JPH11267523A - Inorganic fiber cloth for substrate of denitration catalyst substrate, manufacture thereof, and denitration catalyst - Google Patents
Inorganic fiber cloth for substrate of denitration catalyst substrate, manufacture thereof, and denitration catalystInfo
- Publication number
- JPH11267523A JPH11267523A JP10075799A JP7579998A JPH11267523A JP H11267523 A JPH11267523 A JP H11267523A JP 10075799 A JP10075799 A JP 10075799A JP 7579998 A JP7579998 A JP 7579998A JP H11267523 A JPH11267523 A JP H11267523A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic fiber
- woven fabric
- denitration catalyst
- catalyst
- cloth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000012784 inorganic fiber Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000004744 fabric Substances 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 4
- 239000002759 woven fabric Substances 0.000 claims description 79
- 238000000034 method Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000000151 deposition Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- 239000000835 fiber Substances 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003014 reinforcing effect Effects 0.000 description 11
- 238000005452 bending Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は脱硝触媒基材用無機
繊維織布およびその製造法ならびに脱硝触媒に関し、さ
らに詳しくは排煙脱硝用の板状触媒の基材として用いら
れる無機繊維織布およびその製造法ならびにこれを用い
た脱硝触媒に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic fiber woven fabric for a denitration catalyst substrate, a method for producing the same, and a denitration catalyst. More specifically, the present invention relates to an inorganic fiber woven fabric used as a substrate for a flue gas denitration plate catalyst. The present invention relates to a production method thereof and a denitration catalyst using the same.
【０００２】[0002]
【従来の技術】板状触媒は基材上に触媒ペーストを圧延
塗布して製造される。該基材には、酸化シリコン（シリ
カ）および酸化アルミニウム（アルミナ）を主成分とす
る金網状の無機繊維織布（以下、織布ということがあ
る）が用いられており、該織布に基材としての機械的強
度や耐熱性および耐酸性を付与するために様々な提案が
なされている。2. Description of the Related Art A plate catalyst is produced by rolling and coating a catalyst paste on a substrate. As the base material, a wire mesh inorganic fiber woven fabric (hereinafter, sometimes referred to as a woven fabric) containing silicon oxide (silica) and aluminum oxide (alumina) as main components is used. Various proposals have been made to impart mechanical strength, heat resistance and acid resistance as a material.
【０００３】例えば、特開平３−６５２４６号公報に
は、織布にチタニアゾル等のゾル状物、チタニア等の安
定酸化物微粉およびポリビニルアルコール等の有機結合
剤からなる中間層を形成させて触媒成分を担持させた脱
硝用触媒が提案されている。また特開平４−７１６４２
号公報には、織布に酸化チタン、シリカ、ポリビニルア
ルコールからなる強化剤を含浸後乾燥して強化スクリー
ンとし、これに触媒ペーストを塗布し、乾燥、焼成する
板状触媒の製造方法が提案されている。For example, Japanese Patent Application Laid-Open No. 3-65246 discloses that an intermediate layer comprising a sol-like substance such as titania sol, a stable oxide fine powder such as titania and an organic binder such as polyvinyl alcohol is formed on a woven fabric. Has been proposed. Also, JP-A-4-71642
In Japanese Patent Application Publication No. 2002-264, a method for producing a plate-shaped catalyst is proposed in which a woven fabric is impregnated with a reinforcing agent composed of titanium oxide, silica, and polyvinyl alcohol, and then dried to form a reinforcing screen, a catalyst paste is applied thereto, and dried and fired. ing.
【０００４】織布に有機結合剤を含む溶液を含浸させて
乾燥することにより、織布を構成する繊維同士が結合し
てヤーンとしての剛性が増大し、また織布を構成する縦
糸と横糸の繊維の接点が拘束され、織布としての曲げ剛
性も高くなり、触媒製造時の取扱性が向上する。このよ
うな効果は有機結合剤を含む被覆膜の膜厚が薄い場合で
も得られるため、特に触媒の薄板化が求められている近
年では重要である。しかし、有機結合剤を用いると、触
媒製造時の焼成により該有機結合剤が酸化してしまうた
め、繊維が触媒成分や雰囲気ガスにさらされやすくな
り、織布の強度が低下するという問題があった。また無
機酸化物のゾルまたはスラリと有機結合剤との混合物を
織布に含浸させる方法では、これらの成分を混合すると
その性状が不安定化しやすいため、工業的な製造方法と
しては汎用性に欠くという問題があった。[0004] By impregnating a woven fabric with a solution containing an organic binder and drying, the fibers constituting the woven fabric are bonded to each other to increase the rigidity as a yarn. The contact points of the fibers are restrained, the bending stiffness as a woven fabric is increased, and the handleability during catalyst production is improved. Since such an effect can be obtained even when the thickness of the coating film containing the organic binder is small, it is particularly important in recent years in which a thinner catalyst is required. However, when an organic binder is used, the organic binder is oxidized by baking during the production of the catalyst, so that the fibers are easily exposed to the catalyst components and atmospheric gas, and the strength of the woven fabric is reduced. Was. In addition, in the method of impregnating a woven fabric with a mixture of a sol or slurry of an inorganic oxide and an organic binder, the properties are liable to be unstable when these components are mixed, and thus lacks versatility as an industrial production method. There was a problem.
【０００５】また特開平５−２２１６９５号公報には、
無機織布繊維に含まれるアルカリ土類金属の酸化物と、
触媒成分や反応ガス中に含まれる酸性成分が反応して織
布の引張強度が低下するのを防止するため、シリカ、ジ
ルコニア、酸化チタン（チタニア）などの無機酸化物の
ゾルやスラリを無機繊維織布に含浸させ、繊維の表面に
無機酸化物の被覆膜を設けて繊維の耐食性を向上させる
方法が提案されている。[0005] Also, Japanese Patent Application Laid-Open No. H5-222195 discloses that
An oxide of an alkaline earth metal contained in the inorganic woven fiber,
In order to prevent the catalytic component and the acidic component contained in the reaction gas from reacting and lowering the tensile strength of the woven fabric, the sol or slurry of an inorganic oxide such as silica, zirconia, or titanium oxide (titania) is used as an inorganic fiber. There has been proposed a method of impregnating a woven fabric and providing a coating film of an inorganic oxide on the surface of the fiber to improve the corrosion resistance of the fiber.
【０００６】しかし、無機結合剤や無機酸化物のみを無
機繊維織布に被覆させた場合には、これらの成分の被覆
量が少ないと繊維同士の充分な結合が確保されず、充分
な織布の剛性が得られない。被覆量を増やすと織布の厚
さが厚くなり、触媒の薄型化の要請に反することとな
る。また触媒の薄板化のために織布自体の厚さが薄くな
っており、それ自体の剛性が低下しているため、上記成
分の被覆量を少なくして膜厚を薄くすると、織布の曲げ
方向の剛性が低下し、触媒製造の取扱性が大幅に低下す
るという問題がある。However, when only the inorganic binder and the inorganic oxide are coated on the inorganic fiber woven fabric, if the coating amount of these components is small, sufficient bonding between the fibers cannot be ensured, and sufficient woven fabric is not obtained. Rigidity cannot be obtained. Increasing the amount of coating increases the thickness of the woven fabric, which is contrary to the demand for a thin catalyst. In addition, the thickness of the woven fabric itself has been reduced due to the thinner catalyst, and the rigidity of the woven fabric itself has been reduced. There is a problem that the stiffness in the direction is reduced, and the handleability of catalyst production is greatly reduced.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記従来技
術の問題を解決し、厚みが薄くても優れた耐久性（機械
的強度、耐食性）を有し、かつ容易に工業的な製造が可
能である脱硝触媒担体用無機繊維織布およびその製造法
ならびに脱硝触媒を提供するものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has excellent durability (mechanical strength and corrosion resistance) even if it is thin, and can be easily manufactured industrially. An object of the present invention is to provide a possible inorganic fiber woven fabric for a denitration catalyst carrier, a method for producing the same, and a denitration catalyst.
【０００８】[0008]
【課題を解決するための手段】本願で特許請求される発
明は以下の通りである。 （１）無機繊維織布に、酸化チタン層および有機結合剤
層を順に形成させたことを特徴とする脱硝触媒基材用無
機繊維織布。 （２）無機繊維織布に酸化チタンのゾルまたはスラリを
含浸させて乾燥した後、酢酸ビニル、アクリル酸アミ
ド、ポリビニルアルコールおよびカルボキシメチルセル
ロースの少なくとも一種からなる有機結合剤のエマルジ
ョンまたは溶液を含浸させて再乾燥することを特徴とす
る脱硝触媒基材用無機繊維織布の製造法。 （３）（１）または（２）に前記の無機繊維織布に触媒
を担持させてなる脱硝触媒。The invention claimed in the present application is as follows. (1) An inorganic fiber woven fabric for a denitration catalyst substrate, wherein a titanium oxide layer and an organic binder layer are sequentially formed on the inorganic fiber woven fabric. (2) After impregnating the inorganic fiber woven fabric with a sol or slurry of titanium oxide and drying, impregnating with an emulsion or solution of an organic binder comprising at least one of vinyl acetate, acrylamide, polyvinyl alcohol and carboxymethylcellulose. A method for producing an inorganic fiber woven fabric for a denitration catalyst substrate, comprising re-drying. (3) A denitration catalyst obtained by supporting a catalyst on the inorganic fiber woven fabric described in (1) or (2).
【０００９】[0009]
【作用】本発明では、無機繊維織布に有機結合剤の被膜
を形成する前に、酸化チタンのゾルまたはスラリを含浸
させて乾燥させ、織布を構成する繊維の表面に耐食性の
ある酸化チタン層を形成する。有機結合剤の被覆層を酸
化チタン層より先に形成すると、触媒製造時の焼成によ
り有機結合剤が酸化し、繊維表面が保護されなくなり、
織布の機械的強度が低下する。また、酸化チタンの被覆
層のみでは繊維表面から剥離しやすく、繊維を目止めす
る働きも弱いため、酸化チタンで被覆した織布に、さら
に有機結合剤のエマルジョンまたは溶液を含浸させて乾
燥し、有機結合剤層を形成する。According to the present invention, before forming a coating of an organic binder on an inorganic fiber woven fabric, the sol or slurry of titanium oxide is impregnated and dried, and the surface of the fiber constituting the woven fabric is made of titanium oxide having corrosion resistance. Form a layer. If the coating layer of the organic binder is formed before the titanium oxide layer, the organic binder is oxidized by baking during the production of the catalyst, and the fiber surface is not protected,
The mechanical strength of the woven fabric decreases. In addition, since the titanium oxide coating layer alone is easy to peel off from the fiber surface and has a weak function of filling the fibers, the woven fabric coated with titanium oxide is further impregnated with an emulsion or solution of an organic binder and dried. An organic binder layer is formed.
【００１０】このような構成および製造法を採用するこ
とにより、欠陥が少なく弾性や延性に富む有機結合剤層
で繊維の周囲を覆うことができるため、光ファイバケー
ブルのように曲げに強く、引張りにも強い無機繊維織布
を得ることができる。また横方向と縦方向の繊維同士が
充分に結合され、織布の曲げに対する優れた剛性を得る
こともできる。さらに触媒製造時の焼成により有機結合
剤が酸化されても、織布の表面は酸化チタン層で被覆さ
れているため、触媒成分や排ガス成分との反応が防止で
き、織布の強度が低下することがない。また本発明で
は、酸化チタン層と有機結合剤層が別工程で形成される
ため、これらの成分を混合して用いる場合に比べ、原料
を自由に選定でき、かつそれぞれの成分の担持量を自由
に調製することができる。従って、要求される織布の性
状が変更された場合でも容易に原料の選定や製造条件等
の最適化を図ることができる。By adopting such a configuration and a manufacturing method, the circumference of the fiber can be covered with an organic binder layer having few defects and having high elasticity and ductility. A strong inorganic fiber woven fabric can be obtained. Further, the fibers in the horizontal direction and the vertical direction are sufficiently bonded to each other, and excellent rigidity against bending of the woven fabric can be obtained. Furthermore, even if the organic binder is oxidized by baking during the production of the catalyst, since the surface of the woven fabric is covered with the titanium oxide layer, the reaction with the catalyst component and the exhaust gas component can be prevented, and the strength of the woven fabric decreases. Nothing. Further, in the present invention, since the titanium oxide layer and the organic binder layer are formed in separate steps, the raw materials can be freely selected and the carrying amount of each component can be freely determined as compared with a case where these components are mixed and used. Can be prepared. Therefore, even when the required properties of the woven fabric are changed, it is possible to easily select the raw materials and optimize the manufacturing conditions and the like.
【００１１】本発明において、触媒成分や排ガス成分に
対する耐食性を向上させる点から、酸化チタン層はでき
るだけ緻密に形成されていることが好ましい。従って、
酸化チタンのスラリを用いる場合にはできるだけ微粒子
の酸化チタンを用いるのが好ましい。酸化チタン層の層
厚には特に制限はないが、層厚が厚いと繊維の耐食性は
向上するが、層剥離が生じ、耐食性が低下し易く、また
薄い織布が得られなくなるため、要求される織布の性状
等に応じて適宜選定するのが好ましい。層厚の調整は、
酸化チタンのゾルまたはスラリの濃度の調製により行う
ことができ、高濃度のゾルまたはスラリを用いると層厚
は厚くなる。In the present invention, the titanium oxide layer is preferably formed as dense as possible from the viewpoint of improving the corrosion resistance to the catalyst component and the exhaust gas component. Therefore,
When using a titanium oxide slurry, it is preferable to use titanium oxide as fine particles as possible. There is no particular limitation on the layer thickness of the titanium oxide layer, but when the layer thickness is large, the corrosion resistance of the fiber is improved, but delamination occurs, the corrosion resistance is easily reduced, and a thin woven fabric cannot be obtained. It is preferable to select as appropriate according to the properties of the woven fabric. Adjustment of layer thickness
It can be carried out by adjusting the concentration of the titanium oxide sol or slurry. If the sol or slurry is used at a high concentration, the layer thickness becomes large.
【００１２】また有機結合剤層の形成には、酢酸ビニ
ル、アクリル酸アミド、、ポリビニルアルコールおよび
カルボキシメチルルロースの少なくとも一種からなるエ
マルジョンまたは溶液が用いられる。有機結合剤層の層
厚にも特に制限はないが、層厚が厚いと繊維間の目止め
効果が向上し、織布の曲げ方向の剛性を高めることがで
きるが、織布の厚さが厚くなり、繊維も切れやすくなる
ため、要求される織布の性状や触媒製造時にかかる外力
等を考慮して適宜選定するのが好ましい。該有機結合剤
の層厚の調製は、有機結合剤の濃度により調製すること
ができる。本発明に用いられる無機繊維織布としては特
に制限はないが、製造コスト等の点から、酸化シリコン
（シリカ）および酸化アルミニウム（アルミナ）を主成
分としたガラス繊維を金網状としたものが好ましい。For the formation of the organic binder layer, an emulsion or solution comprising at least one of vinyl acetate, acrylamide, polyvinyl alcohol and carboxymethyl cellulose is used. There is no particular limitation on the layer thickness of the organic binder layer, but when the layer thickness is large, the effect of filling between the fibers is improved, and the rigidity of the woven fabric in the bending direction can be increased. The thickness of the woven fabric becomes large and the fibers are easily cut, so that it is preferable to appropriately select the woven fabric in consideration of the required properties of the woven fabric and the external force applied during the production of the catalyst. The layer thickness of the organic binder can be adjusted according to the concentration of the organic binder. The inorganic fiber woven fabric used in the present invention is not particularly limited. However, from the viewpoint of production cost and the like, it is preferable that a glass fiber mainly composed of silicon oxide (silica) and aluminum oxide (alumina) is formed into a wire mesh. .
【００１３】[0013]
【発明の実施の形態】以下、本発明の無機繊維織布の製
造法を図面により説明する。図１は、本発明の一実施例
を示す無機繊維織布の製造装置の説明図である。図１に
おいて、この装置は、強化液１が貯留された含浸槽２
と、無機繊維織布３を該含浸槽内に導くガイドローラ４
と、含浸槽２の前記織布出口側に設けられたスポンジロ
ーラ５とから構成される。この装置において、無機繊維
織布３は、ガイドローラ４に導かれて強化液１内に浸漬
されて引き上げられた後、一対のスポンジローラ５に導
かれて余剰の強化液が除かれ、図示しない乾燥装置に導
かれて乾燥される。乾燥手段等には特に制限はなく、通
常は１００〜２００℃の温度で熱風乾燥される。例え
ば、１５０℃程度の温度で３０分〜２時間程度乾燥され
る。強化液１は、(1) 酸化チタンゾルもしくはスラリ、
または(2) 有機結合剤の溶液またはエマルジョンからな
り、無機繊維織布３は(1) からなる強化液で処理、乾燥
した後、(2) からなる強化液で処理される。なお、強化
液１には、本発明の目的が達成される限り他の成分が含
有されていてもよい。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for producing a woven inorganic fiber fabric of the present invention will be described below with reference to the drawings. FIG. 1 is an explanatory diagram of an apparatus for manufacturing a woven inorganic fiber fabric according to an embodiment of the present invention. In FIG. 1, this apparatus is an impregnation tank 2 in which a strengthening liquid 1 is stored.
And a guide roller 4 for guiding the inorganic fiber woven fabric 3 into the impregnation tank.
And a sponge roller 5 provided on the woven fabric outlet side of the impregnation tank 2. In this apparatus, the inorganic fiber woven fabric 3 is guided by the guide roller 4, dipped in the reinforcing liquid 1, pulled up, and then guided by the pair of sponge rollers 5 to remove excess reinforcing liquid, and is not shown. It is led to a drying device and dried. The drying means and the like are not particularly limited, and are usually dried with hot air at a temperature of 100 to 200 ° C. For example, it is dried at a temperature of about 150 ° C. for about 30 minutes to 2 hours. Reinforcing liquid 1 comprises (1) titanium oxide sol or slurry,
Or (2) a solution or emulsion of an organic binder, and the inorganic fiber woven fabric 3 is treated with the reinforcing liquid of (1), dried, and then treated with the reinforcing liquid of (2). In addition, other components may be contained in the fortifying liquid 1 as long as the object of the present invention is achieved.
【００１４】図２は、触媒ペーストの塗布装置の一例を
示す図である。図２において、強化液１で強化された２
枚の無機繊維織布８は、その織布の間に触媒ペースト６
を挟み込むようにして一対の圧延ローラ７に導かれ、圧
延された後、通常の方法で乾燥、焼成されて板状触媒と
される。FIG. 2 is a diagram showing an example of a device for applying a catalyst paste. In FIG. 2, 2
The sheet of inorganic fiber woven fabric 8 has a catalyst paste 6 between the woven fabrics.
After being guided to a pair of rolling rollers 7 so as to sandwich it, and rolled, it is dried and calcined by a usual method to obtain a plate-like catalyst.
【００１５】[0015]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれらに限定されるものではない。なお、無機繊
維織布としては、シリカアルミナガラス繊維を撚り合わ
せた織布（幅５００×長さ５００mm、厚さ０．２５mm、
繊維径６μｍ、繊維束の間隔２mm）を用いた。また強化
液の含浸には図１の装置を用い、乾燥は１５０℃で２時
間熱風乾燥した。触媒ペーストの塗布は図２に示す塗布
装置で行った。触媒ペーストを塗布し、風乾した後、５
００℃で２時間焼成して触媒とした。触媒ペーストに
は、チタニア粉末（比表面積約１００ｍ2 ／ｇ）、モリ
ブデン酸アンモニウムおよびメタバナジン酸アンモニウ
ムを原子比（Ｔｉ／Ｍｏ／Ｖ）で９３／５／２になるよ
うに秤量し、チタニア粉末に対して６０重量パーセント
の水を加え、３０分間ニーダで混練を行った後、原料の
チタニア粉末に対して１５重量パーセントの割合でシリ
カアルミナ繊維を同時に加えてさらに３０分間混練した
ものを用いた。The present invention will be described below with reference to examples, but the present invention is not limited to these examples. As the inorganic fiber woven fabric, a woven fabric obtained by twisting silica-alumina glass fibers (width 500 × length 500 mm, thickness 0.25 mm,
A fiber diameter of 6 μm and a fiber bundle interval of 2 mm) were used. The apparatus shown in FIG. 1 was used for impregnation with the reinforcing liquid, and drying was performed with hot air at 150 ° C. for 2 hours. The application of the catalyst paste was performed by the application device shown in FIG. After applying the catalyst paste and air drying, 5
It was calcined at 00 ° C. for 2 hours to obtain a catalyst. In the catalyst paste, titania powder (specific surface area: about 100 m 2 / g), ammonium molybdate and ammonium metavanadate are weighed so that the atomic ratio (Ti / Mo / V) becomes 93/5/2, and the titania powder is added to the titania powder. After adding 60% by weight of water and kneading with a kneader for 30 minutes, silica alumina fibers were simultaneously added at a ratio of 15% by weight to the titania powder as a raw material and kneaded for another 30 minutes.
【００１６】また例中の曲げ強度および引張強度は以下
のようにして測定した。 （１）曲げ強度 曲げ方法：３点支持法 スパン距離：２０mm 試験片の幅：２０mm 荷重変位速度：２mm／ｍｉｎ （２）引張強度 試験片の寸法：２０mm幅、６０mm長 引張速度：１０mm／ｍｉｎThe bending strength and tensile strength in the examples were measured as follows. (1) Bending strength Bending method: 3-point support method Span distance: 20 mm Specimen width: 20 mm Load displacement speed: 2 mm / min (2) Tensile strength Specimen dimensions: 20 mm width, 60 mm length Tensile speed: 10 mm / min
【００１７】実施例１ シリカアルミナガラス繊維の織布をチタニアゾル（固形
分３０重量％）に浸漬して引上げた後、余剰液を取り除
いて乾燥した。次いで１．６重量％のポリビニルアルコ
ール（重合度約２万）水溶液に浸漬した後、同様にして
乾燥し、本発明の強化無機繊維織布を得た。この織布に
触媒ペーストを塗布し、乾燥、焼成して板状触媒を製造
した。Example 1 A woven fabric of silica-alumina glass fiber was immersed in a titania sol (solid content: 30% by weight), pulled up, and then dried by removing excess liquid. Next, after being immersed in a 1.6% by weight aqueous solution of polyvinyl alcohol (degree of polymerization: about 20,000), it was dried in the same manner to obtain a reinforced inorganic fiber woven fabric of the present invention. The woven fabric was coated with a catalyst paste, dried and fired to produce a plate catalyst.
【００１８】実施例２ 実施例１において、チタニアゾルの濃度を１／２に希釈
して用いた以外は実施例１と同じ条件で強化無機繊維織
布を製造し、これを用いて実施例１と同様にして板状触
媒を得た。 実施例３ 実施例１において、チタニアゾルと固形分５０重量％の
チタニアスラリとを重量比で１：１で混合した強化液
を、チタニアゾルの代わりに用いた以外は実施例１と同
じ条件で強化無機繊維織布および板状触媒を得た。Example 2 A reinforced inorganic fiber woven fabric was produced under the same conditions as in Example 1 except that the titania sol was used after diluting the concentration of the titania sol to 1/2. Similarly, a plate-like catalyst was obtained. Example 3 The same procedure as in Example 1 was repeated except that a fortifying solution obtained by mixing the titania sol and the titania slurry having a solid content of 50% by weight at a weight ratio of 1: 1 was used in place of the titania sol. A fiber woven fabric and a plate catalyst were obtained.
【００１９】実施例４ 実施例１において、ポリビニルアルコールの代わりに酢
酸ビニルのエマルジョン（１．６重量％含有）を用いた
以外は実施例１と同じ条件で強化無機繊維織布および板
状触媒を得た。 実施例５ 実施例１において、チタニアゾルを１重量％の濃度に希
釈して用いた以外は実施例１と同じ条件で強化無機繊維
織布および板状触媒を得た。 実施例６ 実施例１において、チタニアゾルと固形分５０重量％の
チタニアスラリとを重量比で１：１に混合した強化液
を、チタニアゾルの代わりに用いた以外は実施例１と同
じ条件で強化無機繊維織布および板状触媒を得た。Example 4 A reinforced inorganic fiber woven fabric and a plate-like catalyst were used under the same conditions as in Example 1 except that an emulsion of vinyl acetate (containing 1.6% by weight) was used instead of polyvinyl alcohol. Obtained. Example 5 A reinforced inorganic fiber woven fabric and a plate catalyst were obtained under the same conditions as in Example 1 except that the titania sol was diluted to a concentration of 1% by weight and used. Example 6 The same procedure as in Example 1 was carried out except that the fortifying solution obtained by mixing the titania sol and the titania slurry having a solid content of 50% by weight at a weight ratio of 1: 1 was used in place of the titania sol. A fiber woven fabric and a plate catalyst were obtained.
【００２０】比較例１ 実施例１において、織布をチタニアゾルに浸漬したのみ
でポリビニルアルコール水溶液には浸漬しなかった以外
は実施例１と同じ条件で強化無機繊維織布および板状触
媒を得た。 比較例２ 実施例１において、織布をチタニアゾルには浸漬せずに
直接ポリビニルアルコール水溶液のみに浸漬した以外は
実施例１と同じ条件で強化無機繊維織布および板状触媒
を得た。Comparative Example 1 A reinforced inorganic fiber woven fabric and a plate-like catalyst were obtained under the same conditions as in Example 1 except that the woven fabric was only immersed in the titania sol but not in the aqueous polyvinyl alcohol solution. . Comparative Example 2 A reinforced inorganic fiber woven fabric and a plate-like catalyst were obtained under the same conditions as in Example 1 except that the woven fabric was not immersed in the titania sol but was immersed directly in the aqueous polyvinyl alcohol solution.
【００２１】比較例３ 実施例１において、織布を、チタニアゾルとポリビニル
アルコール水溶液を重量比で１：１で混合した混合液に
浸漬した以外は実施例１と同じ条件で強化無機繊維織布
および板状触媒を得た。 比較例４ 実施例１において、織布をポリビニルアルコール水溶液
に浸漬した後、チタニアゾルに浸漬した以外は実施例１
と同じ条件で強化無機繊維織布および板状触媒を得た。Comparative Example 3 A reinforced inorganic fiber woven fabric and a woven fabric were prepared under the same conditions as in Example 1 except that the woven fabric was immersed in a mixture of a titania sol and a polyvinyl alcohol aqueous solution at a weight ratio of 1: 1. A plate catalyst was obtained. Comparative Example 4 Example 1 was repeated except that the woven fabric was immersed in an aqueous solution of polyvinyl alcohol and then immersed in a titania sol.
Under the same conditions as described above, a reinforced inorganic fiber woven fabric and a plate-like catalyst were obtained.
【００２２】比較例５ 実施例１において、チタニアゾルの代わりにシリカゾル
（固形分２０重量％）を用いた以外は実施例１と同じ条
件で強化無機繊維織布および板状触媒を得た。実施例１
〜６および比較例１〜５で得られた強化無機繊維織布の
強化液成分の担持量および厚さを測定し、さらに板状触
媒の引張強度および曲げ強度を測定し、その結果を表１
に示した。Comparative Example 5 A reinforced inorganic fiber woven fabric and a plate-like catalyst were obtained under the same conditions as in Example 1 except that silica sol (solid content: 20% by weight) was used instead of titania sol. Example 1
And the thickness of the reinforcing liquid component of the reinforced inorganic fiber woven fabric obtained in Comparative Examples 1 to 5, and the tensile strength and bending strength of the plate catalyst were measured.
It was shown to.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１から、本発明の無機繊維織布を使用す
ることにより、厚みが薄く、かつ曲げ強度および引張強
度に優れた板状触媒が容易に得られることが示される。
また実施例１〜３の結果からはチタニアゾルまたはスラ
リの濃度を高くすると触媒の板厚が厚くなり強度が向上
し、織布の耐食性も高くなることが示される。実施例４
の結果からは有機結合剤として酢酸ビニルを用いた場合
でも同様の効果が得られるが示される。実施例５の結果
からはチタニアゾルまたはスラリの濃度が低すぎると強
化液成分の担持量が少なくなる傾向にあり、実施例６の
結果からはチタニア濃度が高すぎると触媒の板厚が厚く
なる傾向にあることが示される。Table 1 shows that the use of the inorganic fiber woven fabric of the present invention makes it possible to easily obtain a plate catalyst having a small thickness and excellent bending strength and tensile strength.
Further, the results of Examples 1 to 3 show that when the concentration of titania sol or slurry is increased, the thickness of the catalyst is increased, the strength is improved, and the corrosion resistance of the woven fabric is also increased. Example 4
The results show that the same effect can be obtained when vinyl acetate is used as the organic binder. From the results of Example 5, when the concentration of the titania sol or the slurry is too low, the carrying amount of the reinforcing liquid component tends to decrease, and from the results of Example 6, when the titania concentration is too high, the plate thickness of the catalyst tends to increase. Is shown.
【００２５】これに対し、比較例１では酸化チタン層の
みが形成されているため、また比較例２では有機結合剤
層のみが形成されているため、曲げ強度および引張強度
ともに低下する。特に比較例２では曲げ強度が低く、繊
維の結合が不充分である。比較例３では酸化チタンゾル
と有機結合剤を混合した混合液が用いられているが、混
合によりゲル化が生じたため、強化液成分の担持量の制
御が難しく、触媒の板厚も厚くなった。比較例４ではポ
リビニルアルコール層を形成した後に酸化チタン層を形
成したため、触媒の強度が低下した。さらに比較例５で
は、酸化チタン層の代わりにシリカ層を形成したため、
濃度が低くてもある触媒の板厚が厚くなり、またある程
度の繊維の結合力も得られたが、引張強度が低下した。On the other hand, since only the titanium oxide layer is formed in Comparative Example 1 and only the organic binder layer is formed in Comparative Example 2, both the bending strength and the tensile strength are reduced. In particular, in Comparative Example 2, the bending strength was low, and the bonding of the fibers was insufficient. In Comparative Example 3, a mixed solution in which a titanium oxide sol and an organic binder were mixed was used. However, since the mixing caused gelation, it was difficult to control the amount of the reinforcing liquid component carried, and the thickness of the catalyst was increased. In Comparative Example 4, since the titanium oxide layer was formed after the polyvinyl alcohol layer was formed, the strength of the catalyst was reduced. Further, in Comparative Example 5, since a silica layer was formed instead of the titanium oxide layer,
Although the concentration was low, the thickness of a certain catalyst was increased, and a certain amount of fiber binding force was obtained, but the tensile strength was reduced.
【００２６】[0026]
【発明の効果】本発明の無機繊維織布およびその製造法
によれば、厚みが薄くても優れた耐久性を有し、かつ工
業的な製造を容易に行うことができる。また本発明の無
機繊維織布を用いることにより、脱硝性能に優れた脱硝
触媒を容易に得ることができる。According to the inorganic fiber woven fabric and the method for producing the same of the present invention, even if the thickness is small, the inorganic fiber woven fabric has excellent durability and industrial production can be easily performed. Further, by using the inorganic fiber woven fabric of the present invention, a denitration catalyst having excellent denitration performance can be easily obtained.
【図１】本発明の一実施例を示す無機繊維織布の製造装
置の説明図。FIG. 1 is an explanatory view of an apparatus for producing an inorganic fiber woven fabric according to an embodiment of the present invention.
【図２】触媒ペーストの塗布装置の一例を示す図。FIG. 2 is a diagram showing an example of a catalyst paste application device.
１…強化液、２…含浸槽、３…無機繊維織布、４…ガイ
ドローラ、５…スポンジローラ、６…触媒ペースト、７
…圧延ローラ、８…強化された無機繊維織布。DESCRIPTION OF SYMBOLS 1 ... Reinforcing liquid, 2 ... Impregnation tank, 3 ... Inorganic fiber woven fabric, 4 ... Guide roller, 5 ... Sponge roller, 6 ... Catalyst paste, 7
... rolling rollers, 8 ... reinforced inorganic fiber woven fabric.
Claims (3)
機結合剤層を順に形成させたことを特徴とする脱硝触媒
基材用無機繊維織布。1. An inorganic fiber woven fabric for a denitration catalyst substrate, wherein a titanium oxide layer and an organic binder layer are sequentially formed on the inorganic fiber woven fabric.
スラリを含浸させて乾燥した後、酢酸ビニル、アクリル
酸アミド、ポリビニルアルコールおよびカルボキシメチ
ルセルロースの少なくとも一種からなる有機結合剤のエ
マルジョンまたは溶液を含浸させて再乾燥することを特
徴とする脱硝触媒基材用無機繊維織布の製造法。2. An inorganic fiber woven fabric is impregnated with a sol or slurry of titanium oxide, dried and then impregnated with an emulsion or solution of an organic binder comprising at least one of vinyl acetate, acrylamide, polyvinyl alcohol and carboxymethylcellulose. A method for producing an inorganic fiber woven fabric for a denitration catalyst substrate, comprising drying and drying again.
触媒を担持させてなる脱硝触媒。3. A denitration catalyst comprising a catalyst supported on the woven inorganic fiber fabric according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10075799A JPH11267523A (en) | 1998-03-24 | 1998-03-24 | Inorganic fiber cloth for substrate of denitration catalyst substrate, manufacture thereof, and denitration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10075799A JPH11267523A (en) | 1998-03-24 | 1998-03-24 | Inorganic fiber cloth for substrate of denitration catalyst substrate, manufacture thereof, and denitration catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11267523A true JPH11267523A (en) | 1999-10-05 |
Family
ID=13586620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10075799A Pending JPH11267523A (en) | 1998-03-24 | 1998-03-24 | Inorganic fiber cloth for substrate of denitration catalyst substrate, manufacture thereof, and denitration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11267523A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7772147B2 (en) | 2004-09-13 | 2010-08-10 | Johnson Matthey Public Limited Company | Catalyst carrier substrate coated with washcoat comprising fibrous material |
| CN114471104A (en) * | 2022-03-09 | 2022-05-13 | 清源创新实验室 | Flue gas full-working-condition dry desulfurization and catalytic filter bag dust removal-SCR denitration system and method |
-
1998
- 1998-03-24 JP JP10075799A patent/JPH11267523A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7772147B2 (en) | 2004-09-13 | 2010-08-10 | Johnson Matthey Public Limited Company | Catalyst carrier substrate coated with washcoat comprising fibrous material |
| CN114471104A (en) * | 2022-03-09 | 2022-05-13 | 清源创新实验室 | Flue gas full-working-condition dry desulfurization and catalytic filter bag dust removal-SCR denitration system and method |
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