JPH09155206A - Production of exhaust gas purifying catalyst - Google Patents
Production of exhaust gas purifying catalystInfo
- Publication number
- JPH09155206A JPH09155206A JP31897195A JP31897195A JPH09155206A JP H09155206 A JPH09155206 A JP H09155206A JP 31897195 A JP31897195 A JP 31897195A JP 31897195 A JP31897195 A JP 31897195A JP H09155206 A JPH09155206 A JP H09155206A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carrier
- raw material
- platinum
- catalyst raw
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は排気ガス浄化用触媒
の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an exhaust gas purifying catalyst.
【０００２】[0002]
【従来の技術】従来より、比表面積の大きい触媒担体上
に、金属あるいは金属酸化物等の微粒子を担持した触媒
が広く利用されている。自動車排気ガス浄化用触媒にお
いても、活性アルミナをコートしたモノリス担体上に白
金、パラジウム又はロジウム等の触媒金属を担持した触
媒が広く用いられている。そして、触媒金属を均一微細
に担持することによって高性能の触媒を開発する努力が
なされており、触媒の製造方法として一般的な含浸法に
おいても使用原料や処理方法などが種々検討されてい
る。2. Description of the Related Art Conventionally, catalysts in which fine particles such as metal or metal oxide are supported on a catalyst carrier having a large specific surface area have been widely used. As a catalyst for purifying automobile exhaust gas, a catalyst in which a catalytic metal such as platinum, palladium or rhodium is carried on a monolith carrier coated with activated alumina is widely used. Efforts have been made to develop a high-performance catalyst by uniformly and finely supporting a catalyst metal, and various raw materials and treatment methods have been studied in a general impregnation method as a catalyst production method.
【０００３】前記含浸法以外にも物理的蒸着法（ＰＶＤ
法）や化学的蒸着法（ＣＶＤ法）を用いて触媒金属を均
一微細に担持する試みも行われている。例えば、特開平
２−２０７８４２号公報には、フッ化白金およびフッ化
ロジウム等の混合気体を用いて担持する方法が開示され
ている。また、特開平４−１８７２４７号公報には活性
アルミナをコートしたメタル平板担体を１０００℃以上
に加熱し、ＰＶＤ法またはＣＶＤ法で触媒金属を担持し
た後、モノリスハニカム状に加工する方法が開示されて
いる。In addition to the above impregnation method, a physical vapor deposition method (PVD
Method) or a chemical vapor deposition method (CVD method) is used to uniformly and finely support the catalyst metal. For example, Japanese Patent Application Laid-Open No. 2-207842 discloses a method of supporting using a mixed gas of platinum fluoride and rhodium fluoride. Further, Japanese Patent Application Laid-Open No. 4-187247 discloses a method of heating a metal flat plate carrier coated with activated alumina to 1000 ° C. or higher, carrying a catalyst metal by PVD method or CVD method, and then processing it into a monolith honeycomb shape. ing.
【０００４】[0004]
【発明が解決しようとする課題】含浸法は、含浸させた
溶液が乾燥する際に、触媒成分の凝集が起こりやすい。
一方、溶液を使用しないＰＶＤ法やＣＶＤ法は均一微細
に触媒金属を担持するために有効な手段である。しかし
ＰＶＤ法は触媒原料のまわりこみがないため、複雑な形
状の担体に触媒金属を担持することは困難である。一方
ＣＶＤ法においては原料ガスを担体へ運ぶための窒素等
のキャリアガス、あるいは吸着したガスを還元するため
の水素ガス等を使用する必要があり、ガス配管を伴った
複雑な装置が必要であった。In the impregnation method, when the impregnated solution is dried, the catalyst components tend to aggregate.
On the other hand, the PVD method and the CVD method which do not use a solution are effective means for supporting the catalyst metal uniformly and finely. However, since the PVD method has no wraparound of the catalyst raw material, it is difficult to support the catalyst metal on the carrier having a complicated shape. On the other hand, in the CVD method, it is necessary to use a carrier gas such as nitrogen for carrying the raw material gas to the carrier, or hydrogen gas for reducing the adsorbed gas, and thus a complicated device with gas piping is required. It was
【０００５】本発明の目的は、排気ガス浄化用触媒担体
に、従来の含浸法に比べて触媒金属成分を均一微細に担
持できるＣＶＤ法を簡易な装置で実施する方法を提供す
ることである。An object of the present invention is to provide a method for carrying out a CVD method in which a catalyst metal component can be uniformly and finely loaded on an exhaust gas purifying catalyst carrier in a simple apparatus as compared with a conventional impregnation method.
【０００６】[0006]
【課題を解決するための手段】本発明は請求項１に記載
した排気ガス浄化用触媒の製造方法であり、この方法は
従来のＣＶＤ法の様にキャリアガス等を必要としないた
め、配管等が不要となり、簡単な装置でＣＶＤ法が実施
できる。またこの方法で製造された触媒は、湿式法に比
べ触媒成分が均一微細に担持されており、耐久性能が向
上する。SUMMARY OF THE INVENTION The present invention is a method for producing an exhaust gas purifying catalyst as set forth in claim 1. This method does not require a carrier gas or the like as in the conventional CVD method, and therefore piping and the like. Is unnecessary, and the CVD method can be performed with a simple apparatus. Further, the catalyst produced by this method has the catalyst components uniformly and finely loaded as compared with the wet method, and the durability performance is improved.
【０００７】前記担体の温度は、担体全体に均一に触媒
を担持させるため、担体と原料ガスとの反応確率を低く
抑えられる程度の低温が望ましい。また、このとき原料
の昇華を早める等の理由で、担体と原料に温度差をもう
けてもよい。The temperature of the carrier is preferably low enough to suppress the reaction probability between the carrier and the raw material gas so that the catalyst is uniformly supported on the entire carrier. Further, at this time, a temperature difference may be provided between the carrier and the raw material for the reason of speeding up sublimation of the raw material.
【０００８】密閉容器内は、原料の昇華を早めるため、
なるべく低い圧力に保つことが好ましい。また、前記触
媒担体は活性アルミナをコートしたモノリス担体が好ま
しい。In the closed container, to accelerate the sublimation of the raw materials,
It is preferable to keep the pressure as low as possible. The catalyst carrier is preferably a monolith carrier coated with activated alumina.
【０００９】前記触媒原料は、有機金属化合物が好まし
く、有機金属化合物としては白金、ロジウム、パラジウ
ム、ニッケル、クロム、鉄、モリブデン、コバルト、バ
ナジウム、チタン、ジルコニウム、スズ、ルテニウム、
銅、銀、金、イリジウム、アルカリ土類金属、アルカリ
金属等の有機化合物、具体的にはアセチルアセトナト等
のアセタート、シクロオクタジエンやノボルナジエン等
のジエン、トリフェニルホスフィンやトリエチルホスフ
ィン等のホスフィン、アセトニトリルやベンゾニトリル
等のニトリル、ジベンザルアセトン等のケトン、シクロ
ヘキセンやエチレン等のアルケン、カルボニル、アミ
ン、アニル、硫化ジエチル、ベンゾナート、ペントナー
ト、ブチレート等を含む錯体が挙げられる。The catalyst raw material is preferably an organometallic compound, and as the organometallic compound, platinum, rhodium, palladium, nickel, chromium, iron, molybdenum, cobalt, vanadium, titanium, zirconium, tin, ruthenium,
Organic compounds such as copper, silver, gold, iridium, alkaline earth metals and alkali metals, specifically, acetates such as acetylacetonato, dienes such as cyclooctadiene and nobornadiene, phosphines such as triphenylphosphine and triethylphosphine, Examples thereof include nitriles such as acetonitrile and benzonitrile, ketones such as dibenzalacetone, alkenes such as cyclohexene and ethylene, carbonyl, amine, anyl, diethyl sulfide, benzonate, pentonate, butyrate and the like.
【００１０】本発明の製造方法により調製された触媒
は、ＣＶＤ法により担持されているため、触媒成分が均
一微細に担持されており、触媒活性に優れている。この
とき、キャリアガス、還元ガスなどを使用しないため、
簡単な装置で高性能な触媒を得ることができる。Since the catalyst prepared by the production method of the present invention is supported by the CVD method, the catalyst components are uniformly and finely supported, and the catalyst activity is excellent. At this time, since no carrier gas or reducing gas is used,
A high performance catalyst can be obtained with a simple device.
【００１１】[0011]
（実施例１）図１において、触媒原料の有機金属錯体で
ある白金アセチルアセトナートを装填した石英ボート２
と、モノリス担体１をガラス製真空容器４の中に設置し
た。このモノリス担体は、全体の直径が１２０mm、長さ
１２０mmの円柱形であり、厚さ１８０μｍのコーデェラ
イト壁で断面正方形のセルを形成し、セル密度は１イン
チ平方の中に４００のセルが存在し、さらに活性アルミ
ナをモノリス１Ｌあたり１２０ｇコートしたものであ
る。(Example 1) In FIG. 1, a quartz boat 2 loaded with platinum acetylacetonate, which is an organometallic complex as a catalyst raw material,
Then, the monolith carrier 1 was set in the glass vacuum container 4. This monolithic carrier has a cylindrical shape with a total diameter of 120 mm and a length of 120 mm, and a cordelite wall with a thickness of 180 μm forms a square cell with a cross section. The cell density is 400 cells in 1 inch square. Further, 120 g of activated alumina was coated per 1 L of the monolith.
【００１２】コック５を開き、真空ポンプ６により真空
容器４の中を真空に引いた。コック５を閉じた後真空ホ
ース７をはずし、真空容器４を恒温槽に入れて１５０℃
に加熱した。白金アセチルアセトナートは真空容器４の
中で昇華し、モノリス担体１で分解し白金となった。こ
のため、後処理等が不要であり、またキャリアガスも使
用しないため、簡単な装置によりＣＶＤが実施できた。
このときの白金担持量は、１．５ｇ／Ｌであった。The cock 5 was opened, and the inside of the vacuum container 4 was evacuated by the vacuum pump 6. After closing the cock 5, remove the vacuum hose 7, put the vacuum vessel 4 in a constant temperature bath, and set it at 150 ° C.
Heated. Platinum acetylacetonate sublimated in the vacuum container 4 and decomposed in the monolith carrier 1 to become platinum. Therefore, no post-treatment is required and no carrier gas is used, so that the CVD can be carried out by a simple apparatus.
The amount of platinum carried at this time was 1.5 g / L.
【００１３】（実施例２）図２において、モノリス担体
１を担体設置面が通気可能な構造である台８の上に設置
し、白金アセチルアセトナートを装填した石英ボート
２、ロジウムアセチルアセトナートを装填した石英ボー
ト３とともに真空容器４の中に設置したこと以外は、実
施例１と同じ方法で触媒を製造した。このときの担持量
は白金１．５ｇ／Ｌ、ロジウム０．３ｇ／Ｌであった。(Embodiment 2) In FIG. 2, a monolith carrier 1 is placed on a table 8 having a structure where the carrier mounting surface is ventilated, and a quartz boat 2 loaded with platinum acetylacetonate and rhodium acetylacetonate are installed. A catalyst was produced in the same manner as in Example 1, except that the catalyst was installed in the vacuum vessel 4 together with the loaded quartz boat 3. The supported amounts at this time were 1.5 g / L of platinum and 0.3 g / L of rhodium.
【００１４】（比較例１）実施例１，２で使用したのと
同じ、活性アルミナをコートしたモノリス担体を、ジニ
トロジアンミン白金溶液に１時間浸漬し、１００℃で１
時間乾燥した後、４００℃で焼成した。このときの白金
担持量は１．５ｇ／Ｌであった。Comparative Example 1 The same monolith carrier coated with activated alumina as used in Examples 1 and 2 was immersed in a dinitrodiammine platinum solution for 1 hour, and the monolith carrier was heated at 100 ° C. for 1 hour.
After drying for an hour, it was baked at 400 ° C. The amount of platinum supported at this time was 1.5 g / L.
【００１５】（比較例２）実施例１，２で使用したのと
同じ、活性アルミナをコートしたモノリス担体を用い、
比較例１と同じ方法で白金１．５ｇ／Ｌを担持した。さ
らに塩化ロジウム溶液を用いて、同様にロジウム０．３
ｇ／Ｌを担持した。Comparative Example 2 The same monolith carrier coated with activated alumina as used in Examples 1 and 2 was used.
Platinum (1.5 g / L) was loaded in the same manner as in Comparative Example 1. Furthermore, using a rhodium chloride solution, rhodium 0.3
Supported g / L.
【００１６】（試験例１）前記実施例１、比較例１で製
造された触媒を、大気中で９００℃、８０Hr加熱し耐久
試験を行った。この結果を表１に示す。この後、試験片
として直径１５mm、長さ１０mmの円柱形に切り出し、下
記の条件で一酸化炭素の浄化率を測定した。さらに、触
媒の粒径をＴＥＭ（透過型電子顕微鏡）観察により測定
した。 条件：触媒温度：４００，４５０，５００℃；空間速度
（ＳＶ）＝５０，０００hr-1；空燃比（Ａ／Ｆ）＝１
４．６相当モデルガス。 その結果を表１に示す。(Test Example 1) The catalysts produced in Example 1 and Comparative Example 1 were heated in the air at 900 ° C. for 80 hours to carry out a durability test. Table 1 shows the results. Then, a test piece was cut into a cylindrical shape having a diameter of 15 mm and a length of 10 mm, and the carbon monoxide purification rate was measured under the following conditions. Further, the particle size of the catalyst was measured by TEM (transmission electron microscope) observation. Conditions: catalyst temperature: 400, 450, 500 ° C .; space velocity (SV) = 50,000 hr −1 ; air-fuel ratio (A / F) = 1
4.6 equivalent model gas. Table 1 shows the results.
【００１７】（試験例２）前記実施例２、比較例２で製
造された触媒を大気中で９００℃、８０Hr加熱し耐久試
験を行った。この結果を表２に示す。この後、試験片と
して直径１５mm、長さ１０mmの円柱形に切り出し、下記
の条件で、一酸化炭素、プロパン、一酸化窒素の浄化率
を測定した。さらに触媒の粒径をＴＥＭ観察により測定
した。 条件：触媒温度：４００，５００，６００℃；ＳＶ＝４
２，０００hr-1；Ａ／Ｆ＝１４．６。 その結果を表２に示す。(Test Example 2) The catalysts produced in Example 2 and Comparative Example 2 were heated in the air at 900 ° C. for 80 hours to carry out a durability test. Table 2 shows the results. Thereafter, a test piece was cut into a cylindrical shape having a diameter of 15 mm and a length of 10 mm, and the purification rates of carbon monoxide, propane and nitric oxide were measured under the following conditions. Further, the particle size of the catalyst was measured by TEM observation. Conditions: catalyst temperature: 400, 500, 600 ° C .; SV = 4
2,000 hr −1 ; A / F = 14.6. Table 2 shows the results.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】表１，２から明らかなように、実施例１及
び２で製造された排ガス浄化用触媒は、白金等の触媒金
属がＣＶＤ法により担体に均一微細に担持されているた
め、比較例により製造された排ガス浄化用触媒よりも耐
久性能がすぐれている。As is clear from Tables 1 and 2, the exhaust gas-purifying catalysts produced in Examples 1 and 2 have a comparatively fine catalytic metal such as platinum supported on the carrier by the CVD method. Durability is superior to the exhaust gas purifying catalyst manufactured by.
【図１】実施例１で用いた装置の概略側面図。FIG. 1 is a schematic side view of an apparatus used in Example 1.
【図２】実施例２で用いた装置の概略側面図。FIG. 2 is a schematic side view of an apparatus used in Example 2.
１…モノリス担体 ２，３…触媒原料 ４…密閉容器 ５…コック ６…真空ポンプ ７…真空ホース 1 ... Monolith carrier 2, 3 ... Catalyst raw material 4 ... Closed container 5 ... Cock 6 ... Vacuum pump 7 ... Vacuum hose
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大山 尚久 愛知県西尾市下羽角町岩谷14番地 株式会 社日本自動車部品総合研究所内 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Naohisa Oyama 14 Iwatani, Shimohakaku-cho, Nishio-shi, Aichi Japan Auto Parts Research Institute, Inc.
Claims (5)
閉容器内に配置し、前記触媒原料を昇華させ、担体上に
分解温度以上で分解担持させることを特徴とする排気ガ
ス浄化用触媒の製造方法。1. An exhaust gas purifying catalyst, characterized in that a catalyst carrier and a sublimable catalyst raw material are placed in the same closed container, the catalyst raw material is sublimated, and decomposed and supported on the carrier at a decomposition temperature or higher. Manufacturing method.
したモノリス担体である請求項１の製造方法。2. The method according to claim 1, wherein the catalyst carrier is a monolith carrier coated with activated alumina.
請求項１又は２の製造方法。3. The method according to claim 1, wherein the catalyst raw material is an organometallic compound.
属錯体である請求項３の製造方法。4. The method according to claim 3, wherein the catalyst raw material is an acetylacetonato metal complex.
加熱してゆく請求項１〜４のいずれかの製造方法。5. The manufacturing method according to claim 1, wherein the whole is heated while the pressure inside the closed container is reduced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31897195A JPH09155206A (en) | 1995-12-07 | 1995-12-07 | Production of exhaust gas purifying catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31897195A JPH09155206A (en) | 1995-12-07 | 1995-12-07 | Production of exhaust gas purifying catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09155206A true JPH09155206A (en) | 1997-06-17 |
Family
ID=18105044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31897195A Withdrawn JPH09155206A (en) | 1995-12-07 | 1995-12-07 | Production of exhaust gas purifying catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09155206A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008149289A (en) * | 2006-12-20 | 2008-07-03 | Hitachi Ltd | Gas cleaning method, gas cleaning catalyst, and exhaust gas cleaning apparatus |
| JP2008259993A (en) * | 2007-04-13 | 2008-10-30 | Tokyo Metropolitan Univ | Method for dispersing and fixing gold fine particle to carrier, gold fine particle-deposited carrier obtained thereby, catalyst and colorant |
-
1995
- 1995-12-07 JP JP31897195A patent/JPH09155206A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008149289A (en) * | 2006-12-20 | 2008-07-03 | Hitachi Ltd | Gas cleaning method, gas cleaning catalyst, and exhaust gas cleaning apparatus |
| JP2008259993A (en) * | 2007-04-13 | 2008-10-30 | Tokyo Metropolitan Univ | Method for dispersing and fixing gold fine particle to carrier, gold fine particle-deposited carrier obtained thereby, catalyst and colorant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7166323B2 (en) | Method of coating catalyst carrier layer of metal-metal oxide, method of depositing active catalyst particles onto metal substrates for preparing metal monolith catalyst modules, and module thereby | |
| CN101052743B (en) | Divided solid composition made from particles with continuous metal deposition, and its manufacturing method and its application as catalyst mode | |
| Tanaka et al. | Preparation of palladium and silver alloy membrane on a porous α-alumina tube via simultaneous electroless plating | |
| US5782959A (en) | Process for preparing a composite inorganic membrane for hydrogen separation | |
| Hierso et al. | MOCVD of rhodium, palladium and platinum complexes on fluidized divided substrates: Novel process for one‐step preparation of noble‐metal catalysts | |
| CN1306459A (en) | Method for producing shell catalysts by CVD process | |
| JPS61245848A (en) | Manufacture of catalyst for purifying waste gas | |
| US8518845B2 (en) | Catalytic nanoporous membranes | |
| JPS62155937A (en) | Production of catalytic body carrying gold and gold composite oxide | |
| CN109277109B (en) | Composite catalyst and preparation method thereof, application | |
| US5217939A (en) | Catalyst for the prduction of nitric acid by oxidation of ammonia | |
| CA2883503A1 (en) | Catalyst for producing hydrogen and method for producing hydrogen | |
| JP2014065033A (en) | Method for producing metal-carbon composite supported catalyst using co-vaporization method for producing hydrogen, and metal-carbon composite supported catalyst for producing hydrogen produced thereby | |
| US5256387A (en) | Catalyst for the production of nitric acid by oxidation of ammonia | |
| Lam et al. | A new system design for the preparation of copper/activated carbon catalyst by metal-organic chemical vapor deposition method | |
| JP2001522408A (en) | Skeletal columnar coating | |
| JPH09155206A (en) | Production of exhaust gas purifying catalyst | |
| Carlton et al. | Fundamental considerations of carbonyl metallurgy | |
| JP2005518277A (en) | Method for producing shell-type catalyst | |
| JP2005528981A (en) | Hydrometallurgical process for the production of supported catalysts | |
| JP2019167266A (en) | Manufacturing method and manufacturing apparatus of carbon structure | |
| JPH08206517A (en) | Exhaust gas purifying catalyst | |
| US20030022788A1 (en) | Ceramic catalyst body | |
| JP4758081B2 (en) | Catalyst body, catalyst body for exhaust gas purification, and method for producing catalyst body | |
| US20140066299A1 (en) | Particles Containing One Or More Multi-Layered Dots On Their Surface, Their Use, and Preparation of Such Particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20030304 |