JP2014524833A - Catalyst fine particle filter and coating method of fine particle filter - Google Patents

Catalyst fine particle filter and coating method of fine particle filter Download PDF

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JP2014524833A
JP2014524833A JP2014519477A JP2014519477A JP2014524833A JP 2014524833 A JP2014524833 A JP 2014524833A JP 2014519477 A JP2014519477 A JP 2014519477A JP 2014519477 A JP2014519477 A JP 2014519477A JP 2014524833 A JP2014524833 A JP 2014524833A
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catalyst
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ammonia
washcoat
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JP6395602B2 (en
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ガブリエルソン・ペル・エル
ヨハンセン・ケル
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ハルドール・トプサー・アクチエゼルスカベット
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2832—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support granular, e.g. pellets
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
    • B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
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    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/915—Catalyst supported on particulate filters
    • B01D2255/9155—Wall flow filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
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    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/0219—Coating the coating containing organic compounds
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    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F01N3/2073—Selective catalytic reduction [SCR] with means for generating a reducing substance from the exhaust gases
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    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Abstract

残留炭化水素及び一酸化炭素を除去する際に活性を有しかつリッチ燃焼エンジン動作条件で窒素酸化物と水素及び／又は一酸化炭素とのアンモニアへの反応を触媒する第１触媒によりその入口側で触媒され、しかも出口側で形成されるアンモニアとの反応によるＮＯｘの選択的還元に活性を有する第２触媒によりその出口側で触媒される壁流微粒子フィルターの製造方法を提供する。この方法は、フィルター壁の平均孔径よりも小さな粒径を有する第１触媒及びフィルター壁の平均孔径よりも大きな孔径を有する第２触媒を与え、そして該第１触媒及び第２触媒を混合して一つの懸濁液にし、これを出口端からウォッシュコートするために使用することを含む。これにより、第１触媒は、隔壁に分散する。  Inlet side by a first catalyst that is active in removing residual hydrocarbons and carbon monoxide and catalyzes the reaction of nitrogen oxides with hydrogen and / or carbon monoxide to ammonia under rich combustion engine operating conditions And a method for producing a wall flow particulate filter catalyzed at the outlet side by a second catalyst that is catalyzed by the second catalyst and is active in the selective reduction of NOx by reaction with ammonia formed at the outlet side. The method provides a first catalyst having a particle size smaller than the average pore size of the filter wall and a second catalyst having a pore size larger than the average pore size of the filter wall, and mixing the first catalyst and the second catalyst. Including a single suspension, which is used to washcoat from the exit end. Thereby, the first catalyst is dispersed in the partition walls.

Description

本発明は、多機能触媒エンジン排気微粒子フィルターに関する。特に、本発明は、三元触媒（ＴＷＣ）及び既知のＮＨ３−選択接触還元（ＳＣＲ）方法により窒素酸化物を除去する際に活性である触媒、及び随意に過剰のアンモニアを窒素に酸化する際に活性を有する触媒で触媒される多機能触媒微粒子フィルターの製造方法である。   The present invention relates to a multifunctional catalyst engine exhaust particulate filter. In particular, the present invention relates to a catalyst that is active in removing nitrogen oxides by a three-way catalyst (TWC) and known NH3-selective catalytic reduction (SCR) process, and optionally in oxidizing excess ammonia to nitrogen. It is a manufacturing method of the multifunctional catalyst fine particle filter catalyzed by the catalyst which has activity in this.

多機能触媒フィルターは、特に、直噴ガソリン（ＧＤＩ）エンジンなどのリーンバーンガソリンエンジンからの排気ガスを浄化するのに有用である。   Multifunctional catalytic filters are particularly useful for purifying exhaust gases from lean burn gasoline engines such as direct injection gasoline (GDI) engines.

ＧＤＩエンジンは、ガソリン予備混合噴射エンジンよりも多い炭素状すすを発生する。欧州では、ユーロ５＋ディーゼル法は、将来的に、４．５ｍｇ／ｋｍの微粒子質量限度を有するＧＤＩについて採用されることが見込まれるところ、これは、上記限度を達成するためにエンジンの濾過を必要とする。   GDI engines generate more carbonous soot than gasoline premixed injection engines. In Europe, the Euro 5+ diesel method is expected to be adopted in the future for GDI with a particulate mass limit of 4.5 mg / km, which requires engine filtration to achieve the above limit And

典型的には、自動車用途に使用するためのフィルターは、粒状物質をハニカム構造の隔壁上又は隔壁中に捕捉する、ハニカム構造体からなる壁流型フィルターである。これらのフィルターは、ガス透過性隔壁によって隔てられた複数の長手方向流路を有する。ガス入口チャネルは、それらのガス入口側で開き、かつ、反対側の出口端で閉鎖され、ガス出口チャネルは、出口端で開き、かつ、入口端で閉鎖され、それにより、壁流フィルターに入るガス流は、出口チャネルに入る前に隔壁に集中する。   Typically, a filter for use in an automotive application is a wall flow filter made of a honeycomb structure that traps particulate matter on or in the honeycomb partition walls. These filters have a plurality of longitudinal channels separated by gas permeable septa. The gas inlet channels open at their gas inlet side and closed at the opposite outlet end, and the gas outlet channel opens at the outlet end and closed at the inlet end, thereby entering the wall flow filter The gas flow is concentrated on the septum before entering the outlet channel.

すす粒子の他に、ガソリンエンジンからの排気ガスは、窒素酸化物（ＮＯｘ）、一酸化炭素及び未燃焼炭化水素を含有することろ、これらは、健康及び環境リスクを示す化学化合物であり、排気ガスから減少又は除去されなければならない。   In addition to soot particles, the exhaust gas from gasoline engines contains nitrogen oxides (NOx), carbon monoxide and unburned hydrocarbons, which are chemical compounds that represent health and environmental risks, Must be reduced or removed from the gas.

ＮＯｘ、一酸化炭素及び炭化水素を除去する又は無害な化合物に還元するのに活性な触媒は、それ自体当該技術分野において知られている。   Catalysts that are active in removing NOx, carbon monoxide and hydrocarbons or reducing them to harmless compounds are known per se in the art.

特許文献には、エンジン排気ガスから有害な化合物を除去するための別個の触媒単位を含む多数の浄化システムが開示されている。   The patent literature discloses a number of purification systems that include a separate catalytic unit for removing harmful compounds from engine exhaust.

また、当該技術分野においては、炭化水素及び粒状物質の酸化を触媒すると共に、排気ガスにそのまま又は先駆物質として添加されるアンモニアとの反応によりＮＯｘを選択接触還元（ＳＣＲ）する触媒が被覆された排気ガス微粒子フィルターも知られている。   Also, in this technical field, a catalyst that catalyzes the oxidation of hydrocarbons and particulate matter, and selectively catalytic reduction (SCR) of NOx by reaction with ammonia added to the exhaust gas as it is or as a precursor is coated. Exhaust gas particulate filters are also known.

また、当該技術分野においては、上記反応を触媒する異なる触媒で被覆された多機能ディーゼル微粒子フィルターも知られている。   Also known in the art are multifunctional diesel particulate filters coated with different catalysts that catalyze the above reactions.

既知の多機能フィルターでは、異なる触媒がフィルターの異なる区域に部分又はゾーン被覆される。   In known multifunction filters, different catalysts are partially or zone coated in different areas of the filter.

該フィルター上への異なる触媒の部分又はゾーン被覆は、高価であり、かつ、困難な製造方法である。   Different catalyst parts or zone coatings on the filter are expensive and difficult manufacturing methods.

本発明は、公知技術と比較して、アンモニアによる窒素酸化物の選択的還元と炭化水素、一酸化炭素及び過剰のアンモニアの除去とのための異なる触媒で触媒された微粒子フィルターの容易な製造方法を提案する。   The present invention is an easy process for producing particulate filters catalyzed with different catalysts for the selective reduction of nitrogen oxides with ammonia and the removal of hydrocarbons, carbon monoxide and excess ammonia compared to the prior art. Propose.

すなわち、本発明は、触媒壁流フィルターの製造方法であって、次の工程：
（ａ）壁流フィルター本体に、ガス透過性多孔質隔壁によって隔てられた複数の長手入口流路及び出口流路を与え；
（ｂ）窒素酸化物と一酸化炭素及び水素とを反応させてアンモニアにするのに活性のある第１触媒組成物と共に、アンモニアと反応することにより窒素酸化物を窒素に選択的還元するのに活性のある第２触媒組成物を含む触媒ウォッシュコートを与え、ここで、該第１触媒組成物は、該多孔質隔壁の平均孔径よりも小さな粒径を有し、該第２触媒組成物は、該多孔質隔壁の平均孔径よりも大きな粒径を有するものとし；
（ｃ）該触媒ウォッシュコートを該出口流路の出口端に導入することによって該フィルター本体を該ウォッシュコートで被覆し；そして
（ｄ）該被覆フィルター本体を乾燥させ熱処理して触媒微粒子フィルターを得ること
を含む方法を提供する。 That is, this invention is a manufacturing method of a catalyst wall flow filter, Comprising:
(A) providing the wall flow filter body with a plurality of longitudinal inlet channels and outlet channels separated by a gas permeable porous partition;
(B) To selectively reduce nitrogen oxides to nitrogen by reacting with ammonia together with a first catalyst composition active to react nitrogen oxides with carbon monoxide and hydrogen to ammonia. Providing a catalyst washcoat comprising an active second catalyst composition, wherein the first catalyst composition has a particle size smaller than the average pore size of the porous partition; And having a particle size larger than the average pore size of the porous partition;
(C) coating the filter body with the washcoat by introducing the catalyst washcoat into the outlet end of the outlet channel; and (d) drying and heat treating the coated filter body to obtain a catalyst particulate filter. A method comprising:

第１触媒が隔壁の平均孔径よりも小さな粒径を有し、第２触媒粒子が隔壁の平均孔径よりも大きな粒径を有することの利点は、第１触媒粒子が隔壁に効果的に分散されること、そして第２触媒が、特定の触媒活性が望まれない流路に分散するのを防ぐことである。   The advantage that the first catalyst has a particle size smaller than the average pore diameter of the partition walls and the second catalyst particle has a particle size larger than the average pore diameter of the partition walls is that the first catalyst particles are effectively dispersed in the partition walls. And preventing the second catalyst from dispersing in channels where a particular catalytic activity is not desired.

続いて、異なる触媒入口及び出口流路を有するフィルター本体を単一のウォッシュコートで被覆することが可能である。   Subsequently, the filter body with different catalyst inlet and outlet channels can be coated with a single washcoat.

次の反応：
ＮＯｘ＋Ｈ２／ＣＯ＝ＮＨ３＋ＣＯ２＋Ｈ２Ｏ
によってＮＯｘをアンモニアにする反応に有用な触媒は、パラジウム、白金、パラジウムとロジウムとの混合物及びパラジウムと白金とロジウムとの混合物である。 Next reaction:
NOx + H 2 / CO = NH 3 + CO 2 + H 2 O
Catalysts useful for the reaction of NOx to ammonia by palladium are palladium, platinum, a mixture of palladium and rhodium and a mixture of palladium, platinum and rhodium.

これらの触媒は、ガソリンエンジンのリッチ燃焼動作条件下、すなわちλ＜１でアンモニア形成を触媒する。パラジウムは、アンモニア形成が最も高い、好ましい触媒である。   These catalysts catalyze the formation of ammonia under the rich combustion operating conditions of the gasoline engine, ie λ <1. Palladium is the preferred catalyst with the highest ammonia formation.

このようにして上記反応により入口流路内に形成されるアンモニアは、フィルターの隔壁を通して出口流路に透過し、かつ、リッチ動作状態中に出口流路内のＳＣＲ触媒に吸収される。   Thus, the ammonia formed in the inlet channel by the above reaction permeates the outlet channel through the partition wall of the filter and is absorbed by the SCR catalyst in the outlet channel during the rich operation state.

アンモニア形成触媒及びＳＣＲ触媒の両方は、好ましくは、それぞれ入口流路及び出口流路に面した側の隔壁に被着される。   Both the ammonia forming catalyst and the SCR catalyst are preferably deposited on the partition walls facing the inlet and outlet channels, respectively.

エンジンのその後のリーン燃焼動作サイクルにおいて、排気ガス中に存在するＮＯｘは、次の反応によりＳＣＲ触媒中に保存されたアンモニアと反応する：
ＮＯｘ＋ＮＨ３＝Ｎ２＋Ｈ２Ｏ。 In the subsequent lean combustion cycle of the engine, NOx present in the exhaust gas reacts with ammonia stored in the SCR catalyst by the following reaction:
NOx + NH 3 = N 2 + H 2 O.

既に上で述べたように、ＳＣＲ触媒は、それ自体当該技術分野において知られているものである。本発明で使用するために、窒素酸化物の選択的還元に活性な好ましい触媒は、ゼオライト、シリカアルミニウムホスフェート、イオン交換ゼオライト、鉄及び／又は銅により活性が高められたシリカアルミニウムホスフェート、１種以上の卑金属酸化物の少なくとも一つを含む。   As already mentioned above, SCR catalysts are known per se in the art. Preferred catalysts active for the selective reduction of nitrogen oxides for use in the present invention are zeolites, silica aluminum phosphates, ion exchange zeolites, silica aluminum phosphates enhanced by iron and / or copper, one or more. At least one of the base metal oxides.

本発明で使用するのにさらに好ましいＳＣＲ触媒は、銅及び／又は鉄で活性が高められた、ＳＡＰＯ３４などのチャバサイト構造を有するシリカアルミニウムホスフェートである。   A further preferred SCR catalyst for use in the present invention is a silica aluminum phosphate having a chabasite structure such as SAPO34, enhanced in activity with copper and / or iron.

ＮＯｘとは反応しなかった過剰のアンモニアを除去するために、壁流フィルターは、本発明の実施形態では、少なくともフィルターの出口端の領域内にある各出口流路内に配置されるアンモニア酸化触媒をさらに含む。   In order to remove excess ammonia that did not react with NOx, the wall flow filter, in an embodiment of the present invention, is an ammonia oxidation catalyst that is placed in each outlet channel at least in the region of the outlet end of the filter. Further included.

好ましいアンモニア酸化触媒は、パラジウム、白金又はそれらの混合物を含む。   Preferred ammonia oxidation catalysts include palladium, platinum or mixtures thereof.

アンモニアは、アンモニア酸化触媒との接触により、窒素と水に酸化される。   Ammonia is oxidized to nitrogen and water by contact with the ammonia oxidation catalyst.

アンモニア酸化触媒は、出口領域内にあるフィルターの出口流路内の隔壁上に直接被着され、又はＳＣＲ触媒相の表面上に表層として設けられる場合がある。   The ammonia oxidation catalyst may be deposited directly on the partition in the outlet channel of the filter in the outlet region or may be provided as a surface layer on the surface of the SCR catalyst phase.

本発明は、さらに、触媒壁流フィルターの製造方法を提供する。   The present invention further provides a method for producing a catalyst wall flow filter.

その広い実施形態では、本発明は、触媒壁流フィルターの製造方法であって、次の工程：
（ａ）壁流フィルター本体に、ガス透過性多孔質隔壁によって隔てられた複数の長手入口流路及び出口流路を与え；
（ｂ）窒素酸化物と一酸化炭素及び水素とを反応させてアンモニアにするのに活性のある第１触媒組成物と、アンモニアと反応することにより窒素酸化物を窒素に選択的還元するのに活性のある第２触媒組成物とを含む触媒ウォッシュコートを与え、ここで、該第１触媒組成物は、該多孔質隔壁の平均粒径よりも小さいモード粒径を有し、該第２触媒組成物は、該多孔質隔壁の平均粒径よりも大きいモード粒径を有するものとし；
（ｃ）該触媒ウォッシュコートを該出口流路の出口端に導入することによって該フィルター本体に該ウォッシュコートを被覆し；そして
（ｄ）該被覆フィルター本体を乾燥させ熱処理して触媒微粒子フィルターを得ること
を含む方法を提供する。 In its broad embodiment, the present invention is a method for producing a catalytic wall flow filter comprising the following steps:
(A) providing the wall flow filter body with a plurality of longitudinal inlet channels and outlet channels separated by a gas permeable porous partition;
(B) a first catalyst composition that is active in reacting nitrogen oxides with carbon monoxide and hydrogen to form ammonia, and selectively reducing nitrogen oxides to nitrogen by reacting with ammonia; A catalyst washcoat comprising an active second catalyst composition, wherein the first catalyst composition has a mode particle size smaller than the average particle size of the porous partition walls, and the second catalyst The composition has a mode particle size larger than the average particle size of the porous partition;
(C) coating the filter body with the washcoat by introducing the catalyst washcoat into the outlet end of the outlet channel; and (d) drying and heat-treating the coated filter body to obtain a catalyst particulate filter. A method comprising:

本発明に使用するための特定の触媒は、上で言及しており、またさらに請求項２〜４に開示されている。   Specific catalysts for use in the present invention are referred to above and are further disclosed in claims 2-4.

本発明のさらなる実施形態では、フィルターは、アンモニアの過剰分を窒素と水に酸化するのに活性な触媒である、いわゆるアンモニアスリップ触媒でさらに被覆される。   In a further embodiment of the invention, the filter is further coated with a so-called ammonia slip catalyst, which is an active catalyst for oxidizing the excess of ammonia to nitrogen and water.

したがって、この実施形態では、本発明の方法は、次の工程：
アンモニアの選択的酸化に活性な触媒組成物を含有する第２ウォッシュコートを与え；そして
出口流路の少なくとも一部分に該ウォッシュコートを被覆し、その後触媒ウォッシュコートを被覆すること
を含む。 Thus, in this embodiment, the method of the present invention comprises the following steps:
Providing a second washcoat containing a catalyst composition active in the selective oxidation of ammonia; and coating at least a portion of the outlet flow path followed by coating the catalyst washcoat.

本発明で使用するためのウォッシュコートを製造する場合、通常は粒子の形態である触媒を必要な粒径まで磨砕又は凝集させ、そして水又は有機溶媒に、随意にバインダー、粘度調節剤、発泡剤その他の加工助剤を添加して懸濁する。   In preparing a washcoat for use in the present invention, the catalyst, usually in the form of particles, is ground or agglomerated to the required particle size and optionally in water or an organic solvent, binder, viscosity modifier, foaming. Add the agent and other processing aids and suspend.

その後、フィルターを、フィルターに真空を加え、ウォッシュコートを加圧し又は浸漬被覆することを含めて、一般的な方法に従ってウォッシュコートする。   The filter is then washcoated according to conventional methods, including applying a vacuum to the filter and pressurizing or dip-coating the washcoat.

フィルターに被覆される第１触媒の量は、典型的には１０〜１４０ｇ／ｌであり、フィルターに被覆される第２触媒の量は、典型的には１０〜１００ｇ／ｌである。フィルター上の全触媒添加量は、典型的には４０〜２００ｇ／ｌの範囲である。   The amount of the first catalyst coated on the filter is typically 10-140 g / l, and the amount of the second catalyst coated on the filter is typically 10-100 g / l. The total catalyst loading on the filter is typically in the range of 40-200 g / l.

本発明で使用するのに好適なフィルター材料の例は、炭化ケイ素、チタン酸アルミニウム、コーディエライト、アルミナ、ムライト又はそれらの組み合わせである。   Examples of suitable filter materials for use in the present invention are silicon carbide, aluminum titanate, cordierite, alumina, mullite or combinations thereof.

例
第１触媒組成物の懸濁液を、第１工程で、フィルター壁の平均孔径よりも小さな粒径の酸化セリウム及びアルミナ粒子上に被着されたパラジウムロジウムの粉末混合物から調製する。 EXAMPLE A suspension of a first catalyst composition is prepared in a first step from a powder mixture of cerium oxide having a particle size smaller than the average pore size of the filter wall and palladium rhodium deposited on alumina particles.

混合第１触媒の懸濁液を、リットルフィルターにつき４０ｍｌの脱イオン水にこれらの粉末２０ｇを混合させることによって調製する。分散剤のＺｅｐｈｒｙｍ ＰＤ−７０００及び消泡剤を添加する。この懸濁液をビーズミルで磨砕する。最終懸濁液の粒径は、壁流フィルターの壁部内の孔の平均孔径よりも小さくなければならない。   A mixed first catalyst suspension is prepared by mixing 20 g of these powders in 40 ml of deionized water per liter filter. Add the dispersant Zephrym PD-7000 and antifoam. This suspension is ground in a bead mill. The particle size of the final suspension must be smaller than the average pore size of the pores in the wall flow filter wall.

第２触媒の懸濁液を、２％の銅で活性が高められたシリカアルミニウムホスフェートＳＡＰＯ−３４の１００ｇをリットルフィルターにつき２００ｍｌの脱イオン水に混合分散させることによって作製する。分散剤Ｚｅｐｈｒｙｍ ＰＤ−７０００及び消泡剤を添加する。粒径は、壁流フィルターの壁部内の孔の平均孔径よりも大きくなければならない。   A suspension of the second catalyst is made by mixing and dispersing 100 g of silica aluminum phosphate SAPO-34 enhanced with 2% copper in 200 ml of deionized water per liter filter. Add the dispersant Zephrym PD-7000 and antifoam. The particle size must be larger than the average pore size of the pores in the wall of the wall flow filter.

その後、第１触媒及び第２触媒の懸濁液を混合して一つの懸濁液とする。   Thereafter, the suspensions of the first catalyst and the second catalyst are mixed to form one suspension.

高い多孔度（約６０％及び壁平均孔径約１８μｍ）の従来のプラグＳｉＣ壁流フィルターを使用する。   A conventional plug SiC wall flow filter with high porosity (about 60% and wall average pore size about 18 μm) is used.

第１及び第２触媒の混合懸濁液を、標準的なウォッシュコート方法によってフィルターの透過側のフィルター出口端からウォッシュコートし、乾燥させ、そして７５０℃で焼結させる。   The mixed suspension of the first and second catalysts is washcoated from the filter outlet end on the permeate side of the filter by standard washcoat methods, dried and sintered at 750 ° C.

Claims (6)

触媒壁流フィルターの製造方法であって、次の工程：
（ａ）壁流フィルター本体に、ガス透過性多孔質隔壁によって隔てられた複数の長手入口流路及び出口流路を与え；
（ｂ）窒素酸化物と一酸化炭素及び水素とを反応させてアンモニアにするのに活性のある第１触媒組成物と、アンモニアと反応することにより窒素酸化物を窒素に選択的還元するのに活性のある第２触媒組成物とを含む触媒ウォッシュコートを与え、ここで、該第１触媒組成物は、該多孔質隔壁の平均粒径よりも小さいモード粒径を有し、該第２触媒組成物は、該多孔質隔壁の平均粒径よりも大きいモード粒径を有するものとし；
（ｃ）該触媒ウォッシュコートを該出口流路の出口端に導入することによって該フィルター本体に該ウォッシュコートを被覆し；そして
（ｄ）該被覆フィルター本体を乾燥させ熱処理して触媒微粒子フィルターを得ることを含む、前記製造方法。 A method for producing a catalyst wall flow filter comprising the following steps:
(A) providing the wall flow filter body with a plurality of longitudinal inlet channels and outlet channels separated by a gas permeable porous partition;
(B) a first catalyst composition that is active in reacting nitrogen oxides with carbon monoxide and hydrogen to form ammonia, and selectively reducing nitrogen oxides to nitrogen by reacting with ammonia; A catalyst washcoat comprising an active second catalyst composition, wherein the first catalyst composition has a mode particle size smaller than the average particle size of the porous partition walls, and the second catalyst The composition has a mode particle size larger than the average particle size of the porous partition;
(C) coating the filter body with the washcoat by introducing the catalyst washcoat into the outlet end of the outlet channel; and (d) drying and heat-treating the coated filter body to obtain a catalyst particulate filter. The manufacturing method. 前記窒素酸化物をアンモニアに転化させるのに活性な触媒がパラジウム、白金、パラジウムとロジウムとの混合物及びパラジウムと白金とロジウムとの混合物を含む、請求項１に記載の方法。   The process of claim 1, wherein the catalyst active to convert the nitrogen oxides to ammonia comprises palladium, platinum, a mixture of palladium and rhodium and a mixture of palladium, platinum and rhodium. 前記窒素酸化物をアンモニアに転化させるのに活性な触媒がパラジウムからなる、請求項１に記載の方法。   The process of claim 1 wherein the catalyst active to convert the nitrogen oxides to ammonia comprises palladium. 前記窒素酸化物の選択的還元に活性な触媒がゼオライト、シリカアルミニウムホスフェート、イオン交換ゼオライト、鉄及び／又は銅で活性の高められたシリカアルミニウムホスフェート、１種以上の卑金属酸化物、のうちの少なくとも一つを含む、請求項１〜３のいずれか一つに記載の方法。   The active catalyst for selective reduction of nitrogen oxide is at least one of zeolite, silica aluminum phosphate, ion exchange zeolite, silica aluminum phosphate enhanced with iron and / or copper, and one or more base metal oxides. 4. The method according to any one of claims 1 to 3, comprising one. 次の工程：
アンモニアの酸化に活性な触媒組成物を含有する第２ウォッシュコートを与え；そして
出口流路の一部に出口端の領域で該第２ウォッシュコートを被覆すること
をさらに含む、請求項１〜４のいずれか一つに記載の方法。 Next step:
The method further comprises providing a second washcoat containing a catalyst composition active in oxidizing ammonia; and coating a portion of the outlet flow path with the second washcoat in the region of the outlet end. The method as described in any one of. 請求項１〜５のいずれか一つに従って製造される触媒壁流フィルター。   A catalyst wall flow filter produced according to any one of claims 1-5.
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