JP3076421B2 - DeNOx catalyst suppressing sulfur dioxide oxidation and method for producing the same - Google Patents
DeNOx catalyst suppressing sulfur dioxide oxidation and method for producing the sameInfo
- Publication number
- JP3076421B2 JP3076421B2 JP03260839A JP26083991A JP3076421B2 JP 3076421 B2 JP3076421 B2 JP 3076421B2 JP 03260839 A JP03260839 A JP 03260839A JP 26083991 A JP26083991 A JP 26083991A JP 3076421 B2 JP3076421 B2 JP 3076421B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- component
- sulfur dioxide
- oxidation
- denitration
- 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 94
- 238000007254 oxidation reaction Methods 0.000 title claims description 43
- 230000003647 oxidation Effects 0.000 title claims description 32
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 150000003682 vanadium compounds Chemical class 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- MCPTUMJSKDUTAQ-UHFFFAOYSA-N vanadium;hydrate Chemical compound O.[V] MCPTUMJSKDUTAQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052720 vanadium Inorganic materials 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 3
- 239000012784 inorganic fiber Substances 0.000 description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 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 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- -1 oxo acid salt Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 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、二酸化硫黄の酸化を抑
制した脱硝触媒およびその製造方法に関し、特に排ガス
に含有される二酸化硫黄（ＳＯ2 ）の三酸化硫黄（ＳＯ
3 ）への転加率を最小限に抑えて高脱硝率を得ることの
できる脱硝触媒とその製造方法に関する。The present invention relates to relates to a denitration catalyst and manufacturing method thereof suppress oxidation of the sulfur dioxide, in particular sulfur trioxide (SO sulfur dioxide (SO 2) contained in the exhaust gas
The present invention relates to a denitration catalyst capable of obtaining a high denitration rate by minimizing the conversion rate to 3 ) and a method for producing the same.
【０００２】[0002]
【従来の技術】発電所、各種工場、自動車などから排出
される排煙中のＮＯｘは、光化学スモッグや酸性雨の原
因物質であり、その効果的な除去方法として、アンモニ
ア（ＮＨ3 ）を還元剤とし、触媒を使用した選択的接触
還元による排煙脱硝法が火力発電所を中心に幅広く用い
られている。触媒には、バナジウム（Ｖ）、モリブデン
（Ｍｏ）またはタングステン（Ｗ）を活性成分にした酸
化チタン（ＴｉＯ2 ）系触媒が使用されており、特に活
性成分の１つとしてバナジウムを含むものは活性が高い
だけでなく、排ガス中に含まれている不純物による劣化
が小さいこと、より低温から使用できることなどから現
在の脱硝触媒の主流になっている（特開昭５０−８９２
９１号公報、特開昭４９−１２２４７３号公報等）。2. Description of the Related Art NOx in flue gas emitted from power plants, various factories, automobiles, and the like is a causative substance of photochemical smog and acid rain. As an effective method for removing NOx, ammonia (NH 3 ) is reduced. The flue gas denitration method by selective catalytic reduction using a catalyst as a catalyst is widely used mainly in thermal power plants. As the catalyst, a titanium oxide (TiO 2 ) -based catalyst containing vanadium (V), molybdenum (Mo) or tungsten (W) as an active component is used. In particular, those containing vanadium as one of the active components are active. Not only is high, but it is also the mainstream of the current denitration catalysts because it is less deteriorated by impurities contained in the exhaust gas and can be used at lower temperatures (Japanese Patent Laid-Open No. 50-892).
No. 91, JP-A-49-122473, etc.).
【０００３】一方、近年排ガス浄化を高度に行おうとす
る傾向にあり、脱硝装置も触媒の充填量を増加して高い
脱硝率で運転する機会が増大している。このような条件
で、上記Ｖ含有触媒を用いてＳＯ2 含有排ガスの脱硝を
行わせると、Ｖの触媒作用によりＳＯ2 が酸化されＳＯ
3 を生成し後続機器の腐食、未反応ＮＨ3 との反応によ
る酸性硫安（ＮＨ4 ＨＳＯ4 ）析出等の問題を引き起こ
す。さらに、ＳＯ3は湿式脱硫装置で除去され難いため
大半が大気中に放出され、新たな公害の原因になる。Ｓ
Ｏ3 はＳＯ2 に比し呼吸器の傷害を起こし易く、またミ
ストになって大気中に浮遊し地球の温暖化にも作用する
と言われている。On the other hand, in recent years, there has been a tendency to purify exhaust gas at a high level, and the chance of operating a denitration device at a high denitration rate by increasing the amount of catalyst charged has also increased. In such conditions, when to perform denitration of SO 2 containing exhaust gas by using the V-containing catalyst, SO 2 is oxidized by the catalytic action of V SO
3 is generated to cause problems such as corrosion of the subsequent equipment and precipitation of acidic ammonium sulfate (NH 4 HSO 4 ) due to reaction with unreacted NH 3 . Furthermore, since SO 3 is difficult to be removed by a wet desulfurization unit, most of the SO 3 is released into the atmosphere, causing new pollution. S
O 3 is said to be more susceptible to respiratory injury than SO 2 , and also to become a mist and float in the air to act on global warming.
【０００４】このため、最近、特に西欧諸国ではＳＯ2
の酸化の低い、かつＮＯｘに対する高活性脱硝触媒に対
する需要が高まっており、Ｖ含有量等の触媒組成を最適
化することでＳＯ2 酸化率を低減する試みがなされてい
る。[0004] For this reason, recently, especially in Western Europe, SO 2
Low oxidation, and there is an increasing demand for high activity denitration catalyst for NOx, attempt to reduce the SO 2 oxidation rate by optimizing the catalyst composition such as a V content it has been made.
【０００５】[0005]
【発明が解決しようとする課題】上記した従来技術で示
した触媒中のバナジウム含有量の最適化等でＳＯ2 酸化
率を下げようとすると脱硝率が低下する現象が生じる。
このため、ＳＯ2 酸化を低くしようとすると活性の低い
触媒を多量に使用する必要がある。その増加量は、より
高い脱硝率で運用しようとする最近の装置ではさらに顕
著になる。If the SO 2 oxidation rate is reduced by optimizing the vanadium content in the catalyst shown in the above-mentioned prior art, a phenomenon occurs in which the denitration rate decreases.
For this reason, it is necessary to use a large amount of a catalyst having low activity in order to reduce SO 2 oxidation. The increase is even more pronounced in modern devices that attempt to operate at higher denitration rates.
【０００６】これは、ＳＯ2 酸化と脱硝がバナジウムの
形成する同一活性点で進行するためであり、均一組成の
Ｖ含有触媒を使用する従来触媒では避け難い問題であ
る。本発明の目的は、上記した従来技術の問題点をなく
し、ＳＯ2 酸化率の小さい高脱硝率を実現した新規な触
媒とその製造方法を提供することにある。This is because SO 2 oxidation and denitration proceed at the same active site where vanadium is formed, which is a problem that cannot be avoided with a conventional catalyst using a V-containing catalyst having a uniform composition. An object of the present invention is to provide a novel catalyst which eliminates the above-mentioned problems of the prior art and realizes a high denitration rate with a small SO 2 oxidation rate, and a method for producing the same.
【０００７】[0007]
【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、二酸化硫黄を含有する排ガス中の
窒素酸化物をアンモニアにより接触還元する脱硝触媒に
おいて、モリブデン（Ｍｏ）および／またはタングステ
ン（Ｗ）とチタン（Ｔｉ）の各酸化物からなる第一構成
粒子と、バナジウム（Ｖ）およびチタン（Ｔｉ）の各酸
化物からなる第二構成粒子とからなり、その両者が物理
的な混合状態を維持したまま成形されていることを特徴
とする二酸化硫黄の酸化を抑制した脱硝触媒に関する。Means for Solving the Problems To achieve the above object, a first invention of the present application is directed to a denitration catalyst for catalytically reducing nitrogen oxides in an exhaust gas containing sulfur dioxide with ammonia, comprising molybdenum (Mo) and / or molybdenum (Mo). Alternatively, first constituent particles made of tungsten (W) and titanium (Ti) oxides, and second constituent particles made of vanadium (V) and titanium (Ti) oxides, both of which are physically The present invention relates to a denitration catalyst in which the oxidation of sulfur dioxide is suppressed, characterized in that the catalyst is formed while maintaining a proper mixed state.
【０００８】本願第２の発明は、二酸化硫黄含有排ガス
中の窒素酸化物をアンモニアにより接触還元する脱硝触
媒の製造方法において、酸化チタンまたはその前駆体と
モリブデンおよび／またはタングステンの酸化物もしく
は加熱することによりそれらの酸化物を生成する化合物
と水とを混合したのち乾燥、焼成した第一成分と、酸化
チタンまたはその前駆体とバナジウム化合物と水とを混
合したのち乾燥、焼成した第二成分とを、それぞれ粉砕
したのち、両者の粉末を水を加えて混練し、成形、乾
燥、焼成することを特徴とする二酸化硫黄の酸化を抑制
した脱硝触媒の製造方法に関する。The second invention of the present application relates to a method for producing a denitration catalyst for catalytically reducing nitrogen oxides in a sulfur dioxide-containing exhaust gas with ammonia, wherein titanium oxide or a precursor thereof and an oxide of molybdenum and / or tungsten are heated or heated. The first component, which is dried and then baked after mixing the compound and water that produce those oxides, and the second component, which is dried after mixing titanium oxide or its precursor and the vanadium compound and water, and then baked And a method for producing a denitration catalyst in which oxidation of sulfur dioxide is suppressed, characterized in that water and water are added and kneaded, then molded, dried and calcined.
【０００９】本願第３の発明は、二酸化硫黄を含有する
排ガス中の窒素酸化物をアンモニアにより接触還元する
脱硝触媒の製造方法において、あらかじめモリブデンお
よび／またはタングステンの化合物と酸化チタンもしく
はその前駆体とから第一構成成分を調製し、これとは別
にあらかじめバナジウム化合物と酸化チタンもしくはそ
の前駆体とから第二構成成分を調製し、両成分を粒径１
００メッシュないし３５０メッシュ以下に粉砕したの
ち、第一構成成分に対する第二構成成分の重量比を１／
９９〜５０／５０で混練、成形、乾燥、焼成することを
特徴とする二酸化硫黄の酸化を抑制した脱硝触媒の製造
方法に関する。The third invention of the present application is directed to a method for producing a denitration catalyst for catalytically reducing nitrogen oxides in an exhaust gas containing sulfur dioxide with ammonia, wherein a compound of molybdenum and / or tungsten and titanium oxide or a precursor thereof are prepared in advance. To prepare a second component from a vanadium compound and titanium oxide or a precursor thereof in advance.
After pulverizing to less than 00 mesh to 350 mesh, the weight ratio of the second component to the first component is reduced to 1 /
The present invention relates to a method for producing a denitration catalyst in which oxidation of sulfur dioxide is suppressed, which is characterized by kneading, molding, drying and firing at 99 to 50/50.
【００１０】[0010]
【作用】本発明は、次のような触媒反応の特性を巧みに
利用した結果、達成されたものである。発明者らが脱硝
触媒の反応機構およびＳＯ2 酸化反応機構について詳細
に研究した結果、脱硝反応（１）式の速度は触媒体内の
マクロポア（約５００オングストローム以上）内面に存
在する活性成分の濃度に比例することを見出した。The present invention has been achieved as a result of skillful use of the following catalytic reaction characteristics. As a result of detailed studies on the reaction mechanism of the denitration catalyst and the SO 2 oxidation reaction mechanism, the inventors have found that the rate of the denitration reaction (1) depends on the concentration of the active component present on the inner surface of the macropore (about 500 Å or more) in the catalyst. Found to be proportional.
【００１１】[0011]
【化１】 ＮＯ＋ＮＨ3 ＋１／４Ｏ2 → Ｎ2 ＋３／２Ｈ2 Ｏ （１） また、（２）式のＳＯ2 酸化反応の速度はマクロポア内
面のバナジウム濃度に比例して増加するものの直線的に
は増加しないことが判明した。Embedded image NO + NH 3 + ／ O 2 → N 2 + 3 / 2H 2 O (1) The rate of the SO 2 oxidation reaction in the equation (2) increases linearly with the vanadium concentration on the inner surface of the macropore. Turned out not to increase.
【００１２】[0012]
【化２】 ＳＯ2 ＋１／２Ｏ2 → ＳＯ3 （２） さらに、図２はＴｉＯ2 −Ｖ2 Ｏ5 触媒のみ用いてＳＯ
2 の酸化速度がＳＯ2 濃度に対しどのように影響するか
についてみたものであるが、ＳＯ2 濃度の増加に伴いＳ
Ｏ3 の生成量は増加するものの酸化率は逆に大きく減少
している。これはＳＯ2 酸化反応の結果生成したＳＯ3
濃度が高くなるとＳＯ3 の脱離する速度が遅くなり、触
媒上に長く吸着されたまま存在して（２）式の反応を阻
害するからである。上述した触媒内のバナジウム濃度を
増加させた場合にＳＯ2 酸化率がバナジウム量に比例し
て直線的には増加しないのはこのためである。Embedded image SO 2 + 1 / 2O 2 → SO 3 (2) Furthermore, FIG. 2 shows that SO 2 + SO 2 is used only with a TiO 2 -V 2 O 5 catalyst.
2 shows how the oxidation rate of SO 2 affects the SO 2 concentration.
Although the production amount of O 3 increases, the oxidation rate decreases greatly. This is the SO 3 generated as a result of the SO 2 oxidation reaction.
This is because the higher the concentration, the slower the rate at which SO 3 is desorbed, and the longer the SO 3 remains adsorbed on the catalyst, which inhibits the reaction of the formula (2). This is why the SO 2 oxidation rate does not increase linearly in proportion to the amount of vanadium when the vanadium concentration in the catalyst is increased.
【００１３】上記知見は、もし触媒内のバナジウムの存
在する部分だけがＳＯ3 濃度の高い状態にできればＳＯ
2 酸化反応を非常に小さく抑えながら脱硝率を向上させ
た触媒を実現できることを示すものである。図３のＡお
よびＢはそれぞれバナジウム含有量が同一である本発明
の触媒と従来触媒とのマクロポアの状態を模式的に表わ
したものである。本発明になる触媒ではバナジウムを全
く含まない第一成分からなる部分と高濃度で含む第二成
分からなる部分の２種類の部分で触媒細孔内面が構成さ
れている。逆に従来触媒ではバナジウムを低濃度で含む
均一な組成で触媒細孔が構成される。両者で触媒のマク
ロポア内面に存在するバナジウムの量は全体の含有量が
同じであるのでほぼ等しく、脱硝率は両者で大差がな
い。The above findings indicate that if only the portion where vanadium is present in the catalyst can be made to have a high SO 3 concentration,
This shows that it is possible to realize a catalyst with an improved denitration rate while keeping the oxidation reaction extremely small. FIGS. 3A and 3B schematically show the state of the macropores of the catalyst of the present invention and the conventional catalyst having the same vanadium content, respectively. In the catalyst according to the present invention, the inner surface of the catalyst pores is composed of two types of portions, a portion consisting of the first component containing no vanadium and a portion consisting of the second component containing a high concentration. Conversely, in the conventional catalyst, the catalyst pores have a uniform composition containing vanadium at a low concentration. In both cases, the amount of vanadium present on the inner surface of the macropores of the catalyst is almost the same because the total content is the same, and the denitration rates are not significantly different between the two.
【００１４】一方、ＳＯ2 酸化反応はバナジウムの存在
するところだけで起こるため様相が異なる。本発明の触
媒では、酸化反応はバナジウムが高濃度で存在する第二
成分の形成する細孔内だけで進行しかつその酸化率が高
いため、細孔内には高濃度のＳＯ3 が存在する状態に保
たれる。このため上記したＳＯ3 によるＳＯ2 酸化反応
阻害作用により酸化速度は大きく抑制される。これに対
し従来触媒ではバナジウム濃度の低い細孔内全体でＳＯ
2 酸化反応が低率で生じるため、バナジウムの存在する
細孔中のＳＯ3 は低濃度のままであり反応抑制はあまり
生じない。このため同一バナジウム含有量であれば反応
抑制の大きく発現できる本発明の触媒は、反応抑制が少
ししか働かない従来触媒に較べると、触媒全体で見たＳ
Ｏ2 酸化反応速度を著しく小さくできる。On the other hand, the SO 2 oxidation reaction is different only in that vanadium is present only. In the catalyst of the present invention, the oxidation reaction proceeds only in the pores formed by the second component in which vanadium is present at a high concentration and the oxidation rate is high, so that a high concentration of SO 3 exists in the pores. Kept in state. For this reason, the oxidation rate is largely suppressed by the above-mentioned action of inhibiting SO 2 oxidation reaction by SO 3 . On the other hand, in the case of the conventional catalyst, SO 2
Since the 2 oxidation reaction occurs at a low rate, SO 3 in the pores where vanadium is present remains at a low concentration, and the reaction is hardly suppressed. For this reason, the catalyst of the present invention, which can express a large amount of reaction inhibition with the same vanadium content, has an S
O 2 oxidation reaction rate can be significantly reduced.
【００１５】以上に示したように、本発明になる触媒は
触媒内にバナジウムが局在化した部分を作ることにより
ＳＯ2 酸化の結果として生成したＳＯ3 によるＳＯ2 酸
化反応の抑制が効果的に生じるようにして触媒全体のＳ
Ｏ2 酸化反応速度を低減せしめたものである。この方法
によれば、従来と同様の触媒構成元素からなるにもかか
わらず、ＳＯ2 酸化活性の小さい高脱硝活性触媒を実現
できる。As described above, the catalyst according to the present invention effectively suppresses the SO 2 oxidation reaction by SO 3 generated as a result of SO 2 oxidation by forming a portion where vanadium is localized in the catalyst. S of the entire catalyst
The O 2 oxidation reaction rate was reduced. According to this method, it is possible to realize a high denitration activity catalyst having a small SO 2 oxidation activity despite being composed of the same catalyst constituent elements as the conventional one.
【００１６】[0016]
（ｉ）全体の構成 本発明は上記したように、あらかじめ調製されたモリブ
デンまたはタングステン化合物を酸化チタンに担持して
なるものを第一成分、酸化バナジウムを担持せしめた酸
化チタンを第二成分にし、その両者を一定の不均質さを
保持した状態で混合した後、成形したことを特徴とする
ものである。図１にその構成を模式的に示す。(I) Overall Configuration As described above, the present invention uses, as a first component, a component prepared by supporting a molybdenum or tungsten compound prepared in advance on titanium oxide, and a second component, using titanium oxide having vanadium oxide supported thereon, The two are mixed while maintaining a certain degree of inhomogeneity and then molded. FIG. 1 schematically shows the configuration.
【００１７】ここであらかじめ調製された第一成分は、
酸化チタン、オルトチタン酸もしくはメタチタン酸のス
ラリ、または上記粉末に水を加えたものと、モリブデン
もしくはタングステンの酸化物、またはオキソ酸塩等の
熱分解により酸化物を生成する化合物とを混合した後、
加熱混練、蒸発乾固等の通常触媒調製に用いられる方法
によって水を蒸発させながら担持し、得られたペースト
を乾燥、さらに４００〜６００℃で焼成して得る。また
第二成分はメタバナジン酸アンモン、硫酸バナジルなど
のバナジウム化合物と、メタチタン酸またはオルトチタ
ン酸とを用いて第一成分と同様の方法で調製される。Here, the first component prepared in advance is:
After mixing a slurry of titanium oxide, orthotitanic acid or metatitanic acid, or a powder obtained by adding water to the above powder, and a compound that generates an oxide by thermal decomposition such as an oxide of molybdenum or tungsten, or an oxo acid salt ,
Water is evaporated and supported by a method usually used for catalyst preparation such as heat kneading and evaporation to dryness, and the obtained paste is dried and further calcined at 400 to 600 ° C. The second component is prepared in the same manner as the first component using a vanadium compound such as ammonium metavanadate or vanadyl sulfate and metatitanic acid or orthotitanic acid.
【００１８】第一成分と第二成分は混合に先立ち粉砕さ
れ、両者の比が５０／５０から９５／５になるように混
合され、水とともにニーダ等の混練機でペースト状に混
練される。この際必要に応じてセラミックス製繊維、有
機または無機バインダ等を加えることができる。得られ
た触媒ペーストは、そのまま押出し成形機を用いてハニ
カム、柱状、円筒状等に成形されるか、ローラを用いて
メタルラス等の金属基板やセラミック、ガラス製網状織
布などに塗布して板状に成形される。成形体はその後、
必要形状に切断、型付けされ、乾燥後４００℃から６０
０℃で焼成される。 （ii）構成部分の相互作用・作用 本発明の触媒は以上のような簡単な工程により調製され
るが、発明の効果を充分得るためには各工程に次のよう
な配慮をするとよい。The first component and the second component are pulverized prior to mixing, mixed so that the ratio of both becomes 50/50 to 95/5, and kneaded together with water in a kneader such as a kneader into a paste. At this time, ceramic fibers, an organic or inorganic binder, or the like can be added as necessary. The obtained catalyst paste is directly formed into a honeycomb, a columnar shape, a cylindrical shape, or the like by using an extruder, or is applied to a metal substrate such as a metal lath, a ceramic, or a glass woven fabric by using a roller. Molded into a shape. The molded body is then
Cut to required shape, molded, and dried to 400 to 60
Fired at 0 ° C. (Ii) Interaction and Action of Constituents The catalyst of the present invention is prepared by the above simple steps, but in order to sufficiently obtain the effects of the present invention, the following considerations should be given to each step.
【００１９】第一成分と第二成分の組成は、本発明の効
果を限定するものではないが、次のような範囲にすると
実用上必要な活性を得易い。 第一成分：Ｗ ｏｒ Ｍｏ／Ｔｉ＝３／９７〜１０／９
０ 第二成分： Ｖ／Ｔｉ＝１／９９〜５／９５ 第一成分中のＷまたはＭｏは酸化チタンの熱的安定性を
増し、成形体強度を向上させると同時に脱硝活性の一部
を担うため多い方が好結果を得易いが、あまり多いと触
媒価格の上昇につながり実用的ではない。また第二成分
中のＶ量も高い方が第二成分と混合したときＳＯ2 酸化
の抑制作用が強く、また脱硝活性も高く望ましいが、上
記範囲を超えるとその差が顕著でなくなる。また一定Ｖ
量にしようとした場合に第二成分との混合比が大きくな
り過ぎ混合状態を一定に維持しにくくなるため望ましく
ない。Although the composition of the first component and the second component does not limit the effects of the present invention, it is easy to obtain a practically necessary activity in the following range. First component: W or Mo / Ti = 3/97 to 10/9
0 Second component: V / Ti = 1/99 to 5/95 W or Mo in the first component increases the thermal stability of the titanium oxide, improves the strength of the compact, and plays a part in the denitration activity. Therefore, it is easy to obtain good results when the amount is large, but when the amount is too large, it leads to an increase in the price of the catalyst and is not practical. Also, the higher the V content in the second component, the stronger the action of suppressing SO 2 oxidation when mixed with the second component, and the higher the denitration activity, which is desirable. However, if it exceeds the above range, the difference will not be remarkable. Also constant V
If the amount is to be increased, the mixing ratio with the second component becomes too large, and it becomes difficult to maintain a constant mixing state, which is not desirable.
【００２０】両成分はあらかじめ焼成されることが望ま
しく、この段階で活性成分が不溶化され、引き続く混合
操作で活性成分が溶解して互いに混ざり合って不均一度
が低下することが防止される。第一成分と第二成分の混
合比は触媒の使用条件下で上記組成との兼ね合わせで決
定されるものでありどのような比率であってもよいが、
混合比があまり大きいと作り難くなり、逆に小さいと効
果が小さくなる。通常の混練による操作では第二成分／
第一成分の重量比が１／９９ないし５０／５０、好まし
くは５／９５から５０／５０程度の範囲が選ばれる。Preferably, both components are calcined in advance. At this stage, the active components are insolubilized, and the subsequent mixing operation dissolves the active components and prevents them from mixing with each other to reduce the nonuniformity. The mixing ratio of the first component and the second component is determined by a combination of the above composition under the conditions of use of the catalyst, and may be any ratio,
If the mixing ratio is too large, it will be difficult to produce, and if it is small, the effect will be small. In the usual kneading operation, the second component /
The weight ratio of the first component is selected in the range of 1/99 to 50/50, preferably about 5/95 to 50/50.
【００２１】さらに第一成分と第二成分は混合に先立ち
粉砕され、その粒径は通常１００から３５０メッシュ以
下に選定される。脱硝性能面からは微粉が好ましいがＳ
Ｏ2 酸化抑制からは粗粒が好ましい。ＳＯ2 酸化抑制に
効果があるためには第二成分粒子中に５００オングスト
ローム以上の細孔が一定以上存在することが好ましく、
第二成分粒子は特に粗粒で用いると好結果が得られる。Further, the first component and the second component are pulverized prior to mixing, and the particle size is usually selected from 100 to 350 mesh or less. Fine powder is preferable from the viewpoint of denitration performance,
Coarse grains are preferred from the viewpoint of suppressing O 2 oxidation. In order to be effective in suppressing SO 2 oxidation, it is preferable that pores of 500 Å or more exist in the second component particles in a certain amount or more,
Good results are obtained especially when the second component particles are used in coarse particles.
【００２２】以下、具体的実施例を用いて本発明を詳細
に説明する。 実施例１ メタチタン酸スラリ（ＴｉＯ2 含有量：３０ｗｔ％、Ｓ
Ｏ4 含有量：８ｗｔ％）６７kgにパラモリブデン酸アン
モン（（ＮＨ4 ）6 ・Ｍｏ7 Ｏ24・４Ｈ2 Ｏ）を４．９
kg加え、加熱ニーダを用いて水を蒸発させながら混練し
て水分約３６％のペーストを得た。これを直径３mmの柱
状に押出し造粒後流動層乾燥機で乾燥し、次に大気中５
００℃で２時間焼成した。得られた顆粒をハンマーミル
で平均粒径５μｍの粒径に粉砕し第一成分とした。この
ときの組成はＭｏ／Ｔｉ＝１／９（原子比）である。Hereinafter, the present invention will be described in detail with reference to specific examples. Example 1 Metatitanate slurry (TiO 2 content: 30 wt%, S
O 4 content: 8 wt%) 67 kg para molybdate ammonium and ((NH 4) 6 · Mo 7 O 24 · 4H 2 O) 4.9
kg, and kneaded while evaporating water using a heating kneader to obtain a paste having a water content of about 36%. This was extruded into a column having a diameter of 3 mm, granulated, dried with a fluidized bed drier, and then dried in air.
Baking was performed at 00 ° C. for 2 hours. The obtained granules were pulverized with a hammer mill to a particle diameter of an average particle diameter of 5 μm to obtain a first component. The composition at this time is Mo / Ti = 1/9 (atomic ratio).
【００２３】一方、上記パラモリブデン酸アンモンに替
えメタバナジン酸アンモン（ＮＨ4 ＶＯ3 ）を１．５４
kg用い、同様の方法で第二成分を調製した。この組成は
Ｖ／Ｔｉ＝５／９５（原子比）である。以上の方法で得
られた第一成分粉末１６kg、第二成分粉末４kg、Ａｌ2
Ｏ3 ・ＳｉＯ2 系無機繊維（商品名カオウール）３kg、
水１０kgとをニーダを用いて１時間混練し、粘土状にし
た。この触媒ペーストを０．２mm厚さのＳＵＳ３０４製
メタルラス基板（金属多孔板）にＡｌ溶射を施して粗面
化した基板にローラを用いてラス目間および表面に塗布
して厚さ約０．９mmの板状触媒を得た。この触媒を風乾
後大気中で、５５０℃で２時間焼成した。触媒の最終組
成はＶ／Ｍｏ／Ｔｉ＝１／８／９１である。 比較例１および２ 実施例１に用いた第一成分単独、および第二成分単独で
同様の方法により触媒を調製した。 比較例３ メタチタン酸スラリ（ＴｉＯ2 含有量：３０ｗｔ％、Ｓ
Ｏ4 含有量：８ｗｔ％）６７kgにパラモリブデン酸アン
モン（（ＮＨ4 ）6 ・Ｍｏ7 Ｏ24・４Ｈ2 Ｏ）を４．９
kgおよびメタバナジン酸アンモン０．３１kgとを加え、
加熱ニーダを用いて水を蒸発させながら混練し水分約３
６％のペーストを得た。これを直径３mmの柱状に押出し
造粒後流動層乾燥機で乾燥し、次に大気中５００℃で２
時間焼成した。得られた顆粒をハンマーミルで平均粒径
５μｍの粒径に粉砕し触媒粉末を得た。このときの組成
はＶ／Ｍｏ／Ｔｉ＝１／１０／９０（原子比）である。On the other hand, ammonium metavanadate (NH 4 VO 3 ) was replaced with 1.54 ammonium paramolybdate.
kg, and the second component was prepared in the same manner. This composition is V / Ti = 5/95 (atomic ratio). 16 kg of the first component powder, 4 kg of the second component powder, Al 2
3 kg of O 3 · SiO 2 inorganic fiber (Kao wool)
10 kg of water was kneaded with a kneader for 1 hour to make a clay. This catalyst paste is applied to a 0.2 mm-thick SUS304 metal lath substrate (metal perforated plate) that has been subjected to Al thermal spraying and roughened to a gap between the laths and the surface by using a roller to have a thickness of about 0.9 mm. Was obtained. The catalyst was air-dried and calcined at 550 ° C. for 2 hours in the air. The final composition of the catalyst is V / Mo / Ti = 1/8/91. Comparative Examples 1 and 2 A catalyst was prepared by a similar method using only the first component and the second component used in Example 1. Comparative Example 3 Metatitanate slurry (TiO 2 content: 30 wt%, S
O 4 content: 8 wt%) 67 kg para molybdate ammonium and ((NH 4) 6 · Mo 7 O 24 · 4H 2 O) 4.9
kg and 0.31 kg of ammonium metavanadate,
Using a heating kneader, knead the water while evaporating the water.
6% paste was obtained. This was extruded into a column having a diameter of 3 mm, dried by a fluidized bed drier after granulation, and then dried at 500 ° C. in the atmosphere.
Fired for hours. The obtained granules were pulverized with a hammer mill to a particle diameter of 5 μm to obtain a catalyst powder. The composition at this time is V / Mo / Ti = 1/10/90 (atomic ratio).
【００２４】以上の方法で得られた粉末２０kg、Ａｌ2
Ｏ3 ・ＳｉＯ2 系無機繊維３kg、水１０kgとをニーダを
用いて１時間混練し、粘土状にした。この触媒ペースト
を０．２mm厚さのＳＵＳ３０４製メタルラス基板にＡｌ
溶射を施して粗面化した基板にローラを用いてラス目間
および表面に塗布して厚さ約０．９mmの板状触媒を得
た。この触媒を風乾後大気中で５５０℃で２時間焼成し
た。 比較例４ メタチタン酸スラリ（ＴｉＯ2 含有量：３０ｗｔ％、Ｓ
Ｏ4 含有量：８ｗｔ％）６７kgにパラモリブデン酸アン
モン（（ＮＨ4 ）6 ・Ｍｏ7 Ｏ24・４Ｈ2 Ｏ）を４．９
kgを加え加熱ニーダを用いて水を蒸発させながら混練し
水分約３６％のペーストを得た。これを直径３mmの柱状
に押出し造粒後流動層乾燥機で乾燥し、次に大気中５０
０℃で２時間焼成した。得られた顆粒をハンマーミルで
平均粒径５μｍの粒径に粉砕し触媒粉末を得た。20 kg of the powder obtained by the above method, Al 2
3 kg of O 3 · SiO 2 -based inorganic fiber and 10 kg of water were kneaded for 1 hour using a kneader to form a clay. This catalyst paste was applied to a 0.2 mm thick SUS304 metal lath substrate by Al.
Using a roller, the thermal sprayed and roughened substrate was applied to the gaps between the laths and the surface to obtain a plate-like catalyst having a thickness of about 0.9 mm. The catalyst was air-dried and calcined at 550 ° C. for 2 hours in air. Comparative Example 4 Metatitanate slurry (TiO 2 content: 30 wt%, S
O 4 content: 8 wt%) 67 kg para molybdate ammonium and ((NH 4) 6 · Mo 7 O 24 · 4H 2 O) 4.9
The resulting mixture was kneaded while evaporating water using a heating kneader to obtain a paste having a water content of about 36%. This was extruded into a column having a diameter of 3 mm, granulated, dried with a fluidized bed drier, and then dried in air.
It was baked at 0 ° C. for 2 hours. The obtained granules were pulverized with a hammer mill to a particle diameter of 5 μm to obtain a catalyst powder.
【００２５】以上の方法で得られた粉末２０kg、メタバ
ナジン酸アンモン０．２５kg、Ａｌ 2 Ｏ3 ・ＳｉＯ2 系
無機繊維３kg、水１０kgとをニーダを用いて１時間混練
し、粘土状にした。この触媒ペーストを０．２mm厚さの
ＳＵＳ３０４製メタルラス基板にＡｌ溶射を施して粗面
化した基板にローラを用いてラス目間および表面に塗布
して厚さ約０．９mmの板状触媒を得た。この触媒を風乾
後大気中で５５０℃で２時間焼成した。この触媒の組成
はＶ／Ｍｏ／Ｔｉ＝１／１０／９０（原子比）である。20 kg of the powder obtained by the above method
Ammonium nadate 0.25kg, Al TwoOThree・ SiOTwosystem
Kneading 3 kg of inorganic fiber and 10 kg of water for 1 hour using a kneader
And made it clay-like. This catalyst paste is 0.2mm thick
SUS304 metal lath substrate is sprayed with Al and rough surface
Using a roller to apply to the gap between the laths and the surface
As a result, a plate-like catalyst having a thickness of about 0.9 mm was obtained. Air dry this catalyst
Thereafter, it was fired in the air at 550 ° C. for 2 hours. Composition of this catalyst
Is V / Mo / Ti = 1/10/90 (atomic ratio).
【００２６】得られた実施例１の触媒、比較例１から４
の触媒について表１に示した条件で脱硝率を、表２に示
した条件でＳＯ2 酸化率をそれぞれ測定した。The obtained catalyst of Example 1 and Comparative Examples 1 to 4
The denitration rate and the SO 2 oxidation rate of the catalyst of No. 1 were measured under the conditions shown in Table 1, respectively.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 得られた実施例１と比較例１および２の結果を図４に示
した。実施例１の触媒は比較例１と比較例２の触媒を混
合することによって得られたにもかかわらず脱硝率は比
較例２とほとんど同程度の高い値が得られ、ＳＯ2 酸化
率は比較例１の触媒と同程度のきわめて低い値であっ
た。これは本発明の触媒が低ＳＯ2 酸化と高脱硝活性を
実現する優れたものであることを示している。[Table 2] The obtained results of Example 1 and Comparative Examples 1 and 2 are shown in FIG. Although the catalyst of Example 1 was obtained by mixing the catalysts of Comparative Example 1 and Comparative Example 2, the denitration rate was almost as high as that of Comparative Example 2, and the SO 2 oxidation rate was relatively low. It was very low, comparable to the catalyst of Example 1. This indicates that the catalyst of the present invention is excellent in realizing low SO 2 oxidation and high denitration activity.
【００２９】また図５には実施例１と比較例３、４によ
る触媒の脱硝率とＳＯ2 酸化率とを示した。この図から
もわかるようにバナジウムが触媒成分中に均一に存在す
るような調製法で作った比較例３および４触媒に較べ実
施例触媒は高脱硝率を示すにもかかわらずＳＯ2 酸化率
はきわめて低くなっている。３者はほとんど同組成の触
媒であることを考え合わせると本発明の効果がきわめて
大きいことがわかる。 実施例２ 実施例１のメタバナジン酸アンモンの添加量を０．７２
kgに替え同様に触媒を調製した。 実施例３〜６ 実施例１の触媒における第二成分と第一成分の混合比４
／６を１／９９、５／９５、２０／８０、５０／５０に
変えて触媒を調製した。 比較例５〜８ 比較例３におけるメタバナジン酸アンモンの添加量０．
３１kgに替え、０．０３１kg、０．１６kg、０．６１kg
および０．７８kg用いて触媒を調製した。 比較例９〜１２ 比較例４におけるメタバナジン酸アンモンの添加量０．
２５kgに替え、０．０２５kg、０．１３kg、０．５０kg
および０．６３kg用いて触媒を調製した。FIG. 5 shows the denitration rate and SO 2 oxidation rate of the catalyst according to Example 1 and Comparative Examples 3 and 4. As can be seen from this figure, the SO 2 oxidation rate of the Example catalyst was higher than that of Comparative Examples 3 and 4 prepared by a preparation method in which vanadium was uniformly present in the catalyst component, although the catalyst had a higher denitration rate. Very low. Considering that the three catalysts have almost the same composition, it can be seen that the effect of the present invention is extremely large. Example 2 The addition amount of ammonium metavanadate of Example 1 was 0.72.
A catalyst was prepared in the same manner as in Example 1, except that the amount was changed to kg. Examples 3 to 6 The mixing ratio of the second component to the first component in the catalyst of Example 1 was 4
/ 6 was changed to 1/99, 5/95, 20/80, 50/50 to prepare a catalyst. Comparative Examples 5 to 8 The amount of ammonium metavanadate added in Comparative Example 3 was 0.
Replace with 31kg, 0.031kg, 0.16kg, 0.61kg
And 0.78 kg were used to prepare the catalyst. Comparative Examples 9 to 12 The amount of ammonium metavanadate added in Comparative Example 4 was 0.1.
0.025kg, 0.13kg, 0.50kg instead of 25kg
The catalyst was prepared using and 0.63 kg.
【００３０】実施例１〜６および比較例３〜１２の触媒
について３８０℃における脱硝率とＳＯ2 酸化率を測定
し、得られた結果を図６にまとめて示した。同一脱硝率
で見ると実施例触媒はいずれも高脱硝率かつ低ＳＯ2 酸
化率を示している。なお、実施例３になると比較例との
差異が小さくなっておりあまり混合比が小さいと効果が
小さくなることがわかる。The denitration rate and SO 2 oxidation rate at 380 ° C. of the catalysts of Examples 1 to 6 and Comparative Examples 3 to 12 were measured, and the obtained results are shown in FIG. When viewed at the same denitration rate, the catalysts of the examples all show a high denitration rate and a low SO 2 oxidation rate. In Example 3, the difference from the comparative example is small, and it can be seen that the effect is small when the mixing ratio is too small.
【００３１】[0031]
【発明の効果】本発明によりＳＯ2 の酸化率が非常に小
さい高活性な脱硝触媒を実現できる。これにより触媒を
多量に使用して高脱硝率運転を行う装置で問題となるＳ
Ｏ3 生成に起因する問題点を軽減できる。また脱硝装置
から放出されるＳＯ3 の量を低減でき環境保全に寄与す
ることができる。According to the present invention, a highly active denitration catalyst having a very small SO 2 oxidation rate can be realized. This causes a problem in a device that uses a large amount of catalyst to perform a high denitration operation.
Problems caused by O 3 generation can be reduced. Further, the amount of SO 3 released from the denitration device can be reduced, which can contribute to environmental conservation.
【図１】図１は、本発明になる触媒の特色を示すための
触媒断面の模式図である。FIG. 1 is a schematic cross-sectional view of a catalyst according to an embodiment of the present invention, showing characteristics of the catalyst.
【図２】、FIG.
【図３】図２および図３は、本発明の作用・効果を示す
ための図である。FIGS. 2 and 3 are diagrams for illustrating the operation and effect of the present invention.
【図４】、FIG.
【図５】、FIG.
【図６】図４、図５および図６は、本発明の実施例触媒
と比較例触媒の脱硝性能とＳＯ 2 酸化率を比較した図で
ある。FIG. 4, FIG. 5, and FIG. 6 show catalysts according to examples of the present invention.
Performance and SO of Comparative Example catalyst TwoIn the figure comparing the oxidation rate
is there.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−35026（ＪＰ，Ａ) 特開 平１−215345（ＪＰ，Ａ) 特開 昭58−210849（ＪＰ，Ａ) 特開 平２−6819（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 37/36 B01D 53/96 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-35026 (JP, A) JP-A-1-215345 (JP, A) JP-A-58-210849 (JP, A) JP-A-2- 6819 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B01J 21/00-37/36 B01D 53/96
Claims (3)
化物をアンモニアにより接触還元する脱硝触媒におい
て、モリブデン（Ｍｏ）および／またはタングステン
（Ｗ）とチタン（Ｔｉ）の酸化物からなる第一構成粒子
と、バナジウム（Ｖ）およびチタン（Ｔｉ）の酸化物か
らなる第二構成粒子とからなり、その両者が物理的な混
合状態を維持したまま成形されていることを特徴とする
二酸化硫黄の酸化を抑制した脱硝触媒。1. A denitration catalyst for catalytically reducing nitrogen oxides in an exhaust gas containing sulfur dioxide with ammonia, the first configuration comprising molybdenum (Mo) and / or tungsten (W) and an oxide of titanium (Ti). Oxidation of sulfur dioxide, comprising particles and second constituent particles composed of oxides of vanadium (V) and titanium (Ti), both of which are formed while maintaining a physical mixed state. Denitration catalyst with reduced odor.
アンモニアにより接触還元する脱硝触媒の製造方法にお
いて、酸化チタンまたはその前駆体とモリブデンおよび
／またはタングステンの酸化物もしくは加熱することに
よりそれらの酸化物を生成する化合物と水とを混合した
のち乾燥、焼成した第一成分と、酸化チタンまたはその
前駆体とバナジウム化合物と水とを混合したのち乾燥、
焼成した第二成分とを、それぞれ粉砕したのち、両者の
粉末を水を加えて混練し、成形、乾燥、焼成することを
特徴とする二酸化硫黄の酸化を抑制した脱硝触媒の製造
方法。2. A method for producing a denitration catalyst for catalytically reducing nitrogen oxides in an exhaust gas containing sulfur dioxide with ammonia, the method comprising oxidizing titanium oxide or a precursor thereof and molybdenum and / or tungsten by heating or heating them. Drying after mixing the compound to produce the product and water, drying and calcining the first component, mixing the titanium oxide or its precursor with the vanadium compound and water,
A method for producing a denitration catalyst in which oxidation of sulfur dioxide is suppressed, characterized in that the calcined second component is pulverized, then both powders are kneaded with water, molded, dried and calcined.
化物をアンモニアにより接触還元する脱硝触媒の製造方
法において、あらかじめモリブデンおよび／またはタン
グステンの化合物と酸化チタンもしくはその前駆体とか
ら第一構成成分を調製し、これとは別にあらかじめバナ
ジウム化合物と酸化チタンもしくはその前駆体とから第
二構成成分を調製し、両成分を粒径１００メッシュない
し３５０メッシュ以下に粉砕したのち、第一構成成分に
対する第二構成成分の重量比を１／９９〜５０／５０で
混練、成形、乾燥、焼成することを特徴とする二酸化硫
黄の酸化を抑制した脱硝触媒の製造方法。3. A method for producing a denitration catalyst for catalytically reducing nitrogen oxides in an exhaust gas containing sulfur dioxide with ammonia, wherein a first constituent component is prepared from a compound of molybdenum and / or tungsten and titanium oxide or a precursor thereof in advance. And separately prepared a second component from a vanadium compound and titanium oxide or a precursor thereof in advance, pulverizing both components to a particle size of 100 mesh to 350 mesh or less. A method for producing a denitration catalyst in which oxidation of sulfur dioxide is suppressed, characterized by kneading, molding, drying and calcining the two components at a weight ratio of 1/99 to 50/50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03260839A JP3076421B2 (en) | 1991-10-08 | 1991-10-08 | DeNOx catalyst suppressing sulfur dioxide oxidation and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03260839A JP3076421B2 (en) | 1991-10-08 | 1991-10-08 | DeNOx catalyst suppressing sulfur dioxide oxidation and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0596165A JPH0596165A (en) | 1993-04-20 |
| JP3076421B2 true JP3076421B2 (en) | 2000-08-14 |
Family
ID=17353477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03260839A Expired - Fee Related JP3076421B2 (en) | 1991-10-08 | 1991-10-08 | DeNOx catalyst suppressing sulfur dioxide oxidation and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3076421B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2054139B1 (en) * | 2006-08-01 | 2011-02-16 | Cormetech, Inc. | Method for treating exhaust gases |
| CA2676953A1 (en) | 2007-01-30 | 2008-08-07 | Babcock-Hitachi Kabushiki Kaisha | Exhaust gas purification catalyst and method of producing the same |
| JP5681990B2 (en) * | 2011-06-13 | 2015-03-11 | 三菱日立パワーシステムズ株式会社 | Method for producing denitration catalyst |
| JP6833494B2 (en) * | 2016-12-15 | 2021-02-24 | 三菱パワー株式会社 | Catalysts and methods for removing NOx from flue gas |
-
1991
- 1991-10-08 JP JP03260839A patent/JP3076421B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0596165A (en) | 1993-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100370460B1 (en) | DeNOx CATALYST FOR REDUCING THE NOx CONCENTRATION IN A STREAM OF FLUID, AND METHOD OF MANUFACTURING THE CATALYST | |
| KR101102714B1 (en) | Method for preparing a catalyst for removal of nitrogen oxides using dry ball-milling | |
| EP2324903B1 (en) | Method for purifying exhaust gas containing mercury metal, oxidation catalyst for mercury metal in exhaust gas and method for producing the same | |
| JPH0242536B2 (en) | ||
| KR20180113551A (en) | A catalyst for the oxidation reaction of metallic mercury and the reduction reaction of nitrogen oxides, and a method for purifying the exhaust gas | |
| JP3076421B2 (en) | DeNOx catalyst suppressing sulfur dioxide oxidation and method for producing the same | |
| JP2005342711A (en) | Denitration method of diesel engine exhaust gas | |
| JP4824516B2 (en) | Method for producing catalyst for removing nitrogen oxides in exhaust gas | |
| JP6132498B2 (en) | Titanium / silicon / tungsten oxide, denitration catalyst using the same, method for preparing the oxide, and denitration method | |
| JP3495591B2 (en) | Method for reduction treatment of nitrogen oxides and SO3 in exhaust gas | |
| JP4508597B2 (en) | Exhaust gas treatment catalyst capable of SO3 reduction treatment, method for producing the same, and exhaust gas treatment method using the exhaust gas treatment catalyst | |
| KR102558168B1 (en) | Catalyst for ammonia oxidation, and method for producing the same | |
| JP3496964B2 (en) | Catalyst for ammonia reduction of nitrogen oxides in exhaust gas and method for producing the same | |
| JP2001286734A (en) | Method for decomposing chlorinated organic compound and method for treating combustion exhaust gas | |
| JPH09220468A (en) | Catalyst for removal of nox in exhaust gas, its production and method for removing nox in exhaust gas using same | |
| JP2002361092A (en) | Catalyst slurry for denitrating exhaust gas, denitration catalyst and method of producing them | |
| JPH01317545A (en) | Preparation of denitrification catalyst | |
| JP2002292245A (en) | Denitration catalyst and dioxin decomposing catalyst | |
| JP3219613B2 (en) | Ammonia decomposition catalyst and method for decomposing and removing ammonia | |
| JPH07114964B2 (en) | Nitrogen oxide reduction catalyst and method for producing the same | |
| JP4959218B2 (en) | Method for producing plate-shaped denitration catalyst | |
| JPH05154350A (en) | Catalyst for removing nitrogen oxide and production thereof | |
| JP3749078B2 (en) | NOx removal catalyst and NOx removal method | |
| JPS58210849A (en) | Denitration catalyst for catalytic reduction with ammonia | |
| JPH08309188A (en) | Ammonia decomposition catalyst and ammonia decomposition method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080609 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090609 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100609 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110609 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |