JP3234217B2 - Plate catalyst for removing nitrogen oxides, base material thereof, and methods for producing them - Google Patents
Plate catalyst for removing nitrogen oxides, base material thereof, and methods for producing themInfo
- Publication number
- JP3234217B2 JP3234217B2 JP29314990A JP29314990A JP3234217B2 JP 3234217 B2 JP3234217 B2 JP 3234217B2 JP 29314990 A JP29314990 A JP 29314990A JP 29314990 A JP29314990 A JP 29314990A JP 3234217 B2 JP3234217 B2 JP 3234217B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- plate
- woven fabric
- mesh
- nitrogen oxides
- 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 75
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 17
- 239000000463 material Substances 0.000 title claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000012784 inorganic fiber Substances 0.000 claims description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 17
- 239000002759 woven fabric Substances 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 150000003658 tungsten compounds Chemical class 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- CDQFODAJQFUTJR-UHFFFAOYSA-M [NH4+].[O-]C(=O)C(=O)O[Ti] Chemical compound [NH4+].[O-]C(=O)C(=O)O[Ti] CDQFODAJQFUTJR-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007581 slurry coating method Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は窒素酸化物除去用板状触媒、その基材および
それらの製造方法に係り、特に排ガス中のSOXによる強
度劣化の少ない、無機繊維製織布もしくは網状体よりな
る触媒基材またはその基材に脱硝触媒を担持させた窒素
酸化物除去用板状触媒、およびそれらの製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [INDUSTRIAL FIELD] The present invention for removing nitrogen oxides plate catalyst, relates to the substrate and methods for their preparation, in particular less strength deterioration due to SO X in the exhaust gas, inorganic The present invention relates to a catalyst substrate made of a woven fabric or a net made of fiber, a plate catalyst for removing nitrogen oxides on which a denitration catalyst is supported, and methods for producing the same.
ボイラからの燃焼排ガス中の窒素酸化物（NOX）を処
理する触媒には、次のような特性が要求される。The catalyst for the process of nitrogen oxides in the combustion exhaust gas from boiler (NO X), the following characteristics are required.
（１）圧力損失が小さい。(1) The pressure loss is small.
（２）排ガス中のダストが堆積しにくい。(2) Dust in exhaust gas is not easily deposited.
（３）大容量の排ガスを処理するためサイズの大きな触
媒が必要となり、構造体として充分な強度が得られるよ
うに非常に高強度なものが必要とされる。(3) A large-sized catalyst is required for treating a large amount of exhaust gas, and a very high-strength one is required so that a sufficient strength can be obtained as a structure.
このような要求を満たすものとして、板状またはハニ
カム状のものが用いられており、その触媒としては、金
属基板に触媒成分を塗布したもの（特公昭61−28377号
公報）、触媒成分をハニカム状に押出成形したもの（特
公昭60−3856号公報等）、セラミックス繊維製マットや
紙をハニカム状に成形後触媒前駆体物質を塗布したもの
（特公昭58−11253号公報等）または、無機繊維製クロ
スに触媒組成物を塗布したものがある（特願平01−2000
72号）。In order to satisfy such requirements, a plate-shaped or honeycomb-shaped catalyst is used. As the catalyst, a catalyst obtained by coating a metal substrate with a catalyst component (Japanese Patent Publication No. 61-28377) and a catalyst comprising a honeycomb component are used. Extrusion molding (Japanese Patent Publication No. 60-3856, etc.), a ceramic fiber mat or paper formed into a honeycomb shape and then coated with a catalyst precursor (Japanese Patent Publication No. 58-11253, etc.) or inorganic There is a fiber cloth coated with a catalyst composition (Japanese Patent Application No. 01-2000).
No. 72).
上記従来技術のうち、金属基板に触媒を塗布したもの
は、重量が大きくまた、金属基板が高温雰囲気下で酸化
されるという難点があった。Among the above-mentioned prior arts, the one in which a catalyst is applied to a metal substrate has a problem that the weight is large and the metal substrate is oxidized in a high-temperature atmosphere.
また、触媒成分をハニカム状に成形したものはコーナ
ー部が多く、板状触媒を組合わせたものに較べ圧力損失
が大きいという問題があった。Further, the catalyst component formed into a honeycomb shape has many corners, and has a problem that the pressure loss is larger than that obtained by combining a plate-shaped catalyst.
また、無機繊維製の布や紙等の表面に触媒成分を含浸
したものは、触媒の密度を大きくすることが難しく機械
的強度が小さいという問題を有していた。Further, those obtained by impregnating a catalyst component on the surface of an inorganic fiber cloth or paper have a problem that it is difficult to increase the density of the catalyst and the mechanical strength is low.
さらに、上記問題点を回避するために創案された無機
繊維製クロスを基材とし、それに触媒組成物を塗布した
後成形して板状触媒とするもの（特願平01−200072号）
は、密度の高いペースト状の触媒を無機繊維製クロスに
塗布するため高密度な触媒を得易く機械的強度が大きい
という優れた点を有している。しかし、この触媒を高濃
度の硫黄酸化物（SOX）等の腐食性ガスを含む排ガス中
で長期間使用すると無機繊維の機械的強度が低下し、結
局、触媒の強度が低下してしまうという問題点を有して
いた。Further, a plate-shaped catalyst is prepared by applying a catalyst composition to a cloth made of inorganic fiber, which has been devised in order to avoid the above-mentioned problems, and forming the catalyst (Japanese Patent Application No. 01-200072).
Has an excellent point that a high-density catalyst is easily obtained and a mechanical strength is large because a paste-like catalyst having a high density is applied to an inorganic fiber cloth. However, if this catalyst is used for a long time in exhaust gas containing corrosive gas such as high concentration sulfur oxide (SO X ), the mechanical strength of the inorganic fiber is reduced, and eventually the strength of the catalyst is reduced. Had problems.
本発明の目的は、硫黄酸化物等の腐食性ガスを含む排
ガス中で使用しても強度低下の起きないか、または強度
低下をきわめて小さくした、窒素酸化物除去用板状触
媒、その基材およびそれらの製造方法を提供することに
ある。An object of the present invention is to provide a plate catalyst for removing nitrogen oxides, which does not cause a decrease in strength even when used in an exhaust gas containing a corrosive gas such as a sulfur oxide or has a very small decrease in strength, and a base material thereof. And a method for producing them.
上記目的は、カルシウム成分を含有する無機繊維布ま
たは網状体に脱硝触媒を担持させた窒素酸化物除去用板
状触媒において、前記無機繊維織布または網状体の繊維
表面に設けられたカルシウムとタングステンを含む反応
生成物からなる第１層と、該第１層上に設けられたチタ
ン化合物を含む脱硝触媒からなる第２層とを有すること
を特徴とする窒素酸化物除去用板状触媒、 カルシウム成分含有無機繊維織布または網状体からな
り、脱硝触媒を担持させるための窒素酸化物除去用触媒
基材において、上記無機繊維織布または網状体がタング
ステン化合物と、チタニア、ジルコニア、コージエライ
トから選ばれた１種以上の酸化物と、ポリビニルアルコ
ール、酢酸ビニル、カルボキシメチルセルローズから選
ばれた１種以上の有機結合剤とからなるコーティング層
を形成してなることを特徴とする窒素酸化物除去用板状
触媒基材、 カルシウム成分含有無機繊維織布または網状体に脱硝
触媒を担持させる窒素酸化物除去用板状触媒の製造方法
において、上記無機繊維織布または網状体にタングステ
ン化合物を含む液状体を含浸または塗布し、これを乾燥
または乾燥したのち焼成して、これにチタン化合物を含
む脱硝触媒を塗布し、さらに乾燥、焼成することを特徴
とする窒素酸化物除去用板状触媒の製造方法、 およびカルシウム成分含有無機繊維織布または網状体
からなり、脱硝触媒を担持する窒素酸化物除去用板状触
媒基材の製造方法において、タングステン化合物をシュ
ウ酸水溶液に溶解し、これにポリビニルアルコールと塩
素法により製造されたチタニアとを混合してスラリ状コ
ーティング液となし、これを上記織布または網状体に含
浸または塗布し、その後乾燥、または乾燥したのち焼成
することを特徴とする窒素酸化物除去用板状触媒基材の
製造方法により達成される。An object of the present invention is to provide a plate catalyst for removing nitrogen oxide in which a denitration catalyst is supported on an inorganic fiber cloth or mesh containing a calcium component, wherein calcium and tungsten provided on the fiber surface of the inorganic fiber woven fabric or mesh are used. A plate catalyst for removing nitrogen oxides, comprising: a first layer made of a reaction product containing: and a second layer made of a denitration catalyst containing a titanium compound provided on the first layer; In the catalyst substrate for removing nitrogen oxides for supporting a denitration catalyst, the inorganic fiber woven fabric or mesh is selected from a tungsten compound, titania, zirconia, and cordierite. From at least one oxide and at least one organic binder selected from polyvinyl alcohol, vinyl acetate, and carboxymethyl cellulose. Of a nitrogen oxide removing plate-shaped catalyst substrate comprising a coating layer formed thereon, and a nitrogen component-removing plate-shaped catalyst in which a denitration catalyst is supported on a calcium component-containing inorganic fiber woven fabric or mesh. In the method, a liquid containing a tungsten compound is impregnated or applied to the inorganic fiber woven fabric or mesh, dried or dried and then fired, and a denitration catalyst containing a titanium compound is applied thereto, and further dried, A method for producing a plate catalyst for removing nitrogen oxides, characterized by firing, and a method for producing a plate catalyst substrate for removing nitrogen oxides, comprising a calcium component-containing inorganic fiber woven fabric or a network, carrying a denitration catalyst. In the method, a tungsten compound is dissolved in an aqueous oxalic acid solution, and polyvinyl alcohol and titania produced by a chlorine method are mixed with the solution to form a slurry. A coating liquid, which is impregnated or coated on the woven fabric or net-like body, and then dried or dried and then calcined. .
無機繊維製縒り糸を網状に織ったシートに、触媒組成
物を塗布して得た板状触媒を高濃度のSOXを含む排ガス
中に放置すると、無機繊維中の成分であるCaとSOXが反
応して無機繊維の強度低下を引き起こしていた。本発明
の特徴である溶液状となしたタングステン化合物を含む
コーティング液を縒り糸表面にコーティングしたもの
（基材）に触媒組成物を塗布して、焼成し板状触媒とし
たものは、焼成時、コーティング層中のタングステン化
合物が無機繊維中の成分であるCaと反応し、無機繊維製
縒り糸表面にタングステン酸カルシウム等の反応性の小
さい被膜を形成するため、SOXを含有する排ガス中にお
いても、排ガス中のSOXと無機繊維中の成分であるCaが
上記形成被膜で隔てられるため反応することがなく強度
の低下を防止できる。The inorganic fibers made of strands into a sheet woven reticulated, upon standing the plate catalyst obtained by coating a catalyst composition in the exhaust gas containing a high concentration of SO X, which is a component of the inorganic fibers Ca and SO X Reacted to cause a decrease in the strength of the inorganic fibers. The coating composition containing the tungsten compound in the form of a solution, which is a feature of the present invention, is coated on the surface of a twisted yarn (substrate), and the catalyst composition is applied to the coating. , tungsten compounds in the coating layer reacts with Ca which is a component of the inorganic fibers, to form a reactive small film such as calcium tungstate inorganic textile strands surfaces, in exhaust gas containing SO X Also, since SO X in the exhaust gas and Ca as a component in the inorganic fibers are separated by the above-mentioned formed film, they do not react with each other, so that a decrease in strength can be prevented.
なお、溶液状のタングステン化合物とともに、酸化チ
タン等の微粒子とポリビニルアルコール等の有機物結合
剤をコーティングするのは、基材に触媒ペーストを塗布
する際に、無機繊維製シートの網目状体の形状が保持で
きるように、上記シートの剛性を持たせるためである。It should be noted that the coating of the fine particles such as titanium oxide and the organic binder such as polyvinyl alcohol together with the solution-like tungsten compound is performed when the catalyst paste is applied to the base material because the shape of the mesh-like body of the inorganic fiber sheet is reduced. This is because the sheet has rigidity so that it can be held.
本発明に用いられる無機繊維としては、外径数ミクロ
ンなしに数十ミクロンのガラス繊維を縒り合わせて８な
いし20メッシュ（厚さ0.3〜1mm）程度の平織りにしたも
のが好結果を与える。As the inorganic fiber used in the present invention, a glass fiber of several tens of microns without twisting the outer diameter of several microns and having a plain weave of about 8 to 20 mesh (thickness of 0.3 to 1 mm) gives good results.
このガラス繊維織布（以下、スクリーンと呼ぶ）に、
タングステン化合物としてタングステン酸アンモニウム
あるいは三酸化タングステンをシュウ酸あるいは過酸化
水素水に溶解させたものと、１ミクロン（μ）以下の粒
径のものが90％程度の酸化チタン粉末およびポリビニル
アルコールとを含有するスラリを浸漬法あるいはスプレ
ー法によって担持し、しかる後100〜200℃で乾燥する。
また、必要によっては500〜600℃で焼成してもよい。上
記の操作により、触媒担持用基材が得られる。ここで特
徴的なのはタングステン化合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、１μ以下の微粒子酸化チタン
のスクリーン表面への付着性を向上させるため、前記ス
ラリにさらに、シュウ酸チタンを添加する方法、あるい
は１μ以下の微粒子酸化チタンの代わりに微粒子ジルコ
ニアや微粒子コージエライト等の耐熱、耐酸性微粒子を
使用すること、また有機バインダとしてポリビニルアル
コールの他にカルボキシメチルセルロース、酢酸ビニル
等を用いることもできる。This glass fiber woven fabric (hereinafter called screen)
As a tungsten compound, ammonium tungstate or tungsten trioxide dissolved in oxalic acid or hydrogen peroxide solution, titanium oxide powder having a particle diameter of 1 micron (μ) or less contains about 90% and polyvinyl alcohol The slurry is carried by a dipping method or a spray method, and then dried at 100 to 200 ° C.
Moreover, you may bake at 500-600 degreeC as needed. By the above operation, a catalyst-carrying substrate is obtained. Here, the feature is that a tungsten compound is supported on the screen surface. Other methods for improving the rigidity of the screen, for example, the above-mentioned slurry for improving the adhesion of fine titanium oxide particles of 1 μ or less to the screen surface are used. Furthermore, a method of adding titanium oxalate, or using heat-resistant and acid-resistant fine particles such as fine particle zirconia and fine particle cordierite in place of fine particle titanium oxide of 1 μ or less, and carboxymethyl cellulose other than polyvinyl alcohol as an organic binder, Vinyl acetate or the like can also be used.
得られた基材は、通常酸化チタンを主成分とする公知
の触媒成分（例えば、チタンの他に、タングステン、モ
リブデン、バナジウム、鉄、銅などの化合物の１種以上
を含んだ）粉末と、セラミックス繊維の混合したものに
水を混ぜて粘土状にした脱硝触媒成分がローラを用いて
塗布され、厚み1mm程度の触媒シートに加工される。こ
れはさらに任意の形状に加工された後、乾燥し、さらに
400〜600℃で焼成されて板状触媒体となる。The obtained base material is a known catalyst component mainly containing titanium oxide (for example, in addition to titanium, containing one or more compounds such as tungsten, molybdenum, vanadium, iron, and copper) powder, A denitration catalyst component obtained by mixing water with a mixture of ceramic fibers to form a clay is applied using a roller, and processed into a catalyst sheet having a thickness of about 1 mm. This is further processed into any shape, then dried,
It is calcined at 400 to 600 ° C to form a plate-shaped catalyst.
実施例１ 水400gにシュウ酸30gとパラタングステン酸アンモニ
ウム40gとポリビニルアルコール（キシダ化学社製、重
合度約２万）20gを溶解させた後、この溶液に塩素法に
より製造されたチタニア（石原産業社製CR−50）500gを
混合し、スラリー状コーティング液を調製した。このス
ラリ中に、繊維径６μｍのＥガラス製繊維2000本からな
る縒り糸を目開き約10メッシュに織った平織布（幅500
×長さ500mm）を浸漬後、スポンジローラを通し液切り
し、風乾後150℃で0.5h乾燥して基材を得た。TiO2とMoO
3とV2O5とからなりその原子比率がTi/Mo/V＝91/5/4であ
る触媒組成物に無機繊維（イソライト製カオウールバル
ク）を25wt％と、水を水分が30％になるように添加・混
練してペーストを得た。この触媒組成物ペーストを前記
した基材にローラで圧着して厚さ約1mmの板状成形体を
得た。それを乾燥した後550℃で2hr焼成して板状触媒を
得た。Example 1 After dissolving 30 g of oxalic acid, 40 g of ammonium paratungstate and 20 g of polyvinyl alcohol (manufactured by Kishida Chemical Co., Ltd., degree of polymerization: about 20,000) in 400 g of water, the titania (Ishihara Sangyo Sangyo) produced by the chlorine method was added to this solution. 500 g of CR-50 (manufactured by Sharp Corporation) were mixed to prepare a slurry-like coating solution. In this slurry, a plain woven cloth (width 500) in which a twisted yarn consisting of 2,000 E glass fibers having a fiber diameter of 6 μm is woven to an opening of about 10 mesh.
× 500 mm in length) was immersed, drained through a sponge roller, air-dried, and dried at 150 ° C for 0.5 h to obtain a substrate. TiO 2 and MoO
The catalyst composition consisting of 3 and V 2 O 5 and having an atomic ratio of Ti / Mo / V = 91/5/4 contains 25% by weight of inorganic fiber (Khao wool bulk made of Isolite) and 30% of water. The mixture was added and kneaded so as to obtain a paste. This catalyst composition paste was pressure-bonded to the above-mentioned base material with a roller to obtain a plate-like molded body having a thickness of about 1 mm. After drying it, it was calcined at 550 ° C for 2 hours to obtain a plate catalyst.
実施例２ 水400gにシュウ酸90gとパラタングステン酸アンモニ
ウム110gとシュウ酸チタンアンモニウム210gとポリビニ
ルアルコール20gを溶解させた後、この溶液に塩素法に
より製造されたチタニア500gを混合し、スラリ状コーテ
ィング液を調製した。Example 2 After dissolving 90 g of oxalic acid, 110 g of ammonium paratungstate, 210 g of titanium ammonium oxalate and 20 g of polyvinyl alcohol in 400 g of water, 500 g of titania produced by a chlorine method was mixed with this solution, and a slurry-like coating solution was obtained. Was prepared.
それ以外は実施例１と同一方法で触媒を得た。 Otherwise, a catalyst was obtained in the same manner as in Example 1.
実施例３ 水400gにシュウ酸30gとパラタングステン酸アンモニ
ウム40gとシュウ酸チタンアンモニウム70gとポリビニル
アルコール20gを溶解させた後、この溶液に塩素法によ
り製造されたチタニア500gを混合し、スラリー状コーテ
ィング液を調製した。これ以外は実施例１と同一の方法
で触媒を得た。Example 3 After dissolving 30 g of oxalic acid, 40 g of ammonium paratungstate, 70 g of titanium ammonium oxalate, and 20 g of polyvinyl alcohol in 400 g of water, 500 g of titania produced by a chlorine method was mixed with this solution, and a slurry coating solution was obtained. Was prepared. Except for this, a catalyst was obtained in the same manner as in Example 1.
実施例４ 水400gにシュウ酸12gとパラタングステン酸アンモニ
ウム15gとシュウ酸チタンアンモニウム30gとポリビニル
アルコール20gを溶解させた後、この溶液に塩素法によ
り製造されたチタニア500gを混合し、スラリ状コーティ
ング液を調製した。Example 4 After dissolving 12 g of oxalic acid, 15 g of ammonium paratungstate, 30 g of titanium ammonium oxalate and 20 g of polyvinyl alcohol in 400 g of water, 500 g of titania produced by a chlorine method was mixed with this solution, and a slurry-like coating solution was obtained. Was prepared.
それ以外は実施例１と同一方法で触媒を得た。 Otherwise, a catalyst was obtained in the same manner as in Example 1.
実施例５ 水400gにシュウ酸3gとパラタングステン酸アンモニウ
ム4gとシュウ酸チタンアンモニウム7gとポリビニルアル
コール20gを溶解させた後、この溶液に塩素法により製
造されたチタニア500gを混合し、スラリー状コーティン
グ液を調製した。これ以外は実施例１と同一の方法で触
媒を得た。Example 5 After dissolving 3 g of oxalic acid, 4 g of ammonium paratungstate, 7 g of titanium ammonium oxalate and 20 g of polyvinyl alcohol in 400 g of water, 500 g of titania produced by a chlorine method was mixed with this solution, and a slurry coating solution was obtained. Was prepared. Except for this, a catalyst was obtained in the same manner as in Example 1.
実施例６ 実施例３で得たと同一の基材を550℃で2h焼成したも
のを基材とした以外は、実施例１と同一の方法で触媒を
得た。Example 6 A catalyst was obtained in the same manner as in Example 1, except that the same substrate as obtained in Example 3 was calcined at 550 ° C. for 2 hours.
比較例１ 2wt％のポリビニルアルコールを実施例１で用いた同
一のＥガラス製スクリーンに担持させ、150℃で0.5h乾
燥させ基材とした以外は、実施例１と同一の方法で触媒
を得た。Comparative Example 1 A catalyst was obtained in the same manner as in Example 1 except that 2 wt% of polyvinyl alcohol was supported on the same screen made of E glass used in Example 1 and dried at 150 ° C. for 0.5 hour to obtain a base material. Was.
比較例２ 水480gにポリビニルアルコール20gを溶解させた後、
これに、実施例１で用いたと同一のチタニア粉末500gを
混合してコーティング液を調製した。これ以外は実施例
１と同一の方法で触媒を得た。Comparative Example 2 After dissolving 20 g of polyvinyl alcohol in 480 g of water,
This was mixed with 500 g of the same titania powder as used in Example 1 to prepare a coating solution. Except for this, a catalyst was obtained in the same manner as in Example 1.
実施例１〜４および比較例１、２の触媒について下記
条件で耐酸性テストをする前後の引張強度を測定し、本
発明の効果を確認した。The tensile strength of the catalysts of Examples 1 to 4 and Comparative Examples 1 and 2 was measured before and after the acid resistance test under the following conditions, and the effect of the present invention was confirmed.
耐酸性テスト条件 温度−時間:350℃−1000h SO2:500ppm SO3:50ppm O2 :3％ N2 :Balance 引張強度測定条件 試験片寸法:20mm幅×50mm長 引張速度 :2mm/min 得られた結果を第１表に示す。Acid resistance test conditions Temperature-time: 350 ° C-1000h SO 2 : 500ppm SO 3 : 50ppm O 2 : 3% N 2 : Balance Tensile strength measurement conditions Specimen dimensions: 20mm width x 50mm length Peeling speed: 2mm / min The results are shown in Table 1.
比較例１、２は耐酸性テストを行った後では引張強度
が大きく低下してしまうが、パラタングステン酸アンモ
ニウムを混入したコーティング剤を担持させた本発明の
ものは、耐酸性テスト前の引張強度が少し低下するもの
の、耐酸性テスト後の強度は、いずれもテスト前の強度
から若干低下するだけで優れた耐酸性を示した。 In Comparative Examples 1 and 2, the tensile strength was significantly reduced after the acid resistance test was performed, but the tensile strength before the acid resistance test of the present invention supporting the coating agent mixed with ammonium paratungstate was large. Although the strength slightly decreased, the strength after the acid resistance test showed excellent acid resistance with only a slight decrease from the strength before the test.
本発明によれば、耐酸性に優れた無機繊維織布の基材
が得られるので、それを使用した板状触媒も耐酸性に優
れた長寿命のものとなる。したがって、石炭燃焼排ガス
等のように高SOX濃度の排ガス脱硝でも経時的な強度低
下の少ない触媒が得られる。According to the present invention, a substrate of an inorganic fiber woven fabric having excellent acid resistance can be obtained, so that a plate catalyst using the same has a long life and excellent acid resistance. Therefore, even with the denitration of exhaust gas having a high SO X concentration, such as coal combustion exhaust gas, it is possible to obtain a catalyst with a small decrease in strength over time.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−258746（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 37/36 B01D 53/86 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-258746 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00-37/36 B01D 53 / 86
Claims (5)
たは網状体に脱硝触媒を担持させた窒素酸化物除去用板
状触媒において、前記無機繊維織布または網状体の繊維
表面に設けられたカルシウムとタングステンを含む反応
生成物からなる第１層と、該第１層上に設けられたチタ
ン化合物を含む脱硝触媒からなる第２層とを有すること
を特徴とする窒素酸化物除去用板状触媒。1. A nitrogen-oxide-removing plate catalyst in which a denitration catalyst is supported on an inorganic fiber woven fabric or mesh containing a calcium component, wherein the calcium is provided on the fiber surface of the inorganic fiber woven fabric or mesh. A nitrogen-oxide-removing plate catalyst comprising: a first layer made of a reaction product containing titanium and tungsten; and a second layer made of a denitration catalyst containing a titanium compound provided on the first layer. .
状体からなり、脱硝触媒を担持させるための窒素酸化物
除去用板状触媒基材において、上記無機繊維織布または
網状体がタングステン化合物と、チタニア、ジルコニ
ア、コージエライトから選ばれた１種以上の酸化物と、
ポリビニルアルコール、酢酸ビニル、カルボキシルメチ
ルセルローズから選ばれた１種以上の有機結合剤とから
なるコーティング層を形成してなることを特徴とする窒
素酸化物除去用板状触媒基材。2. A plate-like catalyst substrate for removing nitrogen oxides for supporting a denitration catalyst, comprising a calcium component-containing inorganic fiber woven fabric or mesh, wherein the inorganic fiber woven fabric or mesh is a tungsten compound, One or more oxides selected from titania, zirconia, cordierite,
A plate catalyst substrate for removing nitrogen oxides, comprising a coating layer comprising at least one organic binder selected from polyvinyl alcohol, vinyl acetate and carboxymethyl cellulose.
機繊維がガラス繊維であることを特徴とする窒素酸化物
除去用板状触媒基材。3. The plate-shaped catalyst substrate for removing nitrogen oxides according to claim 2, wherein the calcium-containing inorganic fibers are glass fibers.
状体に脱硝触媒を担持させる窒素酸化物除去用板状触媒
の製造方法において、上記無機繊維織布または網状体に
タングステン化合物を含む液状体を含浸または塗布し、
これを乾燥または乾燥したのち焼成して、これにチタン
化合物を含む脱硝触媒を塗布し、さらに乾燥、焼成する
ことを特徴とする窒素酸化物除去用板状触媒の製造方
法。4. A process for producing a plate catalyst for removing nitrogen oxides in which a denitration catalyst is supported on a woven fabric or mesh containing calcium components, wherein the liquid containing a tungsten compound is contained in the woven fabric or mesh. Impregnated or coated,
A method for producing a nitrogen-oxide-removing plate catalyst, comprising drying or drying and calcining, applying a denitration catalyst containing a titanium compound, and further drying and calcining.
状体からなり、脱硝触媒を担持する窒素酸化物除去用板
状触媒基材の製造方法において、タングステン化合物を
シュウ酸水溶液に溶解し、これにポリビニルアルコール
と塩素法により製造されたチタニアとを混合してスラリ
ー状コーティング液となし、これを上記織布または網状
体に含浸または塗布し、その後乾燥、または乾燥したの
ち焼成することを特徴とする窒素酸化物除去用板状触媒
基材の製造方法。5. A method for producing a nitrogen-oxide-removing plate-shaped catalyst base material comprising a calcium component-containing inorganic fiber woven fabric or a net-like material and carrying a denitration catalyst, wherein a tungsten compound is dissolved in an oxalic acid aqueous solution. Mixing polyvinyl alcohol and titania produced by the chlorine method to form a slurry-like coating liquid, impregnating or coating the woven fabric or net, and then drying, or drying and firing. A method for producing a plate-like catalyst substrate for removing nitrogen oxides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29314990A JP3234217B2 (en) | 1990-10-30 | 1990-10-30 | Plate catalyst for removing nitrogen oxides, base material thereof, and methods for producing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29314990A JP3234217B2 (en) | 1990-10-30 | 1990-10-30 | Plate catalyst for removing nitrogen oxides, base material thereof, and methods for producing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04166235A JPH04166235A (en) | 1992-06-12 |
| JP3234217B2 true JP3234217B2 (en) | 2001-12-04 |
Family
ID=17791055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29314990A Expired - Fee Related JP3234217B2 (en) | 1990-10-30 | 1990-10-30 | Plate catalyst for removing nitrogen oxides, base material thereof, and methods for producing them |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3234217B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997015526A1 (en) * | 1995-10-27 | 1997-05-01 | E.I. Du Pont De Nemours And Company | Hydrothermal process for making ultrafine metal oxide powders |
-
1990
- 1990-10-30 JP JP29314990A patent/JP3234217B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04166235A (en) | 1992-06-12 |
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