JPH0796195A - Exhaust gas purification catalyst - Google Patents
Exhaust gas purification catalystInfo
- Publication number
- JPH0796195A JPH0796195A JP5265670A JP26567093A JPH0796195A JP H0796195 A JPH0796195 A JP H0796195A JP 5265670 A JP5265670 A JP 5265670A JP 26567093 A JP26567093 A JP 26567093A JP H0796195 A JPH0796195 A JP H0796195A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- pronto
- powder
- zeolite
- purifying catalyst
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000000746 purification Methods 0.000 title abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 26
- 239000010457 zeolite Substances 0.000 claims abstract description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229940018489 pronto Drugs 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- -1 lanthanum alkoxide Chemical class 0.000 claims 2
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 150000002603 lanthanum Chemical class 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- QIMZHEUFJYROIY-UHFFFAOYSA-N [Co].[La] Chemical group [Co].[La] QIMZHEUFJYROIY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000010757 Reduction Activity Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 241000877463 Lanio Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明に関係ある分野】この発明は、自動車の排ガスに
含まれるＮＯx の処理に使用される排ガス浄化触媒、特
に、プロント交換ゼオライトを改良するところの排ガス
浄化触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying catalyst used for treating NO x contained in an automobile exhaust gas, and more particularly to an exhaust gas purifying catalyst for improving a pronto exchange zeolite.
【０００２】[0002]
【背景技術】自動車の排ガスに含まれる有害成分は、Ｃ
Ｏ、低級炭化水素（ＨＣ）、ＮＯx、およびＳＯx など
で、近年は、それらを処理する各種の触媒が開発されて
きた。ところが、その開発された触媒の処理条件は極め
て狭い温度範囲に限定され、例えば、ＮＯx 処理のため
に開発された銅−ゼオライト（Ｃｕ−ＺＳＭ−５）で
は、ＮＯx 除去能は、高温域で高いが、低温域（２００
〜４００℃）で低く、また、プロント交換ゼオライト
（Ｈ−ＺＳＭ−５）では、ＮＯx 除去能は、低温域で高
いが、高温域（４００〜６００℃）で低いので、実車に
搭載することを難しくしているのが現状である。BACKGROUND ART Hazardous components contained in automobile exhaust gas are C
In recent years, various catalysts for treating O, lower hydrocarbons (HC), NO x , SO x, etc. have been developed. However, the treatment conditions of the developed catalyst are limited to an extremely narrow temperature range. For example, in the case of copper-zeolite (Cu-ZSM-5) developed for NO x treatment, the NO x removal ability is high. High in low temperature range (200
It is low at ~ 400 ° C), and with Pronto exchanged zeolite (H-ZSM-5), the NO x removal capacity is high in the low temperature range, but low in the high temperature range (400 to 600 ° C). It is the current situation that makes it difficult.
【０００３】[0003]
【発明の課題】この発明の課題は、広い温度範囲におい
て高いＮＯx 除去能を有し、そして、自動車の排ガスに
含まれるＮＯx を低減して環境汚染を抑制するところの
排ガス浄化触媒の提供にある。An object of the present invention is to provide an exhaust gas purifying catalyst which has a high NO x removal ability in a wide temperature range and reduces NO x contained in the exhaust gas of an automobile to suppress environmental pollution. It is in.
【０００４】[0004]
【課題に相応する手段およびそれの作用】この発明は、
ペロブスカイトをプロント交換ゼオライトに加え、広い
温度範囲で高いＮＯx 除去能を得て自動車の排ガスに含
まれるＮＯx を触媒処理可能にするところである。[Means corresponding to the problem and its action]
By adding perovskite to the pronto exchanged zeolite, a high NO x removal ability can be obtained in a wide temperature range to enable catalytic treatment of NO x contained in automobile exhaust gas.
【０００５】[0005]
【具体例の説明】以下、この発明の排ガス浄化触媒の特
定された具体例について説明する。その排ガス浄化触媒
は、ペロブスカイト（ＬａＣｏＯ3 、ＬａＮｉＯ3 な
ど）から選択されるランタン・コバルト系ペロブスカイ
ト（ＬａＣｏＯ3 ）をプロント交換ゼオライト（Ｈ−Ｚ
ＳＭ−５）に加えるところであって、先ず、そのプロン
ト交換ゼオライトの粉末にアルコキシド溶液から製され
るランタン・コバルト系ペロブスカイトの粉末を混合さ
せて製造される。そのプロブスカイト、すなわち、その
ランタン・コバルト系ペロブスカイト（ＬａＣｏＯ3 ）
の添加量は２０〜９０％が最適範囲である。そして、そ
の排ガス浄化触媒は粉末で反応管にセットされて評価試
験が行なわれた。そのサンプル評価試験は、常圧固定床
流通型反応装置で実施した。また、その際、ガスの組成
が、ＮＯ：５００ｐｐｍ、Ｏ2 ：４％、Ｃ3 Ｈ8 ：１０
００ｐｐｍ、ＳＯ2 ：１００ｐｐｍになるようにＨｅで
バランスをとった混合ガスを使用した。そして、反応生
成物の分析および定量は、ガスクロマト・グラフで行な
った。また、後述する触媒活性は、全てＮＯx 転化率で
評価した。[Explanation of Specific Examples] Specific examples of the exhaust gas purifying catalyst of the present invention will be described below. The exhaust gas purifying catalyst is a lanthanum-cobalt-based perovskite (LaCoO 3 ) selected from perovskites (LaCoO 3 , LaNiO 3 etc.) as a pronto exchange zeolite (H-Z).
It is added to SM-5), and it is produced by first mixing the powder of the pronto-exchanged zeolite with the powder of lanthanum-cobalt-based perovskite produced from the alkoxide solution. The perovskite, that is, the lanthanum-cobalt-based perovskite (LaCoO 3 ).
The optimum addition amount of 20 to 90% is. Then, the exhaust gas purifying catalyst was set as powder in a reaction tube and an evaluation test was conducted. The sample evaluation test was carried out in an atmospheric fixed bed flow reactor. At that time, the composition of the gas is NO: 500 ppm, O 2 : 4%, C 3 H 8 : 10
A mixed gas that was balanced with He so that the concentration was 00 ppm and SO 2 : 100 ppm was used. Then, the analysis and quantification of the reaction product was carried out by gas chromatography. In addition, all the catalytic activities described below were evaluated by the NO x conversion rate.
【０００６】そのようにして製造されたその排ガス浄化
触媒を使ってそのガスに含まれているＮＯx を除去処理
したところ、図１に示されたＮＯ還元活性の反応温度依
存性が得られた。その排ガス浄化触媒、すなわち、その
ランタン・コバルト系ペロブスカイト（ＬａＣｏＯ3 ）
添加のプロント交換ゼオライト（Ｈ−ＺＳＭ−５）のＮ
Ｏx 転化率１、２、３と、そのペロブスカイトを添加し
ないプロント交換ゼオライト（Ｈ−ＺＳＭ−５）とを比
較して、そのランタン・コバルト系プロブスカイト（Ｌ
ａＣｏＯ3 ）添加のプロント交換ゼオライト（Ｈ−ＺＳ
Ｍ−５）の活性は高温域（４００〜６００℃）でその無
添加のプロント交換ゼオライト（Ｈ−ＺＳＭ−５）のそ
れよりも向上された。その結果、このランタン・コバル
ト系プロブスカイト（ＬａＣｏＯ3 ）添加のプロント交
換ゼオライト（Ｈ−ＺＳＭ−５）では、広い温度範囲で
高いＮＯx 転化率、所謂、高いＮＯx 浄化率を示す領域
であるウィンドウがその無添加のプロント交換ゼオライ
ト（Ｈ−ＺＳＭ−５）に比べて幅広くなった。When the NO x contained in the gas was removed by using the thus produced exhaust gas purifying catalyst, the reaction temperature dependence of NO reduction activity shown in FIG. 1 was obtained. . The exhaust gas purifying catalyst, that is, the lanthanum-cobalt-based perovskite (LaCoO 3 ).
N of added pronto exchanged zeolite (H-ZSM-5)
The O x conversions 1, 2, and 3 were compared with the pronto exchange zeolite (H-ZSM-5) to which the perovskite was not added, and the lanthanum-cobalt-based perovskite (L
aCoO 3 ) added pronto exchanged zeolite (H-ZS
The activity of M-5) was improved in the high temperature range (400 to 600 ° C.) as compared with that of the additive-free pronto exchanged zeolite (H-ZSM-5). As a result, this lanthanum-cobalt-based perovskite (LaCoO 3 ) -added pronto exchange zeolite (H-ZSM-5) has a high NO x conversion rate in a wide temperature range, a so-called high NO x purification rate. The window became wider than that of the non-added pronto exchanged zeolite (H-ZSM-5).
【０００７】その前述された排ガス浄化触媒では、その
プロント交換ゼオライトの粉末にアルコキシド溶液から
製されるランタン・コバルト系ペロブスカイトの粉末を
混合させて製造されるところで説明されたが、そのプロ
ント交換ゼオライトの粉末にＬａおよびＮｉのアルコキ
シド溶液を直接含浸させ、乾燥させ、そして、焼成され
て製造されてもよく、また、ペロブスカイトは、例え
ば、Ｌａ塩の水溶液とＣｏ塩の水溶液との混合溶液を直
接そのプロント交換ゼオライト（Ｈ−ＺＳＭ−５）の粉
末に含浸させて乾燥し、そして、焼成してもよく、そし
て、それらの場合にも同様のＮＯ還元活性の反応温度依
存性が得られた。In the above-mentioned exhaust gas purifying catalyst, it was explained that it was produced by mixing the powder of the pronto-exchanged zeolite with the powder of lanthanum-cobalt-based perovskite produced from the alkoxide solution. The powder may be manufactured by directly impregnating an alkoxide solution of La and Ni, drying and calcining, and the perovskite may be prepared, for example, by directly mixing a mixed solution of an aqueous solution of La salt and an aqueous solution of Co salt. It may be impregnated with powder of pronto exchanged zeolite (H-ZSM-5), dried and calcined, and in these cases similar reaction temperature dependence of NO reduction activity was obtained.
【０００８】先に図面を参照して説明されたところのこ
の発明の特定された具体例から明らかであるように、こ
の発明の属する技術の分野における通常の知識を有する
者にとって、この発明の内容は、その発明の性質（ｎａ
ｔｕｒｅ）および本質（ｓｕｂｓｔａｎｃｅ）に由来
し、そして、それらを内在させると客観的に認められる
その他の態様に容易に具体化される。勿論、この発明の
内容は、その発明の課題に相応してその発明の成立に必
須である。As will be apparent from the specific embodiments of the present invention described above with reference to the drawings, those of ordinary skill in the art to which the present invention pertains have the subject matter of the present invention. Is the nature of the invention (na
It is easily embodied in other embodiments that are derived from the true) and substance and that are objectively recognized as having them internalized. Of course, the contents of the present invention are essential to the establishment of the invention in accordance with the problems of the invention.
【０００９】上述から理解されるように、この発明の排
ガス浄化触媒は、ペロブスカイトをプロント交換ゼオラ
イトに加えるので、この発明の排ガス浄化触媒では、高
温域（４００〜６００℃）においてＮＯx 除去能が向上
されて広い温度範囲で高いＮＯx 除去能が得られ、自動
車の排ガスに含まれるＮＯx が広い温度範囲で除去・低
減可能になり、それに伴って自動車の走行条件に広い範
囲で適応可能になり、そして、そのＮＯx による環境汚
染が抑制され、その結果、自動車にとって非常に有用で
実用的である。As can be understood from the above, since the exhaust gas purifying catalyst of the present invention adds perovskite to the pronto exchange zeolite, the exhaust gas purifying catalyst of the present invention has a NO x removing ability in a high temperature range (400 to 600 ° C.). high NO x removal performance in a wide temperature range is improved is obtained, NO x contained in the exhaust gas of the automobile to allow removal and reduced in a wide temperature range, adaptively with it a wide range of driving conditions of the motor vehicle becomes, and environmental pollution is suppressed due to the NO x, the result is a very useful and practical for automobiles.
【図面の簡単な説明】[Brief description of drawings]
【図１】この発明の排ガス浄化触媒の具体例でランタン
・コバルト系ペロブスカイト（ＬａＣｏＯ3 ）をプロン
ト交換ゼオライト（Ｈ−ＺＳＭ−５）に加えたところの
排ガス浄化触媒および無添加のプロント交換ゼオライト
のＮＯ還元活性の反応温度依存性を示すグラフである。FIG. 1 shows a specific example of the exhaust gas purifying catalyst of the present invention, in which a lanthanum-cobalt-based perovskite (LaCoO 3 ) is added to a pronto exchange zeolite (H-ZSM-5), It is a graph which shows reaction temperature dependence of NO reduction activity.
１ ペロブスカイト添加のプロント交換ゼオライト ２ ペロブスカイト添加のプロント交換ゼオライト ３ ペロブスカイト添加のプロント交換ゼオライト ４ 無添加のプロント交換ゼオライト 1 Perovskite-added pronto-exchanged zeolite 2 Perovskite-added pronto-exchanged zeolite 3 Perovskite-added pronto-exchanged zeolite 4 Non-added pronto-exchanged zeolite
───────────────────────────────────────────────────── 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 53/36 １０２ Ｈ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B01D 53/36 102 H
Claims (4)
トに加えるところの排ガス浄化触媒。1. An exhaust gas purifying catalyst in which a perovskite is added to a pronto exchange zeolite.
粉末で互いに混合される請求項１に記載の排ガス浄化触
媒。2. The exhaust gas purifying catalyst according to claim 1, wherein the zeolite and the perovskite are mixed with each other in the form of powder.
コキシド溶液およびコバルト・アルコキシド溶液の水溶
液を含浸する請求項１に記載の排ガス浄化触媒。3. The exhaust gas purifying catalyst according to claim 1, wherein the zeolite is a powder and is impregnated with an aqueous solution of a lanthanum alkoxide solution and a cobalt alkoxide solution.
びニッケル塩の水溶液を含浸する請求項１に記載の排ガ
ス浄化触媒。4. The exhaust gas purifying catalyst according to claim 1, wherein the zeolite is a powder and is impregnated with an aqueous solution of a lanthanum salt and a nickel salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5265670A JPH0796195A (en) | 1993-09-29 | 1993-09-29 | Exhaust gas purification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5265670A JPH0796195A (en) | 1993-09-29 | 1993-09-29 | Exhaust gas purification catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0796195A true JPH0796195A (en) | 1995-04-11 |
Family
ID=17420362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5265670A Pending JPH0796195A (en) | 1993-09-29 | 1993-09-29 | Exhaust gas purification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0796195A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2321416A (en) * | 1996-12-21 | 1998-07-29 | Daimler Benz Ag | Process and catalyst for decreasing pollutants in gases |
| CN102309971A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for hydro-treating catalyst |
| CN102310003A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN102309975A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst |
| CN102309970A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Hydro-treating catalyst and preparation method thereof |
| CN105680057A (en) * | 2016-01-12 | 2016-06-15 | 山东联星能源集团有限公司 | Preparation method for novel graphene catalyst used for metal air battery electrode |
| WO2018221692A1 (en) * | 2017-05-31 | 2018-12-06 | 国立大学法人北海道大学 | Functional structure and production method for functional structure |
| EP3632554A4 (en) * | 2017-05-31 | 2021-04-21 | Furukawa Electric Co., Ltd. | Oxidation catalyst structure for exhaust gas purification and production method thereof, exhaust gas treatment device for vehicle, catalyst molded body, and gas purification method |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
| US11648542B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11648538B2 (en) | 2017-05-31 | 2023-05-16 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11655157B2 (en) | 2017-05-31 | 2023-05-23 | National University Corporation Hokkaido University | Functional structural body and method for making functional structural body |
| US11654422B2 (en) | 2017-05-31 | 2023-05-23 | Furukawa Electric Co., Ltd. | Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization |
| US11666894B2 (en) | 2017-05-31 | 2023-06-06 | Furukawa Electric Co., Ltd. | Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water |
| US11680211B2 (en) | 2017-05-31 | 2023-06-20 | Furukawa Electric Co., Ltd. | Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization |
| US11684909B2 (en) | 2017-05-31 | 2023-06-27 | Furukawa Electric Co., Ltd. | Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon |
| US12030041B2 (en) | 2017-05-31 | 2024-07-09 | Furukawa Electric Co., Ltd. | Structured catalyst for steam reforming, reforming apparatus provided with structured catalyst for steam reforming, and method for manufacturing structured catalyst for steam reforming |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6168764B1 (en) | 1996-12-12 | 2001-01-02 | Daimlerchrysler Ag | Method and catalyst for reducing pollutants in gases |
| GB2321416A (en) * | 1996-12-21 | 1998-07-29 | Daimler Benz Ag | Process and catalyst for decreasing pollutants in gases |
| GB2321416B (en) * | 1996-12-21 | 1999-04-21 | Daimler Benz Ag | Process and catalyst for decreasing pollutants in gases |
| CN102309971A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for hydro-treating catalyst |
| CN102310003A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN102309975A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst |
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