JPH08131837A - Catalyst for purification of exhaust gas from combustion engine - Google Patents
Catalyst for purification of exhaust gas from combustion engineInfo
- Publication number
- JPH08131837A JPH08131837A JP6272209A JP27220994A JPH08131837A JP H08131837 A JPH08131837 A JP H08131837A JP 6272209 A JP6272209 A JP 6272209A JP 27220994 A JP27220994 A JP 27220994A JP H08131837 A JPH08131837 A JP H08131837A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- exhaust gas
- combustion engine
- internal combustion
- adsorption
- 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 180
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 47
- 238000000746 purification Methods 0.000 title description 55
- 238000001179 sorption measurement Methods 0.000 claims abstract description 90
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 74
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 74
- 239000003463 adsorbent Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000010457 zeolite Substances 0.000 claims description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims description 25
- 238000011144 upstream manufacturing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 79
- 230000000052 comparative effect Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- 230000020169 heat generation Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 6
- 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 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
- F01N2240/18—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an adsorber or absorber
-
- 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
- F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
- F01N2570/12—Hydrocarbons
Landscapes
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は内燃機関の排気ガス浄化
用触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying catalyst for an internal combustion engine.
【０００２】[0002]
【従来の技術】自動車の内燃機関から排出される炭化水
素は一般には三元触媒によって分解されているが、内燃
機関のコールドスタート時のように三元触媒が活性温度
に達していない場合には、これによる炭化水素の浄化を
期待することができない。これに対して、炭化水素を吸
着するＨＣ（ＨＣは炭化水素を表わす。以下、同じ）吸
着剤を内燃機関の排気系に配置して炭化水素が未浄化の
まま排出されることを防止する技術が一般に知られてい
る。2. Description of the Related Art Hydrocarbons emitted from an internal combustion engine of an automobile are generally decomposed by a three-way catalyst, but when the three-way catalyst does not reach an activation temperature such as at the cold start of the internal combustion engine, However, the purification of hydrocarbons by this cannot be expected. On the other hand, a technique for arranging an HC adsorbent that adsorbs hydrocarbons (HC represents hydrocarbons; the same applies hereinafter) in the exhaust system of an internal combustion engine to prevent hydrocarbons from being discharged unpurified. Is generally known.
【０００３】例えば、特開平４−２９３５１９号公報に
は、ＺＳＭ−５（ＭＦＩ型ゼオライト）に銅（Ｃｕ）を
イオン交換によって担持させてなる粉末と、ＺＳＭ−５
にパラジウム（Ｐｄ）をイオン交換によって担持させて
なる粉末とを混合しなる混合粉末を吸着剤とし、該吸着
剤をモノリス担体にコートしてなるものが開示されてい
る。このものは、適宜の金属をゼオライトに担持させる
ことによって、各ゼオライトの吸着性能のピークが異な
る温度域で現れるようにし、これによって広い温度範囲
で炭化水素吸着能を発揮させようとするものである。排
気ガス温度が低いときに上記吸着剤によって吸着された
炭化水素は排気ガス温度の上昇に伴って放出される。上
記公報のものでは、吸着剤から放出された炭化水素をそ
の下流側に配置した三元触媒によって浄化するようにな
されている。For example, JP-A-4-293519 discloses a powder in which ZSM-5 (MFI type zeolite) is loaded with copper (Cu) by ion exchange, and ZSM-5.
Patent Document 1 discloses that a mixed powder obtained by mixing powder of palladium (Pd) supported by ion exchange is used as an adsorbent, and the adsorbent is coated on a monolith carrier. This is intended to allow a suitable metal to be supported on zeolite so that the peak of the adsorption performance of each zeolite appears in a different temperature range, thereby exerting a hydrocarbon adsorption ability in a wide temperature range. . The hydrocarbons adsorbed by the adsorbent when the exhaust gas temperature is low are released as the exhaust gas temperature rises. In the above publication, the hydrocarbon released from the adsorbent is purified by the three-way catalyst arranged on the downstream side.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上述の如きＨ
Ｃ吸着剤が炭化水素を吸着することができる温度域は一
般には百数十度までであって、それよりも高温（例えば
２００℃前後）になると炭化水素を実質的には吸着する
ことができず、吸着していた炭化水素の放出が始まる
が、その一方、上記三元触媒は２００℃前後の温度では
未だ充分な活性を呈しない。特に、ＨＣ吸着剤の下流側
に配置されている三元触媒は排気ガスの熱による温度上
昇がＨＣ吸着剤よりも遅れる。However, the above-mentioned H
The temperature range in which the C adsorbent can adsorb hydrocarbons is generally up to a hundred and several tens of degrees Celsius, and at higher temperatures (for example, around 200 ° C.), hydrocarbons can be substantially adsorbed. However, the adsorbed hydrocarbons start to be released, but on the other hand, the above three-way catalyst does not yet exhibit sufficient activity at temperatures around 200 ° C. In particular, the temperature increase due to the heat of the exhaust gas of the three-way catalyst arranged downstream of the HC adsorbent is delayed as compared with that of the HC adsorbent.
【０００５】これに対して、上述のＨＣ吸着剤に炭化水
素を分解する触媒金属を担持させることによって、排気
ガス中の炭化水素を吸着するとともに、この吸着した炭
化水素を分解して放出させることが考えられる。しか
し、その場合でも、ＨＣ吸着剤が炭化水素を放出する温
度に達しても、上記触媒金属は未だ十分な活性を呈さ
ず、従って炭化水素を浄化する能力が低い若しくは零で
あるのが通常であり、該触媒金属が充分な活性を呈する
ようになるまでは吸着していた炭化水素が分解されない
まま放出されることになる。On the other hand, by supporting a catalyst metal for decomposing hydrocarbons on the above HC adsorbent, hydrocarbons in exhaust gas are adsorbed and the adsorbed hydrocarbons are decomposed and released. Can be considered. However, even in that case, even when the HC adsorbent reaches the temperature at which hydrocarbons are released, the above-mentioned catalyst metal does not yet exhibit sufficient activity, and therefore the ability to purify hydrocarbons is usually low or zero. Therefore, the adsorbed hydrocarbons are released without being decomposed until the catalytic metal becomes sufficiently active.
【０００６】そこで、本発明は、内燃機関の排気ガス中
の炭化水素を単に吸着するのではなく、この吸着した炭
化水素を効率良く分解して放出させることができる排気
ガス浄化用触媒を提供することにある。Therefore, the present invention provides an exhaust gas purifying catalyst capable of efficiently decomposing and adsorbing the adsorbed hydrocarbons instead of simply adsorbing the hydrocarbons in the exhaust gas of the internal combustion engine. Especially.
【０００７】[0007]
【課題を解決するための手段及びその作用】本発明は、
上記課題に対して、ＨＣ吸着剤に炭化水素を分解する触
媒金属を担持させた吸着触媒とは別に、排気ガス中の水
分を吸して発熱する発熱剤を設け、該発熱を利用して吸
着触媒が炭化水素放出温度に達した後の昇温を促進し、
該吸着触媒が早く活性温度に達するようにするものであ
る。以下、特許請求の範囲の各請求項に係る発明につい
て具体的に説明する。SUMMARY OF THE INVENTION The present invention provides
In order to solve the above problems, a heat generating agent that absorbs moisture in exhaust gas to generate heat is provided separately from the adsorption catalyst in which a catalyst metal that decomposes hydrocarbons is supported on the HC adsorbent, and the generated heat is used for adsorption. Accelerates the temperature rise after the catalyst reaches the hydrocarbon release temperature,
It is intended to allow the adsorption catalyst to reach the activation temperature quickly. Hereinafter, the invention according to each claim of the claims will be specifically described.
【０００８】＜請求項１に係る発明＞この発明は、内燃
機関の排気ガス中の炭化水素及び水分を吸着する吸着剤
に該炭化水素を分解する触媒金属を担持させてなる吸着
触媒を有する吸着触媒部と、上記吸着触媒部に隣接して
排気ガス流れ方向の下流側に配設され上記水分の吸収に
よって発熱する発熱剤を有する発熱部とを備えているこ
とを特徴とする内燃機関の排気ガス浄化用触媒である。<Invention of Claim 1> The present invention is an adsorption having an adsorption catalyst in which an adsorbent for adsorbing hydrocarbons and water in exhaust gas of an internal combustion engine carries a catalytic metal for decomposing the hydrocarbons. Exhaust gas of an internal combustion engine, comprising: a catalyst portion, and a heat generating portion having a heat generating agent disposed adjacent to the adsorption catalyst portion in a downstream side in the exhaust gas flow direction to generate heat by absorbing the moisture. It is a gas purification catalyst.
【０００９】上記吸着触媒部においては、排気ガス温度
が低く吸着触媒の温度が低いときにはその吸着剤によっ
て排気ガス中の炭化水素が吸着されその排出を防止され
る。この吸着剤に吸着されていた炭化水素は排気ガス温
度（吸着剤の温度）が高くなると放出されるが、この吸
着剤には炭化水素を分解する触媒金属が担持されている
ため、これによって上記炭化水素は分解されて放出され
ることになる。但し、吸着剤が炭化水素の放出を開始す
るときに、上記触媒金属が十分な活性を呈するに至って
いなければ、炭化水素は分解されないまま放出されるこ
とになる。In the adsorption catalyst section, when the temperature of the exhaust gas is low and the temperature of the adsorption catalyst is low, the adsorbent adsorbs hydrocarbons in the exhaust gas and prevents their discharge. The hydrocarbons adsorbed by this adsorbent are released when the exhaust gas temperature (the temperature of the adsorbent) rises, but since this adsorbent carries a catalytic metal that decomposes hydrocarbons, Hydrocarbons will be decomposed and released. However, if the catalytic metal does not exhibit sufficient activity when the adsorbent starts to release hydrocarbons, the hydrocarbons will be released without being decomposed.
【００１０】これに対して、上記吸着触媒部に隣接して
その下流側に配設されている発熱部では、発熱剤が排気
ガス中の水分を吸収することによって発熱する。この発
熱剤の発熱は、内燃機関が排気ガスを排出し始める当初
にはほとんどなく、それから所定時間を経過した後に当
該発熱が盛んになる。これは、上記吸着触媒の吸着剤は
排気ガス中の炭化水素だけでなく水分をも吸着するもの
であるから、排気ガスの排出当初はその水分が上記吸着
剤によって吸着されて上記発熱剤までは多量に流れない
からである。On the other hand, in the heat generating portion disposed adjacent to and downstream of the adsorption catalyst portion, the heat generating agent absorbs moisture in the exhaust gas to generate heat. The heat generation of the exothermic agent is hardly present at the beginning of discharging the exhaust gas from the internal combustion engine, and the heat generation becomes vigorous after a predetermined time has elapsed. This is because the adsorbent of the adsorption catalyst adsorbs not only the hydrocarbons in the exhaust gas but also the moisture, so that the moisture is adsorbed by the adsorbent at the beginning of the exhaust gas discharge and the heat generating agent is not absorbed. Because it does not flow in large quantities.
【００１１】つまり、内燃機関の排気ガスの排出開始か
ら上記所定時間を経過するまでは上記発熱剤の水分吸収
による発熱はほとんどなく、上記吸着触媒は上記発熱剤
によって不必要に加熱されてその炭化水素吸着能が低下
してしまうことはない。そして、上記吸着剤の水分吸着
能が低下し上記発熱剤に多量の水分が到達するようにな
って初めて、該発熱剤の水分の吸収による発熱が盛んに
なり、これにより、上記吸着触媒は排気ガスの熱と発熱
剤の発熱とによって前後から加熱され、温度が急激に上
昇していくことになる。That is, from the start of exhaust gas emission from the internal combustion engine until the lapse of the predetermined time, there is almost no heat generation due to the absorption of water by the exothermic agent, and the adsorption catalyst is unnecessarily heated by the exothermic agent and carbonized. The hydrogen adsorption capacity does not decrease. Only when a large amount of water reaches the exothermic agent due to a decrease in the water adsorbing ability of the adsorbent, heat generation due to absorption of water by the exothermic agent becomes active, whereby the adsorption catalyst is exhausted. The heat of the gas and the heat of the exothermic agent heat the material from the front and back, causing the temperature to rise rapidly.
【００１２】このように、発熱剤の発熱による吸着触媒
の加熱が排気ガスの排出開始から所定時間を経過した後
に生ずるから、上記吸着触媒は、所期の炭化水素吸着能
が発熱剤によって損なわれることはなく、その炭化水素
吸着能が低下し、ひいては吸着していた炭化水素を放出
するようになった後に、上述の如く前後から加熱されて
触媒金属が活性を呈する温度に速やかに到達することに
なる。よって、吸着剤の炭化水素吸着能が低くなってか
ら触媒金属が炭化水素を分解するようになるまでの時
間、あるいは吸着剤が炭化水素を放出するようになって
から触媒金属が炭化水素を分解するようになるまでの時
間が短くなり、一旦吸着した炭化水素を未浄化のまま排
出してしまう量が少なくなる。As described above, since the heating of the adsorption catalyst due to the heat generation of the exothermic agent occurs after a predetermined time has elapsed from the start of exhaust gas emission, the desired adsorption capacity of the hydrocarbon of the adsorption catalyst is impaired by the exothermic agent. That is, the hydrocarbon adsorbing capacity of the catalyst metal decreases, and after that, the adsorbed hydrocarbons are released, and the catalyst metal is quickly heated to the temperature at which the catalyst metal becomes active as described above. become. Therefore, the time from when the adsorbent's ability to adsorb hydrocarbons decreases until the catalytic metal begins to decompose hydrocarbons, or when the adsorbent releases hydrocarbons and the catalytic metal decomposes hydrocarbons. Therefore, the time until it comes to be reduced becomes shorter, and the amount of hydrocarbons once adsorbed is discharged unpurified.
【００１３】ここに、上記吸着触媒の吸着剤としては、
ゼオライトのような結晶格子に金属が含まれミクロの細
孔を有する結晶質の金属含有シリケートが好適である。
この金属含有シリケートとしては、結晶格子を形成する
金属としてＡｌを用いたアルミノシリケート（ゼオライ
ト）であっても、Ａｌに代えて或いはＡｌと共にＧａ、
Ｃｅ、Ｍｎ、Ｔｂ等の他の金属を骨格形成材料として用
いた金属含有シリケートであってもよい。ゼオライトに
ついても、Ａ型、Ｘ型、Ｙ型、モルデナイト、ＺＳＭ−
５などいずれでもよい。Here, as the adsorbent of the adsorption catalyst,
A crystalline metal-containing silicate containing a metal in a crystal lattice such as zeolite and having micropores is preferable.
As the metal-containing silicate, even if aluminosilicate (zeolite) using Al as a metal forming a crystal lattice, Ga is used instead of Al or together with Al,
It may be a metal-containing silicate using another metal such as Ce, Mn, or Tb as a skeleton-forming material. As for zeolite, A type, X type, Y type, mordenite, ZSM-
5 or the like may be used.
【００１４】また、上記触媒金属の種類についても特に
限定されるものでなく、Ｐｔ、Ｐｄ、Ｉｒ、Ｒｈ等の貴
金属を初めとして、貴金属以外の遷移金属、あるいはア
ルカリ土類金属等の典型元素であっても、炭化水素分解
触媒として機能する限りその適用が可能である。The type of the above-mentioned catalyst metal is not particularly limited, and it is possible to use a noble metal such as Pt, Pd, Ir, and Rh, a transition metal other than the noble metal, or a typical element such as an alkaline earth metal. Even if it exists, its application is possible as long as it functions as a hydrocarbon decomposition catalyst.
【００１５】発熱剤についても、ＣａＯ、ＭｇＯなど水
と反応して発熱するものであれば、その種類は問わな
い。The heat generating agent may be of any type as long as it generates heat by reacting with water, such as CaO and MgO.
【００１６】そうして、上記吸着触媒部及び発熱部は、
上記吸着触媒及び発熱剤の各々を別個のモノリス担体に
担持させてこれらを排気ガス流れ方向の前後に合わせる
ことによって形成することができ、あるいは１つのモノ
リス担体の上流側部位と下流側部位とに上記吸着触媒と
発熱剤とを分けて担持させることによって形成すること
ができる。さらには、上記吸着触媒及び発熱剤の各々を
ペレット状に成形し、多数の吸着触媒ペレットを排気ガ
ス流れ方向の上流側に、多数の発熱剤ペレットをその下
流側に配置することによって吸着触媒部及び発熱部を形
成するようにしてもよい。Thus, the adsorption catalyst portion and the heat generating portion are
Each of the adsorption catalyst and the exothermic agent can be formed by supporting each of them on a separate monolithic carrier and aligning them before and after in the exhaust gas flow direction, or at the upstream side part and the downstream side part of one monolithic carrier. It can be formed by separately supporting the adsorption catalyst and the exothermic agent. Further, each of the adsorption catalyst and the exothermic agent is formed into a pellet shape, and a large number of adsorption catalyst pellets are arranged on the upstream side in the exhaust gas flow direction, and a large number of exothermic agent pellets are arranged on the downstream side thereof to form an adsorption catalyst section. Also, the heat generating portion may be formed.
【００１７】＜請求項２に係る発明＞この発明は、上記
請求項１に記載されている内燃機関の排気ガス浄化用触
媒において、上記発熱剤がＣａＯであることを特徴とす
る。<Invention of Claim 2> This invention is characterized in that, in the exhaust gas purifying catalyst for an internal combustion engine described in claim 1, the exothermic agent is CaO.
【００１８】当該発明において、発熱剤としてＣａＯを
用いるのは、これが発熱剤としての取扱い、発熱量等の
観点から好ましいためである。In the present invention, CaO is used as the exothermic agent because it is preferable from the viewpoint of handling as the exothermic agent, heat generation amount, and the like.
【００１９】＜請求項３に係る発明＞この発明は、上記
請求項１又は請求項２に記載されている内燃機関の排気
ガス浄化用触媒において、上記吸着触媒がセラミック製
のモノリス担体の排気ガス流れ方向の上流側の部位に担
持されて上記吸着触媒部が形成され、上記発熱剤が上記
モノリス担体の排気ガス流れ方向の下流側の部位に担持
されて上記発熱部が形成されていることを特徴とする。<Invention of Claim 3> The present invention is the exhaust gas purifying catalyst for an internal combustion engine according to claim 1 or 2, wherein the adsorption catalyst is an exhaust gas of a ceramic monolith carrier. The adsorption catalyst portion is formed on the upstream side portion in the flow direction, and the exothermic agent is formed on the downstream side portion in the exhaust gas flow direction of the monolith carrier to form the exothermic portion. Characterize.
【００２０】当該発明において、吸着触媒及び発熱剤を
セラミック製のモノリス担体に担持させているのは、メ
タル担体に比べて吸着触媒等の担持性がよく、また、耐
久性も得られるためである。このようなセラミック製の
モノリス担体としては、コージェライト製のものが好適
である。In the present invention, the reason why the adsorption catalyst and the exothermic agent are supported on the ceramic monolith carrier is that the adsorption catalyst and the like can be carried better than the metal carrier and the durability can be obtained. . As such a ceramic monolithic carrier, one made of cordierite is suitable.
【００２１】＜請求項４に係る発明＞この発明は、上記
請求項３に記載されている内燃機関の排気ガス浄化用触
媒において、上記吸着剤がゼオライトであることを特徴
とする。<Invention of Claim 4> The present invention is characterized in that, in the exhaust gas purifying catalyst for an internal combustion engine described in claim 3, the adsorbent is zeolite.
【００２２】当該発明において、吸着剤にゼオライトを
採用しているのは、該ゼオライトが炭化水素及び水の吸
着性に優れているからであり、また、触媒金属を担持さ
せ易いからである。炭化水素の吸着性の観点からはＹ型
ゼオライトが好適である。In the present invention, the reason why zeolite is used as the adsorbent is that the zeolite has excellent adsorbability for hydrocarbons and water, and it is easy to support the catalytic metal. From the viewpoint of hydrocarbon adsorption, Y-type zeolite is suitable.
【００２３】＜請求項５に係る発明＞この発明は、上記
請求項４に記載されている内燃機関の排気ガス浄化用触
媒において、上記モノリス担体１リットル当りのＣａＯ
の担持量が１５ｇ以上であることを特徴とする。<Invention of Claim 5> The present invention is the exhaust gas purifying catalyst for an internal combustion engine according to claim 4, wherein CaO per liter of the monolith carrier is used.
Is carried by 15 g or more.
【００２４】当該発明において、上記ＣａＯの担持量を
１５ｇ以上としているのは、それによって発熱剤による
吸着触媒の加熱の影響が炭化水素の浄化率の向上に明確
に現れてくるためである。In the present invention, the amount of CaO supported is set to 15 g or more because the effect of heating the adsorption catalyst by the exothermic agent clearly appears in the improvement of the hydrocarbon purification rate.
【００２５】＜請求項６に係る発明＞この発明は、上記
請求項４に記載されている内燃機関の排気ガス浄化用触
媒において、上記モノリス担体１リットル当りのＣａＯ
の担持量が２０〜３０ｇであることを特徴とする。<Invention of Claim 6> The present invention provides the catalyst for purifying exhaust gas of an internal combustion engine according to claim 4, wherein CaO per liter of the monolith carrier is used.
Is carried in an amount of 20 to 30 g.
【００２６】当該発明において、上記ＣａＯの担持量を
２０〜３０ｇとしているのは、それによって炭化水素の
浄化率の向上効果が顕著になるためである。In the present invention, the amount of CaO supported is set to 20 to 30 g because the effect of improving the purification rate of hydrocarbon becomes remarkable.
【００２７】＜請求項７に係る発明＞この発明は、上記
請求項４に記載されている内燃機関の排気ガス浄化用触
媒において、上記発熱部が上記モノリス担体の下流端か
ら該モノリス担体の全長の１／１０〜２／５の範囲にわ
たる部位に形成されていることを特徴とする。<Invention of Claim 7> According to the present invention, in the catalyst for purifying exhaust gas of an internal combustion engine according to claim 4, the heat generating portion is from the downstream end of the monolith carrier to the entire length of the monolith carrier. It is characterized in that it is formed in a site ranging from 1/10 to 2/5.
【００２８】当該発明において、発熱部を設ける範囲を
上記の通りに設定しているのは、その範囲がモノリス担
体の下流側１／１０未満であれば発熱剤による吸着触媒
の加熱の影響が炭化水素の浄化率の向上に十分に現れ
ず、また、その範囲がモノリス担体の下流側２／５を越
える場合には、相対的に吸着触媒の量が少なくなって炭
化水素の吸着量が減り、結果的には炭化水素の浄化率が
低くなってしまうからである。In the present invention, the range in which the heat generating portion is provided is set as described above because if the range is less than 1/10 on the downstream side of the monolith carrier, the effect of heating the adsorption catalyst by the heat generating agent is carbonized. When it does not appear enough to improve the purification rate of hydrogen, and when the range exceeds 2/5 on the downstream side of the monolith carrier, the amount of the adsorbing catalyst becomes relatively small and the adsorbing amount of hydrocarbons decreases, As a result, the purification rate of hydrocarbons becomes low.
【００２９】＜請求項８に係る発明＞この発明は、上記
請求項４に記載されている内燃機関の排気ガス浄化用触
媒において、上記発熱部が上記モノリス担体の下流端か
ら該モノリス担体の全長の１／５〜１／３の範囲にわた
る部位に形成されていることを特徴とする。<Invention of Claim 8> According to the present invention, in the exhaust gas purifying catalyst for an internal combustion engine according to claim 4, the heat generating portion is from the downstream end of the monolith carrier to the entire length of the monolith carrier. It is characterized in that it is formed in a site ranging from 1/5 to 1/3.
【００３０】当該発明において、発熱部を設ける範囲を
上記の通りに設定しているのは、それによって炭化水素
浄化率の向上の効果が顕著になるからである。In the present invention, the range in which the heat generating portion is provided is set as described above because the effect of improving the hydrocarbon purification rate becomes remarkable.
【００３１】＜請求項９に係る発明＞この発明は、上記
請求項４に記載されている内燃機関の排気ガス浄化用触
媒において、上記吸着触媒が、ゼオライトにＰｄとセリ
アとを担持させてなることを特徴とする。<Invention of Claim 9> According to the present invention, in the exhaust gas purifying catalyst for an internal combustion engine according to claim 4, the adsorption catalyst comprises zeolite carrying Pd and ceria. It is characterized by
【００３２】当該発明の場合、触媒金属としてのＰｄは
他の貴金属等に比べて低い温度から炭化水素の分解を開
始するため、吸着触媒から炭化水素が未浄化のまま放出
される量を少なくする上で有利になり、また、上記炭化
水素の分解には酸素の存在が必要であるところ、セリア
はＯ2 ストレージ効果を奏し、排気ガス中の酸素濃度が
変動してもＰｄによる炭化水素の分解に必要な酸素を確
保する。従って、当該排気ガス浄化用触媒よりも上流側
に三元触媒を配置して排気ガスを浄化させる場合におい
て、該三元触媒によって排気ガス中の酸素が消費されて
も、該三元触媒が活性を呈する前にセリアによって吸蔵
していた酸素を上記吸着触媒のＰｄによる炭化水素の分
解に利用することができる。In the case of the present invention, since Pd as the catalytic metal starts decomposing hydrocarbons at a temperature lower than that of other noble metals and the like, the amount of hydrocarbons released from the adsorption catalyst without being purified is reduced. In addition, the presence of oxygen is required for the above hydrocarbon decomposition, and ceria has an O 2 storage effect, and even if the oxygen concentration in the exhaust gas fluctuates, the decomposition of hydrocarbons by Pd To secure the oxygen needed for. Therefore, when the three-way catalyst is arranged upstream of the exhaust gas purifying catalyst to purify the exhaust gas, the three-way catalyst is activated even if oxygen in the exhaust gas is consumed by the three-way catalyst. Oxygen stored by the ceria before the occurrence of C can be utilized for the decomposition of hydrocarbons by Pd of the adsorption catalyst.
【００３３】[0033]
【発明の効果】請求項１に係る発明によれば、炭化水素
及び水分を吸着する吸着剤に該炭化水素を分解する触媒
金属を担持させてなる吸着触媒を有する吸着触媒部と、
水分の吸収によって発熱する発熱剤を有する発熱部と
を、排気ガス流れ方向の上流側と下流側とに隣接させて
配設したから、内燃機関の始動後の所定時間は吸着触媒
の温度上昇を加速しないようにして排気ガス中の炭化水
素を該吸着触媒に確実に吸着させながら、該所定時間を
経過した後は吸着触媒の温度を急激に上昇させて触媒金
属を活性温度に速やかに到達させることができ、一旦吸
着した炭化水素を未浄化のまま排出してしまう量が少な
くなる。According to the invention of claim 1, an adsorption catalyst section having an adsorption catalyst in which an adsorbent for adsorbing hydrocarbons and moisture carries a catalytic metal for decomposing the hydrocarbons,
Since the heat generating portion having a heat generating agent that generates heat due to absorption of water is arranged adjacent to the upstream side and the downstream side in the exhaust gas flow direction, the temperature of the adsorption catalyst does not rise for a predetermined time after the start of the internal combustion engine. While surely adsorbing the hydrocarbon in the exhaust gas to the adsorption catalyst without accelerating, the temperature of the adsorption catalyst is rapidly increased after the predetermined time has passed so that the catalytic metal quickly reaches the activation temperature. It is possible to reduce the amount of hydrocarbons that have once been adsorbed and discharged without being purified.
【００３４】請求項２に係る発明によれば、上記請求項
１に記載されている内燃機関の排気ガス浄化用触媒にお
いて上記発熱剤をＣａＯとしたものであるから、発熱部
が期する機能を確実に発揮し、所期の効果を上げること
ができる。According to the invention of claim 2, in the exhaust gas purifying catalyst for an internal combustion engine according to claim 1, the exothermic agent is CaO, so that the function of the exothermic part is desired. It can be demonstrated reliably and the desired effect can be achieved.
【００３５】請求項３に係る発明によれば、上記請求項
１又は請求項２に記載されている内燃機関の排気ガス浄
化用触媒において、上記吸着触媒がセラミック製のモノ
リス担体の排気ガス流れ方向の上流側の部位に担持され
て上記吸着触媒部が形成され、上記発熱剤が上記モノリ
ス担体の排気ガス流れ方向の下流側の部位に担持されて
上記発熱部が形成されたものであるから、吸着触媒部及
び発熱部が期する機能を確実に発揮し、所期の効果を上
げることができる。According to the invention of claim 3, in the exhaust gas purifying catalyst for an internal combustion engine according to claim 1 or 2, the adsorption catalyst is a ceramic monolith carrier in the exhaust gas flow direction. The adsorption catalyst portion is formed by being carried on the upstream side portion of the above, and the exothermic agent is formed on the downstream side portion of the monolith carrier in the exhaust gas flow direction to form the heating portion. The desired function of the adsorption catalyst section and the heat generation section can be surely exhibited, and desired effects can be achieved.
【００３６】請求項４に係る発明によれば、上記請求項
３に記載されている内燃機関の排気ガス浄化用触媒にお
いて上記吸着剤がゼオライトとされたものであるから、
ゼオライトが吸着剤として期する機能を確実に発揮し、
所期の効果が得られる。According to the invention of claim 4, in the exhaust gas purifying catalyst for an internal combustion engine according to claim 3, the adsorbent is zeolite.
Zeolites surely exhibit the function expected as an adsorbent,
The desired effect is obtained.
【００３７】請求項５に係る発明によれば、上記請求項
４に記載されている内燃機関の排気ガス浄化用触媒にお
いて上記モノリス担体１リットル当りのＣａＯの担持量
が１５ｇ以上とされているから、炭化水素の浄化率が確
実に高くなるという効果が得られる。According to the invention of claim 5, in the exhaust gas purifying catalyst for an internal combustion engine according to claim 4, the amount of CaO carried per liter of the monolith carrier is 15 g or more. Therefore, the effect of surely increasing the purification rate of hydrocarbons can be obtained.
【００３８】請求項６に係る発明によれば、上記請求項
４に記載されている内燃機関の排気ガス浄化用触媒にお
いて上記モノリス担体１リットル当りのＣａＯの担持量
が２０〜３０ｇとされているから、炭化水素の浄化率の
向上効果が顕著になる。According to the invention of claim 6, in the exhaust gas purifying catalyst for internal combustion engine according to claim 4, the amount of CaO carried per liter of the monolith carrier is 20 to 30 g. Therefore, the effect of improving the purification rate of hydrocarbons becomes remarkable.
【００３９】請求項７に係る発明によれば、上記請求項
４に記載されている内燃機関の排気ガス浄化用触媒にお
いて上記発熱部が上記モノリス担体の下流側１／１０〜
２／５の部位に形成されたものであるから、吸着触媒に
よる吸着量の低下を最小限に抑えながら、発熱部によっ
て吸着触媒を加熱して所期の効果を上げることができ
る。According to the seventh aspect of the invention, in the exhaust gas purifying catalyst for an internal combustion engine according to the fourth aspect, the heat generating portion is the downstream side 1/10 to the monolith carrier.
Since it is formed at 2/5, the adsorbing catalyst can be heated by the heat generating part and the desired effect can be achieved while minimizing the decrease in the adsorption amount due to the adsorbing catalyst.
【００４０】請求項８に係る発明によれば、上記請求項
４に記載されている内燃機関の排気ガス浄化用触媒にお
いて上記発熱部が上記モノリス担体の下流側１／５〜１
／３の部位に形成されたものであるから、炭化水素の浄
化率の向上の効果が顕著になる。According to the eighth aspect of the present invention, in the exhaust gas purifying catalyst for an internal combustion engine according to the fourth aspect, the heat generating portion has the downstream side 1/5 to 1 of the monolith carrier.
Since it is formed in the part of / 3, the effect of improving the purification rate of hydrocarbons becomes remarkable.
【００４１】請求項９に係る発明によれば、上記請求項
４に記載されている内燃機関の排気ガス浄化用触媒にお
いて上記吸着触媒がゼオライトにＰｄとセリアとを担持
させてなるものであるから、排気ガス中の酸素濃度が変
動する場合でも、吸着触媒に吸着した炭化水素を比較的
低い温度から分解することができ、発熱剤による加熱効
果と相俟って炭化水素の浄化率を格段と高めることがで
きるようになる。According to the invention of claim 9, in the exhaust gas purifying catalyst for an internal combustion engine according to claim 4, the adsorption catalyst comprises zeolite carrying Pd and ceria. Even if the oxygen concentration in the exhaust gas fluctuates, the hydrocarbons adsorbed on the adsorption catalyst can be decomposed from a relatively low temperature, and the heating efficiency of the exothermic agent makes the purification rate of hydrocarbons remarkable. You will be able to raise it.
【００４２】[0042]
【実施例】以下、本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００４３】＜実施例１〜５の排気ガス浄化用触媒の調
製＞ −実施例１− 断面積６４cm2 、長さ１４．５cmのコージェライト製モ
ノリス（ハニカム）担体に、吸着剤として超安定Ｙ型ゼ
オライトを該担体１リットル当り１５０ｇとなるように
ウォッシュコートによって担持させて焼成を行なった。
これに、ＣｅＯ2 とＰｄとを前者が担体１リットル当り
７０ｇ、後者が担体１リットル当り１０ｇとなるように
含浸法によって担持させることにより、上記担体の表面
（ハニカム孔の表面）に吸着触媒層を形成した。次に、
当該担体の排気ガス流れ方向における下流側１／５の部
位（担体の下流端から該担体全長の１／５の範囲にわた
る部位）に発熱剤としてＣａＯを担体１リットル当り１
０ｇとなるように担持させることにより、自動車の内燃
機関用の排気ガス浄化用触媒を得た。この場合、排気ガ
ス浄化用触媒における排気ガス流れ方向の上流側４／５
の部位（担体の上流端から該担体全長の４／５の範囲に
わたる部位）が上記担体に吸着触媒層が形成されてなる
吸着触媒部であり、下流側１／５の部位が上記吸着触媒
層の上にさらにＣａＯが担持されてなる発熱部である。<Preparation of Exhaust Gas Purifying Catalysts of Examples 1 to 5> -Example 1-A superstable Y as an adsorbent on a cordierite monolith (honeycomb) carrier having a cross-sectional area of 64 cm 2 and a length of 14.5 cm. Calcium-type zeolite was carried by a wash coat so as to be 150 g per liter of the carrier and calcined.
Then, CeO 2 and Pd were supported by an impregnation method so that the former was 70 g per liter of the carrier and the latter was 10 g per liter of the carrier, and the adsorption catalyst layer was formed on the surface of the carrier (the surface of the honeycomb holes). Was formed. next,
CaO is used as a heat generating agent at 1/5 downstream of the carrier in the exhaust gas flow direction (a region extending from the downstream end of the carrier to 1/5 of the entire length of the carrier) per liter of the carrier.
By loading so as to be 0 g, an exhaust gas purifying catalyst for an automobile internal combustion engine was obtained. In this case, the upstream side 4/5 in the exhaust gas flow direction in the exhaust gas purification catalyst
Is a part of the adsorption catalyst formed by forming an adsorption catalyst layer on the carrier (the part extending from the upstream end of the carrier to a range of 4/5 of the entire length of the carrier), and the downstream 1/5 part is the adsorption catalyst layer. It is a heat generating part in which CaO is further supported on the above.
【００４４】−実施例２− ＣａＯの担持量を担体１リットル当り２０ｇとなるよう
にする他は上記実施例１と同様にして排気ガス浄化用触
媒を得た。-Example 2- An exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that the amount of CaO supported was 20 g per liter of the carrier.
【００４５】−実施例３− ＣａＯの担持量を担体１リットル当り３０ｇとなるよう
にする他は上記実施例１と同様にして排気ガス浄化用触
媒を得た。Example 3 An exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that the supported amount of CaO was 30 g per liter of the carrier.
【００４６】−実施例４− ＣａＯの担持量を担体１リットル当り３０ｇとなるよう
にするとともに、発熱部を上記下流側１／３の範囲とす
る他は上記実施例１と同様にして排気ガス浄化用触媒を
得た。Example 4-Exhaust gas as in Example 1 except that the carried amount of CaO was 30 g per liter of the carrier and the heat generating part was in the range of 1/3 on the downstream side. A purification catalyst was obtained.
【００４７】−実施例５− ＣａＯの担持量を担体１リットル当り３０ｇとなるよう
にするとともに、発熱部を上記下流側２／５の範囲とす
る他は上記実施例１と同様にして排気ガス浄化用触媒を
得た。Example 5-Exhaust gas as in Example 1 except that the supported amount of CaO is 30 g per liter of the carrier and the heat generating portion is in the range of 2/5 on the downstream side. A purification catalyst was obtained.
【００４８】−実施例６− 断面積８８cm2 、長さ１０．５cmのコージェライト製モ
ノリス（ハニカム）担体に、吸着剤として超安定Ｙ型ゼ
オライトを該担体１リットル当り１５０ｇとなるように
ウォッシュコートによって担持させて焼成を行なった。
これに、ＣｅＯ2 とＰｄとを前者が担体１リットル当り
７０ｇ、後者が担体１リットル当り１０ｇとなるように
含浸法によって担持させることにより、上記担体の表面
（ハニカム孔の表面）に吸着触媒層を形成した。次に、
当該担体の排気ガス流れ方向における下流側１／３の部
位に発熱剤としてＣａＯを担体１リットル当り３０ｇと
なるように担持させることにより、自動車の内燃機関用
の排気ガス浄化用触媒を得た。Example 6 A cordierite monolith (honeycomb) carrier having a cross-sectional area of 88 cm 2 and a length of 10.5 cm was wash-coated with 150 g of ultra-stable Y zeolite as an adsorbent per liter of the carrier. Was carried and baked.
Then, CeO 2 and Pd were supported by an impregnation method so that the former was 70 g per liter of the carrier and the latter was 10 g per liter of the carrier, and the adsorption catalyst layer was formed on the surface of the carrier (the surface of the honeycomb holes). Was formed. next,
An exhaust gas purifying catalyst for an internal combustion engine of an automobile was obtained by carrying CaO as a heat generating agent on the downstream side ⅓ of the carrier in the exhaust gas flow direction so that the amount of CaO was 30 g per liter of the carrier.
【００４９】＜比較例１，２の排気ガス浄化用触媒の調
製＞ −比較例１− 上記実施例１と同じ担体に、吸着剤として超安定Ｙ型ゼ
オライトを該担体１リットル当り１５０ｇとなるように
ウォッシュコートによって担持させて焼成を行ない、さ
らに、ＣｅＯ2 とＰｄとを前者が担体１リットル当り７
０ｇ、後者が担体１リットル当り１０ｇとなるように含
浸法によって担持させることにより、上記担体の表面に
吸着触媒層が形成された排気ガス浄化用触媒を得た。当
該比較例１の実施例１との相違点は発熱剤が担持されて
いない点にある。<Preparation of Exhaust Gas Purifying Catalysts of Comparative Examples 1 and 2> -Comparative Example 1-In the same carrier as in Example 1 above, 150 g of ultra-stable Y zeolite as an adsorbent was added per liter of the carrier. Is carried by a washcoat and baked, and CeO 2 and Pd are added to the former in an amount of 7 per liter of the carrier.
An exhaust gas purifying catalyst having an adsorption catalyst layer formed on the surface of the carrier was obtained by supporting the carrier by an impregnation method so that the carrier was 0 g and the latter was 10 g per liter of the carrier. The difference between Comparative Example 1 and Example 1 is that the exothermic agent is not supported.
【００５０】−比較例２− 上記実施例６と同じ担体に、吸着剤として超安定Ｙ型ゼ
オライトを該担体１リットル当り１５０ｇとなるように
ウォッシュコートによって担持させて焼成を行ない、さ
らに、ＣｅＯ2 とＰｄとを前者が担体１リットル当り７
０ｇ、後者が担体１リットル当り１０ｇとなるように含
浸法によって担持させることにより、上記担体の表面に
吸着触媒層が形成された排気ガス浄化用触媒を得た。当
該比較例２の実施例６との相違点は発熱剤が担持されて
いない点にある。[0050] - the same support as in Comparative Example 2 Example 6 above, the ultrastable Y-type zeolite as an adsorbent is supported by the washcoat so that the carrier per liter of 150g performs firing, further, CeO 2 And Pd is 7 for each liter of carrier.
An exhaust gas purifying catalyst having an adsorption catalyst layer formed on the surface of the carrier was obtained by supporting the carrier by an impregnation method so that the carrier was 0 g and the latter was 10 g per liter of the carrier. The difference between the comparative example 2 and the example 6 is that the exothermic agent is not supported.
【００５１】＜実施例及び比較例のＨＣ吸着率及びＹ１
浄化率の評価＞上記各例の排気ガス浄化用触媒を実車に
装着し、ＬＡ−４−Ｙ１テストモードにて排出ガスの試
験を行ない、スタートから６０秒経過までのＨＣ吸着率
（炭化水素の浄化率のことであるが、６０秒を経過する
までは触媒が炭化水素を分解する温度にまで達しないた
め、当該浄化率は当該触媒による炭化水素の吸着率に相
当する）と、Ｙ１浄化率（Ｙ１テストモードでの炭化水
素の浄化率）とを測定した。結果は表１に示されてい
る。<HC Adsorption Rate and Y1 of Examples and Comparative Examples
Evaluation of purification rate> The exhaust gas purification catalyst of each of the above examples was mounted on an actual vehicle, and an exhaust gas test was performed in the LA-4-Y1 test mode. The HC adsorption rate (hydrocarbon content) from the start to 60 seconds The purification rate means that the catalyst does not reach the temperature at which the catalyst decomposes hydrocarbons until 60 seconds have passed, so the purification rate corresponds to the adsorption rate of hydrocarbons by the catalyst) and the Y1 purification rate. (The purification rate of hydrocarbons in the Y1 test mode) was measured. The results are shown in Table 1.
【００５２】[0052]
【表１】 [Table 1]
【００５３】実施例１〜５と比較例１とを比べた場合、
実施例ではＨＣ吸着率が比較例よりも少し低くなってい
るものの、Ｙ１浄化率は実施例の方が高くなっている。
実施例のＨＣ吸着率が比較例のそれよりも低くなってい
るのは、触媒下流部位へのＣａＯの担持によって吸着触
媒部の絶対量が比較例よりも少なくなっているためと認
められる。実施例のＹ１浄化率が比較例のそれよりも高
くなっているのは、上記ＣａＯが排気ガス中の水分を吸
収するようになった後に、該吸収による発熱によって触
媒温度が急激に上昇し、ＰｄとＣｅＯ2 とによる炭化水
素の分解が比較的早く開始されたためと認められる。When Examples 1 to 5 and Comparative Example 1 are compared,
Although the HC adsorption rate in the example is slightly lower than that in the comparative example, the Y1 purification rate is higher in the example.
The reason why the HC adsorption rate of the example is lower than that of the comparative example is considered to be that the absolute amount of the adsorption catalyst portion is smaller than that of the comparative example due to the loading of CaO on the catalyst downstream portion. The Y1 purification rate of the example is higher than that of the comparative example because the catalyst temperature rises sharply due to the heat generated by the absorption after CaO comes to absorb the water in the exhaust gas, It is considered that the decomposition of hydrocarbons by Pd and CeO 2 was started relatively early.
【００５４】実施例１〜３は、触媒におけるＣａＯの担
持部分の長さ（発熱部の長さ）の担体全長に対する比率
を同じく１／５としてＣａＯの担持量を異なる値にした
ものであるが、図１にも示すように、ＣａＯが１５ｇ／
ｌ以上になると上記ＣａＯの効果が明白なものになり、
２０ｇ／ｌ，３０ｇ／ｌになると、その効果が顕著にな
ることがわかる。なお、図１において、実１〜実３及び
比１の各記号は実施例１〜実施例３及び比較例１の各々
を示す。In Examples 1 to 3, the ratio of the length of the portion carrying CaO in the catalyst (the length of the heat generating portion) to the total length of the carrier was set to 1/5, and the amount of CaO carried was varied. , As shown in FIG. 1, CaO is 15 g /
When it is 1 or more, the effect of CaO becomes obvious,
It can be seen that the effect becomes remarkable at 20 g / l and 30 g / l. In addition, in FIG. 1, the symbols of Ex 1 to Ex 3 and Ratio 1 indicate each of Examples 1 to 3 and Comparative Example 1.
【００５５】実施例３〜５はＣａＯの担持量を３０ｇ／
ｌとして担体におけるＣａＯの担持部分の長さの比率を
異なる値にしたものであるが、図２にも示すように、１
／１０〜２／５において明白な効果が得られ、１／５，
１／３においてその効果が顕著になることがわかる。上
記長さの比率が大きくなるにつれてＹ１浄化率が低くな
っているのは、吸着触媒部の長さが相対的に短くなり、
ＨＣ吸着率自体が低くなっているためであると考えられ
る。なお、図２において、実３〜実６、比１及び比２の
各記号は実施例３〜実施例６、比較例１及び比較例２の
各々を示す。In Examples 3 to 5, the carried amount of CaO was 30 g /
As l, the ratio of the lengths of the CaO-carrying portions of the carrier is set to different values. As shown in FIG.
A clear effect is obtained in / 10 to 2/5,
It can be seen that the effect becomes remarkable at 1/3. The Y1 purification rate decreases as the length ratio increases, because the length of the adsorption catalyst portion becomes relatively short.
It is considered that this is because the HC adsorption rate itself is low. In addition, in FIG. 2, each symbol of Ex 3 to Ex 6, Ratio 1 and Ratio 2 indicates each of Examples 3 to 6, Comparative Example 1 and Comparative Example 2.
【００５６】次に実施例６については、これを比較例２
と比べると、ＨＣ吸着率は比較例２よりも低くなってい
るが、Ｙ１浄化率は比較例２よりも高くなっている。こ
れは上述の実施例１〜５と比較例１との比較の場合と同
様の結果である。よって、基本的には担体の全長及び断
面積のいかんに拘らず、上記発熱剤がＨＣ浄化率の向上
に効を奏する、ということができる。Next, with respect to Example 6, this is compared with Comparative Example 2.
Compared with, the HC adsorption rate is lower than that of Comparative Example 2, but the Y1 purification rate is higher than that of Comparative Example 2. This is the same result as in the case of comparison between Examples 1 to 5 and Comparative Example 1 described above. Therefore, basically, it can be said that the exothermic agent is effective in improving the HC purification rate regardless of the total length and the cross-sectional area of the carrier.
【００５７】＜その他＞以下ではＨＣ吸着剤に触媒金属
を担持させてなるＨＣ吸着触媒のＨＣ浄化率を高める他
の発明について説明する。<Others> Hereinafter, another invention for increasing the HC purification rate of the HC adsorption catalyst in which the catalyst metal is supported on the HC adsorbent will be described.
【００５８】１．本案の概要 エンジンから排出される未燃炭化水素の８割は排ガス浄
化触媒の温度が上がっていないエンジン始動直後に排出
されたものである。そのため低温時のＨＣの処理が重要
となる。1. Outline of the Proposal 80% of unburned hydrocarbons emitted from the engine are emitted immediately after the engine starts when the temperature of the exhaust gas purification catalyst has not risen. Therefore, the treatment of HC at low temperatures is important.
【００５９】本案は、エンジンの冷間時排出された未燃
のＨＣを吸着する高比表面積体（ゼオライト等）よりな
る吸着剤に、該吸着剤の温度が高くなったときに該吸着
剤に吸着されているＨＣを浄化（分解）する触媒金属が
担持されてなるＨＣ吸着触媒を備えているとともに、該
ＨＣ吸着触媒に２次エアをエンジン始動から所定時間供
給する２次エア供給手段を備えていることを特徴とす
る。The present invention is directed to an adsorbent made of a high specific surface area material (such as zeolite) that adsorbs unburned HC discharged during cold engine operation, and to the adsorbent when the temperature of the adsorbent rises. An HC adsorbing catalyst that carries a catalytic metal that purifies (decomposes) the adsorbed HC is provided, and a secondary air supply unit that supplies secondary air to the HC adsorbing catalyst for a predetermined time from engine start. It is characterized by
【００６０】２．従来技術 触媒のＨＣ浄化開始温度を早めるためには酸素過剰な状
態にすればよい。そのため従来はエンジン始動直後から
２次エアーを導入していた。しかし、長時間エアを導入
しなければならず装置が大がかりになっていた。2. 2. Description of the Related Art In order to accelerate the HC purification start temperature of the catalyst, an oxygen excess state may be set. Therefore, conventionally, secondary air was introduced immediately after the engine was started. However, air had to be introduced for a long time, and the size of the device was large.
【００６１】これに対して、ＨＣ吸着触媒を用いると一
定時間２次エアを流せば効率よくＨＣが浄化できること
が判明し、本案が完成されたものである。On the other hand, when the HC adsorption catalyst was used, it was found that the HC can be efficiently purified by flowing the secondary air for a certain time, and the present invention has been completed.
【００６２】３．本案の実施例 −本案の実施例のポイント− ２次エア供給装置に圧縮空気の入ったボンベを使用し、
さらに吸着触媒を併用することで、短時間のエア導入で
効率よくＨＣを浄化可能にする。またエア導入の時間に
ついては触媒入口ガス温度で判定する。3. Example of the Present Invention-Points of Example of the Present Invention-A cylinder containing compressed air is used as a secondary air supply device,
Furthermore, by using an adsorption catalyst together, it is possible to efficiently purify HC by introducing air for a short time. Also, the time of air introduction is determined by the catalyst inlet gas temperature.
【００６３】−吸着触媒の調製− 細孔径０．５ｎｍ以上の高比表面積体（多孔質吸着剤）
をコージェライト製モノリス担体にウォッシュコートし
た。ここで用いる吸着剤は、細孔径が上記の値以上のも
のならなんでもよいが、特にＦＡＵ型やＭＦＩ型のゼオ
ライトが有効である。ゼオライトを用いる場合はＮａ
型，Ｈ型などなんでもよく、イオン交換、含浸等の方法
によって金属修飾してあってもよい。触媒金属として
は、Ｐｄ，Ｐｔ，Ｒｈ，Ｃｏ，Ｎｉ，Ｆｅ等を単独でも
しくは２種以上組み合わせて用いることができ、さら
に、これにセリアを組み合わせて、上記吸着剤に担持さ
せることができる。ウォッシュコートに使用するバイン
ダには水和アルミナ、シリカゾルなどを用いることがで
きるが、その種類は特に問わない。-Preparation of adsorption catalyst-High specific surface area body (porous adsorbent) having a pore size of 0.5 nm or more
Was code-coated on a cordierite monolith carrier. The adsorbent used here may be any adsorbent having a pore diameter of the above value or more, but FAU type or MFI type zeolite is particularly effective. Na when using zeolite
Type, H type, etc., and may be metal-modified by a method such as ion exchange or impregnation. As the catalyst metal, Pd, Pt, Rh, Co, Ni, Fe and the like can be used alone or in combination of two or more kinds, and further, ceria can be combined and supported on the adsorbent. Hydrated alumina, silica sol, or the like can be used as the binder used in the washcoat, but the type thereof is not particularly limited.
【００６４】−吸着触媒の評価− 表２に各金属修飾を行ったＦＡＵ型ゼオライトのトルエ
ン吸着量を、表３にＭＦＩ型ゼオライトのプロピレン吸
着量を、表４に各種の触媒金属を担持させたゼオライト
のライトオフ温度（最高のＨＣ浄化率の半分のＨＣ浄化
率を示す温度）を、表５に当該評価に使用した模擬排気
ガスの組成及び空間速度を、それぞれ示す。表４のゼオ
ライトはＨ型である。-Evaluation of Adsorbed Catalysts-Table 2 shows the amount of toluene adsorbed on the FAU-type zeolite with each metal modification, Table 3 shows the amount of propylene adsorbed on the MFI-type zeolite, and Table 4 shows various catalytic metals. The light-off temperature of zeolite (the temperature at which the HC purification rate is half the maximum HC purification rate) is shown in Table 5, and the composition and space velocity of the simulated exhaust gas used for the evaluation are shown in Table 5, respectively. The zeolites in Table 4 are H type.
【００６５】[0065]
【表２】 [Table 2]
【００６６】[0066]
【表３】 [Table 3]
【００６７】[0067]
【表４】 [Table 4]
【００６８】[0068]
【表５】 [Table 5]
【００６９】−実車評価− 図３に示すように、エンジン１の排気通路に三元触媒
（アルミナ及びセリアにＰｔ及びＲｈを担持させてなる
触媒粉をコージェライト製モノリス担体にウォッシュコ
ートによって担持させ焼成を行なったもの）２とＨＣ吸
着触媒（ケイバン比８０のＨ型−ＦＡＵをコージェライ
ト製モノリス担体にウォッシュコートによって担持させ
焼成を行なった後、これに、ＣｅＯ2 とＰｄとを前者が
担体１リットル当り７０ｇ、後者が担体１リットル当り
１０ｇとなるように含浸法によって担持させたもの）３
とを前者が上流側に、後者が下流側になるように連ねて
配置するとともに、吸着触媒３のさらに下流に三元触媒
４を配置し、上流側の三元触媒２よりも上流側から２次
エアを導入するようにした。エンジン１の仕様等は次の
通りである。２次エアはエンジン始動から２０秒を経過
した時点から２０秒間導入した。エンジン１の排気マニ
ホールドの集合部から上記上流側の三元触媒２までの距
離は２０ｃｍである。-Evaluation of Actual Vehicle- As shown in FIG. 3, a catalyst powder obtained by supporting a three-way catalyst (Pt and Rh on alumina and ceria) in the exhaust passage of the engine 1 was supported on the cordierite monolith carrier by washcoating. Calcination 2) and HC adsorption catalyst (H type-FAU with a Cayvan ratio of 80) were carried on a cordierite monolith carrier by washcoating and calcined, and then CeO 2 and Pd were added to the former carrier. 70 g per liter, the latter being carried by the impregnation method so that the carrier becomes 10 g per liter) 3
Are arranged so that the former is on the upstream side and the latter is on the downstream side, and the three-way catalyst 4 is arranged further downstream of the adsorption catalyst 3 from the upstream side of the upstream three-way catalyst 2. The next air was introduced. The specifications of the engine 1 are as follows. The secondary air was introduced for 20 seconds after 20 seconds had passed since the engine was started. The distance from the exhaust manifold manifold of the engine 1 to the upstream three-way catalyst 2 is 20 cm.
【００７０】 エンジン ；Ｖ型６気筒 排気量３０００ｃｃ 三元触媒２の容量；０．２リットル 吸着触媒３の容量；０．５リットル 三元触媒４の容量；１．６リットル ２次エア流量 ；２００リットル／ｍｉｎ 走行モード ；ＬＡ−４−Ｙ１Engine: V-type 6 cylinder Displacement 3000 cc Capacity of three-way catalyst 2; 0.2 liter Capacity of adsorption catalyst 3; 0.5 liter Capacity of three-way catalyst 4; 1.6 liter Secondary air flow rate; 200 L / min Running mode; LA-4-Y1
【００７１】その結果、このような本案ではＹ１浄化率
が９１．１％になったが、別に、上記吸着触媒を配置せ
ずに三元触媒２，４のみとして、該三元触媒にその上流
側から２次エアを導入する試験を行なったところ（以
下、これを従来例という）、Ｙ１浄化率が８２．５％で
あった。また、上記図３と同じ仕様において、エンジン
のアイドル運転を１分間行なった後にＬＡ−４−Ｙ１モ
ードの走行を行なうようにし、２次エアをＹ１走行開始
より２０秒間導入したところ（以下、これを比較例と
いう）、ＨＣ浄化率（アイドル運転とＹ１モード運転で
の浄化率）は８８．３％になった。さらに、吸着触媒を
配置せずに三元触媒のみとし、１分間のアイドル運転後
にＬＡ−４−Ｙ１モードの走行を行なうようにし、２次
エアを三元触媒にその上流側からＹ１走行開始より２０
秒間導入したところ（以下、これを比較例という）、
ＨＣ浄化率（アイドル運転とＹ１モード運転での浄化
率）は６６．８％になった。As a result, the Y1 purification rate was 91.1% in such a case, but separately, the three-way catalysts 2 and 4 alone without the above-mentioned adsorption catalyst were placed upstream of the three-way catalyst. When a test was conducted in which secondary air was introduced from the side (hereinafter referred to as a conventional example), the Y1 purification rate was 82.5%. Further, in the same specifications as in FIG. 3, when the engine was idle for 1 minute and then the LA-4-Y1 mode was run, and secondary air was introduced for 20 seconds from the start of Y1 running (hereinafter, Is referred to as a comparative example), and the HC purification rate (the purification rate in the idle operation and the Y1 mode operation) was 88.3%. Further, the adsorbing catalyst is not arranged and only the three-way catalyst is used so that the LA-4-Y1 mode traveling is performed after the idle operation for one minute, and the secondary air is supplied to the three-way catalyst from the upstream side of the Y1 traveling. 20
Introduced for a second (hereinafter referred to as Comparative Example),
The HC purification rate (purification rate in idle operation and Y1 mode operation) was 66.8%.
【００７２】以上のことから、上述の吸着触媒を配置
し、エンジン始動から２０秒を経過した時点から２次エ
アを２０秒間導入する本案が優れていることがわかる。
また、従来例ではエンジン始動直後（触媒が暖まってい
ない）のＨＣが浄化できていないが、本案ではＨＣ吸着
触媒があるため浄化（低温時吸着し、高温時浄化）でき
ている。また、比較例，のように長時間のアイドル
等で触媒の温度がなかなか上昇しない場合も本案では一
定時間のエア導入で炭化水素を効率よく浄化することが
できる。From the above, it can be understood that the present invention in which the above-mentioned adsorption catalyst is arranged and the secondary air is introduced for 20 seconds after 20 seconds have passed from the engine start is excellent.
Further, in the conventional example, HC cannot be purified immediately after the engine is started (catalyst is not warmed up), but in the present invention, it can be purified (adsorbed at low temperature and purified at high temperature) due to the HC adsorption catalyst. Further, even in the case where the temperature of the catalyst does not rise easily due to a long period of idling as in the comparative example, the present invention can efficiently purify hydrocarbons by introducing air for a certain period of time.
【００７３】４．２次エア導入量とＨＣ浄化率との関係 図４にリグ評価結果（排気ガス中のＯ2 濃度とＴ５０
（ライトオフ温度）との関係）を示すように、酸素濃度
が２％を越えるとＴ５０が急激に低下（結果としてＨＣ
浄化率の向上に結び付く）することがわかる。このこと
より、実車でも同程度の酸素濃度が確保できれば浄化率
が向上するといえる。しかし実車では加減速等で常に排
気ガス流量が変化するため一定の酸素濃度に保つことが
できない。そこで一定量の空気を流すことで代用するこ
ととしたものである。２次エア流量とＹ１浄化率との関
係を図５に示す。同図から、１００リットル／ｍｉｎ以
上が最適であるといえる。4. Relationship between Secondary Air Introduction Amount and HC Purification Rate FIG. 4 shows the result of rig evaluation (O 2 concentration in exhaust gas and T50).
(Relationship with (light-off temperature)), when oxygen concentration exceeds 2%, T50 sharply decreases (as a result, HC
It leads to improvement of purification rate). From this, it can be said that the purification rate is improved if the same oxygen concentration can be secured even in the actual vehicle. However, in an actual vehicle, the exhaust gas flow rate constantly changes due to acceleration / deceleration, etc., so that a constant oxygen concentration cannot be maintained. Therefore, it was decided to substitute a certain amount of air. The relationship between the secondary air flow rate and the Y1 purification rate is shown in FIG. From the figure, it can be said that 100 liter / min or more is optimal.
【００７４】５．２次エア導入時間とＨＣ浄化率との関
係 図６は２次エアを導入しない場合のＨＣ浄化率、図７は
２次エアをエンジン始動直後から１００秒まで加えた場
合のＨＣ浄化率、図８は２次エアをエンジン始動から２
０秒を経過した時点から２０秒間加えた場合のＨＣ浄化
率を示す。図６〜８において破線で示す曲線が吸着触媒
を配置したもの、実線で示す曲線が吸着触媒を備えてい
ないものである。これによれば、２次エア導入の有無、
２次エア導入開始時間に関係なく、吸着触媒を配置した
ものの方が高いＨＣ浄化率を示している。これは吸着触
媒の存在による。また、これらの図よりＨＣ吸着触媒が
配置されたものは２次エアを常時導入しなくても浄化率
が高いことがわかる。これは、図９に２次エアをエンジ
ン始動直後から１００秒まで加えた場合の触媒出口ガス
温度の経時変化を示し、図１０に２次エアをエンジン始
動から２０秒を経過した時点から２０秒間加えた場合の
触媒出口ガス温度の経時変化を示すように（破線で示す
曲線が吸着触媒を配置したもの、実線で示す曲線が吸着
触媒を備えていないものである。）、吸着触媒に吸着さ
れた大量の炭化水素が酸素過剰雰囲気で一気に燃え触媒
温度が急上昇するためであり、従って、ストイキの状態
（理論空燃比における燃焼状態（λ＝１）、つまり２次
エアを止めて通常の排気ガス組成になった状態）にもど
っても高い浄化率を維持するためである。5. Relationship between Secondary Air Introduction Time and HC Purification Rate FIG. 6 shows the HC purification rate when the secondary air is not introduced, and FIG. 7 shows the case where the secondary air is added up to 100 seconds immediately after the engine is started. HC purification rate, Figure 8 shows secondary air from engine start to 2
The HC purification rate in the case of adding for 20 seconds from the time when 0 seconds has passed is shown. In FIGS. 6 to 8, the curved line shown by the broken line is the one in which the adsorption catalyst is arranged, and the curved line shown by the solid line is that without the adsorption catalyst. According to this, whether the secondary air is introduced,
The HC purification rate is higher in the case where the adsorption catalyst is arranged, regardless of the secondary air introduction start time. This is due to the presence of the adsorption catalyst. Further, from these figures, it is understood that the one in which the HC adsorption catalyst is arranged has a high purification rate without always introducing the secondary air. This shows the change over time in the catalyst outlet gas temperature when secondary air is added for 100 seconds immediately after engine startup, and in FIG. 10 for 20 seconds from the time when 20 seconds have elapsed since the secondary air was started. As shown in the time course of the catalyst outlet gas temperature when added (the curve indicated by the broken line is the one in which the adsorption catalyst is arranged, the curve indicated by the solid line is the one without the adsorption catalyst), and is adsorbed by the adsorption catalyst. This is because a large amount of hydrocarbons burn at once in an oxygen-excess atmosphere and the catalyst temperature rises rapidly. Therefore, the stoichiometric state (combustion state at theoretical air-fuel ratio (λ = 1), that is, secondary air is stopped and normal exhaust gas is exhausted. This is to maintain a high purification rate even after returning to the composition state.
【図１】発熱剤（ＣａＯ）担持量とＹ１浄化率（ＨＣ浄
化率）との関係を示すグラフ図FIG. 1 is a graph showing a relationship between a carrying amount of a heating agent (CaO) and a Y1 purification rate (HC purification rate).
【図２】担体における発熱剤の担持範囲とＹ１浄化率と
の関係を示すグラフ図FIG. 2 is a graph showing the relationship between the carrying range of the exothermic agent on the carrier and the Y1 purification rate.
【図３】エンジンの排気系を示すブロック図FIG. 3 is a block diagram showing an exhaust system of the engine.
【図４】排気ガス中のＯ2 濃度とＴ５０（ライトオフ温
度）との関係を示すグラフ図FIG. 4 is a graph showing the relationship between the O 2 concentration in exhaust gas and T50 (light-off temperature).
【図５】２次エア流量とＹ１浄化率との関係を示すグラ
フ図FIG. 5 is a graph showing the relationship between the secondary air flow rate and the Y1 purification rate.
【図６】２次エアを導入しない場合のＨＣ浄化率の経時
変化を示すグラフ図FIG. 6 is a graph showing the change over time in the HC purification rate when secondary air is not introduced.
【図７】２次エアをエンジン始動直後から１００秒まで
加えた場合のＨＣ浄化率の経時変化を示すグラフ図FIG. 7 is a graph showing the change over time in the HC purification rate when secondary air is added for 100 seconds immediately after engine startup.
【図８】２次エアをエンジン始動から２０秒を経過した
時点から２０秒間加えた場合のＨＣ浄化率の経時変化を
示すグラフ図FIG. 8 is a graph showing the change over time in the HC purification rate when secondary air is added for 20 seconds after 20 seconds have elapsed from the engine start.
【図９】２次エアをエンジン始動直後から１００秒まで
加えた場合の触媒出口ガス温度の経時変化を示すグラフ
図FIG. 9 is a graph showing the change over time in the catalyst outlet gas temperature when secondary air is added for 100 seconds immediately after engine startup.
【図１０】２次エアをエンジン始動から２０秒を経過し
た時点から２０秒間加えた場合の触媒出口ガス温度の経
時変化を示すグラフ図FIG. 10 is a graph showing the change over time in the catalyst outlet gas temperature when secondary air is added for 20 seconds after 20 seconds have elapsed from the engine start.
１ エンジン ２ 三元触媒 ３ ＨＣ吸着触媒 1 engine 2 three-way catalyst 3 HC adsorption catalyst
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｄ 53/72 53/86 ＺＡＢ 53/94 Ｂ０１Ｊ 20/18 ＺＡＢ Ｄ Ｂ０１Ｄ 53/36 ＺＡＢ １０４ Ａ (72)発明者 黒川 貴弘 広島県安芸郡府中町新地３番１号 マツダ 株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location B01D 53/72 53/86 ZAB 53/94 B01J 20/18 ZAB D B01D 53/36 ZAB 104 A ( 72) Inventor Takahiro Kurokawa 3-1, Shinchi Fuchu-cho, Aki-gun, Hiroshima Prefecture Mazda Motor Corporation
Claims (9)
分を吸着する吸着剤に該炭化水素を分解する触媒金属を
担持させてなる吸着触媒を有する吸着触媒部と、 上記吸着触媒部に隣接して排気ガス流れ方向の下流側に
配設され上記水分の吸収によって発熱する発熱剤を有す
る発熱部とを備えていることを特徴とする内燃機関の排
気ガス浄化用触媒。1. An adsorption catalyst section having an adsorption catalyst comprising an adsorbent for adsorbing hydrocarbons and water in exhaust gas of an internal combustion engine and a catalytic metal for decomposing the hydrocarbons, and an adsorbing catalyst section adjacent to the adsorbing catalyst section. An exhaust gas purifying catalyst for an internal combustion engine, further comprising: a heat generating portion that is disposed on the downstream side in the exhaust gas flow direction and has a heat generating agent that generates heat by absorbing the moisture.
気ガス浄化用触媒において、 上記発熱剤がＣａＯであることを特徴とする内燃機関の
排気ガス浄化用触媒。2. The exhaust gas purifying catalyst for an internal combustion engine according to claim 1, wherein the exothermic agent is CaO.
内燃機関の排気ガス浄化用触媒において、 上記吸着触媒がセラミック製のモノリス担体の排気ガス
流れ方向の上流側の部位に担持されて上記吸着触媒部が
形成され、 上記発熱剤が上記モノリス担体の排気ガス流れ方向の下
流側の部位に担持されて上記発熱部が形成されているこ
とを特徴とする内燃機関の排気ガス浄化用触媒。3. The exhaust gas purifying catalyst for an internal combustion engine according to claim 1 or 2, wherein the adsorption catalyst is carried on a site upstream of the ceramic monolith carrier in the exhaust gas flow direction. An exhaust gas purifying catalyst for an internal combustion engine, wherein the adsorption catalyst section is formed, and the exothermic agent is carried on a downstream side portion of the monolith carrier in the exhaust gas flow direction to form the exothermic section. .
気ガス浄化用触媒において、 上記吸着剤がゼオライトであることを特徴とする内燃機
関の排気ガス浄化用触媒。4. The exhaust gas purifying catalyst for an internal combustion engine according to claim 3, wherein the adsorbent is zeolite.
気ガス浄化用触媒において、 上記モノリス担体１リットル当りのＣａＯの担持量が１
５ｇ以上であることを特徴とする内燃機関の排気ガス浄
化用触媒。5. The catalyst for purifying exhaust gas of an internal combustion engine according to claim 4, wherein the carried amount of CaO is 1 per liter of the monolith carrier.
An exhaust gas purifying catalyst for an internal combustion engine, which is 5 g or more.
気ガス浄化用触媒において、 上記モノリス担体１リットル当りのＣａＯの担持量が２
０〜３０ｇであることを特徴とする内燃機関の排気ガス
浄化用触媒。6. The exhaust gas purifying catalyst for an internal combustion engine according to claim 4, wherein the carried amount of CaO is 2 per liter of the monolith carrier.
An exhaust gas purifying catalyst for an internal combustion engine, which has a weight of 0 to 30 g.
気ガス浄化用触媒において、 上記発熱部が上記モノリス担体の下流端から該モノリス
担体の全長の１／１０〜２／５の範囲にわたる部位に形
成されていることを特徴とする内燃機関の排気ガス浄化
用触媒。7. The exhaust gas purifying catalyst for an internal combustion engine according to claim 4, wherein the heat generating portion extends from the downstream end of the monolith carrier to a range of 1/10 to 2/5 of the entire length of the monolith carrier. A catalyst for purifying exhaust gas of an internal combustion engine, which is formed in a portion.
気ガス浄化用触媒において、 上記発熱部が上記モノリス担体の下流端から該モノリス
担体の全長の１／５〜１／３の範囲にわたる部位に形成
されていることを特徴とする内燃機関の排気ガス浄化用
触媒。8. The exhaust gas purifying catalyst for an internal combustion engine according to claim 4, wherein the heat generating portion extends from the downstream end of the monolith carrier to 1/5 to 1/3 of the entire length of the monolith carrier. A catalyst for purifying exhaust gas of an internal combustion engine, which is formed in a portion.
気ガス浄化用触媒において、 上記吸着触媒が、ゼオライトにＰｄとセリアとを担持さ
せてなることを特徴とする内燃機関の排気ガス浄化用触
媒。9. The exhaust gas purifying catalyst for an internal combustion engine according to claim 4, wherein the adsorption catalyst comprises zeolite carrying Pd and ceria. Catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27220994A JP3567507B2 (en) | 1994-11-07 | 1994-11-07 | Exhaust gas purification catalyst for internal combustion engines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27220994A JP3567507B2 (en) | 1994-11-07 | 1994-11-07 | Exhaust gas purification catalyst for internal combustion engines |
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| Publication Number | Publication Date |
|---|---|
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ID=17510634
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017202961A (en) * | 2016-05-12 | 2017-11-16 | 株式会社神戸製鋼所 | Hydrogen gas manufacturing method |
| WO2022112124A1 (en) * | 2020-11-26 | 2022-06-02 | Vitesco Technologies GmbH | Device for exhaust gas aftertreatment |
-
1994
- 1994-11-07 JP JP27220994A patent/JP3567507B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017202961A (en) * | 2016-05-12 | 2017-11-16 | 株式会社神戸製鋼所 | Hydrogen gas manufacturing method |
| WO2022112124A1 (en) * | 2020-11-26 | 2022-06-02 | Vitesco Technologies GmbH | Device for exhaust gas aftertreatment |
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| Publication number | Publication date |
|---|---|
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