JP2731562B2 - Catalyst carrier and method for producing the same - Google Patents
Catalyst carrier and method for producing the sameInfo
- Publication number
- JP2731562B2 JP2731562B2 JP63334147A JP33414788A JP2731562B2 JP 2731562 B2 JP2731562 B2 JP 2731562B2 JP 63334147 A JP63334147 A JP 63334147A JP 33414788 A JP33414788 A JP 33414788A JP 2731562 B2 JP2731562 B2 JP 2731562B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon carbide
- sintered body
- silica film
- catalyst
- catalyst carrier
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910021426 porous silicon Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 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 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明はディーゼルエンジン等の内燃機関における
排気ガスを浄化処理するための触媒成分を担持可能な触
媒担体及びその製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a catalyst carrier capable of supporting a catalyst component for purifying exhaust gas in an internal combustion engine such as a diesel engine and a method for producing the same.
従来、例えばディーゼルエンジンの排気ガスを浄化す
る場合には、コージエライトによってハニカム状に形成
した触媒担体と、その触媒担体に担持された触媒成分と
を有するフィルターをディーゼルエンジンの排気側に接
続し、このフィルターによって前記排気ガス中のカーボ
ン,NOX及びHC等を酸化分解するようになっている。Conventionally, for example, when purifying exhaust gas of a diesel engine, a filter having a catalyst carrier formed in a honeycomb shape by cordierite and a catalyst component supported on the catalyst carrier is connected to the exhaust side of the diesel engine. is adapted to oxidize and decompose the carbon in the exhaust gas, NO X and HC and the like by the filter.
ところが、上記のフィルターにおける触媒担体は融点
（1200〜1300℃）の低いコージエライトによって形成さ
れているため、フィルター内において、排気ガスの不均
一な燃焼が生じて、局部的な温度上昇が生じると、触媒
担体が部分的に溶解する。そして、ディーゼルエンジン
の使用が停止されて、フィルターが冷却された時、前記
溶解部分から触媒担体にクラックが発生し、フィルター
の機能が低下するという問題があった。However, since the catalyst carrier in the filter is formed of cordierite having a low melting point (1200 to 1300 ° C.), in the filter, uneven combustion of exhaust gas occurs, and a local temperature rise occurs. The catalyst support partially dissolves. Then, when the use of the diesel engine is stopped and the filter is cooled, cracks are generated in the catalyst carrier from the dissolving portion, and the function of the filter is deteriorated.
上記の問題を解決するため、触媒担体として耐熱性及
び熱伝導性に優れた炭化珪素焼結体を使用することがす
でに提案されている（特開昭62−45344号公報）。この
４公報に開示された触媒担体においては、炭化珪素焼結
体にコロイダルシリカを浸透させた後に高温で加熱する
ことによって、焼結体内外における炭化珪素粒子の表面
に触媒担持用のシリカ膜を形成するようになっている。In order to solve the above problem, it has been already proposed to use a silicon carbide sintered body having excellent heat resistance and thermal conductivity as a catalyst carrier (Japanese Patent Application Laid-Open No. Sho 62-45344). In the catalyst carrier disclosed in these four publications, a silica film for carrying a catalyst is coated on the surfaces of silicon carbide particles inside and outside the sintered body by infiltrating colloidal silica into the silicon carbide sintered body and then heating it at a high temperature. Is formed.
そのため、コロイダルシリカという特別な材料が必要
になると共に、工程数が増加して手間がかかるばかりで
なく、焼結体の内部の細孔がコロイダルシリカ等の塗布
剤に閉塞され易く、焼結体の圧力損失が増大するという
問題がある。Therefore, a special material called colloidal silica is required, and the number of steps increases, which is not only troublesome, but also the pores inside the sintered body are easily blocked by a coating agent such as colloidal silica. There is a problem that the pressure loss increases.
この発明は上記の事情を考慮してなされたものであっ
て、その目的は炭化珪素焼結体の強度低下を招くことな
く、極めて簡単な方法によって触媒担体の孔部内面に所
望の厚さのシリカ膜を確実に形成することが可能な触媒
担体の製造方法を提供することにある。The present invention has been made in view of the above circumstances, and its purpose is to reduce the strength of a silicon carbide sintered body to a desired thickness on the inner surface of a hole of a catalyst carrier by a very simple method. An object of the present invention is to provide a method for producing a catalyst carrier capable of reliably forming a silica film.
上記の目的を達成するために、この発明では、予めハ
ニカム状に形成した多孔質炭化珪素焼結体を酸化雰囲気
にて所定温度で加熱することにより、この焼結体の孔部
内面において前記焼結体の炭化珪素の一部を酸化して触
媒担持用のシリカ膜を形成するようにしている。In order to achieve the above object, according to the present invention, a porous silicon carbide sintered body previously formed in a honeycomb shape is heated at a predetermined temperature in an oxidizing atmosphere, so that the sintered body is formed on the inner surface of a hole of the sintered body. A part of the silicon carbide of the binder is oxidized to form a silica film for supporting the catalyst.
又、炉の有効容積が0.4m3の場合、前記酸化雰囲気は
炭化珪素焼結体に対して毎分１〜20の割合で供給され
る空気によって形成され、かつ加熱温度及び加熱時間は
それぞれ600〜1200℃及び0.3〜10時間に設定されること
が望ましい。Further, if the effective volume of the furnace is 0.4 m 3, the oxidizing atmosphere is respectively formed by air supplied at a rate per minute to 20 with respect to the silicon carbide sintered body, and the heating temperature and the heating time 600 It is desirable that the temperature be set to ~ 1200 ° C and 0.3 to 10 hours.
上記の製造方法によって触媒担体を製造すると、多孔
質炭化珪素焼結体の孔部内面において、炭化珪素の一部
が酸化されて、炭化珪素結晶の表層部にシリカ膜が形成
される。シリカ膜を含む多孔質炭化珪素焼結体の酸素濃
度は0.005wt％から2wt％の範囲であることが必要であ
る。酸素濃度が0.005wt％より少ないと、前記焼結体の
孔部内面の表層に形成されるシリカ膜が薄く、貴金属元
素を有する酸化物系触媒を担持させる場合に、前記シリ
カ膜が剥離し、前記酸化物系触媒と多孔質炭化珪素焼結
体とのぬれ性が悪く、担体に十分な強度を持たせること
が困難になる。酸素濃度が2wt％より多いと、シリカ膜
が厚くなり、母体の多孔質炭化珪素焼結体との熱膨張の
ミスマッチングが生じて強度の劣化を生じる。酸素濃度
が0.006〜0.1wt％の範囲がより好ましい。When the catalyst carrier is manufactured by the above manufacturing method, a part of the silicon carbide is oxidized on the inner surface of the hole of the porous silicon carbide sintered body, and a silica film is formed on the surface layer of the silicon carbide crystal. The oxygen concentration of the porous silicon carbide sintered body including the silica film needs to be in the range of 0.005 wt% to 2 wt%. When the oxygen concentration is less than 0.005 wt%, the silica film formed on the surface layer on the inner surface of the pores of the sintered body is thin, and when the oxide catalyst having a noble metal element is supported, the silica film peels off. Poor wettability between the oxide catalyst and the porous silicon carbide sintered body makes it difficult for the carrier to have sufficient strength. If the oxygen concentration is more than 2 wt%, the silica film becomes thicker, causing a thermal expansion mismatch with the base porous silicon carbide sintered body, resulting in a deterioration in strength. The oxygen concentration is more preferably in the range of 0.006 to 0.1 wt%.
以下、この発明を図面に従って詳細に説明する。第１
図及び第２図に示すように、触媒担体を構成する基材１
は高い融点（〜3000℃）を有する多孔質炭化珪素焼結体
によってハニカム状に形成されると共に、全体として円
柱状をなしている。そして、この基材１には軸線方向に
平行に延びる多数のガス通過孔２が形成され、各ガス通
過孔２の供給側及び排出側のいずれか一端が炭化珪素質
の小片３によって交互に封止されている。この基材１に
おいて、各ガス通過孔２の内壁面には所定の酸素濃度
（0.005〜2wt％）を有するシリカ膜が形成されている。Hereinafter, the present invention will be described in detail with reference to the drawings. First
As shown in FIG. 2 and FIG.
Is formed in a honeycomb shape by a porous silicon carbide sintered body having a high melting point (up to 3000 ° C.), and has a columnar shape as a whole. A large number of gas passage holes 2 extending in parallel to the axial direction are formed in the substrate 1, and one end of each of the gas passage holes 2 on the supply side and the discharge side is alternately sealed with silicon carbide small pieces 3. Has been stopped. In the substrate 1, a silica film having a predetermined oxygen concentration (0.005 to 2 wt%) is formed on the inner wall surface of each gas passage hole 2.
そこで、触媒担体の製造方法について説明すると、先
ず、炭化珪素粉末を主成分とする原料により、例えば本
件出願人による特開昭61−259763号公報に記載された公
知の方法に従って、所定の密度，曲げ強度，比表面積及
び所定の酸素濃度（0.002〜0.8wt％、好ましくは0.0024
〜0.04wt％）を有するハニカム状基材１を焼成する。そ
して、この基材１を炭化珪素製の炉に入れた後、毎分１
〜20の空気を炉内に強制的に送り込んで循環させると
同時に、炉内の温度を0.3〜10時間にわたって600〜1200
℃の範囲の温度に保持する。Therefore, the method for producing the catalyst carrier will be described. First, a material having a predetermined density and a predetermined density are prepared by using a raw material containing silicon carbide powder as a main component, for example, according to a known method described in Japanese Patent Application Laid-Open No. 61-259763 by the present applicant. Flexural strength, specific surface area and predetermined oxygen concentration (0.002-0.8 wt%, preferably 0.0024
(0.04 wt%) is fired. Then, after placing the substrate 1 in a furnace made of silicon carbide,
~ 20 air is forced into the furnace and circulated, while the temperature in the furnace is raised to 600-1200 for 0.3-10 hours.
Keep at a temperature in the range of ° C.
この加熱温度が600℃未満であると、酸化反応が起こ
り難く、1200℃を越えると、酸化反応が進みすぎて、シ
リカ膜が焼結体内部まで形成されて、強度低下を招く。If the heating temperature is lower than 600 ° C., the oxidation reaction hardly occurs. If the heating temperature is higher than 1200 ° C., the oxidation reaction proceeds too much, and the silica film is formed to the inside of the sintered body, resulting in a decrease in strength.
上記の加熱処理により、各ガス通過孔２の内壁面及び
基材１の表面において、炭化珪素結晶の表層部が酸化さ
れ、所定の酸素濃度（0.005〜2wt％）のシリカ膜が形成
される。このシリカ膜は前記空気量，加熱時間，加熱温
度及び基材１の比表面積等に依存して変化するため、こ
れらを制御することにより、所望の酸素濃度の均一なシ
リカ膜を形成できる。その後、前記シリカ膜に、白金に
代表される白金族元素やその他の金属元素及びその酸化
物等からなる酸化触媒を担持させれば、内燃機関等の排
気ガス浄化用フィルターが形成される。By the above-described heat treatment, the surface layer portion of the silicon carbide crystal is oxidized on the inner wall surface of each gas passage hole 2 and the surface of substrate 1, and a silica film having a predetermined oxygen concentration (0.005 to 2 wt%) is formed. The silica film changes depending on the amount of air, the heating time, the heating temperature, the specific surface area of the substrate 1, and the like. By controlling these, a uniform silica film having a desired oxygen concentration can be formed. Thereafter, an oxidation catalyst comprising a platinum group element represented by platinum, another metal element, an oxide thereof, or the like is supported on the silica film to form an exhaust gas purification filter for an internal combustion engine or the like.
そして、排気ガスが排気通路４内において、第１図に
矢印で示すように、その供給側から基材１内に導入され
ると、ガス通過孔２間の壁部により、排気ガス中のカー
ボンやHC等が濾過されると共に、シリカ膜上の触媒によ
り、酸化される。そして、浄化された排気ガスが基材１
から排出される。When the exhaust gas is introduced into the base material 1 from the supply side as shown by an arrow in FIG. 1 in the exhaust passage 4, the carbon in the exhaust gas is formed by the wall between the gas passage holes 2. And HC are filtered and oxidized by the catalyst on the silica membrane. Then, the purified exhaust gas is supplied to the substrate 1
Is discharged from
尚、触媒を基材１のシリカ膜に担持させるには、下記
の方法を使用できる。即ち、 （ａ） 触媒成分を含むスラリーを基材１の一端面側か
ら吹き掛ける。The following method can be used to support the catalyst on the silica film of the substrate 1. That is, (a) a slurry containing a catalyst component is sprayed from one end surface side of the substrate 1.
（ｂ） 触媒成分を含むスラリー中に基材１を数回浸漬
する。この場合、触媒成分を基材１の中央部よりも両端
部に多く担持させたり、その逆にしたりする。(B) The substrate 1 is immersed several times in the slurry containing the catalyst component. In this case, a larger amount of the catalyst component is supported on both ends than the center of the substrate 1 or vice versa.
（ｃ） 触媒成分を含むスラリーを塗布する。(C) Apply a slurry containing a catalyst component.
β型の結晶構造を有する炭化珪素粉末を主成分とする
原料の押出成形加工により、密度が1.2g/cm3,曲げ強度
が180kg/cm2,比表面積が0.7m2/g,酸素濃度が0.008wt％
のハニカム状基材１を形成し、この基材１を有効容積が
0.4m3の炉内に入れ、その炉内に毎分１の空気を強制
的に供給しながら、800℃で１時間にわたって加熱し
た。それにより、ガス通過孔２の内面全体に、酸素濃度
として0.02wt％のシリカ膜が形成され、シリカ膜の形成
後に基材１の曲げ強度が低下することもなかった。Extrusion molding of a raw material mainly composed of silicon carbide powder having a β-type crystal structure has a density of 1.2 g / cm 3 , a bending strength of 180 kg / cm 2 , a specific surface area of 0.7 m 2 / g, and an oxygen concentration of 0.008wt%
To form a honeycomb substrate 1 having an effective volume of
The furnace was placed in a 0.4 m 3 furnace and heated at 800 ° C. for 1 hour while forcing 1 minute of air into the furnace. As a result, a silica film having an oxygen concentration of 0.02 wt% was formed on the entire inner surface of the gas passage hole 2, and the bending strength of the substrate 1 did not decrease after the formation of the silica film.
以上詳述したように、請求項１記載の発明は炭化珪素
焼結体の強度低下を招くことなく、極めて簡単な方法に
よって触媒担体の孔部内面に所望のシリカ膜を確実に形
成することができるという優れた効果を発揮する。As described in detail above, the invention of claim 1 makes it possible to reliably form a desired silica film on the inner surface of the hole of the catalyst carrier by an extremely simple method without causing a decrease in the strength of the silicon carbide sintered body. It has an excellent effect of being able to do it.
また、請求項２及び３記載の発明は最適な厚さのシリ
カ膜が形成される触媒担体を得ることができるという優
れた効果を発揮する。Further, the inventions according to claims 2 and 3 exhibit an excellent effect that a catalyst support on which a silica film having an optimum thickness is formed can be obtained.
第１図はこの発明の製造方法によって製造される触媒担
体の断面図、第２図は側面図である。 １……基材、２……ガス通過孔。FIG. 1 is a sectional view of a catalyst carrier produced by the production method of the present invention, and FIG. 2 is a side view. 1 ... substrate, 2 ... gas passage holes.
Claims (3)
焼結体を酸化雰囲気にて所定温度で加熱することによ
り、この焼結体の孔部内面において前記焼結体の炭化珪
素の一部を酸化して触媒担持用のシリカ膜を形成するこ
とを特徴とする触媒担体の製造方法。1. A porous silicon carbide sintered body previously formed in a honeycomb shape is heated at a predetermined temperature in an oxidizing atmosphere, so that a portion of the silicon carbide of the sintered body is formed on an inner surface of a hole of the sintered body. Oxidizing to form a silica film for supporting a catalyst.
結体の孔部内面に触媒担持用のシリカ膜が形成され、そ
のシリカ膜を含む多孔質炭化珪素焼結体の酸素濃度は0.
005wt％から2wt％であることを特徴とする触媒担体。2. A catalyst-supporting silica film is formed on the inner surface of the pores of a porous silicon carbide sintered body formed in a honeycomb shape, and the oxygen concentration of the porous silicon carbide sintered body including the silica film is 0%. .
A catalyst carrier characterized by being 005 wt% to 2 wt%.
は炭化珪素結晶の表層部に存在することを特徴とする請
求項２に記載の触媒担体。3. The catalyst carrier according to claim 2, wherein oxygen in the porous sintered body including the silica film is present in a surface portion of a silicon carbide crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63334147A JP2731562B2 (en) | 1988-12-29 | 1988-12-29 | Catalyst carrier and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63334147A JP2731562B2 (en) | 1988-12-29 | 1988-12-29 | Catalyst carrier and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02180641A JPH02180641A (en) | 1990-07-13 |
| JP2731562B2 true JP2731562B2 (en) | 1998-03-25 |
Family
ID=18274056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63334147A Expired - Lifetime JP2731562B2 (en) | 1988-12-29 | 1988-12-29 | Catalyst carrier and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2731562B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790248B2 (en) | 2000-12-25 | 2004-09-14 | Denso Corporation | Exhaust gas purification filter |
| EP2441513A1 (en) * | 2010-10-13 | 2012-04-18 | Ibiden Co., Ltd. | Honeycomb catalyst body and method for manufacturing honeycomb catalyst body |
| JP2012076953A (en) * | 2010-09-30 | 2012-04-19 | Tokyo Yogyo Co Ltd | Silicon carbide honeycomb body |
| JP2012076954A (en) * | 2010-09-30 | 2012-04-19 | Tokyo Yogyo Co Ltd | Method for producing silicon carbide honeycomb body |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2666520B1 (en) * | 1990-09-06 | 1993-12-31 | Pechiney Recherche | METHOD FOR ACTIVATION OF THE SURFACE OF HEAVY METAL CARBIDES WITH A HIGH SPECIFIC SURFACE FOR CATALYTIC REACTIONS. |
| EP1666146A4 (en) * | 2003-08-12 | 2009-07-01 | Ngk Insulators Ltd | Silicon carbide based catalyst material and method for preparation thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0624636B2 (en) * | 1985-08-26 | 1994-04-06 | 工業技術院長 | Catalyst carrier and method for producing the same |
-
1988
- 1988-12-29 JP JP63334147A patent/JP2731562B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790248B2 (en) | 2000-12-25 | 2004-09-14 | Denso Corporation | Exhaust gas purification filter |
| JP2012076953A (en) * | 2010-09-30 | 2012-04-19 | Tokyo Yogyo Co Ltd | Silicon carbide honeycomb body |
| JP2012076954A (en) * | 2010-09-30 | 2012-04-19 | Tokyo Yogyo Co Ltd | Method for producing silicon carbide honeycomb body |
| EP2441513A1 (en) * | 2010-10-13 | 2012-04-18 | Ibiden Co., Ltd. | Honeycomb catalyst body and method for manufacturing honeycomb catalyst body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02180641A (en) | 1990-07-13 |
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