JP2001520569A

JP2001520569A - Catalyst support and catalyst for high temperature treatment and catalytic method using the same

Info

Publication number: JP2001520569A
Application number: JP50762497A
Authority: JP
Inventors: ワン，ルイピン
Original assignee: Tanaka Kikinzoku Kogyo KK
Current assignee: Tanaka Kikinzoku Kogyo KK
Priority date: 1995-07-27
Filing date: 1996-07-16
Publication date: 2001-10-30
Also published as: KR19990035866A; EP0842111A1; EP0842111A4; WO1997005057A1; CA2226291A1; CN1192190A; AU6497496A

Abstract

(57)【要約】本発明は、ＨｆＯ₂の量が１０００℃を越える温度でも触媒担持体に熱安定性を与えられる量である、燃焼触媒などの高温触媒処理で使用するＨｆＯ₂含有触媒担持体に関し、さらに、そのＨｆＯ₂含有担持体に担持された不均一系白金属の金属触媒、および、ＨｆＯ₂含有担持体が活性触媒の担持体ウォッシュコートとして使われている単体触媒構造に関する。また、ＨｆＯ₂含有担持体を利用する触媒および触媒体構造を使った触媒燃焼などの高温触媒処理法を、説明する。 (57) Abstract: The present invention provides an HfO ₂ -containing catalyst support used in a high-temperature catalyst treatment of a combustion catalyst or the like, which is an amount capable of imparting thermal stability to a catalyst support even when the amount of HfO ₂ exceeds 1000 ° C. It relates the body, further, heterogeneous platinum group metal catalyst supported on the HfO ₂ containing carrier, and a unitary catalyst structure HfO ₂ containing carrier is used as a support washcoat of the active catalyst. In addition, a catalyst using an HfO ₂ -containing support and a high-temperature catalyst treatment method such as catalytic combustion using a catalyst structure will be described.

Description

【発明の詳細な説明】高温処理用の触媒担持体と触媒およびそれを使用した触媒法発明の分野本発明は、高温触媒作用のための安定した耐熱性担持体、その耐熱性担持体を使う触媒と触媒体構造、および、その触媒および／または触媒体構造を使用した高温触媒処理法に関する。詳しく言えば、本発明は、反応温度が１０００℃を越えるような処理例においてその担持体に熱安定性を与えられるのに十分な量のＨｆＯ₂などの熱安定性ハフニウム化合物を含有する改良された触媒担持体、その担持体上にディポジットされた１つまたはそれ以上の白金属金属、あるいは、その担持体で被膜された金属基体をもつ触媒体、および、高温における安定作用とその他の作用特性を獲得するために前記の触媒またはその触媒体構造が利用される、部分酸化作用つまり触媒燃料燃焼などの高温触媒処理法を目的とする。発明の背景例えば、ＣＯとＨ₂へのメタンの蒸気改質、合成ガスへの炭化水素類の部分酸化、自動車排気制御を含むガス排気制御のための炭化水素類の完全燃焼、ガスタービン、燃焼炉、ボイラなどにおける燃料の触媒燃焼などの、さまざまな産業上重要な触媒処理は、一般的に高温で行われる。どの場合でも、使われる触媒は、触媒作用をする物質や材質が不活性つまり耐熱性の酸化金属担持体で担持された不均一系触媒である。その触媒作用を最大限にするため、不均一系触媒は、一般的に活性触媒物質の拡大露出面を形成できるよう構成されている。その構成目的とは、触媒の作用の増進に加えて、触媒成分が非常に高価な貴金属を含む場合でも、経済的な利益を得られるよう、触媒成分の利用を最適化することである。不均一系触媒が耐熱性酸化物担持体上に担持された貴金属などの触媒作用金属である場合、触媒物質の露出面を大きくするため、担持体の表面積が重要となる。これに関しては、担持体の大きな表面積と多孔性構造の結果、触媒物質の粒子が酸化物担持体の表面積上に広い間隔をおいて分布されるので、触媒要素が物理的に分離できるのである。しかし、不均一系触媒が高い反応温度で作用すると、金属粒子や金属酸化物粒子などの触媒要素が焼結を起こし、その結果、触媒粒子が大きくなって、触媒露出面が減少してしまう。さらに、高温の環境下で担持体表面積が減少すると、活性触媒成分がいっそうの焼結を起こす。この状態は、触媒作用および触媒利用のコスト効率を低下させるため、望ましいものではない。そのため、活性な触媒成分がディポジットさせるされる広い表面積をもつ熱安定性で耐熱性の担持体が必要となるのである。高温処理における不均一系触媒担体の問題点として、（１）高温での担持体および／または触媒作用物質の表面積の減少、（２）蒸気中における触媒の過度の焼結、（３）担持体／触媒相互作用による触媒作用毒性が挙げられる。今までに、高温での触媒処理（触媒燃焼や自動車排気抑制）において、その高温での耐熱性や活性触媒物質との適合性から、ジルコニウム（ＺｒＯ₂）が担持体として使われてきた。例えば、デラベッタらの米国特許第５、２５９、７５４号では、パラジウムから成る活性触媒物質のジルコニウム含有担持体が金属箔触媒体構造形状で使用されており、燃焼における触媒温度を安定的に制限できるよう、耐熱性の担持体と、少なくとも複数の金属基体面上に被膜された触媒作用金属から成る。しかしながら、空気中で高温処理を行うと、ＺｒＯ₂の表面積がかなり減少してしまう。この表面積の減少は、水蒸気が存在する場合、いっそう加速されることになる。ＺｒＯ₂にシリカ（ＳｉＯ₂）を添加すればＺｒＯ₂の熱安定性を少しは増加できるが、温度が１０００℃ほどになるとその補強安定性も維持できず、ＳｉＯ₂で安定化されたＺｒＯ₂の表面積が大きく減少し、蒸気が存在すれば、表面積の減少がさらにひどくなってしまう。そのため、多様な触媒処理用の担持体としての耐熱性酸化物材の市販リストにおいては、ハフニウムの酸化物や水酸化物がもっとも一般的に取り上げられている。例えば、米国特許第２，３７５，４０２号；４，１８９，４０５号；４，２４０，９８３号；４，２８４，５３１号；４，６４８，９７５号；４，６８１，８６７号；５，２０４，０８号；ヨーロッパ特許出願第０２５７９８３号，日本特許出願（昭５７）１８，６３９号；英国特許第１，３７７，０６３号などである。しかし、その従来例のどれもが、ハフニウム酸化物とジルコニウム酸化物との違いを明白に説明していないし、燃料の触媒燃焼などの高温触媒処理におけるのユニークな安定性を指摘していない。発明の要旨本発明は、広義の意味で、ＨｆＯ₂の量が約１０００℃を越える高温において担持体に熱安定性を確保できる分量である、ＳｉＯ₂またはＳｉＯ₂とＺｒＯ₂とが混合されたＨｆＯ₂から成る不均一系触媒に使用する耐熱性金属酸化物担持体を提供することを目的とする。さらに、本発明による高温での触媒作用のための改良された不均一系触媒は、ＳｉＯ₂またはＳｉＯ₂とＺｒＯ₂の混合物と組み合わされたＨｆＯ₂で構成された前記の耐熱性担持体上にディポジットされた有効触媒作用量の白金属の金属または白金属金属の混合物から成る。さらにまた、本発明の範囲のおける触媒体構造は、流動反応混合物が通過する複数の縦方向通路を具備し、少なくとも通路の一部分が、ＨｆＯ₂、あるいは、ＳｉＯ₂またはＳｉＯ₂とＺｒＯ₂が混合されたＨｆＯ₂から選択されたＨｆＯ₂含有耐熱性担持体で通路ウォッシュコートで被膜されており、前記のウォッシュコートで被覆された少なくとも通路の一部に有効触媒作用量の白金属金属またはその混合物がディポジットされている。さらに本発明の好適な特徴として、気体状または蒸発可能な燃料の部分酸化または完全燃焼に特に有効な触媒体構造は、流動する気体反応混合物の通過のための隣接配備された触媒被膜チャンネルと非触媒チャンネルの束で構成された金属箔基体から成り、触媒が被膜されたチャンネルとそれに隣接する非触媒チャンネルとは熱交換関係で構成されており、かつ、触媒被膜チャンネルが、有効触媒作用量の白金属の金属または白金属金属の混合物で被膜されており、その上に白金属金属の触媒がディポジットされているような、ＨｆＯ₂だけ、または必要に応じて、ＳｉＯ₂またはＳｉＯ₂とＺｒＯ₂の混合物と組み合わされたＨｆＯ₂から成る前記の耐熱性担持体のウォッシュコートを有する。また本発明の範囲における改良された高温触媒処理方法は、前記の本発明の触媒および触媒体構造を使うものであって、特に、本発明の好適実施例の前記の触媒体構造を使って燃料混合物を燃焼する改良処理法を含むものである。本発明の耐熱性担持体の長所は、例えば、ＺｒＯ₂またはＳｉＯ₂安定化ＺｒＯ₂ 担持体などと比較して、酸素および／または水蒸気が存在する高温環境において非常に高い熱安定性を与えるだけでなく、パラジウムなどの白金属金属がＺｒＯ₂ またはＳｉＯ₂安定化ＺｒＯ₂上に担持される場合に高温で見られるような焼結増加が、本発明の耐熱性担持体では観測されないことである。さらに、本発明の耐熱性担持体は、白金属金属触媒と高い親和性をもち、担持体に付随する触媒汚染が発生しない。最後に、白金属金属（特にパラジウム）を使う本発明の触媒体構造におけるウォッシュコートとして利用する場合では、本発明のＨｆＯ₂含有耐熱性担持体は、従来のＺｒＯ₂またはＳｉＯ₂安定化ＺｒＯ₂ のウォッシュコートでの温度よりも低い消火温度（ＬＯＴ）を含む、触媒燃焼処理例において卓越した性能を備えている。図面の簡単な説明図１は、従来技術のＺｒＯ₂含有担持体の安定性を示す温度／表面積のグラフ図である。図２Ａ、２Ｂ、３Ａ、３Ｂは、従来技術のＺｒＯ₂含有担持体の安定性を本発明の耐熱性担持体と表面積および触媒サイズの点で比較した温度特性図である。図４は、２つの異なる温度で所定期間焼成したときの、従来担持体や本発明の担持体を含む多様な耐熱性担持体の表面で発生する変化を示す棒グラフ図である。図５は、蒸気の存在下の高温での拡大期間における、従来担持体や本発明の担持体を含む多様な耐熱性担持体の表面安定性を示す時間グラフ図である。図６は、所定期間の焼成の前後における、本発明の担持Ｐｄ触媒と従来技術の担持Ｐｄ触媒の表面積の比較を示す棒グラフ図である。図７は、蒸気の存在下の高温での拡大期間における、従来技術の耐熱性担持体と触媒と比較した、本発明の耐熱性担持体とそれに担持されたＰｄ触媒の表面安定性を示す時間グラフ図である。発明の詳細な説明本発明のハフニウム含有耐熱性担持体は、かなりの量の蒸気つまり蒸発水分の存在を含む反応条件下で、例えば１０００℃を越える高温での驚くべき非常に高い表面安定性を特徴とするものである。さらに、担持体に白金やパラジウムなどの１つまたはそれ以上の白金属の金属を載置した場合でも、高温安定性を維持できるため、燃焼や部分燃焼などの高温処理における触媒の作用寿命が容易に延ばせる。高温処理での所定レベルの表面安定性を確保するため、本発明の耐熱性担持体の（前述したＳｉＯ₂および／またはＺｒＯ₂に加えた）ＨｆＯ₂の量は、全金属酸化物のおよそ５モル％以下とならないようにし、さらに、１０モル％以上であるのが好ましい。この観点から、耐熱性担持体内の補助金属酸化物成分としてＳｉＯ₂が含まれている場合には、そのＳｉＯ₂の量は担持体酸化物の５〜１５モル％の範囲、耐熱性酸化物担持体内にＳｉＯ₂と共にＺｒＯ₂が含まれている場合には、そのＺｒＯ₂の量は担持体酸化物の５〜８０モル％の範囲であるのが好ましい。高温反応における安定性のための表面積を確保するには、耐熱性酸化物担持体上に特に白金属の金属から成る触媒作用物質がディポジットされる際に、本発明のハフニウム含有耐熱性担持体の表面積が、約１１００℃の温度で１０時間焼成した後に、少なくとも５平方メートル／グラム（ｍ²／ｇ）であることが重要である。また、ハフニウム含有耐熱性担持体の表面積は、約１１００℃の温度で１０時間の焼成の後で、およそ１０ｍ²／ｇ以上、さらに、２０（ｍ²／ｇ）以上であるのが望まれる。本項で説明した表面積値は、ＢＥＴ法または同様方法にて測定されるものである。安定した高温処理のための最少表面積は、本発明のＳｉＯ₂ 安定化ハフニウム含有耐熱性酸化物担持体を準備するためのＳｉＯ₂先駆物質が含浸されたミクロ結晶をも含む、本発明の耐熱性酸化物担持体を準備するのに使う、ＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂の固溶体（下記参照）のミクロ結晶のサイズを正確に制御することにより得られる。本発明の耐熱性酸化物担持体で使うハフニウムとハフニウム／ジルコニアの固溶体は、沈澱や加水分解による適当な酸化物先駆物質から準備でき、生成された固形酸化物は、本発明の耐熱性酸化物担持体で使う所望サイズ範囲のＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂のミクロ結晶を確保するため焼成される。本発明の酸化物担持体内にシリカが含まれている場合は、焼成されたＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂のミクロ結晶材にＳｉＯ₂先駆物質の溶液を含浸し、含浸した固体を加水分解および焼成して、所望のシリカ安定化されたＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂ の固溶体を作成する。ＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂の所望結晶サイズの範囲は、本発明の耐熱性酸化物担持体の目的とする適用例によって異なるが、平均結晶直径において、一般的にはシリカ安定化工程前で５〜１５ナノメータ（ｎｍ）であるのが望ましい。大きな表面積が必要な場合、または、高度な焼結が行われる場合には、５ｎｍと１０ｎｍの間くらいの結晶径が好ましく、焼結処理が少ないか全く行われなくて、より一定な処理を要する場合には、１０〜１５ｎｍくらいの径の結晶を使うのがよい。本発明で先駆物質として使う耐熱性酸化物であるハフニウム（ジルコニア）化合物は、アセテートやアルコキシドなどの水溶性有機金属化合物と共に、オキシハロゲン化物、ニトレート、スルフェートなどの水溶性金属塩を含む。好適な先駆化合物には、ＨｆＯＣｌ₂やＺｒＯＣｌ₂などのオキシハロゲン化物の水和物や、ＨｆＯ（ＮＯ₃）やＺｒＯ（ＮＯ₃）などのオキシニトレートがある。本発明のシリカ安定化耐熱性酸化物担持体の場合、シリカ源は、一般的に水性またはアルコール性の含浸溶液に溶け、加水分解と焼成の処理と同時に酸化物に変わる溶液内で溶解状態のシリコンとなるような、シリコン化合物であればよい。このため、適切なシリカ源には、アルキスシリケート、テトラエチルオルソシリケートなどのアルキルシリケートを含むオルガノシレン、および、テトラエチルオルソシリケートが挙げられる。シリカ先駆物質は、テトラエチルオルソシリケート（ＴＥＯＳ）であるのが最も好ましい。前述のように、本発明の耐熱性酸化物担持体でのＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂固溶体は、多様な出発原料の沈澱や加水分解により準備作成できる。沈澱操作（つまり、ＨｆＯ₂・ＺｒＯ₂固溶体が生成されるときの共沈）の場合、一般的にはアルカリ金属水酸化物つまり水酸化アンモニウムなどの基である適当な沈澱剤が、酸化物先駆化合物、ＨｆＯＣｌ₂などの化合物、または、ＨｆＯＣｌ₂とＺｒＯＣｌ₂の均質混合物の水溶液に添加される。所望しない不必要な化合物または沈澱の生成物が、下記で説明するように焼成時に蒸発し分解が可能となるよう、沈澱剤を選択するのが望ましい。このため、好適な沈澱剤とは、水酸化アンモニウムや炭酸アンモニウムなどのアンモニウム化合物である。沈澱操作は、希薄または濃縮水溶液内で行うことができる。さらに、沈澱剤を添加する比率や撹拌の度合も、必要とする沈澱物の特性によって異なるものである。所定のミクロ結晶サイズ範囲において粒子の荒い沈澱物を生成する場合には、沈澱溶液の希釈を薄く、添加速度をゆるやかに、撹拌を早くするのが望ましい。沈澱剤の添加中の温度は、１５〜９０℃くらいがよい。温度を上げると、粒子の荒い沈澱物が生成できる。通常の沈澱物の添加は、理論上過度に、つまり、ｐＨ値が９〜１１くらいになるまで行う。沈澱操作に続き、必要に応じて焼成の前に、フィルター処理、遠心分離、洗浄などの方法で、沈澱物（ＨｆＯ₂−ＺｒＯ₂固溶体を使用のときは共沈混合物）をスラリーから回収する。本発明の耐熱性担持体で使うＨｆＯ₂とＨｆＯ₂・ＺｒＯ₂固溶体を得るのに加水分解を行う場合、一般的には、先駆物質や酸化物先駆物質の水性溶液を１〜４０ａｔｍの圧力下で１００℃から２５０℃程度の温度まで加熱するような熱水条件下で加水分解が行われる。加水分解の後、固形酸化物粒子を含むスラリー状生成物は、必要に応じて焼成前に、フィルター処理や遠心分離などの周知の液体／固体分離処理を行って、固形生成物を回収して洗浄する。本発明の耐熱性担持体に要するサイズ範囲のＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂ 固溶体のミクロ結晶を得るため、前記の沈澱や加水分解から回収された固形生成物は、およそ４００℃から１０００℃の温度で約５〜１５時間ほど空気中で焼成される。必要な焼成温度は、所望する最終使用温度や安定性レベルによって違う。空気中で１０００℃で約１０時間ほど焼成するのが、望ましい。焼成からの生成物は、本発明の耐熱性担持体に直接利用できるが、利用前に所定量のシリカを添加して安定処理化することが好ましい。前記の焼成されたＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂固溶体に所定量のシリカを添加するには、焼成固形物を、シリカ先駆物質を加水分解できる分量の適当な無機酸または有機酸と共に、水または水／アルコール混合液にシリカ先駆化合物を溶かした溶液に接触させる。加水分解中、シリカはイオン状の焼成固形物の表面で吸収され、加水分解が終了すると、シリコンの酸化物または水酸化物に変化する。加水分解は、シリカ先駆物質に接触させた焼成固形物を６０〜１００℃くらい約６〜１６時間程度加熱するのが望ましい。焼成固形物をシリカ先駆物質溶液に接触させるには従来のどのような方法でもよいが、初期ウェット含浸法で焼成固形物をシリカ先駆物質溶液に浸すのが望ましい。含浸操作の後、ＳｉＯ₂で安定化処理されたＨｆＯ₂またはＨｆＯ₂・ＺｒＯ₂固溶体は、最終使用温度に従って空気中で８００℃から１１００℃くらいで焼成される。本発明の触媒は、ＨｆＯ₂、ＳｉＯ₂安定化ＨｆＯ₂、ＳｉＯ₂安定化ＨｆＯ₂・ＺｒＯ₂固溶体から選択できるハフニウム含有耐熱性金属酸化物担持体上にディポジットされた、白金、ルテニウム、パラジウム、イリジウム、ロジウムなどの触媒有効作用量の白金属の金属であって、ＨｆＯ₂の量は、１０００℃を越える温度において触媒の熱安定性を確保できる量である。なお、白金属の金属は、白金、パラジウム、または、その混合物から選択、かつ、耐熱性金属酸化物担持体は、ＨｆＯ₂の量が１０００℃を越える温度において触媒の熱安定性を確保できる量である、ＳｉＯ₂またはＳｉＯ₂とＺｒＯ₂が添加されたＨｆＯ₂から選択するのが望ましい。さらに好ましくは、触媒は、ＳｉＯ₂またはＳｉＯ₂とＺｒＯ₂が添加されたＨｆＯ₂から選択された耐熱性金属酸化物担持体上の触媒有効作用量のパラジウムから成り、その担持体には、ＨｆＯ₂が少なくとも全金属酸化物量の２０モル％含まれ、担持体の表面積は１１００℃で１０時間の焼成の後において少なくとも５ｍ²／ｇほどである。本発明の触媒を作成するには、触媒技術においては周知の金属ディポジット法により、所定量の白金属金属またはその混合物を、ハフニウム含有耐熱性酸化物担持体上にディポジットさせる。焼成された担持体上に添加される白金属金属の量は、所望の適用例において触媒作用が行える分量とする。ハフニウム含有担持体に添加する量は、触媒処理を行う反応工程、使われる供給材料、経済性、作用レベル、寿命、汚染物質の有無などの、いろんな要素や要件によって異なる。不要な触媒焼結や作用の付随損失を発生させることなく最大量の担持体をカバーできるような、金属の理論最大量であればよい。考慮すべき要素が存在し、最終触媒の単位重量あたりの最大触媒作用は、白金属の金属による担持体の高い表面被覆率を必要とするが、表面積被覆を高くすると、焼結の増進つまり白金属金属の粒子サイズの生長を促す結果となる。さらに、触媒担持体の形状も考慮する必要がある。早い空間速度環境で担持体を使用すると、滞留時間が少なくても十分な変換を維持するためには触媒負荷を高くしなければならない。経済性の面からは、所望の作用を行える最少限の触媒量を使うことが目標となる。結果的に、触媒燃焼における燃料などの反応供給材内の汚染物質の存在により、不活性による触媒の劣化を相殺するために、高い触媒負荷をかけることが余儀なくされるのである。一般的な事例において、本発明の触媒に使う白金属の金属量は、触媒担体のごく一部であって、焼成された担持体の２５重量％を越えることはない。広い利用範囲でも高い作用能力を経済的に維持するための量は、約０．０１％から２０％くらいである。これらパーセンテージは、焼成された担持体の重量に基づいた値であって、例えば、金属箔基体など（下記に説明）の不活性基体上で触媒担体を使う場合には、触媒担体は基体の１０％〜２５％重量くらいで、基体と触媒担体の総重量に対する白金属金属の％重量は相対的に低くなる。前記の使用する白金属金属またはその混合物は、特定の触媒の化学反応である所定の触媒処理例、所定の反応条件、経済性などにより決定されるものである。利用可能な白金属の金属には、白金、ルテニウム、パラジウム、イリジウム、ロジウム、および、それらの混合物がある。触媒燃焼や部分燃焼の処理においては、白金、パラジウム、および、白金とパラジウムの混合物の利用がよいが、パラジウムが最も好ましい。前記の白金属の金属は、白金属金属を含んだ金属の錯体、化合物、分散体などを使った多様な方法で、ハフニウム含有担持体と結合させる。その化合物や錯体は、水や炭化水素溶剤に溶解できるものである。白金属金属を、溶液から沈澱させる。一般的に液は、担持体上で白金属金属を分散状態に放置しておく間、揮発や分解により触媒担体から除去できるものであればよい。適当な白金属金属の錯体や化合物の例として、白金属金属の塩化物、酸化物、硫化物、窒化物、窒化パラジウムジアミン、水酸化パラジウムテトラミン、第２塩化白金酸、塩化パラジウムテトラミン、塩化ナトリウムパラジウム、２エチルカプロン酸パラジウム、塩化ヘキサミンロジウム、塩化ヘキサミンイリジウム、塩化カリウムパラチナ、および、その他の白金属金属の塩や錯体がある。塩化化合物からは非常に活性度の高い触媒が作成できるが、ガスタービンの燃焼装置で触媒を使う場合にはよい選択とは言えない。塩化物はたとえ少量であっても、タービンの羽根や水受け部で錆を発生させる。そのため、触媒がガスタービンの燃焼装置で使われる場合には、窒素含有のパラジウムや白金の先駆物質が最も望ましい。ハフニウム含有担持体上での分解処理の後、白金属金属の錯体や化合物を、焼成などの処理をして、白金属金属のほとんど全部をその元素形態または酸化物に変える。本発明の触媒が担持された触媒担体は、所望の最終適用目的や反応条件に従った多様な従来形態で利用することが可能である。例えば、本発明の触媒担体は、直径が０．２５インチかそれ以下の球、ペレット、リングなどの粒形状で構わない。また、燃焼や部分燃焼で使う場合には、触媒担体がその縦方向配置のチャンネルの少なくとも一部分にディポジットするよう、燃焼ガス混合体の通過のため縦方向に配備されたチャンネル束で構成される単体つまり一体構造の金属またはセラミック製の基体の表面に本発明の触媒担体をコートするのが好ましい。さらに、その一体構造基体は、縦方向配備のチャンネルつまり通路におけるその適用例に必要な高速の空間速度を最少限の圧力低下で可能にできるような、ハニカム形状、波板の螺旋形状（平らな分離シート材で挟みこむ）、コラム形状（ストロー束）、その他の形状の金属製であるのが望ましい。それら基体は展延性を有するので、周囲の構成部に簡単に取り付けられ、また、セラミック担持体よりも薄壁状に形成できるため、流体抵抗が低くなる。また、金属製基体の別の実際的長所は、熱衝撃に強いことである。そのような熱衝撃は、ガスタービン動作中にタービンを始動したり停止したりするときに発生するものであって、特に、タービンを瞬間的に停止させねばならない場合に発生する。後者の場合、燃料供給を遮断する、つまり、発電機残留歪などのタービンへの物理的負荷が除去されるのでタービンがトリップする。タービンへの燃料供給を瞬間的に遮断すると、速度オーバーが防止できる。すると、（本発明に関する処理が行われる）燃焼室内の温度が急激に落ちて、燃焼温度から圧縮空気温度へ変わる。この温度落下の速度は、１秒以内に１０００℃以上である。この結果、前記のように、金属製基体のチャンネルや通路内の壁上の触媒担体がディポジット（あるいは、着床）することになる。この作用では、触媒層が金属表面にディポジットできるよう、アルミニウム、アルミ含有鋼またはアルミ処理鋼、ステンレス鋼、その他、コバルト合金やニッケル合金などの高温金属合金など、満足できる基体素材がいくつかある。前記の素材の好適例として、エージェンらの米国特許第４，４１４，０２３号；チャップマンらの同第４，３３１，６３１号；チェアンズらの同第３，９６９，０８２号などにそのアルミ含有鋼が記述されている。それら鋼は、川崎製鉄（リバーライトＲ２０−５ＳＲ）、ベレイングドイツ金属社（アルムクロムＩＲＥ）、アレゲニルドラム社（アリアＩＶ）などから市販されており、触媒担体のウォッシュコートへの接着をよくするための荒い化学的反応表面を形成するため、酸化した場合アルミニウムが鋼の表面にアルミナのウィスカーつまり結晶を生成できるよう、十分な溶解アルミニウムが含まれている。前述のように一体構造の形成の前あるいは後に、所定の方法にて、本発明の触媒担体を金属製基体の所定域に被覆する。例えば、螺旋ロール形状の一体構造を作成できるよう所定の形状に型成形または組立巻成形する前あるいは後に、触媒基体構造を構成する複数シートの片面または両面に被膜を生成する。このとき、平板シートと波形シートの交互構成に加えて、非入子式に巻かれたヘリンボーン形状の波板で螺旋ロールを形成してもよい。本発明の触媒担体を、ステップ工程により金属製基体に形成することも可能であって、まず最初に、ハフニウム含有耐熱性担持体を、仕上げ担持体の微細分散形態で、または、（前述の）所定の担持先駆物質を使って生成し、次に、加水分解および／または焼成を行って、金属製基体面上に所望のハフニウム含有耐熱性担持体の層つまりウォッシュコートを形成するのである。金属製基体面上にハフニウム含有耐熱性担持体のウォッシュコートを形成する際、スプレーまたは基体をウォッシュコートに直接に浸積させるなどして、表面に塗布するするのと同じ要領で行うことも可能である。耐熱性担持体の層又はウォッシュコートを形成した後、前述の方法で、白金属金属をウォッシュコートヘディポジットさせてから、焼成して本発明の触媒体構造を完成させる。別の方法として、最終の触媒担体組成物を、前記方法で別途に準備してから、スプレーや浸積などにより微細分散状態あるは所定液担体内の浮遊状態にて金属製基体表面に塗布しても構わない。特に液体燃料の触媒燃焼や部分燃焼に有効利用できる本発明の好適実施例は、流動する気体反応混合物の通過のための縦方向に隣接配備された触媒被膜チャンネルと非触媒チャンネルの束で構成された金属箔基体から成る触媒体構造であって、触媒が被膜されたチャンネルとそれに隣接する非触媒チャンネルとは熱交換関係で構成されており、かつ、触媒被膜チャンネルの内面の少なくとも一部分が、ＨｆＯ₂だけ、または必要に応じて、ＳｉＯ₂とＺｒＯ₂と、ＨｆＯ₂／ＳｉＯ₂ と、好適にはＳｉＯ₂／ＨｆＯ₂・ＺｒＯ₂混合物と組み合わせたＨｆＯ₂でできた、好ましくはパラジウムである、有効触媒作用量の白金属金属をウオッシュコートでディポジットされている。例えば、前記のような螺旋波板構造の片面に、耐熱性担持体ウォッシュコートと触媒で被覆する。そして、被覆した波板構造を、ロール状に一体に巻く。また、同様素材のシートの片面に触媒担体を被膜してから、波板シートといっしよにロール形状にして螺旋一体構造に作成することもできる。このとき、触媒が被膜された一体構造の表面は、燃焼処理において熱を発生する。この熱は、ガス流体に遷移されるか、または、触媒体構造を経由して隣接した非触媒体構造へ、つまり冷たい面へ伝わる。そこからさらに、熱はその表面に沿って未燃焼ガス通路へ伝播される。これにより、空気希釈や外部熱交換装置などの手段の必要のなく一体熱交換されるので、触媒体構造における触媒面の温度制御が可能となる。そのような温度制御は、例えば、導入ガスの予備熱温度がきわめて高く、ガス流量が不安定な場合に最適である。前記の触媒体構造は、触媒体構造の縦方向チャンネルを通過するガスの平均線速度が、触媒体構造全体に渡っておよそ０．２ｍ／秒以上で、かつ、６０ｍ／秒より早くならないようなサイズ形状で形成されている。この下限値はメタンの火炎前端速度より大きく、上限値は現在市販されているタイプの担持体に対して実効的な値である。なお平均速度は、メタン以外の燃料では当然異なる。本発明の触媒や触媒体構造を利用する処理では、担持された不均一系の白金属金属触媒が使われており、反応温度は十分に高く、および／または、通常動作において１０００℃付近あるいはそれを越えるような温度に触媒が曝されること、あるいは、処理が何度も動揺して触媒の焼結つまり不活性化を生ずることが必ずしも起こるとは限らないがその恐れがあるような反応の発熱性がある。そのような触媒処理では、アンモニアの硝酸への酸化、メタンのＣＯとＨ₂へのスチーム改質、自動車排ガス制御を含む排気ガス制御のための炭化水素の完全酸化、燃料の燃焼または部分燃焼が行われる。好適実施例における本発明の処理法は、燃料の燃焼または部分燃焼を行うことである。その好適実施例では、ガス状または蒸発した燃料を空気などの酸素含有気体と混合し、金属箔基体から成る触媒体構造を通過させるが、前記金属箔基体は、縦方向に隣接配備された触媒被膜チャンネルと非触媒チャンネルの束で構成されており、触媒が被膜されたチャンネルとそれに隣接する非触媒チャンネルとは熱交換関係で構成されており、かつ、触媒被膜チャンネルの内面の少なくとも一部分が、ＳｉＯ₂あるいはＳｉＯ₂とＺｒＯ₂が混合されたＨｆＯ₂でできた耐熱性担持体をウォッシュコート上にディポジットされた有効触媒作用量のパラジウムで被膜されており、その耐熱性担持体は、１０００℃で１０時間の焼成の後で、少なくとも全金属酸化物成分のほぼ５モル％のＨｆＯ₂を有していて、その表面積が少なくとも５ｍ²／ｇくらいであるので、燃料と酸素含有気体のガス混合物が、触媒体構造の触媒被膜チャンネルを通過するとき少なくとも部分燃焼されるのである。触媒燃焼の後、かなりの量のＮＯｘが生成される温度以下、例えば、１５００℃または１６００℃以下、にて燃料の燃焼が行われる同質の燃焼区域が続いている。この方法は、様々な種類の燃料や広い条件範囲でも実行できる。通常の燃料には、炭化水素系燃料以外に、Ｈ₂やＣＯ／Ｈ₂混合物がある。メタン、エタン、プロパンなどの普通の気体炭化水素は前記の処理燃料源としてふさわしいけれども、下記のような、処理温度で蒸発可能な炭化水素系燃料のほうがより好ましい。例えば、燃料は室内での温度と圧力下では液体または気体である。その例として、ブタン、ペンタン、ヘキサン、ヘプタン、オクタンなどの低分子重量の脂肪族炭化水素、ガソリン、ベンゼン、トルエン、エチルベンゼン、キシレンなどの芳香族炭化水素、ナフサ、ディーゼル燃料、ケロシン、ジェット燃料、中間精製物、重油（好ましくは、窒素化合物や硫黄化合物を除去するため水素処理したもの）、メタノール、エタノール、イソプロパノール、ブタノールなどのアルコールである酸素含有燃料、ジエチルエーテル、エチルフェニルエーテル、ＭＴＢＥなどのエーテルが挙げられる。また、都市ガスやシンガス(syngas)などの低ＢＴＵガスも、燃料として使用することが可能である。燃料は、一般的に燃焼空気と所定量混合されて、好適実施例の処理で発生する温度よりも高い断熱燃焼温度をもつ混合物になる。その断熱燃焼温度はおよそ９００℃以上であるのが望ましく、さらに、１０００℃以上のほうがより好ましい。非気体燃料は、触媒面に接触させる前に、少なくとも部分的に蒸発させねばならない。燃焼空気は、大気圧またはそれ以下の圧力であって、あるいは、３５ａｔｍかそれ以下に圧縮しても構わない。基本的に本方法にて作成するガスを使う固定ガスタービンは、８から３５ａｔｍの範囲の計器圧力下で作動するものである。そのため、本処理は、ほぼ０と３５ａｔｍの中間の圧力、好ましくは０から１７ａｔｍまでの圧力で作用させるのがよい。触媒に付与される燃料／空気の混合物はよく混合しておく必要があり、気体導入温度は使われる燃料によって異なる。この温度は、熱交換器へのガスを予備加熱、または、断熱燃焼により与えることが可能である。本処理では、ハフニウム含有耐熱性担持体上にディポジットされたパラジウム含有材の触媒作用量が、ガス流体に対して低い抵抗値をもつように、金属製の一体基体上に被膜される。触媒を含む区域から離れる部分燃焼ガスの排出内部温度、および、触媒の壁面温度は、断熱温度つまり燃料が完全に燃焼する際のガス温度よりも低い。通常は、触媒を励起するガス温度は７２０℃から９５０℃程度である。また、触媒基体の温度は１１００℃以下であって、９５０℃を越えないのが望ましい。これら温度は、装置の圧力、酸素の分圧、燃料のカロリー値、ガスタービンの特定設計構造や性能要件などの多様な要素に依存するものである。にもかかわらず、触媒は部分的な燃料の酸化を起こすが、燃料／空気混合物の断熱温度以下の温度値に制限されるのである。実験例本発明の耐熱性触媒担持体の準備、その耐熱性触媒担持体を使った本発明の触媒担体、本発明の耐熱性担持体を一体金属製基体上のウォッシュコートとして利用し、そのウォッシュコート上に触媒作用する白金属の金属かディポジットされているような、触媒体構造の適用例、および、本発明の触媒や触媒体構造で使う本発明の耐熱性担持体の高温安定性や性能を示す実験例を、以下に説明する。同時に、比較のための耐熱性担持体、触媒、触媒体構造も説明する。大気中または蒸気中における高温安定性を試験するため、２つの異なる方法を使った。大気中での熱処理のため、サンプル材を空気静止式マッフル炉にてランプ比（ramp rato）１０℃／分で所定の温度まで加熱し、所定時間だけその温度で放置した。蒸気付加の大気中での熱処理のため、サンプル材を筒炉において空気と１０％の水分蒸気の混合気体を流しながらランプ比３℃／分で加熱した。そしてサンプル材の安定性を、良好な担持体の主たる特性は高温度における高表面積および低結晶粒子サイズであって、高表面積と低結晶粒子サイズとは相互関係があるため、高温処理後のその表面積および／または結晶粒子サイズを計測した。全面積は、通常は単位ｍ²／ｇで記録されるＢＥＴ法で計測した。ここで注意してほしいのは、ＨｆＯ₂の密度が、ＺｒＯ₂の密度の１．７倍であることである。それゆえ、ＨｆＯ₂とＺｒＯ₂の粒子サイズが同じだと、ＺｒＯ₂のＢＥＴ表面積は１．７倍大きくなる。さらに、この事例において重要なのは基体またはウォッシュコートの厚さであり、ウォッシュコート厚を同じにする場合、重量部がＨＰＯ₂のほぼ１．７倍のものを使う必要がある。ゆえに、比較例のためには、純粋のＺｒＯ₂に対する密度差を補正することにより、ＢＥＴ表面積をジルコニウム等価表面積つまりＺＥＳＡに変換する。このＺＥＳＡは、dxとSxが密度および試験素材のＢＥＴ表面積で、dx／dZrO₂がＺｒＯ₂の密度であるＺＥＳＡ＝（dx／dZ rO₂）×sXの演算式を使って個別事例において算定した。触媒体構造の性能の試験は、ガスタービン燃焼器内の条件をシミュレートできる高圧の反応装置内で行った。試験装置は、断熱セラミックで覆われた鋼製の圧力容器とその出口に配備された圧力調整用のバルブから成る。高温の空気蒸気を得るため、高圧空気を電気抵抗加熱器に送り込んだ。メタン燃料を噴入して、スタティックミキサーにより通路で混合した。この燃料と空気の混合物を触媒へ導入し、触媒後工程部へと送った。熱電対を触媒の上流側に設置し、触媒に導入される気体の温度を測定し、触媒内部の触媒表面に接触させて基体温度を測定し、触媒の下流側で触媒作用後の同様燃焼域での気体の温度を測定した。ＬＯＴを判断する消火試験では、燃料を空気と混ぜ、触媒への気体導入口の温度を一定速度で増加させる。触媒の作用性によって異なるが、導入口温度で触媒は燃料との反応を開始し、触媒温度と排出口気体温度が導入口温度よりも高くなる。ＬＯＴは、排出口気体温度がすぐに変化するときの導入口気体温度として判断されるが、つまり、導入口温度／排出口温度の特性図内の変化点で示される。安定性測定では、反応装置の条件を一定に保ち、安定性をみるため、触媒基体と排出口の気体温度を１時間またはそれ以上の期間モニターする。試験例１（サンプル準備）サンプルを準備または供給業者から直接に入手して、安定性試験などが報告される続く試験例における識別目的のため用語の説明を行う。サンプルＡ（ＺｒＯ₂の比較サンプル）ＤＫＫ社（ダイイチキゲンソ化学工業）から、ＲＣ−１００ＺｒＯ₂粉末である表面積が１００ｍ²／ｇで孔容積が約０．３ｃｃ／ｇのＢＥＴ表面をもつＺｒＯ₂を入手した。サンプルＢ（ＳｉＯ₂／ＺｒＯ₂の比較サンプル）ＤＫＫ社（ＲＣ−１００）からのＺｒＯ₂粉末を、初期湿潤法を使って、テトラエチルオルソシリケート（ＴＥＯＳ）が２１．１ｇ、２ｍＭＨＮＯ₃が６．０ｇ、およびエタノールから成る３０ｍｌ溶液内に浸積された。その結果の湿潤混合物を密閉容器に入れて、６０℃で約１８時間加熱し、ＴＥＯＳ先駆物質の加水分解を行った。加水分解後の固形物を１１０℃で乾燥し、下記で述べる試験例の所定温度までランプ比１０℃／分で１０時間加熱して焼成した。得られたサンプルには、１１モル％のＳｉＯ₂が含まれていた。サンプルＣ（ＨｆＯ₂）テレダインワチャン社（アルバニー、オレゴン州）から、ＨｆＯ₂粉末である表面積が２０ｍ²／ｇ（ＺＥＳＡは３４ｍ²／ｇ）で孔容積が約０．１２ｃｃ／ｇのＢＥＴ初期表面をもつＨｆＯ₂を入手した。サンプルＤ（ＳｉＯ₂／ＨｆＯ₂）テレダインワチャン社（アルバニー、オレゴン州）からのＨｆＯ₂をＺｒＯ₂で代替し、異なる量のＴＥＯＳ（１２．３７ｇ）と２ｍＭＮＯ₃（４．０ｇ）を使ったことを除いて、前記のサンプルＢと同じ方法でＳｉＯ₂／ＨｆＯ₂を準備した。この例での乾燥サンプルにも、１１モル％のＳｉＯ₂が含まれていた。サンプルＥ（ＳｉＯ₂／ＨｆＯ₂）テレダイン社のＨｆＯ₂ウェットケーキ（同社の製品ＲＧＳＨｆＯ₂の中間物）を使ったことを以外は、前記のサンプルＤと同じ方法で、第２のＳｉＯ₂／ＨｆＯ₂サンプルを準備した。このウェットケーキを１１０℃で約２０時間オーブンで乾燥し、ＳｉＯ₂を含浸させる前に４００℃で１０時間予備焼成した結果、平均直径が５ｎｍの単体相の結晶が得られた。この乾燥されたＳｉＯ₂／ＨｆＯ₂サンプルには、１３モル％のＳＩＯ₂が含まれていた。サンプルＦ（Ｓｉ₂／ＺｒＯ₂・ＨｆＯ₂）ＨｆＯ₂・ＺｒＯ₂の固溶体（１０モル％のＨｆＯ₂を含む）を準備するため、蒸留水内でＺｒＯＣｌ₂・８Ｈ₂Ｏ（４０ｇ）とＨｆＯＣｌ₂・８Ｈ₂Ｏ（５．６ｇ）を溶解し、テフロンでライニングしたパーボム容器内にその溶液を密封し、その容器を２００℃で１７時間加熱して、得られた固体相を１１０℃で２０時間オーブンで乾燥した。７モル％のＳＩＯ₂を含む乾燥固形物が生成できるよう出発素材の量を調整したことを除いて前記のサンプルＢと同じ方法で、この乾燥サンプルにＳｉＯ₂を含浸した。サンプルＧ（ＳｉＯ₂／ＺｒＯ₂・ＨｆＯ₂）ＨｆＯ₂・ＺｒＯ₂の固溶体（１７モル％のＨｆＯ₂を含む）を準備するため、１０００ｍｌの蒸留水内でＨｆＯＣ１₂・８Ｈ₂Ｏ（３８．１２ｇ）とＺｒＯＣｌ₂ ・８Ｈ₂０（１５０ｇ）を溶解し、ｐＨ値が１０〜１１となるまでＮＨ₂ＯＨで沈澱させた。沈澱したゲル状物を、塩化物イオンがなくなるまで蒸留水で数回リンスし、ロタバップ容器内で６０℃で（およそ０．５ｍｍＨｇにて約２００分）乾燥して、乾燥粉末を生成した。この粉末を、６００℃で１０時間予備焼成し、ＳｉＯ₂の最終モル％値が１３％となるよう、前記のサンプルＢと同じ方法を使って、ＳｉＯ₂を含浸させた。サンプルＨ（ＳｉＯ₂／ＺｒＯ₂・ＨｆＯ₂）ＨｆＯ₂・ＺｒＯ₂の固溶体（５７モル％のＨｆＯ₂を含む）を準備するため、５００ｍｌの蒸留水内でＨｆＯＣｌ₂・８Ｈ₂Ｏ（２１１ｇ）とＺｒＯＣｌ₂・Ｈ₂ Ｏ（１２３ｇ）を溶解し、ｐＨ値が１０〜１１となるまでＮＨ₄ＯＨで沈澱させた。沈澱したゲル状物を、蒸留水で３回、エタノールで１回撹拌／遠心サイクル法でリンスし、ロタバップ容器内で６０℃で（およそ０．５ｍｍＨｇにて約２００分）乾燥して、乾燥粉末を生成した。この粉末を、５００°で予備焼成し、最終の乾燥生成物には１５モル％のＳｉＯ₂が含まれるよう、前記のサンプルＢと同じ方法でＳｉＯ₂を含浸させた。サンプルＩ（ＳｉＯ₂／ＺｒＯ₂比較サンプルのＰｄ）前記のサンプルＢと同じ方法でＳｉＯ₂／ＺｒＯ₂サンプルを準備し、過剰濃度の硝酸に溶かされたＰｄ（ＮＨ₃）₂（ＮＯ₂）₂の溶液内に浸積し、１１０℃で約１０時間乾燥して、そのＳｉＯ₂／ＺｒＯ₂担持体のＳｉＯ₂が１１モル％であるようなＳｉＯ₂／ＺｒＯ₂触媒上で２０重量％のＰｄを生成した。サンプルＪ（ＳｉＯ₂／ＨｆＯ₂のＰｄ）前記のサンプルＤと同じ方法で準備したＳｉＯ₂／ＨｆＯ₂サンプル（本事例では、ＳｉＯ₂が１１モル％含まれる）に、前記のサンプルＩで説明したのと同じ方法でＰｄを含浸させ、乾燥した後、ＳｉＯ₂／ＨｆＯ₂触媒上で１０重量％のＰｄを生成した。実験例２（比較サンプルの安定性）サンプルのＺｒＯ₂（サンプルＡ）とＳｉＯ₂／ＺｒＯ₂（サンプルＢ）を大気中で６００℃から１１００℃の範囲の様々な温度で１０時間焼成し、焼成されたＢＥＴ表面積を測定した。その測定結果を、図１に示す。図１で図示のように、ＳｉＯ₂安定化ＺｒＯ₂はＺｒＯ₂だけの場合よりもより安定しているが、１０００℃以上で焼成された場合かなりの焼結が発生し、表面積の損失が５ｍ²／ｇ以下程度となっている。実験例３（ＨｆＯ₂およびＳｉＯ₂／ＨｆＯ₂の安定性、ＺｒＯ₂とＳｉＯ₂／ＺｒＯ₂との比較）サンプルのＨｆＯ₂（サンプルＣ）とＳｉＯ₂／ＨｆＯ₂（サンプルＤ）と素材（サンプルＡとＢ）を含む比較サンプルＺｒＯ₂とを、大気中で６００℃から１１００℃の範囲の様々な温度で１０時間焼成し、焼成された各サンプルのＺＥＳＡ表面および結晶サイズを検査して、焼成材料の安定性を測定した。その測定結果を、図２Ａと２Ｂに示す。図２Ａと２Ｂに図示のように、ＨｆＯ₂は８００℃ 以上の場合はＺｒＯ₂よりも安定しており、ＳｉＯ₂安定化ＨｆＯ₂は１１００℃ 以上でも完全に安定しているが、一方、ＳｉＯ₂安定化ＺｒＯ₂では高温においてかなりの焼結が発生している。図２Ａと図２Ｂとの比較において、ＳｉＯ₂安定化ＨｆＯ₂の結晶サイズに変化はないが、表面積の減少が存在し、シリカの焼結が表面積の減少につながっていることを示している。ＳｉＯ₂の表面積が基本的に無視できる１１００℃での焼成の後でも、出発物資であるＳｉＯ₂安定化ＨｆＯ₂のＳｉＯ₂表面積の測定値は、生のＨｆＯ₂のそれと同じである。このように、１１００℃以上の温度での結晶サイズの安定性の観測結果は、目をみはるものがある。実験例４（ＳｉＯ₂／ＨｆＯ₂の安定性、ＳｉＯ₂／ＺｒＯ₂との比較）ＳｉＯ₂安定化ＨｆＯ₂の２つの異なるサンプル（サンプルＤとＥ）と比較サンプルＳｉＯ₂安定化ＺｒＯ₂（サンプルＢ）とを、大気中で８００℃から１１００ ℃の範囲の様々な温度で１０時間焼成し、ＺＥＳＡ表面および結晶サイズを検査して、サンプルの安定性を測定した。図３Ａと３Ｂに示す測定結果から、ＨｆＯ₂ を含むサンプルは両方とも高温でもすばらしい安定性を示しているが、ＳｉＯ２安定化ＺｒＯ₂では表面積の大きな減少が見られ、１１００℃に近い温度では結晶サイズが増加している。実験例５（ＳｉＯ₂安定化ＨｆＯ₂・ＺｒＯ₂固溶体の安定性）様々な量のＨｆＯ₂を含むＨｆＯ₂・ＺｒＯ₂のＳｉＯ₂安定化固溶体（サンプルＦ、Ｇ、Ｈ）と、ＳｉＯ₂安定化されたＺｒＯ₂（サンプルＢ）とＨｆＯ₂（サンプルＣ）とを、大気中で１０００℃から１１００℃の範囲の様々な温度で１０時間焼成し、ＺＥＳＡ表面を測定して、使った焼成温度でのサンプルの安定性を調べた。図４に、その測定結果を示す。図示のように、ＳｉＯ₂安定化ＨｆＯ₂は、１１００℃ではＳｉＯ₂安定化ＺｒＯ₂に比べて非常に優れた安定性を示しており、ＳｉＯ₂安定化ＨｆＯ₂・ＺｒＯ₂固溶体は、ＨｆＯ₂に１０モル％以上の安定化成分が含まれている場合には、（ＳｉＯ₂安定化ＨｆＯ₂と同じような）優れた安定性をもつことが判る。実験例６（蒸気中のＳｉＯ₂／ＺｒＯ₂に対しての、ＳｉＯ₂／ＨｆＯ₂の安定性）２種類の違うＳｉＯ２_安定化ＨｆＯ₂耐熱性担持体（サンプルＤとＥ）と、ＳｉＯ₂安定化ＨｆＯ₂・ＺｒＯ₂固溶体（サンプルＨ）と、比較するＳｉＯ₂安定化ＺｒＯ₂担持体（サンプルＢ）とを、１０％Ｈ₂Ｏと空気のなかで１０３５℃でおよそ５００時間で経時変化させて、それらサンプルの一部分の表面積の変化を定期的（１００時間毎）に調べた。経時変化による表面積測定値の結果を、図５に示す。図５に図示のように、ＺｒＯ₂・ＨｆＯ₂固溶体を含んでいるシリカ安定化ＨｆＯ₂ 組成物は試験期間中ずっとほぼ同じ表面積を維持していたが、ＳｉＯ₂安定化ＺｒＯ₂は、１００時間の経時変化試験期間内に表面積が著しく減少した。このことは、高温で蒸気が存在する環境においての、従来担持体に対する本発明の耐熱性担持体の優位性を示すものである。実験例７（パラジウムを添加したＳｉＯ₂安定化ＺｒＯ₂またはＨｆＯ₂担持体の安定性）ＳｉＯ₂安定化ＺｒＯ₂（サンプルＩ）およびＳｉＯ₂安定化ＨｆＯ₂（サンプルＪ）上にＰｄをディポジットしたパラジウム触媒担体のサンプルを、大気中で１０５０℃で１０時間焼成し、焼成された触媒の表面積を、Ｐｄ金属をディポジットさせる前に大気中で１０００℃で１０時間焼成した担持体の表面積と比較した。その試験結果を、図６示す。図６の結果から判るように、触媒のディポジットと焼成の前後で、ＳｉＯ₂安定化ＨｆＯ₂の表面積では変化がほぼ発生していないが、ＳｉＯ₂安定化ＺｒＯ₂の表面積は基本的に減少している。実験例８（蒸気中におけるＳｉＯ₂／ＨｆＯ₂、ＳｉＯ₂／ＺｒＯ₂、担持体で担持されたＰｄ触媒の安定性）ＳｉＯ₂安定化ＺｒＯ₂（サンプルＩ）およびＳｉＯ₂安定化ＨｆＯ₂（サンプルＪ）上にＰｄをディポジットしたパラジウム触媒担体のサンプル、および、それらの担持体（サンプルＢとＤ）自体とを、それらサンプルの一部分の表面積の変化を定期的（１００時間毎）に調べるため、１０％Ｈ₂Ｏと空気のなかで１０３５℃でおよそ５００時間で経時変化させた。その結果を、図７のグラフに示す。図示のように、ＳｉＯ₂／ＨｆＯ₂上のＰｄ触媒は蒸気中での３００時間の試験期間の間その表面積をほぼ維持していたが、ＳｉＯ₂安定化ＺｒＯ₂上のＰｄ触媒の表面積は、蒸気中での１００時間の経時変化試験期間の間後では低いレベルにまで低下した。このことは、蒸気における担持体の安定性を証明しており、図７に示されているように、蒸気中での５００時間の経時変化期間においてＳｉＯ₂安定化ＨｆＯ₂ではその表面積にほとんど変化がないが、１０３５℃の蒸気中での１００時間目で、ＳｉＯ₂安定化ＺｒＯ₂はその表面積のほぼ全部を喪失したことによる。実験例９（ＨｆＯ₂またはＳｉＯ₂安定化ＨｆＯ₂ を有する触媒一体構造の利用）ＨｆＯ₂とＳｉＯ₂安定化ＨｆＯ₂（両方とも本発明の触媒体構造用）、および、ＺｒＯ₂とＳｉＯ₂安定化ＺｒＯ₂（両方とも比較触媒体構造用）から選択された基体ウォッシュコート上にディポジットされた触媒作用Ｐｄと、Ｆｅ／Ｃｒ／Ａｌ金属箔でできた一体構造基体とから成る実験室規模の触媒体構造を準備し、前述のようなＬＯＴ検査を行った。試験用触媒体構造を準備する際、前記の金属箔はヘリボン形状の波板状に構成し、大気中で９００℃で酸化させて、箔表面にアルミナのウイスカーを形成した。その波板状箔の片面に、水溶液中のＨｆＯ₂ 、ＳｉＯ₂／ＨｆＯ₂、ＺｒＯ₂、ＳｉＯ₂／ＺｒＯ₂のコロイド状のゾルを噴霧してから、被膜された箔を、下記の表１に示されている温度にて大気焼成を行い、それぞれのウォッシュコート処理箔を作成した。前記のウォッシュコート処理箔上に、所定濃度のＰｄ先駆物質（Ｐｄ［ＮＨ₃ ］₂［ＮＯ₂］₂を過剰ＨＮＯ₃と共に水に溶解したもの）を使ってパラジウム金属をディポジットさせ、焼成の後、ウォッシュコート処理箔上に所定量のＰｄを被膜形成した。つまり、前記で説明したウォッシュコートで覆われた金属箔の表面上にＰｄ先駆物質溶液をスプレーし、その箔を大気中で表１に示した温度で焼成し、同じく表１に示す箔表面積ｃｍ²あたりのＰｄ密度を生成した。焼成の後に、波板を重ならせず、触媒体構造の軸方向に延びる縦方向チャンネルを備えた直径が２インチで長さが２または３インチの金属構造体が構成できるよう、波板状箔をロール状にした。上記のように構成した構造体を、前述の周知方法でＬＯＴ検査した。検査は、断熱燃焼温度が１３００℃であるメタン／空気混合物を使って、１１．９大気圧下で行った。使用した触媒体構造のさらなる特性を示す検査結果は、表１に記載されている。（ａ）１５モル％のＳｉＯ₂を有するウォッシュコート。（ｂ）１１モル％のＳｉＯ₂を有するウォッシュコート。（ｃ）１５モル％のＳｉＯ₂を有するウォッシュコート。（ｄ）１１モル％のＳｉＯ₂を有するウォッシュコート。（ｅ）箔面積ｃｍ²あたり０．３５７ｇのＰｄを有する触媒（ｐｄ／ｐｔ原子比率は６／１）。表１に示されているように、どの事例でも、ＨｆＯ₂含有ウォッシュコートを有する本発明の触媒体構造の触媒性能は、従来のＺｒＯ₂含有ウォッシュコートの触媒体構造に比べて、低ＬＯＴの点で同じ、または、優位となっている。例えば、ＳｉＯ₂安定化ＨｆＯ₂担持体ウォッシュコート（６．２ｍｇ／ｃｍ²）上の０．６２ｍｇ／ｃｍ²Ｐｄ触媒ではＬＯＴが４６０℃であるが、ＳｉＯ₂安定化ＺｒＯ₂担持体ウォッシュコート（５ｍｇ／ｃｍ²）を使った１．０ｍｇ／ｃｍ²Ｐｄ量のときはＬＯＴが５００℃になっている。さらに、ＳｉＯ₂安定化ＨｆＯ₂担持体ウォッシュコート（７．４ｍｇ／ｃｍ²）上でＰｄ触媒量が０．１８５ｍｇ／ｃｍ²のときはＬＯＴが５１０℃であるのに、ＳｉＯ₂安定化ＺｒＯ₂担持体ウォッシュコート（５ｍｇ／ｃｍ²）上の高いＰｄ量０．２５ｍｇ／ｃｍ²でもＬＯＴが５４０℃になってしまう。ゆえに、いずれの事例でも、たとえ作用触媒濃度がＺｒＯ₂含有耐熱性担持体ウォッシュコートをもつ比較触媒体構造より低くても、ＨｆＯ₂含有のウォッシュコート触媒体構造ではＬＯＴ温度値が低くなる。上記のように本発明は、実施例と実験例により説明してきた。実験例はあくまでも事例であって、本発明を限定するものではない。さらに、付随する発明の請求項の範囲を逸脱することなく、説明した本発明と同等事例を判断することも、当業者には可能であろう。当然ながら、そのような同等事例も本発明の一部と考えられる。DETAILED DESCRIPTION OF THE INVENTION Catalyst support and catalyst for high temperature treatment and catalytic method using the same Field of the invention The present invention provides a stable heat-resistant support for high-temperature catalytic action, Used catalyst and catalyst body structure, and the catalyst and / or catalyst body structure used The present invention relates to a high-temperature catalyst treatment method. In particular, the present invention provides that the reaction temperature exceeds 1000 ° C. H in sufficient amount to provide thermal stability to the support in such processing examples. fO_TwoAn improved catalyst carrier containing a heat-stable hafnium compound such as One or more platinum metal deposited on the carrier, or A catalyst body having a metal substrate coated with a support of The aforementioned catalyst or its catalyst body structure is used to obtain other working properties. The purpose of the present invention is to provide a method for treating a high-temperature catalyst such as a partial oxidation action, that is, combustion of catalytic fuel. Background of the Invention For example, CO and H_TwoReforming of methane to steam, partial acids of hydrocarbons to synthesis gas Complete combustion of hydrocarbons for gas emission control including For various industries, such as catalytic combustion of fuel in bins, furnaces, boilers, etc. Important catalyst treatments are generally performed at elevated temperatures. In each case, the catalyst used is Catalytic substance or material supported by inert, heat-resistant metal oxide carrier Heterogeneous catalyst. To maximize its catalysis, heterogeneous catalysts are generally It is configured so that an enlarged exposed surface of the active catalyst material can be formed. Its purpose This means that, in addition to enhancing the action of the catalyst, the catalyst component contains very expensive noble metals. Another is to optimize the use of the catalyst components to obtain economic benefits. Unfortunate The homogeneous catalyst is a catalytic metal such as a noble metal supported on a heat-resistant oxide support. In this case, the surface area of the carrier is important in order to increase the exposed surface of the catalyst substance. This In this regard, the large surface area and porous structure of the support result in particles of the catalytic material being acidified. Are widely distributed over the surface area of the They can be separated. However, when heterogeneous catalysts work at high reaction temperatures, metal particles and metal oxide particles Sintering of catalyst elements such as catalysts causes the catalyst particles to become larger, The appearance is reduced. Furthermore, if the surface area of the carrier decreases in a high-temperature environment, The active catalyst component causes further sintering. This condition is due to catalytic and catalytic utilization. It is not desirable because it reduces cost efficiency. Therefore, active catalyst components A heat-stable and heat-resistant support with a large surface area on which the It is important. Problems with heterogeneous catalyst carriers in high-temperature treatment include (1) high temperature support and And / or a reduction in the surface area of the catalytic agent, (2) excessive Sintering, (3) catalytic toxicity due to carrier / catalyst interaction. Until now Heat resistance at high temperature in catalytic treatment at high temperature (catalytic combustion and automobile exhaust control) Zirconium (ZrO)_Two) Is used as a carrier. I have been. For example, US Pat. No. 5,259,754 to Delabetta et al. The zirconium-containing support of active catalyst material consisting of radium is a metal foil catalyst body structure type Heat-resistant so that it can stably limit the catalyst temperature in combustion. And a catalytic metal coated on at least a plurality of metal substrate surfaces . However, when high temperature treatment is performed in air, ZrO_TwoThe surface area of the Would. This reduction in surface area can be further accelerated in the presence of water vapor. And ZrO_TwoSilica (SiO_Two) Can be added to ZrO_TwoA little heat stability Can be increased, but when the temperature is about 1000 ° C., the reinforcement stability cannot be maintained, SiO_TwoStabilized ZrO_TwoIf the surface area of the The reduction in area is even worse. Therefore, it has been added to the commercial list of heat-resistant oxide materials as carriers for various catalyst treatments. In general, oxides and hydroxides of hafnium are most commonly discussed. You. For example, U.S. Patent Nos. 2,375,402; 4,189,405; No. 40,983; 4,284,531; 4,648,975; 4,681. 867; 5,204,08; European Patent Application No. 0257983, Japan Patent application (Showa 57) No. 18,639; British Patent No. 1,377,063, etc. You. However, all of the conventional examples are based on hafnium oxide and zirconium oxide. And does not explicitly explain the difference between high temperature catalytic processes such as catalytic combustion of fuel. Does not point out the unique stability of. Summary of the Invention The present invention relates to HfO in a broad sense._TwoAt a high temperature where the amount of SiO 2, which is an amount that can ensure the thermal stability of the carrier,_TwoOr SiO_TwoAnd ZrO_TwoWhen HfO mixed with_TwoHeat-resistant metal oxide carrier used for heterogeneous catalysts composed of The purpose is to provide. Furthermore, for the catalysis at high temperatures according to the invention, The improved heterogeneous catalyst is SiO 2_TwoOr SiO_TwoAnd ZrO_TwoCombined with a mixture of Forgotten HfO_TwoEffective deposited on the heat-resistant carrier composed of It consists of a catalytic amount of white metal or a mixture of white metal. Furthermore, the book The catalyst structure within the scope of the invention comprises a plurality of longitudinal passages through which the flowing reaction mixture passes. And at least a portion of the passage is made of HfO_TwoOr SiO_TwoOr Si O_TwoAnd ZrO_TwoHfO mixed with_TwoHfO selected from_TwoContaining heat-resistant carrier Road washcoat, and a small amount of At least a portion of the passage is deposited with an effective catalytic amount of platinum metal or a mixture thereof. Has been set. Further preferred features of the present invention include partial oxidation of gaseous or evaporable fuels. A particularly effective catalyst structure for complete combustion is the passage of a flowing gaseous reaction mixture. Composed of bundles of catalyst-coated channels and non-catalyst channels placed adjacent to each other A catalyst-coated channel consisting of a foil substrate and an adjacent non-catalyst channel And a catalyst exchange channel, and the catalyst coating channel Coated with a dose of white metal or a mixture of white metal, on which platinum HfO, such as a metal group catalyst is deposited_TwoOnly or as needed First, SiO_TwoOr SiO_TwoAnd ZrO_TwoHfO combined with a mixture of_TwoConsisting of And a wash coat of the heat resistant carrier described above. An improved high-temperature catalyst treatment method within the scope of the present invention is the same as that of the above-described present invention. And the use of a catalyst and a catalyst body structure, in particular, in the preferred embodiment of the present invention as described above. It includes an improved process for burning a fuel mixture using a media structure. Advantages of the heat-resistant support of the present invention include, for example, ZrO_TwoOr SiO_TwoStabilized ZrO_Two Responsible Compared to a carrier, etc., in a high temperature environment where oxygen and / or water vapor exists, In addition to always providing high thermal stability, ZrO_Two Or SiO_TwoStabilized ZrO_TwoIncreased sintering as seen at high temperatures when supported on Addition is not observed in the heat-resistant carrier of the present invention. Furthermore, the heat-resistant support of the present invention has a high affinity for a white metal catalyst, No body-associated catalyst contamination occurs. Finally, the white metal (especially palladium) When used as a wash coat in the catalyst body structure of the present invention, HfO of the invention_TwoThe heat-resistant support containing the conventional ZrO_TwoOr SiO_TwoStabilized ZrO_Two Catalytic combustion process, including a fire extinguishing temperature (LOT) lower than the temperature in the washcoat It has outstanding performance in theory. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 shows a prior art ZrO._TwoTemperature / surface area graph showing stability of loaded carrier FIG. 2A, 2B, 3A and 3B show prior art ZrO._TwoIntroduced stability of contained carrier FIG. 4 is a temperature characteristic diagram comparing a bright heat-resistant support with a surface area and a catalyst size. FIG. 4 shows the conventional support and the present invention when fired at two different temperatures for a predetermined period. FIG. 5 is a bar graph showing changes occurring on the surface of various heat-resistant supports including a support. FIG. 5 shows the conventional carrier and the present invention during the expansion period at high temperature in the presence of steam. FIG. 4 is a time graph showing the surface stability of various heat-resistant supports including a carrier. FIG. 6 shows the supported Pd catalyst of the present invention and the prior art before and after the calcination for a predetermined period. It is a bar graph which shows the comparison of the surface area of a supported Pd catalyst. FIG. 7 shows a prior art refractory carrier during an extended period at high temperature in the presence of steam. The surface resistance of the heat-resistant support of the present invention and the Pd catalyst supported on it, It is a time graph figure which shows qualitative. Detailed description of the invention The hafnium-containing heat-resistant carrier of the present invention has a considerable amount of vapor, that is, evaporated water. Under reaction conditions including the presence, for example, at surprisingly high It is characterized by high surface stability. In addition, platinum or palladium, etc. High temperature stability can be maintained even when one or more white metal To extend the working life of the catalyst in high-temperature treatments such as combustion and partial combustion. Let In order to ensure a predetermined level of surface stability during high temperature treatment, the heat resistance Of the support (SiO_TwoAnd / or ZrO_TwoHfO)_TwoThe amount of Not more than about 5 mol% of metal oxide, and more than 10 mol% It is preferred that From this viewpoint, the auxiliary metal oxide component in the heat-resistant carrier is T SiO_TwoIs contained, the SiO_TwoAmount of the carrier oxide is 5 to 15 Mol%, SiO 2 in the heat-resistant oxide carrier_TwoWith ZrO_TwoWhere is included In that case, the ZrO_TwoIs preferably in the range of 5 to 80 mol% of the support oxide. Good. To ensure surface area for stability in high temperature reactions, use a heat-resistant oxide support The invention is particularly advantageous when a catalytic substance consisting of a white metal is deposited thereon. Baking at a temperature of about 1100 ° C. for 10 hours After doing so, at least 5 square meters / gram (m^Two/ G) is important is there. The surface area of the hafnium-containing heat-resistant carrier is 1 at a temperature of about 1100 ° C. After firing for 0 hours, about 10m^Two/ G or more, and 20 (m^Two/ G) Hope there is. The surface area value described in this section is measured by the BET method or a similar method. Is defined. The minimum surface area for stable high temperature processing is the minimum surface area of the present invention._Two SiO for preparing stabilized hafnium-containing heat-resistant oxide carrier_TwoPrecursor Used to prepare the refractory oxide support of the present invention, including the impregnated microcrystals. U, HfO_TwoOr HfO_Two・ ZrO_TwoSize of solid solution (see below) Can be obtained by precisely controlling the noise. Hafnium and hafnium / zirconia solids used in the heat-resistant oxide support of the present invention The solution can be prepared and prepared from the appropriate oxide precursor by precipitation or hydrolysis. The solid oxide is HfO in a desired size range used in the heat-resistant oxide carrier of the present invention._TwoMa Or HfO_Two・ ZrO_TwoIs fired in order to secure microcrystals. The oxide of the present invention If the support contains silica, the calcined HfO_TwoOr HfO_Two・ Z rO_TwoSiO in microcrystalline material_TwoImpregnate the precursor solution and hydrate the impregnated solid. Upon melting and calcining, the desired silica-stabilized HfO_TwoOr HfO_Two・ ZrO_Two A solid solution of To achieve. HfO_TwoOr HfO_Two・ ZrO_TwoRange of the desired crystal size of the present invention The average crystal diameter varies depending on the intended application of the heat-resistant oxide support. Therefore, it is generally desired that the thickness be 5 to 15 nanometers (nm) before the silica stabilization step. Good. If a large surface area is required, or if advanced sintering is performed, Crystal diameters between 5 nm and 10 nm are preferred, with little or no sintering If a more constant treatment is required, a crystal with a diameter of about 10 to 15 nm It is better to use Hafnium (zirconia), a heat-resistant oxide used as a precursor in the present invention The compound is combined with a water-soluble organometallic compound such as acetate or alkoxide, Includes water-soluble metal salts such as halides, nitrates and sulfates. Suitable destination HfOCl_TwoAnd ZrOCl_TwoHydrates of oxyhalides such as , HfO (NO_Three) And ZrO (NO_Three). Of the present invention In the case of a silica-stabilized refractory oxide support, the silica source is generally aqueous or alkaline. A solution that dissolves in a coal impregnation solution and turns into an oxide at the same time as hydrolysis and calcination Any silicon compound may be used so as to be dissolved in the silicon. For this reason , Suitable silica sources include alkoxysilicates, tetraethylorthosilicates, etc. Which organosilicate containing alkyl silicate and tetraethylortho Like. The silica precursor is tetraethylorthosilicate (T EOS) is most preferred. As described above, HfO in the heat-resistant oxide support of the present invention is used._TwoOr HfO_Two・ Zr O_TwoSolid solutions can be prepared by precipitation or hydrolysis of various starting materials. Settling operation Product (that is, HfO_Two・ ZrO_Two(Co-precipitation when a solid solution is formed) A suitable precipitate, such as a group such as an alkali metal hydroxide or ammonium hydroxide. The agent is an oxide precursor compound, HfOCl_TwoOr HfOCl_TwoAnd Z rOCl_TwoTo an aqueous solution of a homogeneous mixture of Unwanted unnecessary compounds or Is such that the product of precipitation evaporates during calcination and can be decomposed as described below. It is desirable to select a precipitant. For this reason, preferred precipitants are ammonium hydroxide And ammonium compounds such as ammonium and ammonium carbonate. Precipitation operation is dilute Alternatively, it can be performed in a concentrated aqueous solution. In addition, the ratio of adding the precipitant and the stirring The degree of It depends on the properties of the required precipitate. For a given microcrystal size range If a coarse precipitate is formed in the surrounding area, dilute the precipitate solution and add It is desirable to slow the speed and increase the agitation. The temperature during the addition of the precipitant was 1 About 5 to 90 ° C is good. Increasing the temperature can produce a coarse precipitate. Through Normal addition of the precipitate is theoretically excessive, ie, until the pH value is about 9-11. Do with. Following precipitation, filter and centrifuge, if necessary, before calcination The precipitate (HfO)_Two-ZrO_TwoCo-precipitation mixing when using solid solution From the slurry. HfO used in the heat-resistant carrier of the present invention_TwoAnd HfO_Two・ ZrO_TwoWhen hydrolysis is performed to obtain a solid solution, precursors and oxides are generally used. An aqueous solution of the precursor is heated to a temperature of about 100 ° C. to 250 ° C. under a pressure of 1 to 40 atm. The hydrolysis is carried out under hot water conditions such as heating to a maximum temperature. After hydrolysis, solid acid The slurry-like product containing fluoride particles can be filtered or baked if necessary before firing. Performs well-known liquid / solid separation processes such as centrifugation to collect and wash solid products I do. HfO in the size range required for the heat-resistant carrier of the present invention_TwoOr HfO_Two・ ZrO_Two Solids recovered from the precipitation and hydrolysis described above to obtain solid solution microcrystals The product is fired in air at a temperature of about 400 to 1000 ° C for about 5 to 15 hours. Is done. The required firing temperature depends on the desired end use temperature and stability level . It is desirable to bake in air at 1000 ° C. for about 10 hours. Raw from firing The product can be directly used for the heat-resistant support of the present invention. It is preferable to add and stabilize. The calcined HfO_TwoOr HfO_Two・ ZrO_TwoAdd a certain amount of silica to the solid solution To add, the calcined solids must be dissolved in an appropriate amount sufficient to hydrolyze the silica precursor. Silica precursor compound in water or water / alcohol mixture with mechanical or organic acid Contact with the dissolved solution. During the hydrolysis, the silica remains on the surface of the ionic calcined solid. When the hydrolysis is completed, it is converted to silicon oxide or hydroxide. You. Hydrolysis involves heating the calcined solids in contact with the silica precursor to 60-100 ° C. It is desirable to heat for about 6 to 16 hours. Sintered solids with silica precursor solution Any conventional method can be used to contact the It is desirable to soak the solids in the silica precursor solution. After the impregnation operation, the SiO_TwoCheap Stabilization HfO treated_TwoOr HfO_Two・ ZrO_TwoSolid solution is air In about 800 ° C to 1100 ° C. The catalyst of the present invention comprises HfO_Two, SiO_TwoStabilized HfO_Two, SiO_TwoStabilized HfO_Two・ ZrO_TwoDie on hafnium-containing refractory metal oxide carrier that can be selected from solid solution Platinum, ruthenium, palladium, iridium, rhodium etc. A catalytically effective amount of a white metal, HfO_TwoIs above 1000 ° C. This is an amount that can ensure the thermal stability of the catalyst at the temperature. The white metal is white Gold, palladium, or a mixture thereof, and a heat-resistant metal oxide carrier Is HfO_TwoAt a temperature exceeding 1000 ° C. can secure the thermal stability of the catalyst. SiO 2_TwoOr SiO_TwoAnd ZrO_TwoHfO with added_TwoChoose from It is desirable. More preferably, the catalyst is SiO 2_TwoOr SiO_TwoAnd ZrO_TwoBut HfO added_TwoEffective amount of catalyst on refractory metal oxide carrier selected from And the carrier is HfO_TwoIs at least the total amount of metal oxides , And the surface area of the support was determined after calcination at 1100 ° C. for 10 hours. At least 5m^Two/ G. To make the catalyst of the present invention, a metal deposit method well known in the catalyst technology is used. By using a predetermined amount of a white metal or a mixture thereof, a hafnium-containing heat-resistant oxide Deposit on the carrier. Of white metal added to the fired support The amount is such that the catalyst can be catalyzed in the desired application. Hafnium-containing support The amount to be added to the body depends on the reaction process for catalytic treatment, It depends on various factors and requirements, such as level, lifespan and the presence of pollutants. Unfortunate Covers the largest amount of carrier without the necessary catalyst sintering or associated losses of action The theoretical maximum amount of metal may be sufficient. There are factors to consider and the final touch The maximum catalytic activity per unit weight of the medium is due to the high surface coverage of the Coverage, but a higher surface area coverage enhances sintering, The result is to promote the growth of the particle size. In addition, it is necessary to consider the shape of the catalyst carrier There is. If the carrier is used in a high space velocity environment, sufficient To maintain the conversion, the catalyst load must be high. From an economic perspective The goal is to use the minimum amount of catalyst that can perform the desired action. As a result, the catalyst Burning Due to the presence of contaminants in the reaction feed such as fuel during burning, the catalyst becomes inert High catalyst loads must be applied to offset the degradation of . In the general case, the amount of metal of the white metal used in the catalyst of the present invention depends on the catalyst support. A small portion and does not exceed 25% by weight of the calcined support. The amount to economically maintain high working capacity over a wide range of use is about 0.01% About 20%. These percentages are based on the weight of the calcined support. On an inert substrate such as a metal foil substrate (described below). When a medium carrier is used, the catalyst carrier is about 10% to 25% by weight of the substrate, The percentage weight of white metal relative to the total weight of the catalyst support is relatively low. The used white metal or the mixture thereof is a chemical reaction of a specific catalyst. It is determined by a predetermined example of catalyst treatment, predetermined reaction conditions, economy, and the like. Available white metals include platinum, ruthenium, palladium, iridium, b There are didium and mixtures thereof. In the treatment of catalytic combustion and partial combustion Platinum, palladium, and mixtures of platinum and palladium are preferred. Dium is most preferred. The metal of the white metal is a metal complex containing a white metal, a compound, a dispersion, or the like. Is bonded to the hafnium-containing support in various ways using The compound or complex Is a compound that can be dissolved in water or a hydrocarbon solvent. White metal precipitated from solution Let In general, the liquid evaporates while the white metal is left in a dispersed state on the carrier. Any material that can be removed from the catalyst carrier by decomposition or decomposition may be used. Suitable white metal complex Examples of bodies and compounds include chlorides, oxides, sulfides, nitrides and nitrides of white metal. Radium diamine, palladium hydroxide tetramine, secondary chloroplatinic acid, palladium chloride Umtetramine, sodium palladium chloride, palladium 2-ethylcaproate, Hexamine rhodium chloride, hexamine iridium chloride, potassium chloride palatinum, And other white metal salts and complexes. Very active from chloride compounds Can be made, but it is good when using a catalyst in a gas turbine combustion device. Not a choice. Even in small amounts of chlorides, turbine blades and water receivers Generates rust. Therefore, when the catalyst is used in the combustion device of a gas turbine, Is most preferably a precursor of nitrogen-containing palladium or platinum. Hafnium content carrier After decomposition treatment on the support, the complex or compound of the white metal is subjected to a treatment such as firing. , Almost all of the white metal is converted to its elemental form or oxide. The catalyst carrier on which the catalyst of the present invention is supported may be used according to the desired final application purpose and reaction conditions. It can be used in various conventional forms. For example, the catalyst support of the present invention is: It can be in the form of spheres, pellets, rings, etc. with a diameter of 0.25 inches or less. No. When used for combustion or partial combustion, the catalyst carrier is For the passage of the combustion gas mixture so as to deposit on at least part of the Single or monolithic metal or channel bundles arranged in a vertical direction It is preferable to coat the surface of a ceramic substrate with the catalyst carrier of the present invention. Further In addition, the monolithic substrate is adapted for its application in a vertically deployed channel or passage. Honeycomb that enables the high space velocities required for examples with minimal pressure drop Shape, spiral shape of corrugated sheet (sandwiched between flat separation sheet materials), column shape ( ), And other shapes of metal. The substrates are extensible Therefore, it can be easily attached to surrounding components and is thinner than the ceramic carrier. Since it can be formed in a wall shape, the fluid resistance is reduced. Another practical advantage of metal substrates is that they are resistant to thermal shock. like that Thermal shock occurs when starting and stopping the turbine during gas turbine operation. Especially when the turbine has to be shut down momentarily. Live. In the latter case, shut off the fuel supply, that is, The turbine will trip because the physical load on the turbine is removed. Fuel for turbine If the supply is momentarily shut off, overspeed can be prevented. Then, (related to the present invention) The temperature in the combustion chamber suddenly drops, and the temperature of the compressed air deviates from the combustion temperature. Change to a degree. The speed of this temperature drop is 1000 ° C. or more within one second. This result As a result, as described above, the catalyst carrier on the walls of the channels and passages of the metal substrate is depoted. Jit (or landing). In this effect, the catalyst layer is Aluminum, aluminum-containing or aluminized steel, stainless steel For example, stainless steel, high-temperature metal alloys such as cobalt alloys and nickel alloys, etc. There are several substrate materials that can be added. As a preferable example of the above-mentioned material, U.S. Pat. No. 4,414,023 of Agent et al. No. 4,331,631 of Chapman et al .; No. 3,969 of Cheanes et al. No. 082 describes such aluminum-containing steel. Kawasaki Steel ( River Light R20-5SR), Behring Deutsche Metals Co. (Alm Chrome IRE ), Allegenyl Drum Company (Aria IV), etc. To form a rough chemically reactive surface for better adhesion to the washcoat, Aluminum forms whiskers or crystals of alumina on steel surface when oxidized Sufficient dissolved aluminum is included to make it possible. As described above, before or after the formation of the integral structure, by a predetermined method, The medium carrier is coated on a predetermined area of the metal substrate. For example, an integrated structure of a spiral roll shape Before or after molding or assembling into a predetermined shape so that it can be made, A coating is formed on one or both surfaces of a plurality of sheets constituting a substrate structure. At this time, Herringbone wound non-nested in addition to alternating flat and corrugated sheets The spiral roll may be formed of a corrugated sheet having a shape. The catalyst carrier of the present invention is used in a step process. Can be formed on a metal substrate by using a hafnium-containing material. The heat-resistant carrier may be provided in a finely dispersed form of the finished carrier or in a predetermined carrier (as described above). Produced using proprietary precursors, then hydrolyzed and / or calcined to produce metal A layer of a desired hafnium-containing heat-resistant support, that is, a wash coat, is It forms. Washing hafnium-containing heat-resistant carrier on metal substrate When forming the coat, spray or submerge the substrate directly into the washcoat. For example, it is also possible to carry out in the same manner as when applying to the surface. Heat-resistant After forming the carrier layer or wash coat, the white metal is removed by the above-described method. After depositing to the Oshcoat, it is fired to complete the catalyst structure of the present invention. Let it. As another method, the final catalyst support composition is separately prepared by the method described above. From a finely dispersed state by spraying or immersion, or a floating state in a predetermined liquid carrier. May be applied to the surface of the metal substrate. Particularly, preferred embodiments of the present invention which can be effectively used for catalytic combustion and partial combustion of liquid fuel are as follows: A vertically adjacent catalyst coating chamber for the passage of a flowing gaseous reaction mixture. A catalytic body structure consisting of a metal foil substrate composed of Heat exchange between the catalyst-coated channel and the adjacent non-catalyst channel And at least a portion of the inner surface of the catalyst-coated channel is , HfO_TwoOnly, or if necessary, SiO_TwoAnd ZrO_TwoAnd HfO_Two/ SiO_Two And preferably SiO_Two/ HfO_Two・ ZrO_TwoHfO combined with a mixture_TwoMade of An effective catalytic amount of platinum metal, preferably palladium, Deposited at For example, on one side of the spiral corrugated plate structure as described above, Coat with thermal support washcoat and catalyst. And the coated corrugated sheet structure, Wrap it in a roll. In addition, it is possible to cover the catalyst support on one side of a sheet of the same material. In addition, it can be made into a rolled shape together with the corrugated sheet to create a spiral integrated structure. Wear. At this time, the surface of the integral structure coated with the catalyst generates heat in the combustion process. Live. This heat is transferred to a gaseous fluid or Transfers to the non-catalytic structure in contact, that is, to the cold surface. From there, the heat It propagates along the surface to the unburned gas passage. This allows air dilution and external heat exchange Heat exchange without the need for installation or other means, so that the catalyst surface Temperature control becomes possible. Such a temperature control is, for example, the preliminary heat temperature of the introduced gas. Is extremely high and is optimal when the gas flow rate is unstable. The catalyst structure is an average line of gas passing through the vertical channels of the catalyst structure. The speed is about 0.2 m / sec or more over the entire catalyst body structure and 60 m / sec. It is formed in a size shape that does not become faster. The lower limit is the methane fire It is higher than the flame front speed and the upper limit is It is an effective value. The average speed naturally differs for fuels other than methane. In the treatment using the catalyst or catalyst body structure of the present invention, the supported heterogeneous white metal A metal catalyst is used, the reaction temperature is high enough and / or Subjecting the catalyst to temperatures near or above 1000 ° C. Alternatively, it is essential that the process is shaken many times, causing sintering or deactivation of the catalyst. Although the reaction does not always occur, there is an exothermic reaction that may cause this. Like that In the catalytic treatment, the oxidation of ammonia to nitric acid and the conversion of methane to CO and H_TwoTo steam Reforming, complete oxidation of hydrocarbons for emission control, including vehicle emission control, fuel Combustion or partial combustion is performed. The process of the present invention in a preferred embodiment comprises a fuel Combustion or partial combustion. In a preferred embodiment, the gaseous or steam Departure The mixed fuel is mixed with an oxygen-containing gas such as air to form a catalyst body structure consisting of a metal foil substrate. The metal foil substrate is passed through the catalyst-coated channel disposed adjacently in the longitudinal direction. And a bundle of non-catalyst channels, a channel coated with catalyst and Is formed in a heat exchange relationship with the non-catalyst channel adjacent to the At least a portion of the inner surface of the channel is made of SiO 2_TwoOr SiO_TwoAnd ZrO_TwoBut HfO mixed_TwoDeposit of heat-resistant carrier made of Coated with an effective catalytic activity amount of palladium, and the heat-resistant support is After calcination at 000 ° C. for 10 hours, at least approximately 5 mol% of all metal oxide components HfO_TwoHaving a surface area of at least 5 m^Two/ G A gas mixture of fuel and oxygen-containing gas passes through the catalyst coating channel of the catalyst structure. At least partially burned. After catalytic combustion, a considerable amount of NOx Below the temperature at which is generated, for example, below 1500 ° C. or 1600 ° C. A homogeneous combustion zone in which combustion takes place follows. The method can be performed with various types of fuels and a wide range of conditions. For normal fuel Represents H in addition to hydrocarbon fuels._TwoAnd CO / H_TwoThere is a mixture. Methane, ethane, methane Normal gaseous hydrocarbons such as lopan are suitable as the source of the above processing fuel, The following hydrocarbon fuels that can be evaporated at the processing temperature are more preferable. For example, fuel is a liquid or gas at room temperature and pressure. As an example Low molecular weight aliphatics such as, butane, pentane, hexane, heptane, octane Hydrocarbons, gasoline, benzene, toluene, ethylbenzene, xylene, etc. Aromatic hydrocarbons, naphtha, diesel fuel, kerosene, jet fuel, intermediate refined products , Heavy oil (preferably hydrogen-treated to remove nitrogen compounds and sulfur compounds) ), Alcohols such as methanol, ethanol, isopropanol, butanol Oxygen-containing fuels such as diethyl ether, ethyl phenyl ether, MTBE Any ether is mentioned. In addition, low BTU such as city gas and syngas Gas can also be used as fuel. Fuel is generally mixed with combustion air in a predetermined amount and is generated in the process of the preferred embodiment. It results in a mixture having an adiabatic combustion temperature higher than the temperature. Its adiabatic combustion temperature is about 9 Desirably, the temperature is at least 00 ° C, and more preferably, at least 1000 ° C. . Non-gaseous fuels must be at least partially evaporated before contacting the catalyst surface Absent. The combustion air may be at or below atmospheric pressure, or It may be compressed to m or less. Basically, using the gas created by this method Constant gas turbines operate under instrument pressures ranging from 8 to 35 atm. . Therefore, the process should be performed at a pressure between about 0 and 35 atm, preferably between 0 and 1 atm. It is preferable to operate with a pressure of up to 7 atm. The fuel / air mixture applied to the catalyst must be well mixed, The input temperature depends on the fuel used. This temperature preheats the gas to the heat exchanger. It can be provided by heat or adiabatic combustion. In this treatment, the palladium deposited on the hafnium-containing heat-resistant support The metallic material is designed to have a low catalytic action on the gaseous fluid. Coated on body substrate. Partial combustion gas discharge internal temperature away from the area containing the catalyst And the wall temperature of the catalyst is the adiabatic temperature, that is, the gas temperature when the fuel is completely burned. Lower than the degree. Usually, the temperature of the gas that excites the catalyst is about 720 to 950 ° C. is there. Further, the temperature of the catalyst substrate is 1100 ° C. or less, and does not exceed 950 ° C. Is desirable. These temperatures are determined by the device pressure, oxygen partial pressure, fuel calorie value, gas It depends on various factors such as the specific design structure and performance requirements of the turbine. To Nevertheless, the catalyst causes partial oxidation of the fuel but insulates the fuel / air mixture It is limited to a temperature value below the temperature. Experimental example Preparation of the heat-resistant catalyst carrier of the present invention, the contact of the present invention using the heat-resistant catalyst carrier The medium carrier and the heat-resistant carrier of the present invention are used as a wash coat on an integral metal substrate. Catalyzed white metal or deposited on the washcoat Examples of application of the catalyst body structure, and use in the catalyst and catalyst body structure of the present invention Experimental examples showing the high-temperature stability and performance of the heat-resistant support of the present invention will be described below. same Sometimes, a heat-resistant support, a catalyst, and a catalyst structure for comparison are also described. Two different methods were used to test high temperature stability in air or steam. used. Run the sample material in a static air muffle furnace for heat treatment in the atmosphere Heat to a specified temperature at a ramp rate of 10 ° C / min. Left. Empty the sample material in a tube furnace for heat treatment in the atmosphere with steam added. The mixture was heated at a ramp rate of 3 ° C./min while flowing a gas mixture of gas and 10% moisture vapor. So The main characteristic of a good carrier is high surface temperature at high temperature. Volume and low crystal grain size, where high surface area and low crystal grain size are interrelated Therefore, the surface area and / or crystal particle size after high temperature treatment were measured. . The total area is usually in m^Two/ G measured by the BET method. Be careful here What I want is HfO_TwoHas a density of ZrO_Two1.7 times the density of Therefore, HfO_TwoAnd ZrO_TwoOf the same particle size, ZrO_TwoBET surface area Is 1.7 times larger. Furthermore, what is important in this case is the substrate or watch. When the coat thickness is the same and the wash coat thickness is the same, the weight part is HP O_TwoIt is necessary to use one that is almost 1.7 times as large as. Therefore, for the comparative example, ZrO_TwoThe BET surface area by compensating for the density difference with respect to zirconium It is converted into an equivalent surface area, ie, ZESA. This ZESA has a dx and Sx The BET surface area of the test material, dx / dZrO_TwoIs ZrO_TwoZESA = (dx / dZ) rO_Two) × sX was calculated in the individual case using the formula. Testing the performance of the catalyst structure can simulate the conditions in a gas turbine combustor. In a high pressure reactor. The test equipment is a steel pressure covered with insulating ceramic. It consists of a pressure vessel and a pressure regulating valve arranged at the outlet thereof. Hot air vapor To obtain, high pressure air was pumped into an electric resistance heater. Inject methane fuel Mixing was carried out in a passage by a static mixer. The mixture of fuel and air is led to the catalyst. And sent to the post-catalyst process section. A thermocouple is installed upstream of the catalyst and introduced to the catalyst. Measure the temperature of the gas to be brought into contact with the catalyst surface inside the catalyst, measure the substrate temperature, The temperature of the gas in the same combustion zone after the catalytic action was measured downstream of the catalyst. In a fire extinguishing test to determine LOT, fuel is mixed with air and the temperature of the gas inlet to the catalyst is measured. The degree is increased at a constant rate. Depending on the activity of the catalyst, it depends on the inlet temperature. Starts the reaction with the fuel, and the catalyst temperature and the outlet gas temperature become higher than the inlet temperature. You. LOT is defined as the inlet gas temperature when the outlet gas temperature changes immediately. However, it is indicated by a change point in the characteristic diagram of the inlet temperature / outlet temperature. In the stability measurement, the conditions of the reactor were kept constant, and the stability was checked with the catalyst substrate. Monitor the outlet gas temperature for one hour or more. Test example 1 (sample preparation) Samples should be prepared or obtained directly from the supplier to report stability studies, etc. Explanations of terms are given for identification purposes in subsequent test examples.Sample A (Comparative sample of ZrO ₂ ) RC-100ZrO from DKK (Daichiikigenso Chemical Industry)_TwoPowder 100m surface area^Two/ G with a BET surface of about 0.3 cc / g pore volume O_TwoWas obtained.Sample B (comparison sample of SiO ₂ / ZrO ₂ ) ZrO from DKK (RC-100)_TwoThe powder is tetted using the incipient wetness method. 21.1 g of laethyl orthosilicate (TEOS), 2 mM HNO_ThreeIs 6.0 g and ethanol in a 30 ml solution. The resulting wet blend The mixture was placed in a closed container and heated at 60 ° C. for about 18 hours to add TEOS precursor water. Decomposition was performed. The solid after hydrolysis was dried at 110 ° C. The mixture was heated at a ramp rate of 10 ° C./min for 10 hours to a predetermined temperature and fired. The obtained sump Contains 11 mol% SiO_TwoWas included.Sample C (HfO ₂ ) HfO from Teledyne Wachan, Albany, Oregon_TwoPowder 20m surface area^Two/ G (ZESA is 34m^Two/ G) with a pore volume of about 0.12 cc / g HfO with BET initial surface_TwoWas obtained.Sample D (SiO _₂ / HfO ₂₎ HfO from Teledyne Wachan, Albany, Oregon_TwoTo ZrO_Twoso Alternately, different amounts of TEOS (12.37 g) and 2 mM NO_Three(4.0g) In the same manner as in Sample B, except that_Two/ HfO_TwoPrepared . The dried sample in this example also had 11 mol% SiO_TwoWas included.Sample E (SiO _₂ / HfO ₂₎ Teledyne HfO_TwoWet cake (our company's product RGSHfO_TwoIntermediate) Except that the second SiO 2 was used in the same manner as in Sample D described above._Two/ Hf O_TwoSa A sample was prepared. Dry this wet cake in an oven at 110 ° C for about 20 hours And SiO_TwoPre-baking at 400 ° C for 10 hours before impregnating with Was obtained as a single phase crystal having a thickness of 5 nm. This dried SiO_Two/ HfO_Twosample Has 13 mol% of SIO_TwoWas included.Sample F (Si ₂ / ZrO ₂ · HfO ₂ ) HfO_Two・ ZrO_TwoSolid solution (10 mol% HfO_Two) To prepare ZrOCl in distilled water_Two・ 8H_TwoO (40 g) and HfOCl_Two・ 8H_TwoO (5.6 g ) Is dissolved, the solution is sealed in a Teflon-lined perbomb container, and the solution is sealed. Is heated at 200 ° C. for 17 hours, and the obtained solid phase is heated at 110 ° C. for 20 hours. Dried in oven. 7 mol% SIO_TwoStarting to produce dry solids containing This dried sample was prepared in the same manner as in Sample B, except that the amount of material was adjusted. SiO on pull_TwoWas impregnated.Sample G (SiO ₂ / ZrO ₂ · HfO ₂ ) HfO_Two・ ZrO_TwoSolid solution (17 mol% HfO_Two) To prepare HfOC1 in 1000 ml of distilled water_Two・ 8H_TwoO (38.12 g) and ZrOCl_Two ・ 8H_Two0 (150 g) and dissolve NH3 until the pH value is 10-11._TwoWith OH Settled. The precipitated gel is washed several times with distilled water until chloride ions are gone. At 60 ° C. in a rotavap container (approximately 200 minutes at approximately 0.5 mmHg). Dry to produce a dry powder. This powder is pre-fired at 600 ° C. for 10 hours, SiO_TwoUse the same method as for sample B above, so that the final mole% value of What is SiO_TwoWas impregnated.Sample H (SiO ₂ / ZrO ₂ · HfO ₂ ) HfO_Two・ ZrO_TwoSolid solution (57 mol% HfO_Two) To prepare HfOCl in 500 ml of distilled water_Two・ 8H_TwoO (211 g) and ZrOCl_Two・ H_Two O (123 g) is dissolved and NH is added until the pH value is 10-11._FourPrecipitated with OH Was. The precipitated gel was stirred three times with distilled water and once with ethanol / centrifugation cycle. And rinsed in a rotavap container at 60 ° C. (approximately 0 min) to produce a dry powder. This powder is pre-fired at 500 ° The final dry product has 15 mol% SiO_TwoSo that sample B and S in the same way iO_TwoWas impregnated.Sample I (Pd of SiO ₂ / ZrO ₂ comparison sample) In the same manner as in Sample B above,_Two/ ZrO_TwoPrepare sample and overconcentrate Pd (NH) dissolved in nitric acid_Three)_Two(NO_Two)_TwoImmersion in a solution of After drying for 10 hours, the SiO_Two/ ZrO_TwoCarrier SiO_TwoIs 11 mol% Like SiO_Two/ ZrO_Two20% by weight of Pd was produced on the catalyst.Sample J (Pd of SiO ₂ / HfO ₂ ) SiO prepared in the same manner as in Sample D above_Two/ HfO_TwoSample (in this case Is SiO_Two11 mol%) is the same as that described in the sample I. After impregnating with Pd by a method and drying,_Two/ HfO_Two10% by weight of P on the catalyst d was generated. Experimental example 2 (stability of comparative sample) Sample ZrO_Two(Sample A) and SiO_Two/ ZrO_Two(Sample B) in air For 10 hours at various temperatures ranging from 600 ° C. to 1100 ° C. in The BET surface area was measured. FIG. 1 shows the measurement results. As shown in FIG. SiO_TwoStabilized ZrO_TwoIs ZrO_TwoIs more stable than just When sintering at 0 ° C. or more, considerable sintering occurs and the surface area loss is 5 m.^Two/ G or less It is lower. Experimental Example 3 (stability of HfO ₂ and SiO ₂ / HfO ₂ , Comparison between ZrO ₂ and SiO ₂ / ZrO ₂ ) Sample HfO_Two(Sample C) and SiO_Two/ HfO_Two(Sample D) and Material Comparative sample ZrO containing (Samples A and B)_TwoFrom 600 ° C in air to 1 Baking at various temperatures in the range of 100 ° C. for 10 hours, and ZES of each baked sample The A surface and crystal size were examined to determine the stability of the fired material. The measurement result The results are shown in FIGS. 2A and 2B. As shown in FIGS. 2A and 2B, HfO_TwoIs 800 ° C In the above case, ZrO_TwoMore stable than SiO_TwoStabilized HfO_TwoIs 1100 ° C Above is completely stable, but on the other hand, SiO 2_TwoStabilized ZrO_TwoAt high temperatures Considerable sintering has occurred. In comparison of FIG. 2A and FIG._TwoStable HfO_TwoNo change in crystal size, but there is a decrease in surface area and sintering of silica Decrease in surface area Indicates that it is connected. SiO_Two110 with negligible surface area Even after firing at 0 ° C., the starting material SiO_TwoStabilized HfO_TwoSiO_TwoSurface area Of raw HfO_TwoIt is the same as that of Thus, 1100 ° C or higher Observations on the stability of crystal size at temperature are remarkable. Experimental Example 4 (Stability of SiO ₂ / HfO ₂ , Comparison with SiO ₂ / ZrO ₂ ) SiO_TwoStabilized HfO_TwoTwo different samples (samples D and E) Pull SiO_TwoStabilized ZrO_Two(Sample B) in air at 800 ° C. to 1100 Bake for 10 hours at various temperatures in the range of ℃, inspect ZESA surface and crystal size Then, the stability of the sample was measured. From the measurement results shown in FIGS. 3A and 3B, HfO_Two Both of the samples containing 2-stabilized ZrO_TwoShows a large decrease in surface area, and at temperatures close to 1100 ° C The crystal size is increasing. Experimental Example 5 (SiO ₂ stabilization Stability of HfO ₂ · ZrO ₂ solid solution) Various amounts of HfO_TwoHfO containing_Two・ ZrO_TwoSiO_TwoStabilized solid solution (sample F, G, H) and SiO_TwoStabilized ZrO_Two(Sample B) and HfO_Two(Sun Pull C) in air at various temperatures ranging from 1000 ° C. to 1100 ° C. for 10 hours Calcination, measure the ZESA surface and adjust the stability of the sample at the calcination temperature used. Solid. FIG. 4 shows the measurement results. As shown, SiO 2_TwoStabilized HfO_TwoIs SiO at 1100 ° C_TwoStabilized ZrO_TwoShows very good stability compared to , SiO_TwoStabilized HfO_Two・ ZrO_TwoThe solid solution is HfO_TwoMore than 10 mol% stabilization When a component is contained, (SiO_TwoStabilized HfO_TwoExcellent cheap) It turns out that it has qualitative properties. Experimental Example 6 (for SiO ₂ / ZrO _{2 in} steam, Stability of SiO ₂ / HfO ₂ ) Two different types of SiO2_CheapHfO_TwoHeat-resistant carrier (samples D and E) and S iO_TwoStabilized HfO_Two・ ZrO_TwoSiO to be compared with solid solution (sample H)_TwoStabilization ZrO_Two10% H with the carrier (sample B)_TwoAt 1035 ° C in O and air Changes over time in about 500 hours to determine the change in surface area of a portion of those samples Periodical (1 (Every 00 hours). FIG. 5 shows the results of the surface area measurement values over time. Figure As shown in FIG._Two・ HfO_TwoSilica-stabilized HfO containing solid solution_Two Although the composition maintained approximately the same surface area throughout the test,_TwoStabilized Z rO_TwoThe surface area was significantly reduced during the 100-hour aging test. this child Is the heat resistance of the present invention with respect to a conventional carrier in an environment where steam exists at high temperature. This shows the superiority of the functional carrier. Experimental Example 7 (Stabilization of SiO ₂ with palladium added) Stability of ZrO ₂ or HfO ₂ support) SiO_TwoStabilized ZrO_Two(Sample I) and SiO_TwoStabilized HfO_Two(sample J) A sample of a palladium catalyst carrier with Pd deposited on The catalyst was calcined at 050 ° C for 10 hours, and the surface area of the calcined catalyst was determined by depositing Pd metal. Before being fired in air at 1000 ° C. for 10 hours. . FIG. 6 shows the test results. As can be seen from the results in FIG. And before and after firing, SiO_TwoStabilized HfO_TwoLittle change in surface area But SiO_TwoStabilized ZrO_TwoHas a basically reduced surface area. _{_{_{SiO 2 / HfO 2, SiO 2}}} / ZrO 2 in Experimental Example 8 (vapor, Stability of Pd catalyst supported on support) SiO_TwoStabilized ZrO_Two(Sample I) and SiO_TwoStabilized HfO_Two(sample J) A sample of a palladium catalyst support having Pd deposited thereon, and These carriers (samples B and D) themselves were used to change the surface area of a portion of those samples. 10% H to regularly check the chemical conversion (every 100 hours)_TwoO and 103 in the air Aged at 500C for approximately 500 hours. The results are shown in the graph of FIG. As shown, SiO 2_Two/ HfO_TwoThe above Pd catalyst is for 300 hours test period in steam The surface area was almost maintained for a while._TwoStabilized ZrO_TwoOf the above Pd catalyst The surface area remains low after a 100 hour aging test period in steam. Dropped. This proves the stability of the carrier in steam, and FIG. As shown, during 500 hours of aging in steam, SiO 2_TwoCheap HfO_TwoHas almost no change in its surface area, At the 100th hour, the SiO_TwoStabilized ZrO_TwoHas lost almost all of its surface area by.Experimental Example 9 (HfO ₂ or SiO ₂ stabilized HfO ₂ Use of catalyst integrated structure with HfO_TwoAnd SiO_TwoStabilized HfO_Two(Both for the catalyst body structure of the present invention), and , ZrO_TwoAnd SiO_TwoStabilized ZrO_Two(Both for the comparative catalyst structure) Pd deposited on the washed substrate washcoat and Fe / Cr / Preparing a lab-scale catalyst body structure consisting of a monolithic substrate made of Al metal foil; The LOT inspection was performed as described above. When preparing the test catalyst structure, The foil is composed of a ribbon-shaped corrugated sheet, oxidized in air at 900 ° C, Alumina whiskers were formed. One side of the corrugated foil is coated with HfO in aqueous solution._Two , SiO_Two/ HfO_Two, ZrO_Two, SiO_Two/ ZrO_TwoSpray the colloidal sol of After that, the coated foil was fired in air at the temperature shown in Table 1 below, Each washcoat-treated foil was prepared. A predetermined concentration of a Pd precursor (Pd [NH_Three ]_Two[NO_Two]_TwoExcess HNO_ThreeDissolved in water together with palladium metal After firing, a predetermined amount of Pd is coated on the washcoat-treated foil. A film was formed. In other words, the surface of the metal foil covered with the wash coat described above Spray the Pd precursor solution on top and fire the foil in air at the temperature shown in Table 1. And a foil surface area cm also shown in Table 1.^TwoPer Pd density was generated. After firing A straight channel with longitudinal channels extending axially of the catalyst body structure without overlapping the corrugated plates Corrugated plate to form a metal structure 2 inches in diameter and 2 or 3 inches in length The foil was rolled. The thus constructed structure was subjected to a LOT test by the above-mentioned well-known method. Inspection is 11.9 atmospheric pressure using a methane / air mixture with an adiabatic combustion temperature of 1300 ° C Went under. Inspection results showing further properties of the catalyst structure used are listed in Table 1. Have been.(A) 15 mol% SiO_TwoWash coat with. (B) 11 mol% SiO_TwoWash coat with. (C) 15 mol% SiO_TwoWash coat with. (D) 11 mol% SiO_TwoWash coat with. (E) Foil area cm^TwoCatalyst with 0.357 g of Pd per unit (pd / pt atomic ratio The rate is 6/1). As shown in Table 1, in all cases, HfO_TwoContaining washcoat The catalytic performance of the catalyst body structure of the present invention has the conventional ZrO_TwoContaining washcoat Is the same or superior in terms of low LOT as compared with the catalyst body structure of example For example, SiO_TwoStabilized HfO_TwoCarrier wash coat (6.2 mg / cm^Two)upper 0.62mg / cm^TwoThe POT catalyst has a LOT of 460 ° C._TwoStabilized Z rO_TwoCarrier Wash coat (5mg / cm^Two1.0mg / cm using^TwoFor Pd amount LOT is 500 ° C. Furthermore, SiO_TwoStabilized HfO_TwoCarrier washers Coat (7.4mg / cm^Two) Above, the amount of Pd catalyst is 0.185 mg / cm^TwoWhen Has a LOT of 510 ° C.,_TwoStabilized ZrO_TwoCarrier wash coat (5mg / cm^TwoHigh Pd amount above 0.25mg / cm^TwoBut LOT to 540 ° C turn into. Therefore, in either case, even if the working catalyst concentration is ZrO_TwoContained HfO, even if lower than the comparative catalyst structure with the refractory support washcoat_TwoIncluding In the case of the structure of the existing wash coat catalyst, the LOT temperature value is low. As described above, the present invention has been described with reference to examples and experimental examples. Experimental example is Akuma However, this is only an example and does not limit the present invention. In addition, the contract of the accompanying invention Without departing from the scope of the claims, it is also possible to determine equivalent cases to the described invention, Those skilled in the art will be able to do so. Of course, such equivalent cases are considered part of the present invention. available.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.⁷ 識別記号ＦＩテーマコート゛(参考）Ｆ２３Ｄ 14/18 Ｆ２３Ｄ 14/18 Ｅ (81)指定国ＥＰ(ＡＴ，ＢＥ，ＣＨ，ＤＥ，ＤＫ，ＥＳ，ＦＩ，ＦＲ，ＧＢ，ＧＲ，ＩＥ，ＩＴ，ＬＵ，ＭＣ，ＮＬ，ＰＴ，ＳＥ)，ＯＡ(ＢＦ，ＢＪ，ＣＦ，ＣＧ，ＣＩ，ＣＭ，ＧＡ，ＧＮ，ＭＬ，ＭＲ，ＮＥ，ＳＮ，ＴＤ，ＴＧ)，ＡＰ(ＫＥ，ＬＳ，ＭＷ，ＳＤ，ＳＺ，ＵＧ)，ＥＡ(ＡＭ，ＡＺ，ＢＹ，ＫＧ，ＫＺ，ＭＤ，ＲＵ，ＴＪ，ＴＭ)，ＡＬ，ＡＭ，ＡＴ，ＡＵ，ＡＺ，ＢＢ，ＢＧ，ＢＲ，ＢＹ，ＣＡ，ＣＨ，ＣＮ，ＣＵ，ＣＺ，ＤＥ，ＤＫ，ＥＥ，ＥＳ，ＦＩ，ＧＢ，ＧＥ，ＨＵ，ＩＬ，ＩＳ，ＪＰ，ＫＥ，ＫＧ，ＫＰ，ＫＲ，ＫＺ，ＬＫ，ＬＲ，ＬＳ，ＬＴ，ＬＵ，ＬＶ，ＭＤ，ＭＧ，ＭＫ，ＭＮ，ＭＷ，ＭＸ，ＮＯ，ＮＺ，ＰＬ，ＰＴ，ＲＯ，ＲＵ，ＳＤ，ＳＥ，ＳＧ，ＳＩ，ＳＫ，ＴＪ，ＴＭ，ＴＲ，ＴＴ，ＵＡ，ＵＧ，ＵＺ，ＶＮ──────────────────────────────────────────────────続き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) F23D 14/18 F23D 14/18 E (81) Designated country EP (AT, BE, CH, DE, DK, ES , FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN , TD, TG), AP (KE, LS, MW, SD, SZ, UG), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU , AZ, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, HU, IL, IS, JP, KE KG, KP, KR, KZ, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG , SI, SK, TJ, TM, TR, TT, UA, UG, UZ, VN

Claims

[Claims] 1. A refractory metal oxide support for a catalyst, comprising SiO 2_TwoOr SiO_TwoWhen ZrO_TwoHfO mixed with_TwoHfO_TwoExceeds 1000 ° C At a temperature sufficient to ensure the thermal stability of the carrier. Characterized heat resistant carrier. 2. HfO mentioned above_TwoIs at least about 5 mol% of all metal oxide components of the support. 2. The heat-resistant carrier according to claim 1, wherein the amount of the heat-resistant carrier is the amount of the heat-resistant carrier. 3. After said support is calcined at a temperature of 1100 ° C. for 10 hours, at least 5 m^Two3. A BET surface area of about 1 / g. Heat-resistant carrier. 4. The metal oxide is SiO_TwoHfO mixed with_TwoIs characterized by consisting of The heat-resistant carrier according to claim 3, 5. The aforementioned SiO_TwoIs about 5 to 15 mol% of the total metal oxide component of the support. The heat-resistant carrier according to claim 4, wherein the amount is an amount. 6. The metal oxide is SiO_TwoAnd ZrO_TwoHfO mixed with_TwoConsisting of The heat-resistant carrier according to claim 3, wherein: 7. The aforementioned SiO_TwoIs about 5 to 15 mol% of the total metal oxide component of the support. The amount of said ZrO_TwoIs also about 5 to 80 mol% The heat-resistant carrier according to claim 6, characterized in that: 8. HfO mentioned above_TwoIs greater than 10 mol% of the total metal oxide component of the support The heat-resistant carrier according to claim 7, wherein the heat-resistant carrier is only present. 9. HfO mentioned above_TwoOr ZrO_TwoHfO mixed with_TwoBut SiO_TwoBefore adding Is characterized by being present as microcrystals in the size range of 5 to 15 nm. The heat-resistant carrier according to claim 3, 10. A heterogeneous catalyst having high stability and its HfO_TwoIs 1000 ° C It is present in sufficient amount to ensure the thermal stability of the carrier at temperatures exceeding Una, SiO_TwoOr SiO_TwoAnd ZrO_TwoHfO mixed with_TwoHeat-resistant gold An effective catalytic amount of white metal deposited on a metal oxide support Is white Heterogeneous catalyst consisting of a metal-metal mixture. 11. HfO mentioned above_TwoIs at least about 5 mol% of the total metal oxide component of the support. 11. The heterogeneous catalyst according to claim 10, characterized in that the amount is in the order of magnitude. 12. After the support is calcined at a temperature of 1100 ° C. for 10 hours, at least 5m^Two/ Bg surface area of about 10 g / g. 2. The heterogeneous catalyst according to 1. 13. The metal oxide is SiO_TwoHfO mixed with_TwoCharacterized by consisting of The heterogeneous catalyst according to claim 12, wherein 14． The aforementioned SiO_TwoIs about 5 to 15 mol% of the total metal oxide component of the support. 14. Heterogeneous catalyst according to claim 13, characterized in that the amount is 15. The metal oxide is SiO_TwoAnd ZrO_TwoHfO mixed with_TwoConsisting of The heterogeneous catalyst according to claim 12, characterized in that: 16. The aforementioned SiO_TwoIs about 5 to 15 mol% of the total metal oxide component of the support. In the amount of ZrO_TwoIs also about 5 to 80 mol% The heterogeneous catalyst according to claim 15, characterized in that: 17． HfO mentioned above_TwoIs greater than 10 mol% of the total metal oxide component of the support 17. The heterogeneous catalyst according to claim 16, characterized in that it is present in an amount. 18. HfO mentioned above_TwoOr ZrO_TwoHfO mixed with_TwoBut SiO_TwoBefore addition Characterized in that it exists as a microcrystal having a size in the range of 5 to 15 nm. The heterogeneous catalyst according to claim 12, wherein 19. The white metal is platinum, palladium, or a mixture of platinum and palladium. 13. The heterogeneous catalyst according to claim 12, characterized in that it is selected from: 20. 20. The metal of the white metal is palladium. A heterogeneous catalyst as described. 21. Multiple longitudinal channels positioned adjacent to each other for the passage of a flowing reaction mixture Made of high temperature resistant ceramic or metal substrate formed in one piece structure with A catalyst structure, wherein at least a portion of the inner surface of the channel has its Hf O_TwoIs sufficient to ensure the thermal stability of the support at a temperature exceeding 1000 ° C. SiO that is present in a large amount_TwoOr SiO_TwoAnd ZrO_TwoHfO mixed with_Two Can Coated with a wash coat made of a heat-resistant metal oxide carrier Effective catalytic action is applied to the wash coat on at least a part of the channel. A catalyst structure, wherein an amount of white metal is deposited. 22. HfO mentioned above_TwoIs the total metal oxide of the carrier in the washcoat Be present in the washcoat in an amount of at least about 5 mol% of the components. The catalyst body structure according to claim 21, characterized in that: 23. The washcoat carrier is fired at a temperature of 1100 ° C. for 10 hours. After, at least 5m_Two/ Bg surface area of about 23. The catalyst body structure according to claim 21 or 22. 24. The metal oxide washcoat is SiO 2_TwoHfO mixed with_TwoOr 24. The catalyst body structure according to claim 23, comprising: 25. The aforementioned SiO_TwoIs 5% of all metal oxide components in the washcoat 25. The catalyst body structure according to claim 24, wherein the amount is about 15 mol%. 26. The metal oxide washcoat is SiO 2_TwoAnd ZrO_TwoAnd are mixed HfO_Two24. The catalyst body structure according to claim 23, comprising: 27. The aforementioned SiO_TwoIs 5 of the total metal oxide components of the washcoat carrier About 15 mol% of the above-mentioned ZrO_TwoBut also about 5 to 80 mol% 27. The catalyst body structure according to claim 26, wherein the amount is a degree. 28. HfO mentioned above_TwoIs 10% of the total metal oxide component of the washcoat support. 28. The catalyst structure according to claim 27, characterized in that it is present in an amount greater than mol%. Build. 29. HfO in the washcoat_TwoOr ZrO_TwoHfO mixed with_Two But SiO_TwoBefore the addition of, microcrystals in the size range of 5 to 15 nm The catalyst body structure according to claim 23, wherein the catalyst body exists. 30. The said base | substrate is a refractory metal, The Claim of Claim 23 characterized by the above-mentioned. Catalyst structure. 31. The white metal is platinum, palladium, or a mixture of platinum and palladium. The catalyst body structure according to claim 23, which is selected from the group consisting of: 32. 32. The metal of the white metal is palladium. The described catalyst body structure. 33. Adjacent for passage of reaction mixture consisting of fuel mixed with oxygen-containing gas A gaseous form made of a metal foil substrate formed by a series of arranged longitudinal channels Or a catalyst structure for performing partial or complete combustion of vapor fuel, At least a part of the inner surface of the channel is coated with a combustion catalyst, and the remaining The channel was uncoated and was adjacent to the catalyst-coated channel The non-catalytic channel is configured in a heat exchange relationship with the non-catalytic channel, Of the HfO_TwoIncreases the thermal stability of the support at temperatures exceeding 1000 ° C. SiO that is present in an amount sufficient to secure_TwoOr SiO_TwoAnd ZrO_Two HfO mixed with_TwoMade of a heat-resistant metal oxide carrier made of On the washcoat of the channel coated with the catalyst Is characterized in that an effective catalytic amount of white metal is deposited. Catalyst structure. 34. HfO mentioned above_TwoIs the total metal oxide of the carrier in the washcoat Be present in the washcoat in an amount of at least about 5 mol% of the components. The catalyst body structure according to claim 33, characterized by the following. 35. The washcoat carrier is fired at a temperature of 1100 ° C. for 10 hours. After, at least 5m^Two/ Bg surface area of about 35. The catalyst structure according to claim 33 or 34. 36. The metal oxide washcoat is SiO 2_TwoHfO mixed with_TwoOr 36. The catalyst body structure according to claim 35, comprising: 37. The aforementioned SiO_TwoIs 5% of all metal oxide components in the washcoat 37. The structure of claim 36, wherein the amount is about 15 mol%. 38. The metal oxide washcoat is SiO 2_TwoAnd ZrO_TwoAnd are mixed HfO_Two36. The catalyst body structure according to claim 35, comprising: 39. The aforementioned SiO_TwoIs 5 of the total metal oxide components of the washcoat carrier About 15 mol% of the above-mentioned ZrO_TwoBut also about 5 to 80 mol% 39. The catalyst body structure according to claim 38, wherein the amount is a degree. 40. HfO mentioned above_TwoIs 10% of the total metal oxide component of the washcoat support. 40. The catalyst structure according to claim 39, characterized in that it is present in an amount greater than mol%. Build. 41. HfO in the wash coat_TwoOr ZrO_TwoHfO mixed with_Two But SiO_TwoBefore the addition of, microcrystals in the size range of 5 to 15 nm 36. The catalyst body structure according to claim 35, wherein the catalyst body is present. 42. The substrate is a heat-resistant metal containing aluminum. 36. The catalyst body structure of claim 35. 43. The white metal is platinum, palladium, or a mixture of platinum and palladium. 36. The catalyst body structure according to claim 35, wherein the catalyst body structure is selected from: 44. 45. The metal of the white metal is palladium. The described catalyst body structure. 45. In high temperature catalysis by heterogeneous white metal catalysts in flowing reaction mixtures A method for catalytically converting the reactants of to a reaction product, (A) a step of mixing the above reactants at an appropriate ratio to produce a fluid reaction mixture; About (B) a plurality of adjacent longitudinal channels for the passage of the flowing reaction mixture; It consists of a high temperature resistant ceramic or metal substrate formed in an integral structure with Wherein the inner surface of at least a portion of the channel has its H fO_TwoIs sufficient to ensure the thermal stability of the support at a temperature exceeding 1000 ° C. SiO that is present in a small amount_TwoOr SiO_TwoAnd ZrO_TwoHf mixed with O_TwoCoated with a wash coat consisting of a heat-resistant metal oxide support made of On the washcoat that covers at least a portion of the channel. The catalytic body structure, in which an effective catalytic amount of white metal is deposited, Contacting said mixture at a reaction temperature. 46. A method of burning a combustible fuel mixture, comprising: (A) mixing a fuel and an oxygen-containing gas to produce a combustion mixture; (B) for the passage of a reaction mixture comprising a fuel mixed with said oxygen-containing gas. Composed of a metal foil substrate formed by a series of longitudinal channels arranged adjacent to each other A catalyst structure, wherein at least a part of the inner surface of the channel is a combustion catalyst; Coated, the remaining channels are uncoated and coated with the catalyst described above. Channel and the adjacent non-catalyst channel are configured in a heat exchange relationship. The inner surface of the catalyst coated channel described above is the HfO_TwoIs over 1000 ° C SiO that is present in an amount sufficient to ensure the thermal stability of the carrier_Two Or SiO_TwoAnd ZrO_TwoHfO mixed with_TwoHeat-resistant metal oxide carrier made of And a channel coated with the catalyst described above. An effective catalytic amount of white metal is deposited on the washcoat. Contacting said mixture with said catalyst structure. 47. HfO mentioned above_TwoIs at least 5% of the total metal oxide component of the support. % In the washcoat. Item 47. The combustion method according to Item 46. 48. The carrier in the washcoat is maintained at a temperature of 1100 ° C. for 10 hours. After firing, at least 5m^Two/ G of BET surface area 48. The combustion method according to claim 46 or 47. 49. The metal oxide carrier in the washcoat is made of SiO_TwoWas mixed HfO_Two49. The combustion method according to claim 48, comprising: 50. The aforementioned SiO_TwoIs the total metal oxide component of the washcoat support. 50. The combustion method according to claim 49, wherein the amount is about 5 to 15 mol%. . 51. The metal oxide carrier in the washcoat is made of SiO_TwoAnd ZrO_TwoAnd HfO mixed_Two49. The combustion method according to claim 48, comprising: 52. The aforementioned SiO_TwoIs 5 of the total metal oxide components of the washcoat carrier About 15 mol% of the above-mentioned ZrO_TwoBut also about 5 to 80 mol% 52. The method of claim 51, wherein the amount is a degree. 53. HfO mentioned above_TwoIs 10% of the total metal oxide component of the washcoat support. 53. The combustion method according to claim 52, characterized in that it is present in an amount greater than mol%. . 54. HfO in the washcoat_TwoOr ZrO_TwoHfO mixed with_Two But SiO_TwoBefore the addition of, microcrystals in the size range of 5 to 15 nm 48. The combustion method according to claim 46 or 47, wherein the fuel is present. 55. HfO mentioned above_TwoIs the total metal oxide component of the washcoat support. 49. The method according to claim 48, characterized in that it is present in an amount of at least about 20 mol%. Burning method. 56. The white metal is platinum, palladium, or a mixture of platinum and palladium. 47. The combustion method according to claim 46, wherein the method is selected from: 57. 57. The metal of the white metal is palladium. The combustion method as described.