JP3480867B2 - Catalyst body and method for producing the same - Google Patents
Catalyst body and method for producing the sameInfo
- Publication number
- JP3480867B2 JP3480867B2 JP12251095A JP12251095A JP3480867B2 JP 3480867 B2 JP3480867 B2 JP 3480867B2 JP 12251095 A JP12251095 A JP 12251095A JP 12251095 A JP12251095 A JP 12251095A JP 3480867 B2 JP3480867 B2 JP 3480867B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- catalyst
- base material
- paper
- lath net
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 93
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000843 powder Substances 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 25
- 239000012784 inorganic fiber Substances 0.000 claims description 23
- 229910001220 stainless steel Inorganic materials 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000007084 catalytic combustion reaction Methods 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000002737 fuel gas Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- -1 and for other uses Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、灯油等の液体燃料や都
市ガス等の気体燃料を触媒燃焼させるために使用する触
媒燃焼用触媒体、あるいは家電住設機器や自動車等から
発生する排ガスを無害化するために使用する浄化用触媒
体、およびこれら触媒体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalytic combustion catalyst body used for catalytic combustion of liquid fuel such as kerosene or gaseous fuel such as city gas, or exhaust gas generated from household appliances, household appliances and automobiles. The present invention relates to a purification catalyst body used for detoxification and a method for producing these catalyst bodies.
【０００２】[0002]
【従来の技術】従来、この種触媒体のなかで波形形状を
有する触媒体としては、金属基材を所望の形状に加工
し、これを触媒スラリー中に浸漬し、金属基材表面に触
媒層を被覆したものが一般的であった。また、無機繊維
を主体として湿式抄造法によって得たシート状抄造体を
所望の波形形状に加工し、焼結してある程度の機械的強
度を持たせた後、触媒スラリー中に浸漬し、触媒金属を
分散担持させた触媒体も知られている。2. Description of the Related Art Conventionally, as a catalyst body having a corrugated shape among this type of catalyst body, a metal base material is processed into a desired shape and immersed in a catalyst slurry to form a catalyst layer on the surface of the metal base material. Was generally coated. Further, a sheet-shaped paper body obtained by a wet papermaking method mainly containing inorganic fibers is processed into a desired corrugated shape, sintered to have a certain mechanical strength, and then immersed in a catalyst slurry to form a catalyst metal. A catalyst body in which is dispersed and supported is also known.
【０００３】[0003]
【発明が解決しようとする課題】しかし、従来の触媒体
には以下のような問題点が残されていた。金属基材の表
面に触媒被覆層を形成した触媒体は、金属基材の耐熱性
および圧延加工技術に限界があるため、ある程度以上に
薄くすることはできない。具体的には、耐熱ステンレス
鋼であるアルミニウムを含むフェライト系ステンレス鋼
の場合５０μｍが限界である。そのために触媒体は要望
されるものよりも熱容量の大きなものになっていた。一
方、無機繊維を焼結させた波形形状物に対して熱容量を
小さくしようとすれば、機械的強度を多大に犠牲にしな
ければならないので、安心して実用に耐えられるような
ものはなかなか得られなかった。本発明は、上記従来の
問題点に鑑みて、金属素材をシート状抄造体とハイブリ
ット化することによって、熱容量が小さく、しかも安心
して実用に耐え得る柔軟性と機械的強度を有する触媒体
を提供することを目的とする。本発明は、またそのよう
な触媒体を量産性良く製造する方法を提供することを目
的とする。However, the conventional catalyst body has the following problems. The catalyst body in which the catalyst coating layer is formed on the surface of the metal substrate cannot be made thinner than a certain extent because the heat resistance of the metal substrate and the rolling process technology are limited. Specifically, in the case of ferritic stainless steel containing aluminum, which is heat resistant stainless steel, the limit is 50 μm. Therefore, the catalyst body has a larger heat capacity than required. On the other hand, if it is attempted to reduce the heat capacity of a corrugated product obtained by sintering inorganic fibers, the mechanical strength must be sacrificed significantly, so it is difficult to obtain a product that can be put to practical use with confidence. It was In view of the above-mentioned conventional problems, the present invention provides a catalyst body having a small heat capacity and having flexibility and mechanical strength that can be safely put to practical use by hybridizing a metal material with a sheet-shaped paper product. The purpose is to do. Another object of the present invention is to provide a method for producing such a catalyst body with high productivity.
【０００４】[0004]
【課題を解決するための手段】本発明の触媒体は、耐熱
無機繊維および無機粉末を主成分とするシート状抄造体
と、その両面に接合あるいは埋設した状態で複合化され
たアルミニウムを含むフェライト系ステンレス鋼からな
るラス網とから構成された波形形状の基材、および前記
シート状抄造体と前記ラス網と結合あるいは固定する貴
金属成分を担持した活性アルミナ粉末を主体とした触媒
成分からなるものである。A catalyst body of the present invention comprises a sheet-shaped paper product containing heat-resistant inorganic fibers and inorganic powder as main components, and a ferrite containing aluminum compounded on both sides thereof in a bonded or embedded state. Of a corrugated substrate composed of a lath net made of a series stainless steel, and a catalyst component mainly composed of an activated alumina powder carrying a noble metal component for binding or fixing the sheet-shaped paper product and the lath net Is.
【０００５】本発明の触媒体の製造方法は、耐熱無機繊
維および無機粉末を主成分とするシート状抄造体とアル
ミニウムを含むフェライト系ステンレス鋼からなるラス
網とを圧着しながら波形形状に加工し、所定の長さに切
断して波形形状の基材を得る工程、前記基材を熱処理し
て前記シート状抄造体中に含まれる有機成分を除去する
工程、および前記基材を貴金属成分を含有する活性アル
ミナ粉末を主体とした触媒スラリー中に浸漬し、乾燥
後、熱処理して前記シート状抄造体と前記ラス網とを結
合あるいは固定するとともに前記基材に触媒成分を担持
させる工程を有する。また、本発明の触媒体の製造方法
は、耐熱無機繊維および無機粉末を主成分とするシート
状抄造体とアルミニウムを含むフェライト系ステンレス
鋼からなるラス網とを圧着しながら波形形状に加工し、
所定の長さに切断して波形形状の基材を得る工程、前記
基材を熱処理して前記シート状抄造体中に含まれる有機
成分を除去する工程、および前記基材を活性アルミナ粉
末を主体とした触媒担体スラリー中に浸漬し、乾燥後、
熱処理して前記シート状抄造体と前記ラス網とを結合あ
るいは固定する工程、および前記基材にさらに貴金属成
分を担持させる工程を有する。In the method for producing a catalyst body of the present invention, a sheet-shaped paper body containing heat-resistant inorganic fibers and inorganic powder as main components and a lath net made of ferritic stainless steel containing aluminum are pressed into a corrugated shape. , A step of cutting into a predetermined length to obtain a corrugated base material, a step of heat-treating the base material to remove an organic component contained in the sheet-shaped papermaking product, and a base material containing a noble metal component The step of immersing in a catalyst slurry containing activated alumina powder as a main component, drying and heat-treating the sheet-shaped paper product and the lath net to bond or fix the catalyst component to the base material. Further, the method for producing a catalyst body of the present invention is processed into a corrugated shape while crimping a sheet-shaped paper product having a heat-resistant inorganic fiber and an inorganic powder as a main component and a lath net made of ferritic stainless steel containing aluminum,
A step of cutting into a predetermined length to obtain a corrugated base material, a step of heat-treating the base material to remove an organic component contained in the sheet-shaped papermaking body, and the base material mainly containing activated alumina powder After being dipped in the catalyst carrier slurry and dried,
The method includes a step of heat-treating to bond or fix the sheet-shaped paper product and the lath net, and a step of further supporting a noble metal component on the base material.
【０００６】[0006]
【作用】本発明の触媒体は、その基材が耐熱無機繊維と
無機粉末を主成分とするシート状抄造体およびその両面
に配したラス網とをハイブリット化したもので、熱容量
が小さく、従って立ち上がり特性に優れている。そし
て、実用時に大きな熱歪みが生じても、触媒体自身で応
力を緩和し、恒常的な熱変形に至ることはほとんどな
い。また、ラス網がシート状抄造体の両面に触媒体の芯
材として具備されているので、実用に際して衝撃破壊等
がなく安全性が確保できる。すなわち、外部から衝撃を
受けて、万一シート状抄造体部に亀裂が生じても、それ
がすぐに触媒体の完全な破壊になることはなく、ある程
度の亀裂に抑えられる。これは芯材が形状を保持する機
能を発揮することによる。The base material of the catalyst body of the present invention is a hybrid of a heat-resistant inorganic fiber, a sheet-shaped paper body containing inorganic powder as a main component, and a lath net disposed on both sides thereof, and has a small heat capacity. Excellent start-up characteristics. Further, even if a large thermal strain occurs in practical use, the stress is relieved by the catalyst body itself, and the permanent thermal deformation hardly occurs. In addition, since lath nets are provided on both sides of the sheet-shaped paper product as core materials of the catalyst body, safety can be secured without impact damage during practical use. That is, even if a crack is generated in the sheet-shaped paper-making body portion due to an impact from the outside, it does not immediately cause complete destruction of the catalyst body and can be suppressed to some extent. This is because the core material has a function of retaining the shape.
【０００７】次に、本発明の触媒体の製造方法について
述べる。本発明では、まず耐熱無機繊維と無機粉末を主
成分とするシート状抄造体（以下、ペーパーという）
と、アルミニウムを含むフェライト系ステンレス鋼から
なるラス網とを圧着しながら波状に加工する。ここに用
いる耐熱無機繊維と無機粉末を主成分とするペーパーに
は、抄造時に耐熱無機繊維と無機粉末を凝集させて抄造
し易くする目的、および得られるペーパーに柔軟性を保
持させる目的で、有機成分、主にアクリルアミド系樹脂
を結合剤としてある程度添加することが好ましい。ペー
パーにステンレス鋼からなるラス網を圧着しながら波状
に加工する時、ペーパーの厚み方向にラス網を構成する
金属線が少し噛み込みながらペーパーとラス網が合体し
た状態となる。Next, a method for producing the catalyst body of the present invention will be described. In the present invention, first, a sheet-shaped paper product containing heat-resistant inorganic fibers and inorganic powder as main components (hereinafter referred to as paper)
And a lath net made of ferritic stainless steel containing aluminum while being crimped. The paper mainly composed of the heat-resistant inorganic fiber and the inorganic powder used here is an organic material for the purpose of aggregating the heat-resistant inorganic fiber and the inorganic powder at the time of paper-making to facilitate the paper-making, and for keeping the obtained paper flexible. It is preferable to add a component, mainly an acrylamide resin, as a binder to some extent. When a lath net made of stainless steel is pressure-bonded to paper and processed into a wavy shape, the metal wire forming the lath net is bitten in the thickness direction of the paper and the paper and the lath net are united.
【０００８】ここで言う圧着の方法は、波形形状にする
工程において、ペーパーをラス網でサンドイッチしなが
ら所定の間隔に設定した歯車の間を通過させることによ
って行うものである。そして、前記歯車の隙間は、少な
くともペーパーとラス網の厚みを積算した厚み以下にす
ることが好ましい。歯車の隙間をペーパーとラス網の厚
みを積算した厚み以下にすることで、ラス網を構成する
金属線がペーパーに少し噛み込みながら波形形状に加工
され、歯車通過後にはペーパー部は少し膨らみ元のペー
パーの厚みに復元するが、ラス網の金属線はペーパー部
に噛み込んだままの状態を維持し、ラス網とペーパーが
剥離することはない。歯車の隙間を狭くし過ぎると、金
属線がペーパー層を分断してしまうので、用いる材料と
所望する波形形状に合わせて適当な隙間設定が必要であ
る。この歯車により波形形状に加工する方法は、量産効
率も非常に高く、低コストである。The crimping method referred to here is performed by passing the paper between gears set at a predetermined interval while sandwiching the paper with a lath net in the step of forming the corrugated shape. The gap between the gears is preferably equal to or less than the total thickness of the paper and lath net. By setting the gap between the gears to be less than the total thickness of the paper and lath net, the metal wire that makes up the lath net is bitten into the paper and processed into a corrugated shape, and after passing through the gear, the paper part swells slightly. However, the metal wire of the lath net remains in the state of being caught in the paper portion, and the lath net and the paper are not separated from each other. If the gap between the gears is too narrow, the metal wire will divide the paper layer, so it is necessary to set a proper gap according to the material used and the desired corrugated shape. The method of forming a corrugated shape with this gear has very high mass production efficiency and low cost.
【０００９】その後、合体させたペーパーとラス網から
なる基材を所定の長さに切断し、耐熱無機繊維と無機粉
末を主体としたペーパー中に含まれる有機成分を熱分解
除去する目的と金属素材を表面酸化する目的のために熱
処理する。この熱処理により有機成分が除去されたペー
パーは、最初に比べるとある程度脆弱な状態になるが、
ペーパー中に用いられている無機粉末の保形力でペーパ
ーは形状を充分に維持できる。しかし、ある程度脆弱に
なっているので合体させたペーパーとラス網からなる基
材を注意深く取り扱いながら、次に触媒スラリーあるい
は触媒担体スラリー中に浸漬しなければならない。スラ
リーに浸漬後、引き上げ、乾燥すると、触媒スラリーあ
るいは触媒担体スラリー中に含まれていてペーパー中の
絡まり合った無機繊維の隙間に充填された活性アルミナ
粉末、および最初からペーパーに用いられている無機粉
末が、結合剤として機能し、乾燥凝集によりペーパーに
充分な機械的強度が発現するようになる。さらに、熱処
理を行うことによって活性アルミナ粉末等の焼結が進
み、機械的強度はより向上する。触媒スラリーあるいは
触媒担体スラリーは、有機成分の熱分解で多孔質となっ
たペーパー中に均一に浸透し、触媒担体の活性アルミナ
粉末がペーパーの厚み方向にある程度均一に分散される
ことで、貴金属成分も均一化され、耐久性等で信頼性の
高い触媒体が得られる。また、金属素材は、熱処理によ
って表面酸化されることで、素材中のアルミニウムが表
面に移動し、そこで空気中の酸素により酸化されてアル
ミナ粒子の膜が形成されるので、腐食に対する耐候性、
耐久性が向上する。After that, the base material composed of the combined paper and lath net is cut into a predetermined length to thermally decompose and remove the organic components contained in the paper mainly composed of the heat-resistant inorganic fiber and the inorganic powder, and the metal. Heat treatment for the purpose of surface oxidation of the material. The paper from which organic components have been removed by this heat treatment is in a more fragile state compared to the beginning,
The shape-retaining force of the inorganic powder used in the paper allows the paper to maintain its shape sufficiently. However, since it is somewhat brittle, the substrate consisting of the combined paper and lath net must be carefully handled and then immersed in the catalyst slurry or catalyst carrier slurry. After soaking in the slurry, pulling it up and drying it, the activated alumina powder contained in the catalyst slurry or catalyst carrier slurry and filled in the gaps of the entangled inorganic fibers in the paper, and the inorganic used for the paper from the beginning The powder functions as a binder, and the dry agglomeration allows the paper to exhibit sufficient mechanical strength. Furthermore, by performing heat treatment, sintering of activated alumina powder or the like proceeds, and mechanical strength is further improved. The catalyst slurry or catalyst carrier slurry uniformly penetrates into the paper that has become porous due to the thermal decomposition of the organic component, and the activated alumina powder of the catalyst carrier is evenly dispersed in the thickness direction of the paper to a certain extent, thereby preserving the precious metal component. Is also homogenized, and a highly reliable catalyst body with durability and the like can be obtained. Further, the metal material is surface-oxidized by heat treatment, aluminum in the material is moved to the surface, where it is oxidized by oxygen in the air to form a film of alumina particles.
The durability is improved.
【００１０】ラス網は、耐熱性の金属板から比較的簡単
な加工作業で入手することができる。一方、メッシュ金
網は、まず金属線を製造する課程が必要であり、開口率
の大きな多孔性材料としての入手法として融通がきかな
い面がある。また、パンチングメタルは、材料損失が大
きいので開口率の大きな多孔性材料としては高価なもの
となる。したがって、本発明では耐熱無機繊維と無機粉
末を主成分としたペーパーの両表面部にラス網を接合あ
るいは埋設した状態で複合化させる。このラス網の開口
率は６０％以上、好ましくは７０％以上のものを使用
し、これを波形形状の加工でペーパー中に適当に噛み込
ませ、その金属素材が噛み込んだ付近にも触媒担体粉末
を浸透させ結着力を発揮させることで、ペーパーとラス
網は強固に固定される。The lath net can be obtained from a heat-resistant metal plate by a relatively simple processing operation. On the other hand, the mesh wire mesh first requires a process for manufacturing a metal wire, and is not versatile as a method of obtaining it as a porous material having a large aperture ratio. In addition, since punching metal has a large material loss, it is expensive as a porous material having a large aperture ratio. Therefore, in the present invention, the heat resistant inorganic fiber and the paper containing the inorganic powder as the main components are combined in a state in which the lath net is bonded or embedded in both surfaces. The lath net having an aperture ratio of 60% or more, preferably 70% or more is used, and the lath net is appropriately bitten into paper by corrugation processing, and the catalyst carrier is also present in the vicinity of the biting of the metal material. By permeating the powder and exerting a binding force, the paper and lath net are firmly fixed.
【００１１】[0011]
【実施例】以下、本発明を好ましい実施例によりさらに
詳しく説明する。まず、本発明で使用する耐熱無機繊維
と無機粉末を主成分とするシート状抄造体ついて説明す
る。耐熱無機繊維は、量産性と低コスト化を鑑みて、ア
ルミナシリカ繊維を主体とするものが好ましい。その繊
維組成も量産性を鑑みてアルミナが２０〜７０ｗｔ％と
することが好ましい。さらに、繊維形状はアスペクト比
が少なくとも１００以上のものを使用しないと多孔質の
ペーパーが得られにくい。また、無機粉末はペーパーと
ラス網を複合化させた後に、熱処理してある程度の保形
性を保持させる目的で使用し、安価で耐熱性に優れ、触
媒金属に対して被毒とならないものであるなら特に限定
されない。具体的には、α−アルミナ、高耐熱粘土等が
好ましい。また、その粒径はその後の保形性等を鑑みて
約５μｍ以下が好ましい。耐熱無機繊維と無機粉末の最
適な割合は、所望とする波形形状あるいはペーパーの厚
みによって変化する。その最適な一例を以下の表１に示
す。The present invention will be described in more detail below with reference to preferred embodiments. First, the sheet-shaped paper product containing the heat-resistant inorganic fiber and the inorganic powder as the main components used in the present invention will be described. The heat-resistant inorganic fiber is preferably composed mainly of alumina-silica fiber in view of mass productivity and cost reduction. The fiber composition of the alumina is preferably 20 to 70 wt% in view of mass productivity. Further, it is difficult to obtain a porous paper unless a fiber having an aspect ratio of 100 or more is used. In addition, the inorganic powder is used for the purpose of holding a certain degree of shape retention by heat treating after compounding the paper and lath net, it is cheap and has excellent heat resistance and does not poison the catalytic metal. If there is, it is not particularly limited. Specifically, α-alumina, high heat resistant clay and the like are preferable. Further, the particle size is preferably about 5 μm or less in consideration of the shape retention property thereafter. The optimum ratio of the heat resistant inorganic fiber and the inorganic powder varies depending on the desired corrugated shape or the thickness of the paper. The most suitable example is shown in Table 1 below.
【００１２】[0012]
【表１】 [Table 1]
【００１３】以下の実施例に示すような微細な波形形状
（山谷の高さ１．６ｍｍ、ピッチ２．５ｍｍ）の場合に
は、大体５０：５０の比率が適当であり、ピッチが大き
くなるにしたがって無機粉末の量を低減させてもラス網
はペーパーに接合保持され、またペーパーの厚みが厚く
なるにしたがって無機粉末の量を低減させてもラス網は
ペーパー中により深く噛み込ませることによって接合保
持可能である。さらに、シート状抄造体を製造する課程
で、無機繊維と無機粉末を凝集させる目的で、アクリル
アミド系の有機成分を約２〜８ｗｔ％添加する。これは
得られたペーパーに柔軟性と紙力を付与する目的でもあ
る。有機成分が２ｗｔ％以下では充分な凝集性が得られ
なく、８ｗｔ％以上に多くなるとラス網との接合性には
優れているが、ペーパーとラス網を複合化させた基材を
熱処理した時に、それ以前と比べて脆弱になりすぎるの
で、その後の製造が困難となる。熱処理して有機成分を
除去した場合には、有機成分が多いとそれだけ接合力が
弱くなるので、使用するラス網に対応させて適度な有機
成分量を有したペーパーを選択する必要がある。また、
本発明で使用するペーパーは、薄いシート状態を意味す
る。ラス網と複合化させる場合に、ぺーパーの厚みが厚
くなってくると、無機粉末を含んだペーパーを用いる必
要性が次第に低減してくるためである。したがって、本
発明の効果を得るためには０．５ｍｍ以下、好ましくは
０．３ｍｍ以下のものを選択する。In the case of a fine corrugated shape (height of valleys: 1.6 mm, pitch: 2.5 mm) as shown in the following examples, a ratio of about 50:50 is appropriate, and the pitch becomes large. Therefore, even if the amount of the inorganic powder is reduced, the lath net is bonded and held to the paper, and even if the amount of the inorganic powder is reduced as the thickness of the paper becomes thicker, the lath net is bonded by being deeply caught in the paper. It can be held. Further, in the process of producing a sheet-shaped paper product, about 2 to 8 wt% of an acrylamide-based organic component is added for the purpose of aggregating the inorganic fibers and the inorganic powder. This is also the purpose of imparting flexibility and strength to the obtained paper. When the organic component is 2 wt% or less, sufficient cohesiveness cannot be obtained, and when it is 8 wt% or more, the bondability with the lath net is excellent, but when heat-treating a base material in which paper and lath net are composited. However, it becomes too fragile compared to before, so that subsequent manufacturing becomes difficult. When the organic components are removed by heat treatment, the more the organic components are, the weaker the bonding strength becomes. Therefore, it is necessary to select a paper having an appropriate amount of organic components corresponding to the lath net to be used. Also,
The paper used in the present invention means a thin sheet state. This is because the need to use paper containing inorganic powder gradually decreases as the paper becomes thicker when it is combined with the lath net. Therefore, in order to obtain the effect of the present invention, the thickness of 0.5 mm or less, preferably 0.3 mm or less is selected.
【００１４】本発明で使用するアルミニウムを含むフェ
ライト系ステンレス鋼は、耐熱性、耐食性に優れた材料
であり、一般にはＣｒが１５〜２０ｗｔ％、Ａｌが３〜
５ｗｔ％で、わずかな添加剤と残部がＦｅの組成で使用
されることが好ましい。このステンレス鋼をラス網に加
工し、耐熱無機繊維と無機粉末を主成分とするペーパー
と圧着接合して使用する。その時にラス網を構成する金
属線がペーパーの厚さ方向に噛み込み、充分に接合する
ことが要求されるので、ラス網状態のステンレス鋼は開
口率６０％以上、好ましくは７０％以上のものを使用す
る。その線径は０．２ｍｍ以下のものが良い。しかし、
０．１ｍｍ以下のラス網は製造上で困難を生ずるので、
最大開口率は９０％以下である。したがって、本発明に
使用するラス網は開口率６０〜９０％、線径０．１ｍｍ
〜０．２ｍｍが好ましい。本発明では耐熱無機繊維と無
機粉末を主成分とするペーパーとラス網を圧着させなが
ら波状に加工するが、この方法は歯車の隙間を通過させ
て行う。その隙間は少なくともペーパーとラス網の厚み
を積算した厚み以下に設定し、ラス網が隙間通過時に押
し付けられて噛み込むように調整する。しかし、隙間を
狭くし過ぎるとステンレス鋼が噛み込んだ際にペーパー
を分断することになるので、適当に調整する。The ferritic stainless steel containing aluminum used in the present invention is a material excellent in heat resistance and corrosion resistance. Generally, Cr is 15 to 20 wt% and Al is 3 to 3.
At 5 wt% it is preferred to use a slight additive and the balance Fe composition. This stainless steel is processed into a lath net, and pressure-bonded with heat-resistant inorganic fibers and paper containing inorganic powder as a main component for use. At that time, the metal wire forming the lath net is required to be bitten in the thickness direction of the paper and sufficiently joined, so that the stainless steel in the lath net state has an opening ratio of 60% or more, preferably 70% or more. To use. The wire diameter is preferably 0.2 mm or less. But,
Since lath nets of 0.1 mm or less cause difficulties in manufacturing,
The maximum aperture ratio is 90% or less. Therefore, the lath net used in the present invention has an aperture ratio of 60 to 90% and a wire diameter of 0.1 mm.
~ 0.2 mm is preferred. In the present invention, the heat-resistant inorganic fiber, the paper containing inorganic powder as the main component, and the lath net are crimped while being pressed, but this method is carried out by passing through the gap between the gears. The gap is set to be equal to or less than the total thickness of the paper and the lath net, and is adjusted so that the lath net is pressed and caught when passing through the gap. However, if the gap is made too narrow, the paper will be divided when the stainless steel is caught, so adjust appropriately.
【００１５】本発明で使用する触媒スラリーあるいは触
媒担体スラリーは、活性アルミナを主体としたものであ
り、すなわち活性アルミナの耐熱性を向上させる目的で
アルカリ土類金属が含まれるもの、あるいは助触媒とし
て希土類金属が含まれるものであっても良い。また、そ
の他吸着脱臭のためにゼオライト等をある程度添加した
ものでも良い。また、活性アルミナの無機繊維への結着
性を向上させるために、アルミナゾル等の結合剤を少量
添加することも可能である。貴金属成分は、あらかじめ
担体粉末に担持されているものであっても、あるいは水
溶液の状態で触媒スラリー中に含有され、吸着されたも
のでも良い。また、触媒担体スラリーを使用し、ペーパ
ーとラス網を結合あるいは固定した後、貴金属水溶液に
浸漬、乾燥、熱処理して、最後に担持させても良い。貴
金属成分としては、実施例ではＰｔを使用したが、これ
はイソブタンの触媒燃焼用であり、他の用途にはＰｄ、
Ｒｈ、Ｒｕも使用できる。The catalyst slurry or catalyst carrier slurry used in the present invention is mainly composed of activated alumina, that is, it contains alkaline earth metal for the purpose of improving the heat resistance of activated alumina, or as a co-catalyst. It may contain a rare earth metal. In addition, a material to which zeolite or the like is added to some extent for the purpose of adsorption and deodorization may be used. It is also possible to add a small amount of a binder such as alumina sol in order to improve the binding property of the activated alumina to the inorganic fibers. The noble metal component may be previously supported on the carrier powder, or may be contained in the catalyst slurry in the state of an aqueous solution and adsorbed. Alternatively, the catalyst carrier slurry may be used to bond or fix the paper and the lath net, and then to be immersed in an aqueous solution of noble metal, dried, and heat-treated, and finally supported. As the noble metal component, Pt was used in the examples, but this is for catalytic combustion of isobutane, and for other uses, Pd,
Rh and Ru can also be used.
【００１６】［実施例１］アルミナシリカ繊維（平均繊
維長５ｍｍ、線径２μｍ）５０重量部、α−アルミナ粉
末（平均粒径２μｍ）５０重量部およびアクリルアミド
４重量部を原料として湿式抄造法により抄造して乾燥
し、厚み０．２ｍｍ、幅３０ｍのシート抄造体（以下、
ペーパーという）を得た。また、Ｆｅ−２０Ｃｒ−５Ａ
ｌ系フェライトステンレス鋼（幅３０ｍｍ、厚み５０μ
ｍ）を線径が０．１５ｍｍで、一辺が１．５ｍｍの六角
形の編み目を有するラス網に加工し、１０００ｍｍに切
断した。 前記ぺーパーを前記ラス網でサンドイッチし
た状態で、隙間を０．２ｍｍに設定した波形加工用の歯
車間を通過させることによって、ラス網がペーパーの両
面に噛み込んだ状態で山谷の高さ１．６ｍｍ、ピッチ
２．５ｍｍの波形形状に曲げ加工した基材を得た。次
に、前記基材を９００℃で１０分間熱処理してペーパー
中の有機成分を熱分解除去するとともに金属素材の表面
酸化を行った。Example 1 50 parts by weight of alumina-silica fiber (average fiber length 5 mm, wire diameter 2 μm), 50 parts by weight of α-alumina powder (average particle size 2 μm) and 4 parts by weight of acrylamide were used as a raw material by a wet papermaking method. Papermaking and drying, a sheet papermaking product having a thickness of 0.2 mm and a width of 30 m (hereinafter,
I got the paper). In addition, Fe-20Cr-5A
L series ferritic stainless steel (width 30mm, thickness 50μ
m) was processed into a lath net having a hexagonal stitch having a wire diameter of 0.15 mm and a side of 1.5 mm, and cut into 1000 mm. By sandwiching the paper with the lath net and passing it between corrugation gears with a gap of 0.2 mm, the height of peaks and valleys 1 A base material bent into a corrugated shape with a pitch of 0.6 mm and a pitch of 2.5 mm was obtained. Next, the base material was heat-treated at 900 ° C. for 10 minutes to thermally decompose and remove the organic components in the paper and to oxidize the surface of the metal material.
【００１７】一方、ＢａＯ・Ａｌ2Ｏ3粉末（比表面積１
５０ｍ2／ｇ）１００ｇ、水２５０ｇ、イソプロピルア
ルコール５０ｇ、およびＰｔ換算で３ｇに相当するジニ
トロジアンミン白金水溶液からなる水性混合物をボール
ミル調製し、ＢａＯ・Ａｌ2Ｏ3粉末の平均粒径が３μｍ
の触媒スラリーを得た。前記ペーパーとラス網を複合化
させた基材を前記触媒スラリー中に浸漬し、引き上げた
後、乾燥し、５００℃で５分間熱処理した。その結果、
ラス網が触媒担体粉末（ＢａＯ・Ａｌ2Ｏ3）の結合力で
ペーパー中に充分に固定された触媒体が得られた。図１
に触媒体１の外観図を示す。また、図２に触媒体１の拡
大断面図を模式的に示し、ペーパー２の層にラス網３、
４の金属線が埋設された状態を表している。この触媒体
にはＢａＯ・Ａｌ2Ｏ3粉末５０ｍｇおよびＰｔ１．５ｍ
ｇが分散担持された。On the other hand, BaO.Al 2 O 3 powder (specific surface area 1
50 m 2 / g) 100 g, water 250 g, isopropyl alcohol 50 g, and an aqueous mixture of dinitrodiammine platinum aqueous solution equivalent to 3 g in terms of Pt were ball-milled to have an average particle size of BaO.Al 2 O 3 powder of 3 μm.
A catalyst slurry of was obtained. The substrate in which the paper and lath net were composited was dipped in the catalyst slurry, pulled up, dried, and heat-treated at 500 ° C. for 5 minutes. as a result,
A catalyst body was obtained in which the lath net was sufficiently fixed in the paper by the binding force of the catalyst carrier powder (BaO.Al 2 O 3 ). Figure 1
An external view of the catalyst body 1 is shown in FIG. In addition, an enlarged cross-sectional view of the catalyst body 1 is schematically shown in FIG.
4 shows a state in which the metal wire 4 is buried. This catalyst had 50 mg of BaO.Al 2 O 3 powder and 1.5 m of Pt.
g was dispersed and supported.
【００１８】上記と同様な方法でさらに１つの触媒体を
得て、図３および図４に示すスチーム発生装置を組み立
てた。イソブタンガスを収容したボンベ５とノズル６の
間には、主バルブ７と、バイメタル（図示せず）で開閉
される副バルブ８が設けてある。ノズル６より噴出した
燃料ガスは、ガス流の誘引作用により回りの空気を吸引
し、混合室９で均一にと混合され、燃焼室１０に供給さ
れる。燃焼室１０には２個の触媒体１１と１２が筐体１
３とアルミニウム製熱交換部１４の間に設けられ、触媒
体１１、１２で発生した反応熱（燃焼熱）は熱交換部１
４を介して水蒸気発生室１５側に伝熱する。触媒体１
１、１２の下流には圧電着火素子１６が配設されてい
る。また、水蒸気発生室１５には、ポンプ（図示せず）
に連なったノズル１７が設けられ、ここから室底面に水
滴が供給される。One more catalyst body was obtained in the same manner as above, and the steam generator shown in FIGS. 3 and 4 was assembled. A main valve 7 and a sub valve 8 which is opened and closed by a bimetal (not shown) are provided between the cylinder 5 containing the isobutane gas and the nozzle 6. The fuel gas ejected from the nozzle 6 sucks the surrounding air by the attracting action of the gas flow, is uniformly mixed in the mixing chamber 9, and is supplied to the combustion chamber 10. In the combustion chamber 10, two catalyst bodies 11 and 12 are provided in the housing 1.
3 and the heat exchange part 14 made of aluminum, the reaction heat (combustion heat) generated in the catalyst bodies 11 and 12 is transferred to the heat exchange part 1.
The heat is transferred to the steam generation chamber 15 side via the heat transfer unit 4. Catalyst 1
A piezoelectric ignition element 16 is disposed downstream of the elements 1 and 12. A pump (not shown) is provided in the steam generation chamber 15.
Is provided with a nozzle 17 from which water drops are supplied to the bottom surface of the chamber.
【００１９】次に、動作原理について簡単に述べる。ま
ず、主バルブ７を開くと、ノズル６より燃料ガスが混合
室９に供給され、同時に空気も誘引作用により供給され
る。空気を混合された燃料ガスが燃焼室１０内に導入さ
れた後、圧電着火素子１６で火花をスパークさせること
で触媒体の後方、排気口１８手前付近に一時火炎を形成
させ、その反応熱で触媒体の下流部がすぐに加熱されて
触媒燃焼を開始し、その触媒燃焼は直ちに触媒体最上流
部へと移行する。燃焼排ガスは排気口１８から排出され
る。反応熱（燃焼熱）は熱交換部１４を経て水蒸気発生
室１５側に伝熱する。水蒸気発生室１５の底面が充分な
温度（約２００℃）に達した時点からポンプよってノズ
ル１７から水滴を供給することが可能となり、スチーム
口１９からスチーム供給を行うことができる。バルブ８
はバイメタル方式で、水蒸気発生室側面の１カ所を温度
検知し、ある温度（約２２０℃）以上になると閉塞さ
れ、燃料ガスの供給が停止され、熱交換部の温度調節に
使用される。Next, the operating principle will be briefly described. First, when the main valve 7 is opened, fuel gas is supplied from the nozzle 6 to the mixing chamber 9, and at the same time, air is also supplied by an attracting action. After the fuel gas mixed with air is introduced into the combustion chamber 10, a spark is sparked by the piezoelectric ignition element 16 to form a temporary flame behind the catalyst body and in the vicinity of the exhaust port 18, and the reaction heat is generated by the reaction heat. The downstream portion of the catalyst body is immediately heated to start catalytic combustion, and the catalytic combustion immediately shifts to the upstreammost portion of the catalyst body. The combustion exhaust gas is discharged from the exhaust port 18. Reaction heat (combustion heat) is transferred to the steam generation chamber 15 side through the heat exchange section 14. From the time when the bottom surface of the steam generating chamber 15 reaches a sufficient temperature (about 200 ° C.), it becomes possible to supply water droplets from the nozzle 17 by the pump, and steam can be supplied from the steam port 19. Valve 8
Is a bimetal type, which detects the temperature at one side of the steam generation chamber and closes it when a certain temperature (about 220 ° C.) or higher is reached, and the supply of fuel gas is stopped to control the temperature of the heat exchange section.
【００２０】したがって、本スチーム発生装置は、燃料
ガスの供給、停止が繰り返され、その結果として触媒体
も発熱、冷却を繰り返すことになる。得られた触媒体の
評価は、立ち上がり特性と寿命試験で検討した。イソブ
タンを燃料として空気過剰率（空気／燃料）１．０、２
００ｋｃａｌ／ｈの条件に設定して、水蒸気発生室の底
面が２００℃に達するまでの時間を測定した。また、寿
命試験は同じく空気過剰率（空気／燃料）１．０、２０
０ｋｃａｌ／ｈの条件に設定し、スチームを連続で発生
させながら５００時間燃焼させた。Therefore, in this steam generator, the supply and stop of the fuel gas are repeated, and as a result, the catalyst body also repeats heat generation and cooling. The evaluation of the obtained catalyst body was examined by a rising characteristic and a life test. Air excess ratio using isobutane as fuel (air / fuel) 1.0, 2
The time until the bottom surface of the steam generating chamber reached 200 ° C. was set under the condition of 00 kcal / h. In addition, the life test is the same as the excess air ratio (air / fuel) 1.0, 20
The condition was set to 0 kcal / h, and steam was burned for 500 hours while continuously generating steam.
【００２１】［実施例２］実施例１と同じペーパーとそ
の両面に噛み込ませたラス網からなる波形形状に曲げ加
工し基材を熱処理して、ペーパー中の有機成分を熱分解
除去するとともに金属素材の表面酸化を行った。一方、
ＢａＯ・Ａｌ2Ｏ3粉末（比表面積１５０ｍ2／ｇ）１０
０ｇ、水２５０ｇ、イソプロピルアルコール５０ｇ、お
よび硝酸アルミニウム１５ｇからなる水性混合物をボー
ルミル調製し、粉末の平均粒径が３μｍの触媒担体スラ
リーを得た。[Embodiment 2] The same paper as in Embodiment 1 and a corrugated shape consisting of lath nets caught on both sides of the paper are bent and heat-treated to remove organic components in the paper by thermal decomposition. The surface of the metal material was oxidized. on the other hand,
BaO.Al 2 O 3 powder (specific surface area 150 m 2 / g) 10
An aqueous mixture consisting of 0 g, 250 g of water, 50 g of isopropyl alcohol, and 15 g of aluminum nitrate was ball-milled to obtain a catalyst carrier slurry having an average particle size of powder of 3 μm.
【００２２】前記ペーパーとラス網を複合化させた基材
を前記触媒担体スラリー中に浸漬し、引き上げた後、乾
燥し、５００℃で５分間熱処理した。その結果、ラス網
が触媒担体粉末（ＢａＯ・Ａｌ2Ｏ3）の結合力でペーパ
ー中に固定された。その後、塩化白金酸水溶液中に１分
間浸漬し、引き上げた後、乾燥し、５００℃で５分間熱
処理して、触媒体を得た。この触媒体にはＢａＯ・Ａｌ
2Ｏ3粉末５０ｍｇおよびＰｔ１．５ｍｇが分散担持され
た。上記と同様な方法でさらに１つの触媒体を得て、実
施例１と同様に図３および図４に示すスチーム発生装置
を組み立てた。得られた触媒体の評価は、立ち上がり特
性と寿命試験で実施例１と同様に検討した。The substrate in which the paper and lath net were composited was dipped in the catalyst carrier slurry, pulled up, dried, and heat-treated at 500 ° C. for 5 minutes. As a result, the lath net was fixed in the paper by the binding force of the catalyst carrier powder (BaO.Al 2 O 3 ). Then, it was immersed in a chloroplatinic acid aqueous solution for 1 minute, pulled up, dried, and heat-treated at 500 ° C. for 5 minutes to obtain a catalyst body. BaO.Al is used for this catalyst.
50 mg of 2 O 3 powder and 1.5 mg of Pt were dispersed and supported. One more catalyst body was obtained in the same manner as above, and the steam generator shown in FIGS. 3 and 4 was assembled in the same manner as in Example 1. The evaluation of the obtained catalyst body was conducted in the same manner as in Example 1 by the rising characteristic and life test.
【００２３】［比較例１］アルミナシリカ繊維（平均繊
維長５ｍｍ、線径２μｍ）１００重量部およびアクリル
アミド４重量部の混合物を原料として湿式抄造法により
抄造して乾燥し、厚み０．２ｍｍ、幅３０ｍのペーパー
を得た。このぺーパーを実施例１と同じラス網でサンド
イッチした状態にして、隙間を０．２ｍｍに設定した波
形加工用の歯車間を通過させることによって、ラス網が
両面からペーパーに噛み込んだ状態で山谷の高さ１．６
ｍｍ、ピッチ２．５ｍｍの波形形状に曲げ加工した。し
かし、ラス網とペーパーの接合性は悪く、しばらくする
と剥離した。Comparative Example 1 A mixture of 100 parts by weight of alumina-silica fiber (average fiber length 5 mm, wire diameter 2 μm) and 4 parts by weight of acrylamide was used as a raw material for papermaking by a wet papermaking method and dried to have a thickness of 0.2 mm and a width. 30 m of paper was obtained. This paper was sandwiched with the same lath net as in Example 1, and was passed between the corrugation gears with the gap set to 0.2 mm, so that the lath net was caught in the paper from both sides. Mountain valley height 1.6
mm, pitch 2.5 mm, and bent into a corrugated shape. However, the bond between the lath net and the paper was poor, and it peeled off after a while.
【００２４】［比較例２］アルミナシリカ繊維（平均繊
維長５ｍｍ、線径２μｍ）１００重量部およびアクリル
アミド８重量部の混合物を原料として湿式抄造法により
抄造して乾燥し、厚み０．２ｍｍ、幅３０ｍのペーパー
を得た。このぺーパーを実施例１と同じラス網でサンド
イッチした状態にして、隙間を０．２ｍｍに設定した波
形加工用の歯車間を通過させることによって、ラス網が
両面からペーパーに噛み込んだ状態で山谷の高さ１．６
ｍｍ、ピッチ２．５ｍｍの波形形状に曲げ加工された基
材を得た。次に、前記基材を９００℃で１０分間熱処理
してペーパー中の有機成分を熱分解した。すると、ラス
網とペーパーを複合化させた基材は著しく脆弱となり、
その後に触媒スラリー中に浸漬すると、引き上げ時に壊
れてしまった。[Comparative Example 2] A mixture of 100 parts by weight of alumina-silica fiber (average fiber length 5 mm, wire diameter 2 μm) and 8 parts by weight of acrylamide was used as a raw material, was made into a paper by a wet papermaking method, and was dried to have a thickness of 0.2 mm and a width. 30 m of paper was obtained. This paper was sandwiched with the same lath net as in Example 1 and was passed between corrugation gears with a gap set to 0.2 mm, so that the lath net was caught in the paper from both sides. Mountain valley height 1.6
mm to obtain a base material bent into a corrugated shape with a pitch of 2.5 mm. Next, the substrate was heat-treated at 900 ° C. for 10 minutes to thermally decompose organic components in the paper. Then, the base material that combines the lath net and the paper becomes extremely brittle,
After that, when it was dipped in the catalyst slurry, it was broken when it was pulled up.
【００２５】［比較例３］Ｆｅ−２０Ｃｒ−５Ａｌ系フ
ェライトステンレス鋼（幅３０ｍｍ、厚み５０μｍ）を
５０ｍｍの長さに切断し、波形加工用の歯車間を通過さ
せることにより、山谷の高さ１．６ｍｍ、ピッチ２．５
ｍｍの波形形状に曲げ加工した。次に、このステンレス
鋼からなる基材を９００℃で１０分間熱処理した。一
方、ＢａＯ・Ａｌ2Ｏ3粉末（比表面積１５０ｍ2／ｇ）
１００ｇ、水２００ｇ、ポリエチレングリコール１０
ｇ、界面活性剤１ｇ、およびＰｔ換算で３ｇに相当する
ジニトロジアンミン白金水溶液からなる水性混合物をボ
ールミル調製し、触媒スラリーとした。[Comparative Example 3] Fe-20Cr-5Al ferritic stainless steel (width 30 mm, thickness 50 μm) was cut into a length of 50 mm and passed between gears for corrugation, so that the height of the valley was 1 0.6 mm, pitch 2.5
Bending processing was performed in a corrugated shape of mm. Next, the base material made of this stainless steel was heat-treated at 900 ° C. for 10 minutes. On the other hand, BaO.Al 2 O 3 powder (specific surface area 150 m 2 / g)
100 g, water 200 g, polyethylene glycol 10
g, a surfactant 1 g, and an aqueous mixture of a dinitrodiammine platinum aqueous solution corresponding to 3 g in terms of Pt were ball-milled to obtain a catalyst slurry.
【００２６】前記熱処理後のステンレス鋼基材の上端を
電磁石面で保持しながら、前記触媒スラリー中に浸漬
し、所定の速度で引き上げ、乾燥、熱処理した。さら
に、基材の方向を逆にして同様な操作を行い、触媒被覆
層を形成した。この触媒体にはＢａＯ・Ａｌ2Ｏ3粉末５
０ｍｇおよびＰｔ１．５ｍｇが分散担持されたが、両端
には触媒スラリーの液溜りによって被覆層に少し盛り上
がりがあった。同じようにもう一つ触媒体を調製し、実
施例１と同じスチーム発生装置を組み立てた。得られた
触媒体の評価は、立ち上がり特性と寿命試験で実施例１
と同様に検討した。表２に、実施例１、２および比較例
３の触媒体の立ち上がり特性の比較を示す。表２から明
らかなように、本発明の触媒体は、比較例の金属基材だ
けからなる触媒体に比べると、はるかに立ち上がり特性
に優れていた。While holding the upper end of the heat-treated stainless steel substrate by the electromagnet surface, it was immersed in the catalyst slurry, pulled up at a predetermined speed, dried and heat-treated. Furthermore, the same operation was performed by reversing the direction of the substrate to form a catalyst coating layer. This catalyst body contains BaO.Al 2 O 3 powder 5
Although 0 mg and 1.5 mg of Pt were dispersed and supported, the coating layer was slightly raised at both ends due to the liquid pool of the catalyst slurry. Another catalyst body was prepared in the same manner, and the same steam generator as in Example 1 was assembled. The evaluation of the obtained catalyst body was carried out by the rising characteristics and the life test in Example 1
The same was examined. Table 2 shows a comparison of the rising characteristics of the catalyst bodies of Examples 1 and 2 and Comparative Example 3. As is clear from Table 2, the catalyst body of the present invention was far superior in rising characteristics as compared with the catalyst body of Comparative Example consisting of only the metal substrate.
【００２７】[0027]
【表２】 [Table 2]
【００２８】上記の実施例では、ラス加工網には線径
０．１５ｍｍのものを使用したが、線径をさらに細くす
れば、立ち上がり特性を向上させることが可能であっ
た。しかし、線径を細くすると、ラス加工時あるいは波
形形状加工時に亀裂を生じることになり易いので、０．
１ｍｍ以上が好ましいと考えられる。また、線径が太く
なると、ペーパーとラス網との複合化によるメリットが
少なくなるので、ラス網の線径は０．１〜０．２ｍｍ程
度が好ましい。寿命試験の結果は、実施例についてはほ
とんど顕著な熱変形もなく、上流部での高温熱劣化が懸
念される程度であった。具体的には、上流部６〜７ｍｍ
程度が白色化していた。しかし、触媒燃焼の特性（燃焼
率）に影響が現れる程ではなかった。また、比較例の触
媒体は、熱履歴による熱変形が恒常的に残り、上流部５
ｍｍ程度で金属基材が熱変形していた。さらに、上流部
では一部剥離箇所も存在し、燃焼率が初期に比べて約７
％低下した。実施例と比較例で寿命後の触媒形状に差が
あるのは、実施例の触媒体の方が使用されている金属基
材が少なく、触媒燃焼時の熱応力を触媒体自身が緩和で
きたためと考えられる。In the above-mentioned embodiment, the lath processing net having a wire diameter of 0.15 mm was used, but it was possible to improve the rising characteristics by further reducing the wire diameter. However, if the wire diameter is made thin, cracks are likely to occur during lath processing or corrugated processing, so that the wire diameter is less than 0.
It is considered that 1 mm or more is preferable. Further, as the wire diameter becomes thicker, the merit of combining the paper and the lath net decreases, so the wire diameter of the lath net is preferably about 0.1 to 0.2 mm. The results of the life test showed that there was almost no remarkable thermal deformation in the examples, and there was a concern that high temperature thermal deterioration would occur in the upstream part. Specifically, 6-7 mm upstream
The degree was white. However, the characteristics (burning rate) of catalytic combustion were not so affected. Further, in the catalyst body of the comparative example, thermal deformation due to thermal history remains permanently, and the upstream portion 5
The metal base material was thermally deformed by about mm. Furthermore, there are some peeling points in the upstream part, and the burning rate is about 7% compared to the initial stage.
% Decreased. There is a difference in the catalyst shape after life between the example and the comparative example, because the catalyst body of the example uses less metal base material, and the catalyst body itself can relax the thermal stress at the time of catalyst combustion. it is conceivable that.
【００２９】[0029]
【発明の効果】本発明によれば、ラス網を耐熱無機繊維
と無機粉末を主成分とするシート状抄造体と複合化する
ことによって熱容量が小さく、しかも安心して実用に耐
え得る柔軟性と機械的強度を有する触媒体とその触媒体
を量産性良く製造する製造方法とを提供することができ
る。According to the present invention, by combining a lath net with a heat-resistant inorganic fiber and a sheet-shaped paper product mainly composed of inorganic powder, the heat capacity is small, and the flexibility and the machine which can endure practical use in peace. It is possible to provide a catalyst body having specific strength and a manufacturing method for manufacturing the catalyst body with high mass productivity.
【図１】本発明の実施例によって得られた触媒体の斜視
図である。FIG. 1 is a perspective view of a catalyst body obtained according to an example of the present invention.
【図２】同触媒体を模式的に表す拡大断面図である。FIG. 2 is an enlarged sectional view schematically showing the catalyst body.
【図３】本発明の実施例で使用したスチーム発生装置の
縦断面図である。FIG. 3 is a vertical sectional view of a steam generator used in an embodiment of the present invention.
【図４】図３のIV−IV線断面図である。4 is a sectional view taken along line IV-IV in FIG.
１ 触媒体 ２ シート状抄造体（ペーパー） ３、４ ラス網 1 catalyst 2 Sheet-shaped paper products 3, 4 lath net
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) B01J 21/00-38/74
Claims (3)
するシート状抄造体と、その両面に接合あるいは埋設し
た状態で複合化されたアルミニウムを含むフェライト系
ステンレス鋼からなるラス網とから構成された波形形状
の基材、および前記シート状抄造体と前記ラス網と結合
あるいは固定する貴金属成分を担持した活性アルミナ粉
末を主体とした触媒成分からなることを特徴とする触媒
体。1. A sheet-shaped product comprising heat-resistant inorganic fibers and inorganic powder as main components, and a lath net made of ferritic stainless steel containing aluminum compounded in a state of being bonded or embedded on both sides thereof. A catalyst body comprising a corrugated base material and a catalyst component mainly composed of activated alumina powder carrying a noble metal component for binding or fixing the sheet-shaped paper product and the lath net.
するシート状抄造体とアルミニウムを含むフェライト系
ステンレス鋼からなるラス網とを圧着しながら波形形状
に加工し、所定の長さに切断して波形形状の基材を得る
工程、前記基材を熱処理して前記シート状抄造体中に含
まれる有機成分を除去する工程、および前記基材を貴金
属成分を含有する活性アルミナ粉末を主体とした触媒ス
ラリー中に浸漬し、乾燥後、熱処理して前記シート状抄
造体と前記ラス網とを結合あるいは固定するとともに前
記基材に触媒成分を担持させる工程を有することを特徴
とする触媒体の製造方法。2. A sheet-shaped paper product containing heat-resistant inorganic fibers and inorganic powder as main components and a lath net made of ferritic stainless steel containing aluminum are pressed into a corrugated shape and cut into a predetermined length. To obtain a corrugated base material, a step of heat-treating the base material to remove an organic component contained in the sheet-shaped papermaking body, and the base material mainly made of activated alumina powder containing a noble metal component. Manufacture of a catalyst body, which comprises a step of immersing in a catalyst slurry, drying and then heat-treating to bond or fix the sheet-shaped paper product and the lath net and to carry a catalyst component on the base material. Method.
するシート状抄造体とアルミニウムを含むフェライト系
ステンレス鋼からなるラス網とを圧着しながら波形形状
に加工し、所定の長さに切断して波形形状の基材を得る
工程、前記基材を熱処理して前記シート状抄造体中に含
まれる有機成分を除去する工程、および前記基材を活性
アルミナ粉末を主体とした触媒担体スラリー中に浸漬
し、乾燥後、熱処理して前記シート状抄造体と前記ラス
網とを結合あるいは固定する工程、および前記基材にさ
らに貴金属成分を担持させる工程を有することを特徴と
する触媒体の製造方法。3. A sheet-shaped paper product containing heat-resistant inorganic fibers and inorganic powder as main components and a lath net made of ferritic stainless steel containing aluminum are pressed into a corrugated shape and cut into a predetermined length. To obtain a corrugated base material, a step of heat treating the base material to remove organic components contained in the sheet-shaped papermaking body, and the base material in a catalyst carrier slurry mainly composed of activated alumina powder. A method for producing a catalyst body, which comprises a step of bonding or fixing the sheet-shaped paper product and the lath net by heat treatment after dipping, drying, and supporting a noble metal component on the base material. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12251095A JP3480867B2 (en) | 1995-05-22 | 1995-05-22 | Catalyst body and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12251095A JP3480867B2 (en) | 1995-05-22 | 1995-05-22 | Catalyst body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08309205A JPH08309205A (en) | 1996-11-26 |
| JP3480867B2 true JP3480867B2 (en) | 2003-12-22 |
Family
ID=14837644
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|---|---|---|---|
| JP12251095A Expired - Fee Related JP3480867B2 (en) | 1995-05-22 | 1995-05-22 | Catalyst body and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3480867B2 (en) |
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|---|---|---|---|---|
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| JP2021070004A (en) * | 2019-11-01 | 2021-05-06 | トヨタ自動車株式会社 | Method for producing coating layer for exhaust gas purification catalyst device |
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1995
- 1995-05-22 JP JP12251095A patent/JP3480867B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08309205A (en) | 1996-11-26 |
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