JPH04281068A - Antioxidative inorganic fiber woven fabric, inorganic fiber plate-like catalyst and production thereof - Google Patents
Antioxidative inorganic fiber woven fabric, inorganic fiber plate-like catalyst and production thereofInfo
- Publication number
- JPH04281068A JPH04281068A JP3037507A JP3750791A JPH04281068A JP H04281068 A JPH04281068 A JP H04281068A JP 3037507 A JP3037507 A JP 3037507A JP 3750791 A JP3750791 A JP 3750791A JP H04281068 A JPH04281068 A JP H04281068A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic fiber
- woven fabric
- catalyst
- fiber woven
- silicon carbide
- 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
- 239000012784 inorganic fiber Substances 0.000 title claims abstract description 51
- 239000002759 woven fabric Substances 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 title 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000003365 glass fiber Substances 0.000 claims abstract description 25
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 239000000292 calcium oxide Substances 0.000 abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 19
- 229910052815 sulfur oxide Inorganic materials 0.000 description 13
- 239000010410 layer Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000007581 slurry coating method Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018404 Al2 O3 Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- -1 E-glass and mullite Chemical compound 0.000 description 1
- 239000004063 acid-resistant material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、耐酸性無機繊維織布、
無機繊維板状触媒およびこれらの製造方法に係り、特に
酸性ガスを含有する排煙の脱硝触媒用基材として好適な
耐熱、耐酸性無機繊維織布およびこれを用いた板状触媒
ならびにこれらの製造方法に関する。[Industrial Application Field] The present invention provides acid-resistant inorganic fiber woven fabric,
A heat-resistant and acid-resistant inorganic fiber woven fabric suitable as a base material for a denitrification catalyst for flue gas containing acidic gas, a plate-shaped catalyst using the same, and the production thereof, in particular, related to an inorganic fiber plate-shaped catalyst and a method for producing the same. Regarding the method.
【０００２】0002
【従来の技術】無機繊維からなる織り布は、耐熱性製品
、プラスチックおよびセラミックスとの複合材のほか、
各種触媒基材などに広く用いられている。これら織り布
に用いられている繊維にはＪＩＳ Ｒ ３４１４な
どで規定するＥ、Ｔガラスやシリカガラスなどのガラス
繊維のほか、ムライト製セラミックス、炭化ケイ素など
のファインセラミックス繊維などの各種のものが使用さ
れている（特開昭５０−１０４７８９、特開昭５９−７
３０５３等）。[Prior Art] Woven fabrics made of inorganic fibers are used for heat-resistant products, composite materials with plastics and ceramics, and
Widely used for various catalyst base materials. The fibers used in these woven fabrics include glass fibers such as E and T glass and silica glass specified by JIS R 3414, as well as mullite ceramics and fine ceramic fibers such as silicon carbide. (Japanese Unexamined Patent Publication No. 50-104789, Unexamined Japanese Patent Application No. 59-7
3053 etc.).
【０００３】0003
【発明が解決しようとする課題】これらのうち、Ｅガラ
スやムライト質などのカルシウムやアルミニウム酸化物
を含有するものは安価ではあるものの、排ガス中のＳＯ
ｘ等の酸性ガスと反応し、強度低下を引き起こすという
問題があり、腐食条件下では使用でなきい。一方、炭化
ケイ素繊維、シリカ繊維や、塩酸でシリカ成分以外のも
のを除去したガラス繊維などは、耐酸性に優れているも
のの、前記ガラス製織り布に較べて製造コストが１０〜
１００倍かかるため、排煙脱硝触媒用基材などのように
プラント当たり１０，０００ｍ２ を超える織り布を必
要とする用途に適した安価で耐酸性に優れた無機繊維が
ないのが実情であり、そのような無機繊維の発明が望ま
れている。Problems to be Solved by the Invention Among these, although those containing calcium and aluminum oxide, such as E-glass and mullite, are cheap, they reduce the amount of SO in exhaust gas.
There is a problem that it reacts with acidic gases such as x and causes a decrease in strength, so it cannot be used under corrosive conditions. On the other hand, silicon carbide fibers, silica fibers, and glass fibers from which components other than silica have been removed with hydrochloric acid have excellent acid resistance, but their production costs are 10 to 10% higher than the above-mentioned glass woven fabrics.
The cost is 100 times longer, so the reality is that there are no inexpensive inorganic fibers with excellent acid resistance that are suitable for applications that require more than 10,000 m2 of woven fabric per plant, such as base materials for exhaust gas denitrification catalysts. The invention of such an inorganic fiber is desired.
【０００４】他方、本発明者らは、上記問題を解決すべ
く研究を進め、安定酸化物で覆った無機繊維織り布の網
目内に触媒を塗り込む方法（特願平０１−２０００７２
）を開発し、大寸法、高強度触媒の製造方法として特許
出願している。しかしながら、無機繊維として汎用ガラ
スクロス（Ｅガラスなど）を使用した場合には、初期強
度は高いものの、ＳＯｘを含むガス中で高温下で使用さ
れた場合、経時的に強度低下するという問題があった。On the other hand, the present inventors have conducted research in order to solve the above problem, and have proposed a method of applying a catalyst into the mesh of an inorganic fiber woven cloth covered with a stable oxide (Japanese Patent Application No. 01-200072).
) and has applied for a patent as a method for producing large-sized, high-strength catalysts. However, when general-purpose glass cloth (such as E-glass) is used as the inorganic fiber, although the initial strength is high, there is a problem that the strength decreases over time when used at high temperatures in gas containing SOx. Ta.
【０００５】本発明の目的は、硫黄酸化物等の腐食性ガ
スを含むガス中で、高温で使用しても強度低下を起こさ
ない、または強度低下をきわめて小さくした耐熱・耐酸
性に優れた耐酸性無機繊維織布、無機繊維板状触媒およ
びこれらの製造方法を提供することにある。[0005] The object of the present invention is to provide an acid-resistant material with excellent heat and acid resistance that does not cause a decrease in strength or exhibits extremely small decrease in strength even when used at high temperatures in gases containing corrosive gases such as sulfur oxides. An object of the present invention is to provide a woven inorganic fiber fabric, an inorganic fiber plate-shaped catalyst, and a method for producing these.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
本願の第１の発明は、無機繊維織布表面にジルコニアお
よび炭化物系セラミックスを含むコーティング層を形成
させたことを特徴とする耐酸性無機繊維織布に関する。[Means for Solving the Problems] In order to achieve the above object, the first invention of the present application provides an acid-resistant inorganic material characterized in that a coating layer containing zirconia and carbide ceramics is formed on the surface of an inorganic fiber woven fabric. Regarding textile fabrics.
【０００７】第２の発明は、上記第１の発明の炭化物系
セラミックスが、平均粒径１μｍ以下の炭化物ケイ素粒
子であることを特徴とする耐酸性無機繊維織布に関する
。[0007] A second invention relates to an acid-resistant inorganic fiber woven fabric characterized in that the carbide ceramic of the first invention is silicon carbide particles having an average particle size of 1 μm or less.
【０００８】第３の発明は、カルシウムおよび／または
アルミニウムの酸化物を含有するガラス繊維織布に、コ
ロイダルジルコニアに炭化物系セラミックス粒子を添加
したスラリ状溶液を含浸または塗布し、乾燥または乾燥
後焼成することを特徴とする耐酸性無機繊維織布の製造
方法に関する。[0008] The third invention impregnates or coats a glass fiber woven fabric containing calcium and/or aluminum oxide with a slurry solution containing colloidal zirconia and carbide ceramic particles, and dries or sinters the fabric after drying. The present invention relates to a method for producing an acid-resistant inorganic fiber woven fabric.
【０００９】第４の発明は、上記第３の発明のスラリ状
溶液に有機結合剤を添加することを特徴とする耐酸性無
機繊維織布の製造方法に関する。A fourth invention relates to a method for producing an acid-resistant inorganic fiber woven fabric, characterized in that an organic binder is added to the slurry solution of the third invention.
【００１０】第５の発明は、無機繊維織布表面にジルコ
ニアおよび炭化ケイ素を含むコーティング層を形成した
基材表面に、窒素酸化物除去用触媒を担持させたことを
特徴とする無機繊維板状触媒に関する。[0010] The fifth invention is an inorganic fiber board-like material, characterized in that a catalyst for removing nitrogen oxides is supported on the surface of a base material on which a coating layer containing zirconia and silicon carbide is formed on the surface of an inorganic fiber woven fabric. Regarding catalysts.
【００１１】第６の発明は、カルシウムおよび／または
アルミニウムの酸化物を含有する無機繊維織布に、コロ
イダルジルコニアに炭化ケイ素粒子を添加したスラリ状
溶液を含浸または塗布し、乾燥または乾燥後焼成したの
ち、触媒または触媒原料を塗布し、乾燥および／または
焼成することを特徴とする無機繊維板状触媒の製造方法
に関する。[0011] In the sixth invention, an inorganic fiber woven fabric containing calcium and/or aluminum oxides is impregnated or coated with a slurry solution containing colloidal zirconia and silicon carbide particles, and dried or fired after drying. The present invention then relates to a method for producing an inorganic fiber plate-like catalyst, which comprises applying a catalyst or a catalyst raw material, followed by drying and/or calcination.
【００１２】第７の発明は、上記第６の発明のスラリ状
溶液に有機結合材を添加することを特徴とする無機繊維
板状触媒の製造方法。A seventh invention is a method for producing an inorganic fiber plate catalyst, characterized in that an organic binder is added to the slurry solution according to the sixth invention.
【００１３】第８の発明は、上記第６の発明の炭化ケイ
素粒子が、織布の無機繊維の径の１／１０〜１／１００
の粒子径を有することを特徴とする無機繊維板状触媒の
製造方法に関する。[0013] In an eighth invention, the silicon carbide particles of the sixth invention have a diameter of 1/10 to 1/100 of the diameter of the inorganic fiber of the woven fabric.
The present invention relates to a method for producing an inorganic fiber plate-like catalyst characterized by having a particle size of .
【００１４】[0014]
【作用】本発明者らの研究によれば、強度低下の主原因
はガラス繊維中に含まれるＣａＯおよびＡｌ２ Ｏ３
とＳＯ３ が反応し、ＣａＳＯ４ 、Ａｌ２ （ＳＯ）
４ が繊維表面に生成することが明らかとなり、これに
よって、（１）繊維がお互いに接合し、繊維の動きを阻
害するため、曲げや熱による伸びによって繊維が切断さ
れる。
（２）繊維表面が侵食されるため、単繊維そのものの強
度が低下する。
等の現象が生じることを見出している。[Function] According to the research conducted by the present inventors, the main cause of strength reduction is CaO and Al2 O3 contained in glass fibers.
and SO3 react to form CaSO4, Al2 (SO)
It has become clear that 4 is generated on the fiber surface, and as a result, (1) the fibers bond to each other and inhibit the movement of the fibers, so the fibers are cut by bending or elongation due to heat. (2) Since the fiber surface is eroded, the strength of the single fiber itself decreases. It has been found that the following phenomena occur.
【００１５】この反応は温度が高温になるほど活発とな
り、未処理の繊維は６００℃の高温で、ＳＯｘガスと接
触すると１００時間程度で初期強度の１／５以下となる
ことがわかった。[0015] This reaction becomes more active as the temperature rises, and it has been found that when untreated fibers come into contact with SOx gas at a high temperature of 600°C, they lose less than 1/5 of their initial strength in about 100 hours.
【００１６】このことからもわかるように、ＣａＳＯ４
および／またはＡｌ２ （ＳＯ）４ が表面に生成し
、繊維同士を拘束することを防止することができれば、
強度低下を防ぐことが可能である。そのためには、ガラ
ス繊維表面にＳＯｘと反応しない緻密な層を形成する必
要がある。また、通常、ガラス繊維は数μｍの径で、数
百〜数千本よったものをさらに数本より合わせたヤーン
を平織り、綾織りなどの各種形状に織ったものが用いら
れるため、ガラス繊維同士が拘束されると、小さな曲げ
変形や熱応力で割れが入るため、繊維同士が使用中に拘
束しないことも重要な要素となる。そこで、本発明者ら
は最適なガラス繊維のコーティング方法を探索した結果
、本発明で採用したコロイダルジルコニアに微粒子の炭
化ケイ素を適量添加したスラリ液をコーティングした繊
維が、高温下においてもＳＯｘガスとの反応に対して良
好な耐久性を有していることを見出した。本発明処理を
行ったガラス繊維の表面は、耐熱性に優れ、かつＳＯｘ
との反応に対しても良好なジルコニアの層で表面が均一
に覆われており、ＳＯｘを含むガス中で使用しても、Ｃ
ａＯを含むガラス繊維は直接ＳＯｘガスと接触すること
はなく、ＣａＯとＳＯｘの反応に起因する強度の低下を
防止することができる。ただし、コロイダルジルコニア
単独によるコーティングでは繊維同士がジルコニア層の
みを介して接合・拘束される状態となる。このため、高
温で使用した場合にジルコニア層と繊維の熱膨脹差に起
因する熱応力によりコーティング層やガラス繊維に割れ
が入り易くなる。これに対して、微粒子の炭化ケイ素な
どの炭化物系セラミックス粒子を添加することによって
、繊維間の拘束を防止することができる。また、炭化ケ
イ素のような炭化物系セラミックスを使用することによ
って使用中の熱時効や、コーティング後の熱処理によっ
てガラス繊維と反応し、ガラス繊維表面にＳＯｘガスに
対して不活性な反応層を形成する作用も有している。[0016] As can be seen from this, CaSO4
If it is possible to prevent and/or Al2 (SO)4 from forming on the surface and restraining the fibers,
It is possible to prevent a decrease in strength. For this purpose, it is necessary to form a dense layer on the surface of the glass fiber that does not react with SOx. In addition, glass fibers are usually several micrometers in diameter, and are made by twisting several hundred to several thousand yarns and then twisting several more yarns, woven into various shapes such as plain weave and twill weave. If the fibers are constrained together, cracks will occur due to small bending deformations or thermal stress, so it is also important that the fibers are not constrained during use. Therefore, the present inventors searched for an optimal coating method for glass fibers, and found that fibers coated with a slurry liquid made by adding an appropriate amount of fine particles of silicon carbide to the colloidal zirconia employed in the present invention were found to be resistant to SOx gas even at high temperatures. It has been found that it has good durability against the reaction of The surface of glass fiber treated with the present invention has excellent heat resistance and
The surface is uniformly covered with a layer of zirconia, which is good against reactions with carbon dioxide, and even when used in gas containing SOx,
Glass fibers containing aO do not come into direct contact with SOx gas, and can prevent a decrease in strength due to the reaction between CaO and SOx. However, when coating with colloidal zirconia alone, the fibers are bonded and restrained to each other only through the zirconia layer. Therefore, when used at high temperatures, the coating layer and the glass fibers tend to crack due to thermal stress caused by the difference in thermal expansion between the zirconia layer and the fibers. On the other hand, by adding carbide-based ceramic particles such as fine particles of silicon carbide, binding between the fibers can be prevented. In addition, by using carbide ceramics such as silicon carbide, it reacts with glass fibers during thermal aging during use and heat treatment after coating, forming a reactive layer on the glass fiber surface that is inert to SOx gas. It also has an effect.
【００１７】１）全体の構成
本発明の実施に用いられる無機繊維としては、Ｅガラス
などの無アルカリガラスの３〜１０μｍの単繊維を数百
〜数千本よったものをさらに数本より合わせたヤーンを
平織り、綾織りなどの各種形状に織ったものが用いられ
る。1) Overall structure The inorganic fibers used in the practice of the present invention are made by twisting several hundred to several thousand single fibers of 3 to 10 μm made of alkali-free glass such as E glass, and then twisting several fibers together. Yarns woven into various shapes such as plain weave and twill weave are used.
【００１８】この繊維織り布（以下、スクリーンと呼ぶ
）に、ジルコニアゾルと平均粒径が１μｍ以下の炭化ケ
イ素粒子を含有するスラリを浸漬またはスプレ法によっ
て担持し、しかる後に１００〜２００℃で乾燥する。
また必要に応じて５００〜８００℃で焼成する。A slurry containing zirconia sol and silicon carbide particles with an average particle size of 1 μm or less is supported on this fiber woven cloth (hereinafter referred to as a screen) by dipping or spraying, and then dried at 100 to 200°C. do. Further, baking is performed at 500 to 800°C if necessary.
【００１９】ここで、特長的なのはコロイダルジルコニ
アと炭化ケイ素微粒子からなるスラリ状物をスクリーン
表面に担持させるということであり、その他のスクリー
ンの剛性を向上させる方法、例えばポリビニルアルコー
ル等の有機結合剤を上記スラリ状物に添加してもよい。The feature here is that a slurry consisting of colloidal zirconia and fine silicon carbide particles is supported on the screen surface, and other methods for improving the rigidity of the screen, such as using an organic binder such as polyvinyl alcohol, are also available. It may be added to the slurry.
【００２０】２）各構成部分の相互関係、作用上記の操
作により得られたスクリーンは、図１および図２に示す
ように、ガラス繊維１の表面がジルコニア層２で覆われ
、また、各ガラス繊維は炭化ケイ素微粒子３を介して接
触する構成となっている。ガラス繊維表面を覆ったジル
コニア層は緻密でＳＯｘガスによりガラス繊維が侵され
るのを防止する作用をする。また、炭化ケイ素微粒子は
繊維間の拘束を防止するとともに、スクリーンに応力が
作用した際に、ガラス繊維同士の摺動性を向上させ、ガ
ラス繊維に割れが入るのを防止する役目（すなわち、潤
滑剤としての作用）をする。このためには粒子が繊維間
に均一に分布する必要があり、炭化ケイ素の粒子サイズ
としては繊維径の１／１０〜１／１００程度とするのが
よい。繊維径の１／１０よりも大きくなると繊維間への
分布が不均一となり、また１／１００よりも小さくして
も分布性はそれほど変化しない。2) Interrelationship and function of each constituent part In the screen obtained by the above operation, as shown in FIGS. 1 and 2, the surface of the glass fiber 1 is covered with the zirconia layer 2, and each glass fiber The fibers are in contact with each other through silicon carbide fine particles 3. The zirconia layer covering the glass fiber surface is dense and acts to prevent the glass fiber from being attacked by SOx gas. In addition, the silicon carbide particles prevent the fibers from being constrained, and when stress is applied to the screen, they improve the sliding properties between the glass fibers and prevent the glass fibers from cracking (i.e., lubricate act as an agent). For this purpose, the particles need to be uniformly distributed among the fibers, and the particle size of silicon carbide is preferably about 1/10 to 1/100 of the fiber diameter. When the fiber diameter becomes larger than 1/10, the distribution among the fibers becomes non-uniform, and even when it becomes smaller than 1/100, the distribution does not change much.
【００２１】[0021]
【実施例】以下、本発明を具体的実施例を用いてより詳
細に説明する。
実施例１
コロイダルジルコニア（日産化学製；ジルコニアの含有
量２０％）６００ｇに平均粒径０．３μｍの炭化ケイ素
（揖斐電製ベータランダム）４００ｇを混合し、スラリ
状コーティング液を調整した。このスラリ液中にＳｉＯ
２ ５４ｗｔ％、ＣａＯ １９ｗｔ％、Ａｌ２
Ｏ３ ２０ｗｔ％、Ｂ２ Ｏ３ ５ｗｔ％、そ
の他２ｗｔ％からなる直径９μｍのＥガラス繊維１４０
０本をより合わせたヤーンを１インチ当たり１０目で平
織りした無機繊維織り布に含浸後、スポンジローラを通
して液切りし、風乾後１３０℃で３０分乾燥し、試料と
した。EXAMPLES The present invention will be explained in more detail below using specific examples. Example 1 600 g of colloidal zirconia (manufactured by Nissan Chemical; zirconia content 20%) was mixed with 400 g of silicon carbide (Beta Random, manufactured by Ibiden) having an average particle size of 0.3 μm to prepare a slurry coating liquid. SiO in this slurry liquid
2 54wt%, CaO 19wt%, Al2
E-glass fiber 140 with a diameter of 9 μm, consisting of 20 wt% O3, 5 wt% B2 O3, and 2 wt% others
After impregnating an inorganic fiber woven cloth in which 0 twisted yarns were plain-woven at 10 stitches per inch, the liquid was drained through a sponge roller, air-dried, and then dried at 130° C. for 30 minutes to prepare a sample.
【００２２】実施例２
コロイダルジルコニア６００ｇにポリビニルアルコール
３０ｇを溶解させた後、この溶液に平均粒径０．３μｍ
の炭化ケイ素粒子を４００ｇ混合し、スラリ状コーティ
ング液を調整した。これ以外は実施例１と同一の方法で
試料とした。Example 2 After dissolving 30 g of polyvinyl alcohol in 600 g of colloidal zirconia, particles with an average particle size of 0.3 μm were added to the solution.
400 g of silicon carbide particles were mixed to prepare a slurry coating liquid. A sample was prepared in the same manner as in Example 1 except for this.
【００２３】実施例３
実施例１で得られた無機繊維を大気中５５０℃で２時間
の処理を行い、試料とした。Example 3 The inorganic fibers obtained in Example 1 were treated in the atmosphere at 550° C. for 2 hours and used as samples.
【００２４】実施例４
酸化チタン、３酸化タングステンからなる触媒粉末に水
を加え、ニーダにより混練し、水分が３２％の触媒ペー
ストを得た。実施例３で得られた無機繊維織布２枚を重
ね、その間に上記触媒ペーストを供給し、上下一対の回
転ローラの間に通して、触媒ペーストを上記織布に均一
に伸延塗布した。これを乾燥後、５５０℃で焼成して板
状触媒を得た。なお、触媒ペーストの代わりに、焼成す
ることにより触媒となる触媒原料を織布に含浸あるいは
塗布したのち、焼成してもよい。Example 4 Water was added to catalyst powder consisting of titanium oxide and tungsten trioxide, and the mixture was kneaded in a kneader to obtain a catalyst paste with a water content of 32%. Two inorganic fiber woven fabrics obtained in Example 3 were stacked, the catalyst paste was supplied between them, and passed between a pair of upper and lower rotating rollers to uniformly spread and apply the catalyst paste to the woven fabrics. After drying this, it was calcined at 550°C to obtain a plate-shaped catalyst. Note that instead of the catalyst paste, a catalyst raw material that becomes a catalyst upon firing may be impregnated or applied onto the woven fabric, and then fired.
【００２５】比較例１
実施例１に示した無機繊維織り布にコロイダルジルコニ
ア（ジルコニアの含有量２０％）を含浸後、１３０℃で
３０分乾燥し、試料とした。
比較例２
コロイダルジルコニア６００ｇと平均粒径１μｍのＴｉ
Ｏ２ 粒子を４００ｇを混合し得られたスラリ状コーテ
ィング液を実施例１に示した無機繊維織り布に含浸後、
１３０℃で３０分乾燥した。
比較例３
コロイダルシリカ６００ｇと平均粒径１μｍの酸化チタ
ンを４００ｇを混合して得られたスラリ状コーティング
液を実施例１に示した無機繊維織り布に含浸後、１３０
℃で３０分乾燥した。Comparative Example 1 The inorganic fiber woven fabric shown in Example 1 was impregnated with colloidal zirconia (zirconia content: 20%) and then dried at 130° C. for 30 minutes to prepare a sample. Comparative Example 2 600 g of colloidal zirconia and Ti with an average particle size of 1 μm
After impregnating the inorganic fiber woven cloth shown in Example 1 with a slurry coating liquid obtained by mixing 400 g of O2 particles,
It was dried at 130°C for 30 minutes. Comparative Example 3 After impregnating the inorganic fiber woven fabric shown in Example 1 with a slurry coating liquid obtained by mixing 600 g of colloidal silica and 400 g of titanium oxide with an average particle size of 1 μm,
It was dried at ℃ for 30 minutes.
【００２６】上記実施例１〜３および比較例１〜３の各
試料について、ａ）スクリーンから抜き取ったヤーン１
本の引張り強度、ｂ）６００℃で、ＳＯ２ ５００
ｐｐｍ 、ＳＯ３ ５０ｐｐｍ を含むガスと１０
０時間接触させた後のヤーン１本の引張り強度を測定し
た。引張り試験条件は以下のとおりである。
・治具間距離：２０ｍｍ
・引張り速度：２ｍｍ／ｍｉｎ
・温度 ：室温
・繰返し数 ：５回
図３に、測定結果（平均値）を示す。本図から明らかな
ように、実施例１〜３の各試料は、初期強度は比較例と
同等であるが、ＳＯｘガス含有ガスと接触させた後の強
度は比較例に較べて著しく高い値を示しており、本発明
の方法が耐熱・耐酸性無機繊維を得るのに優れたもので
あることがわかる。For each sample of Examples 1 to 3 and Comparative Examples 1 to 3 above, a) Yarn 1 extracted from the screen
Tensile strength of book, b) at 600℃, SO2 500
ppm, gas containing 50 ppm of SO3 and 10
The tensile strength of one yarn was measured after 0 hours of contact. The tensile test conditions are as follows. - Distance between jigs: 20 mm - Pulling speed: 2 mm/min - Temperature: room temperature - Number of repetitions: 5 times Figure 3 shows the measurement results (average values). As is clear from this figure, the initial strength of each sample of Examples 1 to 3 is equivalent to that of the comparative example, but the strength after contact with the SOx gas-containing gas is significantly higher than that of the comparative example. It can be seen that the method of the present invention is excellent for obtaining heat-resistant and acid-resistant inorganic fibers.
【００２７】実施例３では含浸・乾燥後に大気中で５５
０℃×２時間の熱処理を行っている。これによって、初
期強度は熱処理を行わない実施例１、２に較べてやや低
下しているものの、耐ＳＯｘ試験後の強度の劣化はほと
んどなく、実施例１、２に較べてより耐久性が向上して
いる。熱処理の効果としては、炭化ケイ素のような炭化
物系セラミックスはガラス繊維と反応し、表面に反応層
を形成し易く、ＳＯｘガスとガラス繊維との反応をより
小さくするためと考えられる。こうした効果を得るため
の熱処理温度としては、５００℃からガラス繊維の軟化
温度である８００℃の間とするのが好適である。In Example 3, after impregnation and drying, 55
Heat treatment was performed at 0°C for 2 hours. As a result, although the initial strength is slightly lower than in Examples 1 and 2 without heat treatment, there is almost no deterioration in strength after the SOx resistance test, and the durability is improved compared to Examples 1 and 2. are doing. It is thought that the effect of heat treatment is that carbide ceramics such as silicon carbide react with glass fibers and easily form a reaction layer on the surface, thereby further reducing the reaction between SOx gas and glass fibers. The heat treatment temperature for obtaining these effects is preferably between 500°C and 800°C, which is the softening temperature of glass fiber.
【００２８】実施例３の無機繊維織布を用いて製造した
実施例４の板状触媒は、耐熱、耐酸性に優れ、機械的強
度も高く、長時間の連続運転において高い脱硝性能を示
した。[0028] The plate-shaped catalyst of Example 4 produced using the inorganic fiber woven fabric of Example 3 had excellent heat resistance and acid resistance, high mechanical strength, and exhibited high denitrification performance during long-term continuous operation. .
【００２９】[0029]
【発明の効果】本願の請求項１、２、３および４に記載
した発明によればＥガラス等の安価な汎用ガラス繊維を
酸性ガスを含む腐食環境下で、かつ高温で使用すること
ができるようになる。その結果、シリカガラス、炭化ケ
イ素等の高コストのセラミックス繊維を本発明製品に置
き換えることができ、各種耐食、耐熱製品のコストを大
幅に低減できる。Effects of the Invention: According to the inventions set forth in claims 1, 2, 3, and 4 of the present application, inexpensive general-purpose glass fibers such as E-glass can be used in a corrosive environment containing acidic gas and at high temperatures. It becomes like this. As a result, high-cost ceramic fibers such as silica glass and silicon carbide can be replaced with the products of the present invention, and the costs of various corrosion-resistant and heat-resistant products can be significantly reduced.
【００３０】また、請求項５、６、７および８に記載し
た発明によれば、耐食・耐熱性に優れた無機繊維織布を
ボイラ排ガス等の脱硝用触媒基材として使用することに
より、触媒の耐久性が著しく向上する。Further, according to the invention described in claims 5, 6, 7, and 8, by using an inorganic fiber woven fabric with excellent corrosion resistance and heat resistance as a catalyst base material for denitration of boiler exhaust gas, etc. durability is significantly improved.
【図１】本発明になる無機繊維織集合体の断面模式図で
ある。FIG. 1 is a schematic cross-sectional view of an inorganic fiber woven aggregate according to the present invention.
【図２】本発明の構成要素の作用を示す図である。FIG. 2 is a diagram showing the operation of the components of the present invention.
【図３】実施例と比較例の無機繊維の強度を比較した図
である。FIG. 3 is a diagram comparing the strength of inorganic fibers of Examples and Comparative Examples.
１…無機繊維、２…ジルコニア層、３…炭化ケイ素粒子
。1... Inorganic fiber, 2... Zirconia layer, 3... Silicon carbide particles.
Claims (8)
炭化物系セラミックスを含むコーティング層を形成させ
たことを特徴とする耐酸性無機繊維織布。1. An acid-resistant inorganic fiber woven fabric, characterized in that a coating layer containing zirconia and carbide ceramics is formed on the surface of the inorganic fiber woven fabric.
が、平均粒径１μｍ以下の炭化ケイ素粒子であることを
特徴とする耐酸性無機繊維織布。2. An acid-resistant inorganic fiber woven fabric, wherein the carbide ceramic according to claim 1 is silicon carbide particles having an average particle size of 1 μm or less.
ムの酸化物を含有するガラス繊維織布に、コロイダルジ
ルコニアに炭化物系セラミックス粒子を添加したスラリ
状溶液を含浸または塗布し、乾燥または乾燥後焼成する
ことを特徴とする耐酸性無機繊維織布の製造方法。3. A glass fiber woven fabric containing calcium and/or aluminum oxides is impregnated or coated with a slurry solution containing colloidal zirconia and carbide ceramic particles, and dried or fired after drying. A method for producing an acid-resistant inorganic fiber woven fabric.
合剤を添加することを特徴とする耐酸性無機繊維織布の
製造方法。4. A method for producing an acid-resistant inorganic fiber woven fabric, which comprises adding an organic binder to the slurry solution according to claim 3.
炭化ケイ素を含むコーティング層を形成した基材表面に
、窒素酸化物除去用触媒を担持させたことを特徴とする
無機繊維板状触媒。5. An inorganic fiber plate-like catalyst characterized in that a catalyst for removing nitrogen oxides is supported on the surface of a base material on which a coating layer containing zirconia and silicon carbide is formed on the surface of an inorganic fiber woven fabric.
ムの酸化物を含有する無機繊維織布に、コロイダルジル
コニアに炭化ケイ素粒子を添加したスラリ状溶液を含浸
または塗布し、乾燥または乾燥後焼成したのち、触媒ま
たは触媒原料を塗布し、乾燥および／または焼成するこ
とを特徴とする無機繊維板状触媒の製造方法。6. An inorganic fiber woven fabric containing calcium and/or aluminum oxides is impregnated with or coated with a slurry solution containing colloidal zirconia and silicon carbide particles, dried or fired after drying. A method for producing an inorganic fiber plate-shaped catalyst, which comprises applying a catalyst raw material and drying and/or firing it.
合剤を添加することを特徴とする無機繊維板状触媒の製
造方法。7. A method for producing an inorganic fiber plate catalyst, comprising adding an organic binder to the slurry solution according to claim 6.
布の無機繊維の径の１／１０〜１／１００の粒子径を有
することを特徴とする無機繊維板状触媒の製造方法。8. A method for producing an inorganic fiber plate-shaped catalyst, wherein the silicon carbide particles according to claim 6 have a particle diameter of 1/10 to 1/100 of the diameter of the inorganic fibers of the woven fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3037507A JPH04281068A (en) | 1991-03-04 | 1991-03-04 | Antioxidative inorganic fiber woven fabric, inorganic fiber plate-like catalyst and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3037507A JPH04281068A (en) | 1991-03-04 | 1991-03-04 | Antioxidative inorganic fiber woven fabric, inorganic fiber plate-like catalyst and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04281068A true JPH04281068A (en) | 1992-10-06 |
Family
ID=12499447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3037507A Pending JPH04281068A (en) | 1991-03-04 | 1991-03-04 | Antioxidative inorganic fiber woven fabric, inorganic fiber plate-like catalyst and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04281068A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100694265B1 (en) * | 2000-12-21 | 2007-03-14 | 재단법인 포항산업과학연구원 | A method for wet coating of zirconia on alumina sagger |
| WO2007030410A1 (en) * | 2005-09-08 | 2007-03-15 | 3M Innovative Properties Company | Holding material for pollution control element and pollution control apparatus |
| JP2013540686A (en) * | 2010-10-11 | 2013-11-07 | ヘレーウス マテリアルズ テクノロジー ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト | Reduction of Pt and Rh evaporation loss at high temperature by using a barrier layer |
| CN104963188A (en) * | 2015-07-14 | 2015-10-07 | 河北宁纺集团有限责任公司 | Processing method for chemical-preventing fabric |
-
1991
- 1991-03-04 JP JP3037507A patent/JPH04281068A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100694265B1 (en) * | 2000-12-21 | 2007-03-14 | 재단법인 포항산업과학연구원 | A method for wet coating of zirconia on alumina sagger |
| WO2007030410A1 (en) * | 2005-09-08 | 2007-03-15 | 3M Innovative Properties Company | Holding material for pollution control element and pollution control apparatus |
| US7854905B2 (en) | 2005-09-08 | 2010-12-21 | 3M Innovative Properties Company | Holding material for pollution control element and pollution control apparatus |
| JP2013540686A (en) * | 2010-10-11 | 2013-11-07 | ヘレーウス マテリアルズ テクノロジー ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト | Reduction of Pt and Rh evaporation loss at high temperature by using a barrier layer |
| CN104963188A (en) * | 2015-07-14 | 2015-10-07 | 河北宁纺集团有限责任公司 | Processing method for chemical-preventing fabric |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2400301C2 (en) | Catalyst carrier substrate coated by first coat composition that comprises fibrous material | |
| EP0398752B1 (en) | Catalyst for reducing nitrogen oxides | |
| JP7423600B2 (en) | Selective catalytic reduction catalyst based on vanadium | |
| JP6632062B2 (en) | Non-combustible film material and method for producing the same | |
| KR100571226B1 (en) | Honeycomb structure | |
| KR20160087808A (en) | Denitration catalyst and method for producing same | |
| JP5451993B2 (en) | Inorganic fiber paper and honeycomb structure and filter using the same | |
| EP0934770B1 (en) | Catalyst and process for the production thereof | |
| JPH04281068A (en) | Antioxidative inorganic fiber woven fabric, inorganic fiber plate-like catalyst and production thereof | |
| JP3138312B2 (en) | Heat- and acid-resistant inorganic fibers and method for producing the same | |
| JP4610135B2 (en) | Photocatalyst carrier and method for producing porous substrate | |
| JP4094855B2 (en) | Catalyst body and carrier for catalyst body | |
| JPS63137752A (en) | Carrier and catalyst | |
| JP3091240B2 (en) | Heat- and acid-resistant glass fiber, method for producing the same, and method for producing glass fiber plate catalyst | |
| JPH06218291A (en) | Production of waste gas purifying catalyst and production of base material for catalyst used for the same | |
| JPH05285399A (en) | Production of catalyst for purification of exhaust gas and inorganic fibrous base material for the same | |
| JP2927454B2 (en) | Catalyst for removing nitrogen oxides and method for producing the same | |
| JPH0338256A (en) | Manufacture of plate-shaped catalyst for removing nitrogen oxide | |
| JP5412104B2 (en) | Exhaust gas purification catalyst | |
| JP3234217B2 (en) | Plate catalyst for removing nitrogen oxides, base material thereof, and methods for producing them | |
| JPH02227139A (en) | Denitrification catalyst | |
| JP3110033B2 (en) | Nitrogen oxide removal catalyst | |
| JPH035201B2 (en) | ||
| JP2596614Y2 (en) | Inorganic fiber plate catalyst | |
| JPH08192045A (en) | Nox adsorbent and its production |