は以下に示す方法により行った。
Examples of the present invention will be described below.
The following examples are for illustrative purposes only and are not intended to limit the invention.
In each of the following examples, the physical properties and purification performance of the catalyst were evaluated by the following methods.
１．比表面積
ＢＥＴ１点法で吸着質として窒素を用いて常法により測定した。
測定装置：島津製作所 Micromeritics Flowsorb II 2300
２．リンの蓄積状態
触媒の端面、および触媒を分解したときのガス流れ方向での１０ｍｍ後方の位置で、各々についてＥＰＭＡ（Electron Probe Micro Micro Analyzer：電子線マイクロアナライザ ）を用いてＥＰＭＡ測定を行い、リンの蓄積状態を確認した。
測定装置：島津製作所 ＭＡＣＨＳ−２００
1. Specific surface area was measured by a conventional method using nitrogen as an adsorbate by the BET one-point method.
Measuring device: Shimadzu Micromeritics Flowsorb II 2300
2. Phosphorus accumulation state EPMA measurement was performed using EPMA (Electron Probe Micro Micro Analyzer) for each of the catalyst end face and the position 10 mm behind in the gas flow direction when the catalyst was decomposed. The accumulation state of was confirmed.
Measuring device: Shimadzu MACHS-200
３．リン被毒耐久試験方法
実施例および比較例で得られた触媒を装着して、一定の条件で走行後にも触媒活性を維持しているか否かを確認するために、実際の自動車エンジンを用いて加速劣化試験（耐久試験）を行った。
装着・走行条件：触媒にセラミックマットを巻き、排気管にキャニングし、ハニカムの中央に熱電対を差し込んだ。この排気管をエンジンにセットし、熱電対の温度が９５０℃±２０℃になるようにエンジン回転数／トルク等を調整した。このとき、Ａ／Ｆは１４と１５を一定時間ずつ繰り返すサイクル試験とした。その際に、リン被毒を促進するため、エンジンオイルを１０ｍＬ／時間ずつ触媒の上流に添加し、耐久試験時間を１００時間とした。
3. Phosphorus poisoning endurance test method The actual automobile engine was used to check whether or not the catalyst activity was maintained even after running under certain conditions with the catalysts obtained in the examples and comparative examples. An accelerated deterioration test (endurance test) was conducted.
Installation and running conditions: A ceramic mat was wound around the catalyst, it was canned in the exhaust pipe, and a thermocouple was inserted in the center of the honeycomb. This exhaust pipe was set in the engine, and the engine speed / torque and the like were adjusted so that the temperature of the thermocouple was 950 ° C. ± 20 ° C. At this time, A / F was a cycle test in which 14 and 15 were repeated for a certain time. At that time, in order to promote phosphorus poisoning, engine oil was added to the upstream of the catalyst at 10 mL / hour, and the durability test time was set to 100 hours.
４．触媒の浄化性能試験方法
上記の方法で耐久試験を施した触媒をエンジンに取り付け、触媒前１０ｍｍの位置の温度が５００℃になるように、エンジン回転数／トルクを調整した。そして、Ａ／Ｆが１４．６になるように調整し、触媒の前後のガス濃度差より、浄化率を下記の計算式から算出し、ＴＨＣ浄化率（％表示）として示す。
ＴＨＣ浄化率＝［（触媒の入ガス濃度−触媒の出ガス濃度）／触媒の入りガス濃度］ ｘ１００
4). Catalyst purification performance test method The catalyst subjected to the durability test by the above method was attached to the engine, and the engine speed / torque was adjusted so that the temperature at a position 10 mm before the catalyst was 500 ° C. And it adjusts so that A / F may be set to 14.6, the purification rate is computed from the following formula from the gas concentration difference before and behind the catalyst, and is shown as the THC purification rate (% display).
THC purification rate = [(catalyst inlet gas concentration−catalyst outlet gas concentration) / catalyst inlet gas concentration] × 100
実施例１
１−１ 三元触媒層のコート
希土類元素を含むセリア−ジルコニア複合酸化物（ローディア社製、ＣｅＯ２：５０質量％、ＺｒＯ２：４０質量％、Ｙ２Ｏ３：５質量％、ＬａＯ３：５質量％）に硝酸パラジウム薬液および硝酸ロジウム溶液を含浸担持し、希土類元素を含むγ−アルミナ（サソール社製、Ａｌ２Ｏ３：９６質量％、Ｌａ２Ｏ３：４質量％）と４：６の質量比率で混合した。さらに、アルミナバインダーと混合粉末とを１：１９の質量比率で混合し、水を加えてコート用スラリーとした。
このスラリーをセラミックハニカム（デンソー社製、セル密度６００ｃｅｌｌ／ｉｎｃｈ２、壁厚３ｍｉｌ、φ１０３ｘＬ１０５）の上部から投入し、下部を吸引することでコートし、１２０℃で０．５時間乾燥後、大気中４００℃で１時間焼成した。
コート量は、焼成後の質量が１８０ｇ／Ｌとなるようにした。
Example 1
1-1 Three-way catalyst layer coating Ceria-zirconia composite oxide containing rare earth elements (Rodia Co., CeO 2 : 50% by mass, ZrO 2 : 40% by mass, Y 2 O 3 : 5% by mass, LaO 3 : 5 mass%) impregnated and supported with a palladium nitrate chemical solution and a rhodium nitrate solution, and containing γ-alumina containing rare earth elements (manufactured by Sasol, Al 2 O 3 : 96 mass%, La 2 O 3 : 4 mass%) and 4: Mixed at a mass ratio of 6. Furthermore, the alumina binder and the mixed powder were mixed at a mass ratio of 1:19, and water was added to form a slurry for coating.
This slurry was applied from the top of a ceramic honeycomb (Denso Corp., cell density 600 cell / inch 2 , wall thickness 3 mil, φ103 × L105), coated by sucking the bottom, dried at 120 ° C. for 0.5 hours, and then in the atmosphere Baked at 400 ° C. for 1 hour.
The coating amount was such that the mass after firing was 180 g / L.
１−２ 酸化物材料（被毒抑制層）のコート
比表面積が３ｍ２／ｇのアルミナとアルミナバインダーとを１：１９の比率で混合し、水を加えてスラリーとした。このスラリーを、１−１で作製した三元触媒層がコートされたセラミックハニカムの上部より投入し、下部を吸引することで三元触媒層表面に均一にコートし、１２０℃で０．５時間乾燥後、大気中４００℃で１時間焼成した。
得られた排ガス浄化用触媒の被毒抑制層のコート量は、スラリーの粘度や固形分量、スラリー投入量を調整することで、焼成後の質量が１０ｇ／Ｌとなるようにした。
１−３ 物性測定および評価
得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：Ａｌ２Ｏ３ 比表面積：３ｍ２／ｇ コート量：１０ｇ／Ｌ
２）ＴＨＣ浄化率：８８％
また、耐久試験後の端面でのリン付着量をＥＰＭＡで観察した結果を図４、また流れ方向で上流から１０ｍｍ後方の位置でのリン付着量を観察した結果を図７に示す。
1-2 Coat of oxide material (poisoning suppression layer) Alumina having a specific surface area of 3 m 2 / g and an alumina binder were mixed at a ratio of 1:19, and water was added to form a slurry. This slurry is introduced from the upper part of the ceramic honeycomb coated with the three-way catalyst layer prepared in 1-1, and the lower part is sucked to uniformly coat the surface of the three-way catalyst layer, at 120 ° C. for 0.5 hour. After drying, it was fired at 400 ° C. for 1 hour in the air.
The coating amount of the poisoning suppression layer of the obtained exhaust gas purifying catalyst was adjusted such that the mass after firing was 10 g / L by adjusting the viscosity, solid content, and slurry input amount of the slurry.
1-3 Measurement of physical properties and evaluation The obtained exhaust gas-purifying catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: Al 2 O 3 Specific surface area: 3 m 2 / g Coating amount: 10 g / L
2) THC purification rate: 88%
Moreover, the result of having observed the phosphorus adhesion amount in the end surface after an endurance test by EPMA is shown in FIG. 4, and the result of observing the phosphorus adhesion amount at a position 10 mm behind from the upstream in the flow direction is shown in FIG.
実施例２
実施例１で用いた比表面積が３ｍ２／ｇのアルミナに代えて、比表面積が２ｍ２／ｇのジルコニアを用いた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：ＺｒＯ２ 比表面積：２ｍ２／ｇ コート量：１０ｇ／Ｌ
２）ＴＨＣ浄化率：８３％
Example 2
An exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that zirconia having a specific surface area of 2 m 2 / g was used instead of alumina having a specific surface area of 3 m 2 / g used in Example 1. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: ZrO 2 Specific surface area: 2 m 2 / g Coating amount: 10 g / L
2) THC purification rate: 83%
実施例３
実施例１で用いた比表面積が３ｍ２／ｇのアルミナに代えて、比表面積が１ｍ２／ｇのセリアを用いた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：ＣｅＯ２ 比表面積：１ｍ２／ｇ コート量：１０ｇ／Ｌ
２）ＴＨＣ浄化率：８７％
Example 3
An exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that ceria having a specific surface area of 1 m 2 / g was used instead of alumina having a specific surface area of 3 m 2 / g used in Example 1. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: CeO 2 specific surface area: 1 m 2 / g Coating amount: 10 g / L
2) THC purification rate: 87%
実施例４
実施例１で用いた比表面積が３ｍ２／ｇのアルミナに代えて、比表面積が９ｍ２／ｇのセリアージルコニア複合酸化物を用いた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：ＣｅＺｒＯ４ 比表面積：９ｍ２／ｇ コート量：１０ｇ／Ｌ
２）ＴＨＣ浄化率：８５％
Example 4
An exhaust gas purifying catalyst was prepared in the same manner as in Example 1 except that ceria-zirconia composite oxide with a specific surface area of 9 m 2 / g was used instead of alumina with a specific surface area of 3 m 2 / g used in Example 1. Obtained. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: CeZrO 4 Specific surface area: 9 m 2 / g Coating amount: 10 g / L
2) THC purification rate: 85%
実施例５
実施例１で用いた比表面積が３ｍ２／ｇのアルミナに代えて、比表面積が８ｍ２／ｇのアルミナを用いた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：Ａｌ２Ｏ３ 比表面積：８ｍ２／ｇ コート量：１０ｇ／Ｌ
２）ＴＨＣ浄化率：８４％
Example 5
An exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that alumina having a specific surface area of 8 m 2 / g was used instead of alumina having a specific surface area of 3 m 2 / g used in Example 1. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: Al 2 O 3 Specific surface area: 8 m 2 / g Coating amount: 10 g / L
2) THC purification rate: 84%
実施例６
コート量を１０ｇ／Ｌから３０ｇ／Ｌに変えた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：Ａｌ２Ｏ３ 比表面積：３ｍ２／ｇ コート量：３０ｇ／Ｌ
２）ＴＨＣ浄化率：８１％
Example 6
Exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that the coating amount was changed from 10 g / L to 30 g / L. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: Al 2 O 3 Specific surface area: 3 m 2 / g Coating amount: 30 g / L
2) THC purification rate: 81%
実施例７
コート量を１０ｇ／Ｌから４０ｇ／Ｌに変えた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：Ａｌ２Ｏ３ 比表面積：３ｍ２／ｇ コート量：４０ｇ／Ｌ
２）ＴＨＣ浄化率：７５％
Example 7
Exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that the coating amount was changed from 10 g / L to 40 g / L. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: Al 2 O 3 Specific surface area: 3 m 2 / g Coating amount: 40 g / L
2) THC purification rate: 75%
比較例１
酸化物材料コート層を形成しなかった他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
なし
２）ＴＨＣ浄化率：７２％
また、耐久試験後の端面でのリン付着量をＥＰＭＡで観察した結果を図５、また流れ方向で上流から１０ｍｍ後方の位置でのリン付着量を観察した結果を図８に示す。
Comparative Example 1
Exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that the oxide material coat layer was not formed. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer None 2) THC purification rate: 72%
Moreover, the result of having observed the phosphorus adhesion amount in the end surface after an endurance test by EPMA is shown in FIG. 5, and the result of observing the phosphorus adhesion amount at a position 10 mm behind from the upstream in the flow direction is shown in FIG.
比較例２
実施例１で用いた比表面積が３ｍ２／ｇのアルミナに代えて、比表面積が８６ｍ２／ｇのアルミナを用いた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：Ａｌ２Ｏ３ 比表面積：８６ｍ２／ｇ コート量：１０ｇ／Ｌ
２）ＴＨＣ浄化率：６３％
Comparative Example 2
An exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that alumina having a specific surface area of 86 m 2 / g was used instead of alumina having a specific surface area of 3 m 2 / g used in Example 1. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: Al 2 O 3 specific surface area: 86 m 2 / g Coating amount: 10 g / L
2) THC purification rate: 63%
比較例３
コート量を１０ｇ／Ｌから６０ｇ／Ｌに変えた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：Ａｌ２Ｏ３ 比表面積：３ｍ２／ｇ コート量：６０ｇ／Ｌ
２）ＴＨＣ浄化率：５６％
Comparative Example 3
Exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that the coating amount was changed from 10 g / L to 60 g / L. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: Al 2 O 3 Specific surface area: 3 m 2 / g Coating amount: 60 g / L
2) THC purification rate: 56%
比較例４
コート量を１０ｇ／Ｌから６０ｇ／Ｌに変えた他は実施例２と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：ＺｒＯ２ 比表面積：３ｍ２／ｇ コート量：６０ｇ／Ｌ
２）ＴＨＣ浄化率：５９％
Comparative Example 4
Exhaust gas purification catalyst was obtained in the same manner as in Example 2 except that the coating amount was changed from 10 g / L to 60 g / L. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coat layer Oxide material: ZrO 2 specific surface area: 3 m 2 / g Coat amount: 60 g / L
2) THC purification rate: 59%
比較例４
コート量を１０ｇ／Ｌから２ｇ／Ｌに変えた他は実施例１と同様にして排ガス浄化用触媒を得た。得られた排ガス浄化用触媒について評価を行った。結果を次に示す。
１）酸化物材料コート層
酸化物材料：Ａｌ２Ｏ３ 比表面積：３ｍ２／ｇ コート量：２ｇ／Ｌ
２）ＴＨＣ浄化率：７０％
Comparative Example 4
Exhaust gas purification catalyst was obtained in the same manner as in Example 1 except that the coating amount was changed from 10 g / L to 2 g / L. The obtained exhaust gas purification catalyst was evaluated. The results are shown below.
1) Oxide material coating layer Oxide material: Al 2 O 3 Specific surface area: 3 m 2 / g Coating amount: 2 g / L
2) THC purification rate: 70%
図４と図５との比較から、色が白い（図中の右のバーの上）方がリンの濃度が高いので触媒の端面においては、実施例１の排ガス浄化用触媒は比較例１の排ガス浄化用触媒に比べてリンの付着が顕著に少ないことが確認された。
また、図７と図８との比較から、流れ方向で上流から１０ｍｍ後方の位置でも、実施例１の排ガス浄化用触媒は比較例１の排ガス浄化用触媒に比べてリンの付着が顕著に少ないことが確認された。
また、上記のＴＨＣ浄化率について各実施例と各比較例との比較から、前記酸化物材料コート層の比表面積が９ｍ２／ｇ以下で且つコート量が１０ｇ／Ｌ以上４０ｇ／Ｌ以下であることが必要であることが理解された。
From the comparison between FIG. 4 and FIG. 5, the whiter color (above the right bar in the figure) has a higher phosphorus concentration, so that the exhaust gas purifying catalyst of Example 1 is the same as that of Comparative Example 1 at the end face of the catalyst. It was confirmed that the adhesion of phosphorus was significantly less than that of the exhaust gas purification catalyst.
7 and 8, the exhaust gas purification catalyst of Example 1 has significantly less phosphorus adhesion than the exhaust gas purification catalyst of Comparative Example 1 even at a position 10 mm behind the upstream in the flow direction. It was confirmed.
Further, from the comparison of each example and each comparative example with respect to the above THC purification rate, the specific surface area of the oxide material coating layer is 9 m 2 / g or less and the coating amount is 10 g / L or more and 40 g / L or less. It was understood that it was necessary.
本発明の排ガス浄化用触媒によれば、リン成分を含む排ガスを放出する自動車などからの排ガスであってもリン被毒を抑制し、安定した排ガス浄化性能を達成することが可能である。 According to the exhaust gas purifying catalyst of the present invention, it is possible to suppress phosphorus poisoning and achieve stable exhaust gas purifying performance even for exhaust gas from an automobile or the like that releases exhaust gas containing a phosphorus component.
１ 本発明の排ガス浄化用触媒
２ 基材
３ 三元触媒の触媒コート層
４ 酸化物材料コート層
1 catalyst for purifying exhaust gas of the present invention 2 base material 3 catalyst coat layer of three-way catalyst 4 oxide material coat layer
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009260298A JP5504834B2 (en) | 2009-11-13 | 2009-11-13 | Exhaust gas purification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009260298A JP5504834B2 (en) | 2009-11-13 | 2009-11-13 | Exhaust gas purification catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011104485A true JP2011104485A (en) | 2011-06-02 |
| JP5504834B2 JP5504834B2 (en) | 2014-05-28 |
Family
ID=44228615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009260298A Expired - Fee Related JP5504834B2 (en) | 2009-11-13 | 2009-11-13 | Exhaust gas purification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5504834B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013091585A (en) * | 2011-10-26 | 2013-05-16 | Tosoh Corp | Zirconia powder, method for producing the same, and its application |
| WO2015087873A1 (en) | 2013-12-13 | 2015-06-18 | 株式会社キャタラー | Exhaust purification catalyst |
| WO2020196628A1 (en) * | 2019-03-27 | 2020-10-01 | エヌ・イーケムキャット株式会社 | Selective reduction catalyst for diesel and diesel exhaust gas purification apparatus |
| EP2952251B1 (en) * | 2013-01-31 | 2022-06-01 | Umicore Shokubai Japan Co., Ltd. | Exhaust-gas purification catalyst and its use |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49128893A (en) * | 1973-04-13 | 1974-12-10 | ||
| JPS5579046A (en) * | 1978-12-09 | 1980-06-14 | Mazda Motor Corp | Exhaustion gas cleaning catalyst having undergone phosphorus poisoning preventive treatment |
| JPS55167046A (en) * | 1979-06-15 | 1980-12-26 | Mazda Motor Corp | Waste gas cleaning catalyst subjected to treatment for preventing phosphorus-poisoning |
| JPS614532A (en) * | 1984-06-19 | 1986-01-10 | Nissan Motor Co Ltd | Manufacture of integral structure type catalyst for purifying waste gas |
| JPS6271541A (en) * | 1985-09-24 | 1987-04-02 | Mazda Motor Corp | Production of catalyst for cleaning up exhaust gas of engine |
| JP2004230226A (en) * | 2003-01-28 | 2004-08-19 | Mazda Motor Corp | Catalyst for automobile |
-
2009
- 2009-11-13 JP JP2009260298A patent/JP5504834B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49128893A (en) * | 1973-04-13 | 1974-12-10 | ||
| JPS5579046A (en) * | 1978-12-09 | 1980-06-14 | Mazda Motor Corp | Exhaustion gas cleaning catalyst having undergone phosphorus poisoning preventive treatment |
| JPS55167046A (en) * | 1979-06-15 | 1980-12-26 | Mazda Motor Corp | Waste gas cleaning catalyst subjected to treatment for preventing phosphorus-poisoning |
| JPS614532A (en) * | 1984-06-19 | 1986-01-10 | Nissan Motor Co Ltd | Manufacture of integral structure type catalyst for purifying waste gas |
| JPS6271541A (en) * | 1985-09-24 | 1987-04-02 | Mazda Motor Corp | Production of catalyst for cleaning up exhaust gas of engine |
| JP2004230226A (en) * | 2003-01-28 | 2004-08-19 | Mazda Motor Corp | Catalyst for automobile |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013091585A (en) * | 2011-10-26 | 2013-05-16 | Tosoh Corp | Zirconia powder, method for producing the same, and its application |
| EP2952251B1 (en) * | 2013-01-31 | 2022-06-01 | Umicore Shokubai Japan Co., Ltd. | Exhaust-gas purification catalyst and its use |
| WO2015087873A1 (en) | 2013-12-13 | 2015-06-18 | 株式会社キャタラー | Exhaust purification catalyst |
| CN105813735A (en) * | 2013-12-13 | 2016-07-27 | 株式会社科特拉 | Exhaust purification catalyst |
| JPWO2015087873A1 (en) * | 2013-12-13 | 2017-03-16 | 株式会社キャタラー | Exhaust gas purification catalyst |
| US9849443B2 (en) | 2013-12-13 | 2017-12-26 | Cataler Corporation | Exhaust gas purification catalyst |
| WO2020196628A1 (en) * | 2019-03-27 | 2020-10-01 | エヌ・イーケムキャット株式会社 | Selective reduction catalyst for diesel and diesel exhaust gas purification apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5504834B2 (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5814576A (en) | Catalyst for purifying exhaust gas and method of producing same | |
| JP5807782B2 (en) | Exhaust gas purification catalyst | |
| EP1967263B1 (en) | Catalytic Material And Catalyst For Purifying Exhaust Gas Component | |
| JP4752977B2 (en) | Exhaust gas purification catalyst and method for producing the same | |
| US20090148357A1 (en) | Apparatus and catalyst for purifying exhaust gas | |
| JP2009082915A (en) | Elimination of particles from exhaust gas of internal combustion engine operated mainly by stoichiometric-air/fuel mixture | |
| RU2557056C2 (en) | Trap-type catalyst for cleaning nox-depleted exhaust gases and exhaust gas cleaning system | |
| WO2006057067A1 (en) | Catalyst for exhaust gas purification | |
| RU2017134080A (en) | NOx TRAP CATALYST UNDER THE CONDITIONS OF THE DEED MIXTURE WITH IMPROVED CHARACTERISTICS AT HIGH AND LOW TEMPERATURES | |
| KR20140079233A (en) | LNT Catalysts with Enhanced Storage Capacities of Nitrogen Oxide at Low Temperature | |
| JP3952617B2 (en) | Exhaust gas purification device, exhaust gas purification method and exhaust gas purification catalyst for internal combustion engine | |
| JP3965676B2 (en) | Exhaust gas purification catalyst and exhaust gas purification system | |
| JP4716087B2 (en) | Exhaust gas purification catalyst | |
| JP5684973B2 (en) | Exhaust gas purification catalyst and exhaust gas purification method using the same | |
| JP5504834B2 (en) | Exhaust gas purification catalyst | |
| JP2008221204A (en) | Catalytic material and catalyst for purifying exhaust gas component | |
| JP5676679B2 (en) | Exhaust gas purification catalyst | |
| JP4797838B2 (en) | Gas purification catalyst | |
| JPH09248462A (en) | Exhaust gas-purifying catalyst | |
| JPH09313938A (en) | Catalyst for cleaning exhaust gas | |
| JP4852595B2 (en) | Exhaust gas purification catalyst | |
| JP3748202B2 (en) | Exhaust gas purification catalyst | |
| JP5413279B2 (en) | Exhaust gas purification catalyst | |
| JP4503314B2 (en) | Exhaust gas purification catalyst | |
| JPH0857315A (en) | Catalyst for purification of exhaust gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121019 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131008 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131203 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140122 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140218 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140303 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5504834 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| LAPS | Cancellation because of no payment of annual fees |