JP2562077B2 - Denitration catalyst - Google Patents
Denitration catalystInfo
- Publication number
- JP2562077B2 JP2562077B2 JP2225779A JP22577990A JP2562077B2 JP 2562077 B2 JP2562077 B2 JP 2562077B2 JP 2225779 A JP2225779 A JP 2225779A JP 22577990 A JP22577990 A JP 22577990A JP 2562077 B2 JP2562077 B2 JP 2562077B2
- Authority
- JP
- Japan
- Prior art keywords
- sio
- tio
- catalyst
- sol
- paper
- 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 43
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 43
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 41
- 239000000919 ceramic Substances 0.000 claims description 32
- 239000000835 fiber Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 10
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、排ガス中の窒素酸化物（NOx）のアンモニ
ア（NH3）による選択的接触還元用脱硝触媒に関し、さ
らに詳しくは、ガスタービンやディーゼルエンジンなど
の排ガス中のNOx除去に用いられる脱硝触媒であって、
特に剛性および耐摩耗性に優れた触媒に関する。TECHNICAL FIELD The present invention relates to a denitration catalyst for selective catalytic reduction of nitrogen oxides (NOx) in exhaust gas with ammonia (NH 3 ), and more specifically, to a gas turbine and A denitration catalyst used to remove NOx in exhaust gas from a diesel engine,
In particular, it relates to a catalyst having excellent rigidity and abrasion resistance.
［従来技術および解決すべき課題］ NH3による選択的接触還元用脱硝触媒の一つとして、
基剤としてセラミックスペーパーを用い、これにTiO2微
粉をゾル浸漬法で分散保持されて成る触媒が考えられ
る。一般にセラミックスペーパーの剛性や耐摩耗性は、
セラミックスファイバーの抄紙時に用いられる有機系あ
るいは無機系の接着剤およびTiO2のバインダー効果によ
り保たれているが、有機系接着剤を用いた場合には、こ
れが高温度で焼失してしまうため、触媒の剛性および耐
摩耗性はもっぱらTiO2のバインダー効果のみに頼らざる
を得ず、これでは触媒としての剛性および体摩耗性が欠
ける。[Prior art and problems to be solved] As one of denitration catalysts for selective catalytic reduction with NH 3 ,
A catalyst in which ceramics paper is used as a base material and TiO 2 fine powder is dispersed and held by a sol dipping method is considered. Generally, the rigidity and wear resistance of ceramic paper are
It is maintained by the organic or inorganic adhesive used for paper making of ceramics fiber and the binder effect of TiO 2 , but when an organic adhesive is used, it is burned out at high temperature, so the catalyst the stiffness and abrasion resistance solely inevitably rely only on the binder effect of TiO 2, it lacks rigidity and body wear as a catalyst in this.
本発明は、上記の如き従来技術の問題点を解決するこ
とを目的とし、剛性および耐摩耗性に優れしかも脱硝活
性の点でも遜色のない脱硝触媒を提供するものである。The present invention aims to solve the above-mentioned problems of the prior art, and provides a denitration catalyst excellent in rigidity and abrasion resistance and comparable in denitration activity.
［課題を解決するための手段］ 本発明者らは、上記目的の達成のために鋭意研究を重
ねた結果、セラミックスペーパーにTiO2ゾルを含浸・乾
燥・焼成し、ついでSiO2ゾルを含浸・乾燥させておくこ
とによって、触媒剛性および耐摩耗性の向上が達成され
ることを見い出し、この発明を完成した。[Means for Solving the Problems] As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that ceramic paper is impregnated with TiO 2 sol, dried and fired, and then impregnated with SiO 2 sol. It was found that the improvement of the catalyst rigidity and the wear resistance is achieved by keeping it dried, and the present invention has been completed.
すなわち、本発明による脱硝触媒は、SiO2ゾルを付着
させたセラミックスファイバーの抄紙によって製造され
たセラミックスペーパーに、TiO2ゾルを含浸・乾燥・焼
成し、ついでSiO2ゾルを含浸・乾燥させることにより得
られた、セラミミックスファイバー表面にSiO2皮膜が形
成され、この皮膜表面にTiO2層が形成され、さらにこの
TiO2層表面にSiO2皮膜が形成された固形物保持ペーパー
に、バナジウム酸化物を吸着・担持させて成ることを特
徴とするものである。That is, the denitration catalyst according to the present invention is obtained by impregnating, drying and firing a TiO 2 sol on a ceramics paper produced by papermaking of a ceramic fiber to which a SiO 2 sol is adhered, and then impregnating and drying the SiO 2 sol. A SiO 2 film is formed on the surface of the obtained ceramic powder, and a TiO 2 layer is formed on the surface of this film.
The present invention is characterized in that a vanadium oxide is adsorbed and carried on a solid material holding paper having a SiO 2 film formed on the surface of a TiO 2 layer.
セラミックスペーパーは、シリカ・アルミナ系、アル
ミナ系のセラミックファイバーを抄紙することによって
製造せられたものである。抄紙時にセラミックファイバ
ーに付着させるSiO2分は、あまり多量であるとセラミッ
クペーパーとしての機能、すなわち柔軟性や加工性が劣
ったものとなる。そのため、セラミックペーパに含有せ
しめるSiO2は１〜50g/m2、好ましくは５〜30g/m2であ
る。SiO2ゾルとしては市販のものが使用できる。The ceramics paper is produced by making silica-alumina-based or alumina-based ceramic fibers. If the SiO 2 content attached to the ceramic fibers during papermaking is too large, the function as the ceramic paper, that is, the flexibility and workability will be poor. Therefore, the amount of SiO 2 contained in the ceramic paper is 1 to 50 g / m 2 , preferably 5 to 30 g / m 2 . A commercially available product can be used as the SiO 2 sol.
TiO2としては、硫酸チタン、四塩化チタン、テトラプ
ロピルチタネートなどのチタン塩の加水分解により形成
したアナターゼ型TiO2が好ましい。こうして形成したTi
O2は1000Å以上の大きな細孔を多く有しているため、粉
体内での反応ガスの拡散速度が大きい。As TiO 2 , anatase type TiO 2 formed by hydrolysis of titanium salt such as titanium sulfate, titanium tetrachloride, tetrapropyl titanate is preferable. Ti formed in this way
Since O 2 has many large pores of 1000 Å or more, the diffusion rate of the reaction gas in the powder is high.
TiO2はセラミックスペーパー表面1m2当り20〜300g、
好ましくは30〜200g含ませられる。TiO 2 is 20 to 300 g per 1 m 2 of ceramic paper surface,
It is preferably contained in an amount of 30 to 200 g.
TiO2ゾルおよびSiO2ゾルの含浸は通常ゾル含浸法ある
いは吹き付け法によって行われる。Impregnation of TiO 2 sol and SiO 2 sol is usually performed by a sol impregnation method or a spraying method.
TiO2ゾルの含浸・乾燥・焼成の後、SiO2ゾルを含浸さ
せるさいに、SiO2ゾル中のSiO2含有量が高くなると、剛
性および耐摩耗性を向上するが、空隙が少なくなり、Ti
O2の保持量が低下する。TiO2の保持量が低下すると、バ
ナジウム酸化物の吸着量も少なくなる。こうして、TiO2
へのバナジウム酸化物吸着がSiO2に阻害されるため、バ
ナジウム酸化物吸着量が減少し、触媒活性が低下する。After impregnation, drying and calcination of the TiO 2 sol, the Sai impregnating the SiO 2 sol, the SiO 2 content of SiO 2 in the sol is higher, but to improve the rigidity and wear resistance, air gap is reduced, Ti
The amount of O 2 retained decreases. When the amount of TiO 2 retained decreases, the amount of vanadium oxide adsorbed also decreases. Thus, TiO 2
Since vanadium oxide adsorption to is inhibited SiO 2, vanadium oxide adsorbed amount is decreased, the catalyst activity decreases.
このように、SiO2保持量に対する触媒剛性および耐摩
耗性と触媒活性との関係は、相反する。このため、剛性
面および活性面の双方を考慮すると、セラミックスペー
パーに保持するSiO2量は30g/m2〜100g/m2、好ましくは2
0g/m2〜50g/m2である。As described above, the relationship between the catalyst rigidity and wear resistance and the catalyst activity with respect to the SiO 2 retention amount are contradictory. Therefore, considering both the rigid surface and the active surface, the amount of SiO 2 retained on the ceramic paper is 30 g / m 2 to 100 g / m 2 , and preferably 2
A 0g / m 2 ~50g / m 2 .
バナジウム酸化物は、たとえば、セラミックスペーパ
ーにメタバナジン酸アンモン溶液を含浸させ、乾燥およ
び焼成することによって、セラミックスペーパーに吸着
・担持される。ただし、バナジウム酸化物の前駆物質は
上記のものに限定されない。The vanadium oxide is adsorbed and supported on the ceramics paper, for example, by impregnating the ceramics paper with an ammonium metavanadate solution, drying and firing. However, the precursor of vanadium oxide is not limited to the above.
［作 用］ 本発明による脱硝触媒は、SiO2ゾルを付着させたセラ
ミックスファイバーの抄紙によって製造されたセラミッ
クスペーパーに、TiO2ゾルを含浸・乾燥・焼成し、SiO2
ゾルを含浸・乾燥させた後、バナジウムに酸化物を吸着
・担持させて成るものであるので、第１図に示すよう
に、セラミックスペーパーを構成するファイバー（１）
の表面にSiO2の硬い皮膜（２）が形成され、その表面に
TiO2の微粉が固着して微粉層（３）が形成され、さらに
その上にSiO2ゾル含浸によるSiO2の硬い皮膜（４）が形
成される。これら内外の強固なSiO2皮膜（２）（４）は
ファイバー（１）どうしを互いに固着させるバインダー
の役目を果たし、剛性および耐摩耗性が高められる。Denitration catalyst according to [work for the present invention, the ceramic paper prepared by papermaking ceramic fiber adhered with SiO 2 sol was impregnated, dried and calcined a TiO 2 sol, SiO 2
Since the oxide is adsorbed and supported on vanadium after impregnating and drying the sol, as shown in FIG. 1, the fiber (1) that constitutes the ceramic paper
A hard coating of SiO 2 (2) is formed on the surface of the
The fine powder of TiO 2 adheres to form a fine powder layer (3), and a hard film of SiO 2 (4) is further formed thereon by impregnation with SiO 2 sol. These strong inner and outer SiO 2 coatings (2) and (4) serve as a binder for fixing the fibers (1) to each other, and rigidity and wear resistance are enhanced.
さらに、触媒本来の目的である活性面においても、後
述する実施例に示すように、中高温度域において、本発
明の触媒はTiO2単味の触媒と遜色のない優れた脱硝触媒
活性を示す。Further, in terms of the active surface, which is the original purpose of the catalyst, as shown in Examples described later, the catalyst of the present invention exhibits an excellent denitration catalytic activity comparable to that of TiO 2 alone in the middle and high temperature ranges.
［実 施 例］ つぎに、本発明の実施例およびこれと比較するべく比
較例を挙げる。[Examples] Next, examples of the present invention and comparative examples will be given for comparison.
実施例 抄紙時のセラミックスファイバーにSiO2を5g/m2付着
させたセラミックスペーパーを用い、これにTiO2ゾル
（TiO2含有率35wt％）を含浸させ、同ペーパーを110℃
で１時間乾燥し、300℃１時間焼成した後、SiO2ゾル中
に浸漬し、110℃で１時間乾燥した。こうしてSiO2保持
量およびTiO2保持量の異なる複数のセラミックスペーパ
ーを得た。Example Using a ceramic paper having SiO 2 adhered to the ceramic fiber at the time of papermaking at 5 g / m 2 and impregnated with TiO 2 sol (TiO 2 content rate 35 wt%), the paper was heated at 110 ° C.
After drying for 1 hour at 300 ° C., baking for 1 hour at 300 ° C., immersion in a SiO 2 sol and drying at 110 ° C. for 1 hour. Thus, a plurality of ceramic papers having different SiO 2 holding amounts and TiO 2 holding amounts were obtained.
つぎに、これらセラミックスペーパーをメタバナジン
酸アンモンの室温飽和溶液中にそれぞれ８時間浸漬し、
110℃で１時間乾燥し、300℃で１時間焼成した。かくし
て、TiO2保持量90g/m2でSiO2保持量10〜100g/m2の複数
のV2O5/TiO2系触媒を得た。Next, these ceramic papers were respectively immersed in a room temperature saturated solution of ammonium metavanadate for 8 hours,
It was dried at 110 ° C. for 1 hour and calcined at 300 ° C. for 1 hour. Thus, to obtain a plurality of V 2 O 5 / TiO 2 catalyst of SiO 2 hold weight 10 to 100 g / m 2 in TiO 2 loadings 90 g / m 2.
比較例 上記実施例の触媒との比較のために、上記SiO2付着お
よび保持工程を省略し、以下実施例と同じ操作によっ
て、TiO2のみを保持し、ついでバナジウム酸化物を担持
させた。こうしてTiO2単味保持触媒を得た。Comparative Example For comparison with the catalyst of the above-mentioned example, the above-mentioned SiO 2 adhesion and holding step was omitted, and only TiO 2 was held and then vanadium oxide was carried by the same operation as in the following example. Thus, a TiO 2 plain retention catalyst was obtained.
剛性試験 実施例および比較例で得られた触媒についてそれぞれ
剛性を測定し、セラミックペーパーに含浸・保持したSi
O2保持量およびTiO2保持量と剛性との関係を第２図のグ
ラフに示す。なお剛性は固形物の強度の指標と考えられ
る引張り強度の測定により調べた。引張り強度（kgf/cm
2）は破断加重（kg）／触媒断面積（cm2）により求め
た。Rigidity test The rigidity of each of the catalysts obtained in the examples and comparative examples was measured, and the
The graph of FIG. 2 shows the relationship between the O 2 retention amount and the TiO 2 retention amount and the rigidity. The rigidity was examined by measuring the tensile strength, which is considered as an index of the strength of the solid material. Tensile strength (kgf / cm
2 ) was calculated by breaking load (kg) / catalyst cross-sectional area (cm 2 ).
第２図のグラフから明らかなように、本発明の触媒は
TiO2単味触媒より引張り強度が大巾に向上していること
が認められる。As is clear from the graph of FIG. 2, the catalyst of the present invention
It can be seen that the tensile strength is significantly improved over the TiO 2 plain catalyst.
耐摩耗性試験 上記と同様の操作によって、TiO2保持量50g/m2でSiO2
保持量10〜60g/m2の複数の触媒を調製した。The abrasion resistance test similar to the above operation, SiO 2 in TiO 2 loadings 50 g / m 2
Multiple catalysts with a retention of 10-60 g / m 2 were prepared.
この触媒および比較例で得られた触媒についてそれぞ
れ耐摩耗性を測定し、セラミックペーパーに含浸・保持
したSiO2保持量およびTiO2保持量と耐摩耗性との関係を
第３図のグラフに示す。なお耐摩耗性は第４図に示す粒
子群落下試験器を用いて測定した。すなわち、ホッパ
（５）内の径0.5mmの多数のスティールショットボール
（６）を、内径20mm長さ950mmの垂直パイプ（７）を経
て、45゜に傾斜配置された触媒（８）の面上に落下さ
せ、衝突および摩耗によって、触媒が損傷ないし破損す
るまでのボール落下量を求めることにより、耐摩耗性を
評価した。The wear resistance of each of this catalyst and the catalysts obtained in the comparative examples was measured, and the relationship between the amount of SiO 2 impregnated and held in the ceramic paper and the amount of TiO 2 and the wear resistance is shown in the graph of FIG. . The wear resistance was measured using the particle group drop tester shown in FIG. That is, a large number of steel shot balls (6) with a diameter of 0.5 mm in the hopper (5) are passed through a vertical pipe (7) with an inner diameter of 20 mm and a length of 950 mm, and on the surface of a catalyst (8) inclined at 45 °. The wear resistance was evaluated by determining the amount of balls falling until the catalyst was damaged or broken by collision and wear by dropping the ball.
第３図のグラフから明らかなように、本発明の触媒は
TiO2保持量50g/m2において、TiO2単味触媒より約10倍の
耐摩耗性を有することが認められる。As is clear from the graph of FIG. 3, the catalyst of the present invention
It is recognized that at a TiO 2 retention of 50 g / m 2, it has about 10 times more abrasion resistance than the TiO 2 plain catalyst.
活性試験 抄紙時のセラミックスファイバーにSiO2ゾル（TiO2含
有率35wt％）を含浸させ、同ペーパーを110℃で１時間
乾燥し、300℃で１時間焼成し、その後SiO2ゾルに浸漬
してSiO2を20g/m2保持させ、110℃で１時間乾燥した
後、上記実施例と同様にしてバナジウム酸化物を吸着担
持させ、110℃で１時間乾燥し、300℃で１時間焼成し
た。こうしてSiO2保持量20g/m2でTiO2保持量80g/m2の触
媒を得た。Activity test A ceramic fiber at the time of papermaking was impregnated with SiO 2 sol (TiO 2 content 35 wt%), the paper was dried at 110 ° C for 1 hour, calcined at 300 ° C for 1 hour, and then immersed in SiO 2 sol. After keeping SiO 2 at 20 g / m 2 and drying at 110 ° C. for 1 hour, vanadium oxide was adsorbed and supported in the same manner as in the above example, dried at 110 ° C. for 1 hour, and calcined at 300 ° C. for 1 hour. Thus, a catalyst having a SiO 2 retention of 20 g / m 2 and a TiO 2 retention of 80 g / m 2 was obtained.
この触媒および比較例で得られた触媒について、内径
１インチのステンレス製流通形反応管を用いてそれぞれ
脱硝活性試験を行なった。すなわち、触媒を上記反応管
に充填して固定し、ついで反応温度を所定値に制御し
て、容量で、入口NOx＝ppm、酸素＝15％、水蒸気＝10％
の組成の試験用調整排ガスを反応管に流した。面積速度
（Ａ・Ｖ）すなわち触媒の幾何表面積（m2）当りの通ガ
ス流量（Nm3/時）を43m/時とし、またNH3/NO比を1.2と
し、入口NH3濃度は60ppmとした。With respect to this catalyst and the catalyst obtained in the comparative example, a denitration activity test was conducted using a stainless steel flow type reaction tube having an inner diameter of 1 inch. That is, the catalyst is filled in the above reaction tube and fixed, and then the reaction temperature is controlled to a predetermined value, and by volume, inlet NOx = ppm, oxygen = 15%, steam = 10%.
A test adjusted exhaust gas having the above composition was flown into the reaction tube. The area velocity (A · V), that is, the flow rate (Nm 3 / hour) of the gas per geometric surface area (m 2 ) of the catalyst was 43 m / hour, the NH 3 / NO ratio was 1.2, and the NH 3 concentration at the inlet was 60 ppm. did.
各触媒について、温度100〜400℃の範囲で脱硝率＝
［（入口NOx濃度ppm−出口NOx濃度ppm）／入口NOx濃度p
pm］×100を求めた。得られた脱硝率を第５図のグラフ
に示す。For each catalyst, denitration rate = 100-400 ℃
[(Inlet NOx concentration ppm-Outlet NOx concentration ppm) / Inlet NOx concentration p
pm] × 100 was calculated. The denitration rate thus obtained is shown in the graph of FIG.
同グラフから明らかなように、中高温度域において、
本発明の触媒はTiO2単味の触媒と遜色のない優れた脱硝
触媒活性示すことが認められる。As is clear from the graph, in the middle and high temperature range,
It is recognized that the catalyst of the present invention exhibits an excellent denitration catalytic activity comparable to that of TiO 2 plain catalyst.
［発明の効果］ 本発明の脱硝触媒によれば、SiO2ゾルを付着させたセ
ラミックスファイバーの抄紙によって製造されたセラミ
ックスペーパーに、TiO2ゾルを含浸・乾燥・焼成し、つ
いでSiO2ゾルを含浸・乾燥させることにより得られた、
セラミックスファイバー表面にSiO2皮膜が形成され、こ
の皮膜表面にTiO2層が形成され、さらにこのTiO2層表面
にSiO2皮膜が形成された固形物保持ペーパーに、バナジ
ウム酸化物を吸着・担持させて成るものであるので、内
外の強固なSiO2皮膜がファイバーどうしを互いに固着さ
せるバインダーの役目を果たし、剛性および耐摩耗性が
大巾に向上される。[Effect of the Invention] According to the denitration catalyst of the present invention, a ceramic paper manufactured by paper-making of ceramic fibers to which SiO 2 sol is adhered is impregnated with TiO 2 sol, dried and fired, and then impregnated with SiO 2 sol. .Obtained by drying,
SiO 2 film is formed on the ceramic fiber surface, the TiO 2 layer is formed on the film surface, and further to the SiO 2 coating solids formed holding paper on the TiO 2 layer surface, is adsorbed and supported vanadium oxide As a result, the strong inner and outer SiO 2 films serve as a binder for fixing the fibers to each other, and the rigidity and wear resistance are greatly improved.
さらに、触媒の活性面においても、中高温度域におい
て、本発明の触媒はTiO2単味の触媒と遜色のない優れた
脱硝触媒活性を有する。Further, in terms of the activity of the catalyst, the catalyst of the present invention has an excellent denitration catalytic activity comparable to that of TiO 2 alone in the medium and high temperature range.
第１図はセラミックスペーパーの構造を示す概略図、第
２図はSiO2含有率およびTiO2含有率と引張り強度の関係
を示すグラフ、第３図はSiO2含有率およびTiO2含有率と
ボール落下量の関係を示すグラフ、第４図は粒子群落下
試験器を示す概略図、第５図は反応温度と脱硝率の関係
を示すグラフである。Fig. 1 is a schematic diagram showing the structure of ceramics paper, Fig. 2 is a graph showing the relationship between the SiO 2 content and TiO 2 content and the tensile strength, and Fig. 3 is the SiO 2 content and TiO 2 content and balls. FIG. 4 is a graph showing the relationship between the falling amount, FIG. 4 is a schematic view showing the particle group drop tester, and FIG. 5 is a graph showing the relationship between the reaction temperature and the denitration rate.
Claims (1)
バーの抄紙によって製造されたセラミックスペーパー
に、TiO2ゾルを含浸・乾燥・焼成し、ついでSiO2ゾルを
含浸・乾燥させることにより得られた、セラミックスフ
ァイバー表面にSiO2皮膜が形成され、この皮膜表面にTi
O2層が形成され、さらにこのTiO2層表面にSiO2皮膜が形
成された固形物保持ペーパーに、バナジウム酸化物を吸
着・担持させて成ることを特徴とする、脱硝触媒。1. A ceramic paper produced by paper-making of ceramic fibers to which SiO 2 sol is attached, obtained by impregnating TiO 2 sol, drying and firing, and then impregnating and drying SiO 2 sol. A SiO 2 film is formed on the surface of the ceramic fiber, and Ti film is formed on the surface of this film.
A denitration catalyst, characterized in that vanadium oxide is adsorbed on and supported by a solid holding paper on which an O 2 layer is formed and an SiO 2 film is formed on the surface of the TiO 2 layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2225779A JP2562077B2 (en) | 1990-08-27 | 1990-08-27 | Denitration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2225779A JP2562077B2 (en) | 1990-08-27 | 1990-08-27 | Denitration catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04108538A JPH04108538A (en) | 1992-04-09 |
| JP2562077B2 true JP2562077B2 (en) | 1996-12-11 |
Family
ID=16834657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2225779A Expired - Fee Related JP2562077B2 (en) | 1990-08-27 | 1990-08-27 | Denitration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2562077B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465389B1 (en) | 1999-07-29 | 2002-10-15 | Sumitomo Chemical Company, Limited | Heat resistant catalyst sheet and process for producing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0722709B2 (en) * | 1989-01-14 | 1995-03-15 | 日立造船株式会社 | Method for producing denitration catalyst using ceramics paper |
-
1990
- 1990-08-27 JP JP2225779A patent/JP2562077B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465389B1 (en) | 1999-07-29 | 2002-10-15 | Sumitomo Chemical Company, Limited | Heat resistant catalyst sheet and process for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04108538A (en) | 1992-04-09 |
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