JP3268091B2 - Zeolite-based denitration catalyst - Google Patents
Zeolite-based denitration catalystInfo
- Publication number
- JP3268091B2 JP3268091B2 JP28306893A JP28306893A JP3268091B2 JP 3268091 B2 JP3268091 B2 JP 3268091B2 JP 28306893 A JP28306893 A JP 28306893A JP 28306893 A JP28306893 A JP 28306893A JP 3268091 B2 JP3268091 B2 JP 3268091B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zeolite
- nagasaki
- denitration
- present
- 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 25
- 239000010457 zeolite Substances 0.000 title claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 11
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 10
- 150000001768 cations Chemical group 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 229910000269 smectite group Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910021647 smectite Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- -1 if necessary Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はＮＯｘを含有する排ガス
の浄化作用を有するゼオライト系触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zeolite catalyst having a function of purifying exhaust gas containing NOx.
【０００２】[0002]
【従来の技術】現在、燃焼器排ガスに含まれるＮＯｘの
浄化触媒としてはＴｉＯ2 を主成分としたＴｉＯ2 −Ｗ
Ｏ3 −Ｖ2 Ｏ5 系の触媒が使用されている。使用される
触媒は通常、ガス接触面積が大きく、圧力損失の小さな
ハニカム状のものである。 2. Description of the Related Art At present, as a catalyst for purifying NOx contained in exhaust gas from a combustor, TiO 2 -W containing TiO 2 as a main component is used.
O 3 -V 2 O 5 based catalysts are used. The catalyst used is usually a honeycomb having a large gas contact area and a small pressure loss.
【０００３】[0003]
【発明が解決しようとする課題】従来触媒は脱硝装置コ
スト全体に占める割合が３０％程度と高い。現在、脱硝
装置は地球環境の保全に不可欠なものであるが、この高
コストが導入の大きな障害になっている。従来触媒の高
コストの原因は貴重な金属Ｔｉを主成分とする原料費の
高さと成形性の困難さにある。また従来触媒では適用可
能温度は最高４００℃であり、ガスタービン等の高温排
ガス（５００〜６００℃）には適用困難であった。The ratio of the conventional catalyst to the total cost of the denitration apparatus is as high as about 30%. At present, denitration equipment is indispensable for preserving the global environment, but this high cost is a major obstacle to its introduction. Conventionally, the high cost of the catalyst is due to the high raw material cost containing precious metal Ti as a main component and the difficulty in formability. In addition, the applicable temperature of the conventional catalyst is 400 ° C. at the maximum, and it is difficult to apply to a high temperature exhaust gas (500 to 600 ° C.) of a gas turbine or the like.
【０００４】本発明は上記技術水準に鑑み、低コスト、
高強度でかつ脱硝性能に優れた脱硝触媒を提供しようと
するものである。[0004] In view of the above technical level, the present invention provides a low cost,
An object of the present invention is to provide a denitration catalyst having high strength and excellent denitration performance.
【０００５】[0005]
【課題を解決するための手段】本発明はゼオライトから
なる触媒活性成分：５０〜９５ｗｔ％と、交換性陽イオ
ンをＣａ2+イオンに交換されたスメクタイト族モンモリ
ロナイト鉱物からなる成形助剤：５０〜５ｗｔ％とから
なることを特徴とするゼオライト系脱硝触媒である。Means for Solving the Problems The present invention is a zeolite
A catalytically active component: 50 to 95 wt%; and a forming aid comprising a smectite-group montmorillonite mineral in which exchangeable cations have been exchanged for Ca 2+ ions : 50 to 5 wt%. It is.
【０００６】[0006]
【作用】本発明は従来触媒の触媒活性成分である、Ｖ2
Ｏ5 ，ＷＯ3 ，ＴｉＯ2 の代替としてゼオライトを用い
るものである。ゼオライトは脱硝反応に高活性であり、
資源的にも、Ｓｉ，Ａｌ，Ｎａ等の比較的豊富な元素よ
り構成されており、コストの低減が期待できる。According to the present invention, V 2 , which is a catalytically active component of a conventional catalyst, is used.
Zeolite is used as a substitute for O 5 , WO 3 , and TiO 2 . Zeolites are highly active in denitration reactions,
Since it is composed of relatively abundant elements such as Si, Al, and Na as resources, cost reduction can be expected.
【０００７】残部成分はバインダーであるスメクタイト
族モンモリロナイトである。このモンモリロナイトに含
まれる交換性陽イオンは容易に他の陽イオンに交換でき
る。本発明ではこのイオン交換性を利用し、含有脱硝触
媒作用の被毒性分として作用せず、かつ強度増強作用の
あるＣａ2+イオンをイオン交換して導入したものを使用
するものである。Ｃａ2+を導入することで、強度と脱硝
性能の共に高い脱硝触媒を提供できる。[0007] The remaining component is a smectite montmorillonite as a binder. The exchangeable cation contained in this montmorillonite can be easily exchanged for another cation. In the present invention, utilizing this ion exchange property, Ca 2+ ion which does not act as a toxic component of the contained denitration catalyst action and has a strength enhancing action is introduced by ion exchange. By introducing Ca 2+ , a denitration catalyst having both high strength and high denitration performance can be provided.
【０００８】[0008]
【実施例】触媒活性成分としてＹ型ゼオライト及びＵＳ
Ｙ型ゼオライトを、残部の成形助剤としてスメクタイト
族モンモリロナイトを乾粉として用いた。スメクタイト
族モンモリロナイトは含まれる交換性陽イオンを全てＣ
ａ2+に交換したものを用いた。その他の成形助剤とし
て、グラスファイバーチョプドスライド（長さ５ｍｍ）
を用いた。また、スメクタイト族モンモリロナイトの比
較剤として、ハロサイト鉱物を準備した。EXAMPLES Y-type zeolite and US as catalytically active components
Y-type zeolite was used as the remaining molding aid, and smectite-group montmorillonite was used as a dry powder. Smectite montmorillonite contains all exchangeable cations in C
What was exchanged for a 2+ was used. As other molding aid, glass fiber chopped slide (length 5mm)
Was used. In addition, as a comparative agent for smectite group montmorillonite, a halosite mineral was prepared.
【０００９】この他、本発明を限定するものではない
が、製品であるハニカム形状にするために準備した材料
及びその手順を示す。本発明品に可塑性を与え、ハニカ
ム化を要因にする粘結剤としてメチル・セルロースを該
構成成分１００重量部に対して７重量部添加した（以
下、添加量は全て該構成成分１００重量部に対する
値。）。この他グリセリン３重量部添加した。この２成
分は固定して、この他、気孔付与材として、セルロース
（商品名：アビセル）、パルプ繊維等を必要に応じて添
加し、これらに水を加えて配合した。水の添加量は約４
０重量部を基準として混練状態を見ながら増減した。以
上の材料を可塑性が出る程度に、十分に混練した後、外
形寸法１５０ｍｍ角、肉厚１ｍｍ、ピッチ６ｍｍの断面
寸法の金型でハニカム状に成形した。これを５００ｍｍ
長さを基準に成形した後乾燥した。この乾燥したハニカ
ムを６５０℃×４時間焼成して触媒試験体を得た。[0011] In addition, materials, which are not limited to the present invention, prepared for forming a honeycomb shape as a product and procedures for the materials are shown below. 7 parts by weight of methyl cellulose was added to 100 parts by weight of the component as a binder that imparts plasticity to the product of the present invention and causes honeycombing (hereinafter, all added amounts are based on 100 parts by weight of the component) value.). In addition, 3 parts by weight of glycerin was added. These two components were fixed, and cellulose (trade name: Avicel), pulp fiber, or the like was added as a pore-imparting material, if necessary, and water was added thereto to mix. The amount of water added is about 4
The amount was increased or decreased while observing the kneading state based on 0 parts by weight. The above-mentioned materials were sufficiently kneaded to such an extent that plasticity was obtained, and then formed into a honeycomb shape using a mold having a cross-sectional dimension of 150 mm square, 1 mm in thickness, and 6 mm in pitch. This is 500mm
After molding based on the length, it was dried. The dried honeycomb was fired at 650 ° C. for 4 hours to obtain a catalyst test specimen.
【００１０】触媒試験体の物性評価は、該試験体から切
り出した小試験片の重量を寸法計測から求めた体積で除
したかさ密度、同様の小試験片に水銀を圧入し、その圧
力と体積変化から気孔径を測定する水銀圧入滴ポロシメ
ータを用いた平均気孔径でそれぞれ行った。また触媒試
験体の強度評価は、試験体を１５０ｍｍ立方に切断し、
押出方向に平行な両面壁から圧縮して破壊させる圧縮強
度を求めた。また、触媒試験体の脱硝性能評価は温度４
００℃，５００℃及び６００℃に設定した試験体に約５
００ｐｐｍのＮＯｘ含有ガスを流速２．３ｍ／ｓｅｃで
流し、入口と出口のＮＯｘの差から脱硝率を求めた。[0010] The physical properties of the catalyst specimen were evaluated by dividing the weight of a small specimen cut out from the specimen by the volume determined from dimensional measurement, by applying mercury to the same small specimen, and then measuring the pressure and volume. The average pore diameter was measured using a mercury intrusion porosimeter that measures the pore diameter from the change. In addition, the strength evaluation of the catalyst specimen was performed by cutting the specimen into 150 mm cubes,
The compressive strength to break by compressing from both side walls parallel to the extrusion direction was determined. The denitration performance of the catalyst specimen was evaluated at a temperature of 4
Approximately 5 specimens set at 00 ° C, 500 ° C and 600 ° C
A NOx-containing gas of 00 ppm was flowed at a flow rate of 2.3 m / sec, and the denitration rate was determined from the difference between the NOx at the inlet and the NOx at the outlet.
【００１１】以上の方法で製造・評価した本発明触媒の
特性及び比較例として、上記材料の範囲外の特性を表１
に示す。表中に示した材料以外に、グラスファイバは本
発明触媒、本発明外触媒共、一律に２．６重量比添加し
ている。ハロサイト鉱物を用いたＮｏ．７，Ｎｏ．８
（本発明範囲外）では、強度が低く実用化できない。ま
た、Ｃａ2+未交換のＮｏ．９，Ｎｏ．１０及びＣａ2+交
換したものでも本発明の範囲外のＮｏ．１１では脱硝性
能が低く実用できない。強度、脱硝性能共に優れている
のは本発明触媒Ｎｏ．１〜Ｎｏ．６であるＣａ2+で交換
したモンモリロナイトを成形助剤に用いたものである。As a comparative example, the characteristics of the catalyst of the present invention produced and evaluated by the above method and the characteristics outside the above-mentioned range are shown in Table 1.
Shown in In addition to the materials shown in the table, glass fiber is uniformly added to the catalyst of the present invention and the catalyst of the present invention in a 2.6 weight ratio. No. 1 using the halosite mineral. 7, No. 8
(Outside the range of the present invention), the strength is so low that it cannot be put to practical use. In addition, No. of Ca 2+ non-exchange 9, No. No. 10 and Ca 2+ exchanged Nos. In case of No. 11, the denitration performance is so low that it is not practical. The catalyst of the present invention has excellent strength and denitration performance. 1 to No. Montmorillonite exchanged with Ca 2+ of No. 6 was used as a molding aid.
【００１２】Ｙ型ゼオライトのみを脱硝触媒として使用
可能ではあるが、前述のハニカム構造に形成することが
できないので、成形助剤としてスメクタイト族モンモリ
ロナイトのＣａ2+交換したものを５重量％を混合するこ
とにて、ハニカム構造に形成可能となる。これが最低の
混合割合と考える。又、Ｙ型ゼオライト４０重量％、Ｃ
ａ2+交換モンモリロナイト鉱物６０重量％のものは脱硝
率が５００℃，６００℃において６０％以下となること
から脱硝触媒として不適当である。Although only the Y-type zeolite can be used as a denitration catalyst, it cannot be formed into the above-mentioned honeycomb structure. Therefore, 5% by weight of Ca 2+ -exchanged smectite montmorillonite is mixed as a forming aid. In particular, it can be formed into a honeycomb structure. This is considered the lowest mixing ratio. Also, Y-type zeolite 40% by weight, C
The a 2+ exchanged montmorillonite mineral having a weight percentage of 60% by weight is not suitable as a denitration catalyst because its denitration ratio is 60% or less at 500 ° C. and 600 ° C.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【発明の効果】本発明触媒により、排ガス温度が６００
℃まで適用できる脱硝触媒を提供可能となる。また、資
源的に比較的豊富な元素より構成されているゼオライト
を使用しハニカム構造に形成が可能となり、コスト低減
ができる。According to the catalyst of the present invention, an exhaust gas temperature of 600
It is possible to provide a denitration catalyst applicable to up to ° C. In addition, it is possible to form a honeycomb structure using zeolite composed of relatively abundant elements in terms of resources, thereby reducing costs.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 芹澤 暁 長崎県長崎市飽の浦町１番１号 三菱重 工業株式会社長崎造船所内 (72)発明者 守井 淳 長崎県長崎市飽の浦町１番１号 三菱重 工業株式会社長崎造船所内 (72)発明者 角田 英雄 長崎県長崎市深堀町五丁目717番１号 三菱重工業株式会社長崎研究所内 (72)発明者 佃 洋 長崎県長崎市深堀町五丁目717番１号 三菱重工業株式会社長崎研究所内 (72)発明者 安武 昭典 長崎県長崎市深堀町五丁目717番１号 三菱重工業株式会社長崎研究所内 (56)参考文献 特開 昭61−259761（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 B01D 53/86,53/94 ──────────────────────────────────────────────────続 き Continued on the front page (72) Akira Serizawa, Inventor 1-1, Akunouracho, Nagasaki, Nagasaki Prefecture Mitsubishi Heavy Industries, Ltd. Nagasaki Shipyard (72) Inventor Jun Morii 1-1, Akunouracho, Nagasaki, Nagasaki Mitsubishi (72) Inventor Hideo Tsunoda 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd.Nagasaki Research Center (72) Inventor Hiroshi Tsukuda 5-717, Fukahori-cho, Nagasaki-shi, Nagasaki No. 1 Inside Nagasaki Research Laboratory of Mitsubishi Heavy Industries, Ltd. (72) Inventor Akinori Yasutake 5-717-1 Fukahori-cho, Nagasaki City, Nagasaki Prefecture Mitsubishi Heavy Industries, Ltd. Nagasaki Research Laboratory (56) References JP-A-61-259761 (JP, A (58) Fields surveyed (Int. Cl. 7 , DB name) B01J 21/00-38/74 B01D 53 / 86,53 / 94
Claims (1)
〜９５ｗｔ％と、交換性陽イオンをＣａ2+イオンに交換
されたスメクタイト族モンモリロナイト鉱物からなる成
形助剤：５０〜５ｗｔ％とからなることを特徴とするゼ
オライト系脱硝触媒。1. A catalytically active component comprising zeolite : 50
And 95 wt% and consists of exchangeable cations exchanged Ca 2+ ions smectite group montmorillonite minerals formed
Shape assistant: a zeolite-based denitration catalyst comprising 50 to 5 wt% .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28306893A JP3268091B2 (en) | 1993-11-12 | 1993-11-12 | Zeolite-based denitration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28306893A JP3268091B2 (en) | 1993-11-12 | 1993-11-12 | Zeolite-based denitration catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07136522A JPH07136522A (en) | 1995-05-30 |
| JP3268091B2 true JP3268091B2 (en) | 2002-03-25 |
Family
ID=17660793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28306893A Expired - Fee Related JP3268091B2 (en) | 1993-11-12 | 1993-11-12 | Zeolite-based denitration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3268091B2 (en) |
-
1993
- 1993-11-12 JP JP28306893A patent/JP3268091B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07136522A (en) | 1995-05-30 |
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