JP3506292B2 - Automobile exhaust purification method - Google Patents
Automobile exhaust purification methodInfo
- Publication number
- JP3506292B2 JP3506292B2 JP26143095A JP26143095A JP3506292B2 JP 3506292 B2 JP3506292 B2 JP 3506292B2 JP 26143095 A JP26143095 A JP 26143095A JP 26143095 A JP26143095 A JP 26143095A JP 3506292 B2 JP3506292 B2 JP 3506292B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- alumina
- exhaust gas
- zsm
- silver
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Exhaust Gas After Treatment (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、自動車排気の窒素
酸化物除去触媒及び窒素酸化物除去方法の技術分野に属
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention belongs to the technical field of a catalyst for removing nitrogen oxides from automobile exhaust and a method for removing nitrogen oxides.
【０００２】[0002]
【従来の技術】従来、ディーゼルエンジン等における排
気ガス中の窒素酸化物除去触媒及び窒素酸化物除去方法
としは多々あるが、触媒を直列に配置するタンデム型と
しては、排気通路において、軽油を還元剤とし、上流側
にＣｕ／アルミナ系複合酸化物等を用いた触媒Ａと、下
流側にＡｇ／アルミナ系複合酸化物等を用いたの触媒Ｂ
を配設したものがある（小笠原他；ディーゼル用Ｄｅ-
ＮＯXコンバータの実用化、自動車技術会学術講演会前
刷集２１７（１９９４−５）など）。2. Description of the Related Art Conventionally, there have been many catalysts for removing nitrogen oxides from exhaust gas in diesel engines and methods for removing nitrogen oxides. However, as a tandem type in which catalysts are arranged in series, light oil is reduced in the exhaust passage. Catalyst A using Cu / alumina-based composite oxide or the like on the upstream side, and Catalyst B using Ag / alumina-based composite oxide or the like on the downstream side
There are some that have been installed (Ogasawara et al .; De- for diesel
Practical application of NO X converter, Preprints 217 (1994-5), etc., of the Automotive Engineering Society Academic Lecture).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、このよ
うなリーンバーンエンジンの排気通路において、軽油を
還元剤とし、上流側にＣｕ／アルミナ系複合酸化物等を
用いた触媒Ａと、下流側にＡｇ／アルミナ系複合酸化物
等を用いた触媒Ｂを配設した自動車排気浄化装置では、
低温から幅広い温度範囲でのＮＯX 活性を有し改善はみ
られるものの、自動車用ディーゼルエンジンに必要な３
００℃以下の低温域でのＮＯX 活性が十分でなく、さら
には最高ＮＯX 活性も不十分という欠点がある。However, in the exhaust passage of such a lean burn engine, a catalyst A using light oil as a reducing agent and Cu / alumina-based composite oxide or the like on the upstream side, and Ag on the downstream side are used. In an automobile exhaust gas purification device provided with a catalyst B using / alumina-based composite oxide,
Although improvements have NO X activity in a wide temperature range from low observed, 3 required to automotive diesel engine
There is a drawback that the NO X activity in a low temperature range of 00 ° C. or lower is not sufficient and the maximum NO X activity is also insufficient.
【０００４】 本発明は上記問題を解決するものであっ
て、低温（特に２５０℃以下）から高温（４００℃）ま
での幅広い温度領域で高いＮＯX 浄化性能を発揮させる
ことができる自動車排気浄化方法を提供することを目的
とする。The present invention solves the above problem, and is an automobile exhaust gas purification method capable of exhibiting high NO x purification performance in a wide temperature range from low temperature (especially 250 ° C. or lower) to high temperature (400 ° C.). The purpose is to provide.
【０００５】[0005]
【課題を解決するための手段】そのために従来の窒素酸
化物除去触媒及び窒素酸化物除去方法に対して、まず還
元剤としてメタノール等のアルコールを添加剤として用
い、さらに排気通路の上流側に銀を含有させたアルミナ
を用いた触媒Ａ、下流側にインジウム（Ｉｎ）、ガリウ
ム（Ｇａ）から選ばれた一種の金属を含有させたゼオラ
イトの一種であるＺＳＭ−５を用いた触媒Ｂを配設させ
ている。なお、下流側の触媒Ｂは、これ以外に銀／モル
デナイト等の他の金属担持ゼオライトでもよい。また、
上流側の触媒Ａすなわち銀担持アルミナにおける銀の担
持量は、金属換算で０．１〜５ｗｔ％程度が好ましい。
一方、下流側のインジウム、ガリウム担持量も金属換算
で０．１〜５ｗｔ％程度が好ましい。To this end, an alcohol such as methanol is used as an additive as a reducing agent in the conventional nitrogen oxide removing catalyst and the nitrogen oxide removing method, and silver is further provided upstream of the exhaust passage. And a catalyst B using ZSM-5, which is a kind of zeolite containing one kind of metal selected from indium (In) and gallium (Ga), is provided on the downstream side. I am letting you. The downstream catalyst B may be other metal-supported zeolite such as silver / mordenite. Also,
The amount of silver supported on the upstream catalyst A, that is, silver-supported alumina, is preferably about 0.1 to 5 wt% in terms of metal.
On the other hand, the amount of indium and gallium supported on the downstream side is preferably about 0.1 to 5 wt% in terms of metal.
【０００６】[0006]
【作用および発明の効果】本発明において触媒Ｂに用い
ているインジウム、ガリウムを担持したＺＳＭ−５は、
還元剤としてジメチルエーテルを用いると、絶対値は低
いものの比較的低温でＮＯX 活性を有し、触媒Ａに用い
ている銀担持アルミナ中のアルミナは、メチルアルコー
ルを脱水してジメチルエーテルを生成する作用を有す
る。よって、これら２種の触媒を直列（上流側：Ａｇ／
アルミナ、下流側：Ｉｎ／ＺＳＭ−５またはＧａ／ＺＳ
Ｍ−５）に配設すると、銀担持アルミナがＩｎ／ＺＳＭ
−５またはＧａ／ＺＳＭ−５に有効な還元剤を生成する
ため、低温でＮＯX 活性が発現する。また、銀担持アル
ミナは、比較的高温域でメチルアルコールを還元剤とし
て添加すると、ＮＯX 活性を有することも知られてい
る。ACTION AND EFFECTS OF THE INVENTION ZSM-5 carrying indium and gallium used as the catalyst B in the present invention is
When dimethyl ether is used as the reducing agent, it has a low absolute value but has NO X activity at a relatively low temperature, and the alumina in the silver-supported alumina used for the catalyst A acts to dehydrate methyl alcohol to produce dimethyl ether. Have. Therefore, these two catalysts are connected in series (upstream side: Ag /
Alumina, downstream: In / ZSM-5 or Ga / ZS
M-5), the silver-supported alumina becomes In / ZSM.
To generate an effective reducing agent to -5 or Ga / ZSM-5, NO X activity is expressed at a low temperature. Further, the silver on alumina, upon addition of methyl alcohol at a relatively high temperature region as a reducing agent is also known to have a NO X activity.
【０００７】本発明は、これらの相乗効果、すなわち
銀担持アルミナによって生成したジメチルエーテルによ
るＩｎ／ＺＳＭ−５またはＧａ／ＺＳＭ−５のＮＯX 活
性、銀担持アルミナ自身のメチルアルコールによるＮ
ＯX 活性、により低温から高温まで幅広い温度領域で高
いＮＯX 浄化性能を発揮させることができる。The present invention provides these synergistic effects, namely, the NO x activity of In / ZSM-5 or Ga / ZSM-5 by dimethyl ether produced by silver-supported alumina, N by the methyl alcohol of silver-supported alumina itself.
O X activity, makes it possible to exhibit a high NO X purification performance in a wide temperature range from low temperatures to high temperatures.
【０００８】[0008]
【実施例】以下、本発明の実施例について説明する。EXAMPLES Examples of the present invention will be described below.
【０００９】［実施例１］γ−アルミナを主たる成分と
する比表面積１７０ｍ2／ｇを有する活性アルミナに金
属換算でＡｇが３ｗｔ％となるように硝酸銀に含有させ
た粉末を５０ｇ、アルミナゾル３７．５ｇおよび水１７
２．５ｇを磁性ボールミルに投入し、粉砕してスラリー
を得た。このスラリーを塗布量２ｇ／個になるようにコ
ーデェライト製モノリス担体基材に塗布し乾燥後、５０
０℃で２時間空気中で焼成し、触媒Ａとした。なお、触
媒容量は０．０２６Ｌとした。Example 1 50 g of powder obtained by adding silver nitrate to activated alumina having γ-alumina as a main component and having a specific surface area of 170 m 2 / g so that Ag was 3 wt% in terms of metal, and alumina sol 37. 5 g and water 17
2.5 g was put into a magnetic ball mill and pulverized to obtain a slurry. This slurry was applied to a cordierite monolith carrier base material so that the coating amount was 2 g / piece, and after drying, 50
It was calcined in air at 0 ° C. for 2 hours to obtain a catalyst A. The catalyst capacity was 0.026L.
【００１０】次に、ゼオライトの一種であるＺＳＭ−５
粉末に金属換算でＩｎが３ｗｔ％となるように硝酸イン
ジウム水溶液に含浸させ担持させた。得られた粉末５０
ｇ、アルミナゾル３７．５ｇおよび水１７２．５ｇを磁
性ボールミルに投入し、粉砕してスラリーを得た。この
スラリーを塗布量２ｇ／個になるようにコーデェライト
製モノリス担体基材に塗布し乾燥後、５００℃で２時間
空気中で焼成し、触媒Ｂとした。なお、触媒容量は０．
０２６Ｌとした。Next, ZSM-5 which is a kind of zeolite
The powder was impregnated with and supported by an indium nitrate aqueous solution so that In was 3 wt% in terms of metal. The obtained powder 50
g, 37.5 g of alumina sol and 172.5 g of water were put into a magnetic ball mill and pulverized to obtain a slurry. This slurry was applied to a cordierite monolith carrier substrate so that the coating amount was 2 g / unit, dried, and then calcined in air at 500 ° C. for 2 hours to obtain a catalyst B. The catalyst capacity is 0.
It was set to 026L.
【００１１】図１は本発明に用いた実験装置を示し、得
られたモノリス型触媒Ａ、Ｂを、排気上流側に触媒Ａ、
下流側に触媒Ｂを装填しタンデム触媒とした。従って、
触媒容量はトータル０．０５２Ｌとなった。このタンデ
ム触媒を排ガス中に配置し、メチルアルコールを還元剤
として触媒Ａの前に添加し、触媒Ａの温度をヒータ１に
より２７５℃と４００℃との２段階で変化させ、触媒Ｂ
の温度をヒータ２により２２５℃に調節し、タンデム触
媒の入口と出口でＮＯX 濃度とＨＣ濃度を測定した。FIG. 1 shows an experimental apparatus used in the present invention. The obtained monolithic catalysts A and B are the catalysts A and B on the exhaust upstream side.
A catalyst B was loaded on the downstream side to obtain a tandem catalyst. Therefore,
The total catalyst capacity was 0.052L. This tandem catalyst was placed in the exhaust gas, methyl alcohol was added as a reducing agent before catalyst A, and the temperature of catalyst A was changed by heater 1 in two steps of 275 ° C. and 400 ° C.
Was adjusted to 225 ° C. by the heater 2 and the NO x concentration and the HC concentration were measured at the inlet and outlet of the tandem catalyst.
【００１２】［実施例２］実施例１における触媒Ｂをガ
リウム含有ＺＳＭ−５にする以外は同様にして、タンデ
ム触媒の入口と出口でＮＯX 濃度とＨＣ濃度を測定し
た。[0012] [Example 2] except that the catalyst B in Example 1 to gallium-containing ZSM-5 was similarly measured NO X concentration and HC concentration at the inlet and outlet of the tandem catalyst.
【００１３】［比較例１］実施例１において、触媒Ａに
銅含有アルミナ、触媒Ｂに銀含有アルミナを用いる以外
は同様にして、タンデム触媒の入口と出口でＮＯX 濃度
とＨＣ濃度を測定した。Comparative Example 1 The NO x concentration and the HC concentration were measured at the inlet and outlet of the tandem catalyst in the same manner as in Example 1 except that the catalyst A was copper-containing alumina and the catalyst B was silver-containing alumina. .
【００１４】［比較例２］実施例１において、触媒Ｂに
触媒Ｂと同仕様のＡｇアルミナ（容量０．０２６Ｌ）を
用いる以外は同様にして、タンデム触媒の入口と出口で
ＮＯX 濃度とＨＣ濃度を測定した。[0014] In Comparative Example 2 Example 1, except for using the catalyst B and Ag-alumina having the same specifications (capacity 0.026L) to the catalyst B in the same manner, NO X concentration and HC at the inlet and outlet of the tandem catalyst The concentration was measured.
【００１５】上記各実施例および比較例についてディー
ゼルエンジン排気ガスを用いて下記条件で性能評価試験
を行った結果を表１に示す。表１に示すように、実施例
の触媒は、低温から高温まで幅広い温度領域で優れたＮ
ＯX 浄化性能が得られている。Table 1 shows the results of a performance evaluation test conducted under the following conditions using diesel engine exhaust gas for each of the examples and comparative examples. As shown in Table 1, the catalysts of Examples have excellent N in a wide temperature range from low temperature to high temperature.
O X purification performance is obtained.
【００１６】（性能評価条件） ディーゼル実ガス ＨＣ＝２５００ｐｐｍ（Ｃ1換算） ＮＯ＝６５０ｐｐｍ Ｏ2＝１５％ Ｈ2Ｏ＝０．５％ みかけＳＶ＝１７，５０００ｈ-1 (Performance evaluation conditions) Diesel actual gas HC = 2500 ppm (C 1 conversion) NO = 650 ppm O 2 = 15% H 2 O = 0.5% Apparent SV = 17,5000 h -1
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明において用いた実験装置を説明するため
の図である。FIG. 1 is a diagram for explaining an experimental device used in the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−336（ＪＰ，Ａ) 特開 平７−232035（ＪＰ，Ａ) 特開 平９−85057（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 53/00 - 53/96 B01J 21/00 - 38/74 ＪＳＴＰｌｕｓ（ＪＯＩＳ) ＣＡｐｌｕｓ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-336 (JP, A) JP-A-7-232035 (JP, A) JP-A-9-85057 (JP, A) (58) Field (Int.Cl. 7 , DB name) B01D 53/00-53/96 B01J 21/00-38/74 JSTPlus (JOIS) CAplus (STN)
Claims (2)
を含有させたアルミナを用いた触媒と、下流側に金属を
１種以上含有させたゼオライトの一種であるＺＳＭ−５
を用いた触媒を配設し、メチルアルコールを排ガスに添
加し、該排ガスを前記触媒に２００℃〜４００℃で接触
させることを特徴とする自動車排気浄化方法。In an exhaust passage of an internal combustion engine, a catalyst using alumina containing silver on the upstream side and ZSM-5, which is one of zeolites containing one or more metals on the downstream side.
A catalyst using is used to add methyl alcohol to the exhaust gas.
And contact the exhaust gas with the catalyst at 200 to 400 ° C.
A method for purifying exhaust gas of an automobile, which comprises:
属はインジウム、ガリウムから選ばれた一種以上である
ことを特徴とする請求項１記載の自動車排気浄化方法。2. The method for purifying automobile exhaust gas according to claim 1, wherein in the catalyst using ZSM-5, the metal is at least one selected from indium and gallium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26143095A JP3506292B2 (en) | 1995-10-09 | 1995-10-09 | Automobile exhaust purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26143095A JP3506292B2 (en) | 1995-10-09 | 1995-10-09 | Automobile exhaust purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09103649A JPH09103649A (en) | 1997-04-22 |
| JP3506292B2 true JP3506292B2 (en) | 2004-03-15 |
Family
ID=17361776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26143095A Expired - Fee Related JP3506292B2 (en) | 1995-10-09 | 1995-10-09 | Automobile exhaust purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3506292B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0020287D0 (en) | 2000-08-17 | 2000-10-04 | Aea Technology Plc | The catalytic treatment of gases |
| JP4647960B2 (en) * | 2004-09-10 | 2011-03-09 | バブコック日立株式会社 | Glass melting furnace exhaust gas treatment method and treatment apparatus |
| US7803338B2 (en) * | 2005-06-21 | 2010-09-28 | Exonmobil Research And Engineering Company | Method and apparatus for combination catalyst for reduction of NOx in combustion products |
| US7396517B2 (en) * | 2005-08-05 | 2008-07-08 | Gm Global Technology Operations, Inc. | Reduction of NOx emissions using a staged silver/alumina catalyst system |
| KR100892483B1 (en) * | 2006-08-11 | 2009-04-10 | 현대자동차주식회사 | Dual bed catalytic system for the reduction of NOx |
| US7891171B2 (en) | 2006-12-05 | 2011-02-22 | GM Global Technology Operations LLC | Hybrid catalyst for NOx reduction using fuel hydrocarbons as reductant |
-
1995
- 1995-10-09 JP JP26143095A patent/JP3506292B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09103649A (en) | 1997-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB2514177A (en) | Oxidation catalyst for a compression ignition engine | |
| JP4703818B2 (en) | Exhaust gas purification catalyst and exhaust gas purification method | |
| JP3272019B2 (en) | Exhaust gas purification catalyst | |
| JP3506292B2 (en) | Automobile exhaust purification method | |
| JPH0884911A (en) | Catalyst for decomposing nitrogen oxide and method for purifying diesel engine exhaust using the same | |
| JP3282344B2 (en) | Exhaust gas purification device | |
| KR101274468B1 (en) | Oxidation Catalyst for purifying the exhaust gas of diesel engine | |
| JPH06343829A (en) | Exhaust gas purifying method and catalyst used therefor | |
| KR101094241B1 (en) | Preparation process for oxidation Catalyst for purifying the exhaust gas of diesel engine | |
| KR20070064115A (en) | Catalyst compsition for diesel particulate filter and device for reduction of soot and smoke using the same | |
| JP3695394B2 (en) | Exhaust gas purification device and manufacturing method | |
| JP3252070B2 (en) | Automobile exhaust purification method | |
| JP3446184B2 (en) | Nitrogen oxide removal method | |
| JPH0568888A (en) | Waste gas cleaning catalyst | |
| JP3295989B2 (en) | Exhaust gas purification catalyst | |
| JP4107443B2 (en) | Nitrogen oxide removing catalyst and nitrogen oxide removing method | |
| KR100405470B1 (en) | A composition of diesel oxidation catalyst | |
| JP2848175B2 (en) | Automotive exhaust purification system | |
| KR100389900B1 (en) | Catalyst for the purification of diesel exhaust gas | |
| JP3311370B2 (en) | Exhaust purification catalyst system | |
| KR100809661B1 (en) | A catalyst for inhibiting the no2 generation | |
| JPH0838906A (en) | Catalyst for removing nitrogen oxide and removing method of nitrogen oxide | |
| KR100435365B1 (en) | A de-NOx catalyst for diesel engine and its constitution | |
| JP2966675B2 (en) | Exhaust treatment method | |
| JP3446183B2 (en) | Nitrogen oxide removal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20031210 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20031211 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091226 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091226 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101226 Year of fee payment: 7 |
|
| LAPS | Cancellation because of no payment of annual fees |