JPH09187652A - Production of catalyst for stack gas denitrification - Google Patents
Production of catalyst for stack gas denitrificationInfo
- Publication number
- JPH09187652A JPH09187652A JP8001031A JP103196A JPH09187652A JP H09187652 A JPH09187652 A JP H09187652A JP 8001031 A JP8001031 A JP 8001031A JP 103196 A JP103196 A JP 103196A JP H09187652 A JPH09187652 A JP H09187652A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- raw material
- vanadium
- paste
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 140
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010937 tungsten Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 238000004898 kneading Methods 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003546 flue gas Substances 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 28
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 18
- 239000004480 active ingredient Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000010718 Oxidation Activity Effects 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 150000003658 tungsten compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012784 inorganic fiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- 229940041260 vanadyl sulfate Drugs 0.000 description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 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 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- -1 vanadium (V) compound Chemical class 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、排煙脱硝触媒の製
造方法に係り、特に排ガス中の窒素酸化物をアンモニア
を用いて還元除去する脱硝触媒であって、化学反応を選
択的に進行させる目的で使用する高活性な排煙脱硝触媒
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a flue gas denitration catalyst, and more particularly to a denitration catalyst for reducing and removing nitrogen oxides in exhaust gas by using ammonia, which selectively promotes a chemical reaction. The present invention relates to a method for producing a highly active flue gas denitration catalyst used for the purpose.
【０００２】[0002]
【従来の技術】発電プラントや化学プラントの排ガス中
の窒素酸化物を触媒の存在下でアンモニアによって還元
除去する方法が広く用いられている。この反応に用いら
れる触媒（脱硝触媒）は、通常、チタンおよびバナジウ
ムとともにタングステンまたはモリブデンをはじめとす
る活性成分を含み、これらの原料を混練してペーストと
した後、ハニカム状または板状構造体に成形し、次いで
乾燥、焼成することによって製造される。2. Description of the Related Art A method for reducing and removing nitrogen oxides in exhaust gas from power plants and chemical plants with ammonia in the presence of a catalyst is widely used. The catalyst (denitration catalyst) used in this reaction usually contains active components such as tungsten or molybdenum along with titanium and vanadium, and these raw materials are kneaded into a paste, which is then formed into a honeycomb-shaped or plate-shaped structure. It is manufactured by molding, followed by drying and firing.
【０００３】図５は、ＴｉとＷの原料が異なる、従来の
脱硝触媒の代表的な製造フローを示す図である。担体で
ある酸化チタン（ＴｉＯ2 ）に、触媒活性成分であるタ
ングステン（Ｗ）またはモリブデン（Ｍｏ）の化合物、
バナジウム（Ｖ）化合物、水および必要に応じてその他
の添加物を加えて混練し、触媒ペーストとし、得られた
触媒ペーストをハニカム状に成形するか、または所定の
基板上に塗布することによって触媒成形体とし、この触
媒成形体を乾燥した後、例えば５００〜６００℃の温度
で焼成することによって脱硝触媒が得られる。なお、図
５においてはハニカム触媒を例に製造フローを示した。FIG. 5 is a diagram showing a typical production flow of a conventional denitration catalyst in which the raw materials of Ti and W are different. A compound of tungsten (W) or molybdenum (Mo), which is a catalytically active component, to titanium oxide (TiO 2 ) which is a carrier,
A catalyst is obtained by adding a vanadium (V) compound, water and, if necessary, other additives and kneading to obtain a catalyst paste, and molding the obtained catalyst paste into a honeycomb shape or by applying the catalyst paste on a predetermined substrate. A denitration catalyst is obtained by forming a molded body, drying the catalyst molded body, and then firing the molded body at a temperature of 500 to 600 ° C., for example. In addition, in FIG. 5, the manufacturing flow is shown taking a honeycomb catalyst as an example.
【０００４】原料および添加剤はきわめて広範囲の物質
の中から選択されるが、ＴｉＯ2 とＷ化合物を別々の原
料によって供給するのではなく、ＴｉＯ2 とＷＯ3 の２
成分系混合物として使用することもできる。図６は、Ｔ
ｉＯ2 とＷＯ3 の２成分系混合物を用いた従来の脱硝触
媒の製造フローを示す図である。触媒構成元素の中にあ
って、バナジウムは活性決定元素として特に重要であ
り、バナジウムの添加量と触媒表面上におけるバナジウ
ムの分散状態によって触媒活性は大きく影響される。ガ
ス焚き排ガスのようにＳＯ2 濃度の低い排ガスの脱硝用
触媒では、バナジウム添加量を増大させることによって
触媒活性を高めるという方法がとられ、この場合、高比
表面積のチタニア担体を用いた方が概して高活性な触媒
が得られる。Although the raw materials and additives are selected from a very wide range of materials, the TiO 2 and W compounds are not supplied by separate raw materials, but TiO 2 and WO 3
It can also be used as a component mixture. FIG. 6 shows T
iO is a diagram showing a manufacturing flow of a conventional denitration catalyst using 2-component mixture of 2 and WO 3. Among the catalyst constituent elements, vanadium is particularly important as an activity determining element, and the catalytic activity is greatly affected by the amount of vanadium added and the dispersed state of vanadium on the catalyst surface. In the case of a catalyst for denitration of exhaust gas having a low SO 2 concentration such as gas-fired exhaust gas, a method of increasing the catalytic activity by increasing the amount of vanadium added is adopted. Highly active catalysts are generally obtained.
【０００５】バナジウム添加量が増加するにつれて、通
常脱硝活性は高くなるが、バナジウム添加量をむやみに
増大させることはできない。なぜならば、バナジウム添
加量を増大させ、その分散を図る目的で焼成温度を高め
ると逆に触媒粒子の焼結が起こり、表面積が減少し、こ
れによって脱硝活性が低下するからである。また、バナ
ジウムやモリブデンの添加量を多くすると、ＳＯ2 の酸
化活性が上昇するため、ＳＯ2 酸化活性を抑えることが
要求される。従って、少ない量のバナジウムをいかに高
活性な状態にするかがきわめて重要となる。この点から
もバナジウムなどの添加量は制約を受ける。As the amount of vanadium added increases, the denitration activity usually increases, but the amount of vanadium added cannot be increased excessively. This is because when the firing temperature is increased to increase the amount of vanadium added and to disperse the vanadium, the catalyst particles conversely sinter and the surface area decreases, which reduces the denitration activity. Further, when the addition amount of vanadium or molybdenum is increased, the SO 2 oxidation activity is increased, so that it is required to suppress the SO 2 oxidation activity. Therefore, how highly active a small amount of vanadium is is extremely important. From this point as well, the amount of vanadium added is limited.
【０００６】すなわち、ガス焚き排ガス用脱硝触媒で
は、Ｖ添加量を増大させて触媒活性を高めることができ
るが、Ｖ添加量が増加するにつれて、触媒粒子の焼結が
起こり易くなり、Ｖ添加量を増大させ過ぎると最終的に
表面積および脱硝活性が低下してしまう。この現象は、
Ｖが高濃度で均一に分散していると起こり易いと考えら
れる。That is, in the denitration catalyst for gas-fired exhaust gas, the V addition amount can be increased to enhance the catalytic activity, but as the V addition amount increases, the catalyst particles are more likely to sinter and the V addition amount increases. If it is increased too much, the surface area and the denitration activity will eventually decrease. This phenomenon is
It is considered that V easily occurs when V is highly dispersed uniformly.
【０００７】一方、石炭や油焚き排ガス用脱硝用触媒で
は、ＳＯ2 濃度の高い排ガスを処理対象とするため、バ
ナジウムやモリブデンの添加量を多くするとＳＯ2 の酸
化活性が上昇する。したがって、これらＳＯ2 濃度の高
い排ガスの処理を目的とする触媒では、ＳＯ2 酸化活性
を抑えることが要求され、少ない量のＶをいかに高活性
な状態にするかがきわめて重要となる。その１つの手段
として特開昭５５−３８７２号公報にあるような低濃度
のＶを、先に担体に担持した後、Ｗを担持することによ
って細孔の表面に高濃度のＷを担持する方法がある。On the other hand, in the catalyst for denitration of coal and oil-fired exhaust gas, the exhaust gas having a high SO 2 concentration is targeted for treatment, so that the SO 2 oxidation activity increases when the addition amount of vanadium or molybdenum is increased. Therefore, in the catalysts for treating the exhaust gas having a high SO 2 concentration, it is required to suppress the SO 2 oxidation activity, and it is very important how to make a small amount of V highly active. As one of the means, a method of supporting a high concentration of W on the surface of pores by first supporting a low concentration of V on a carrier as described in JP-A-55-3872 and then supporting W There is.
【０００８】[0008]
【発明が解決しようとする課題】脱硝触媒が今後とも広
く利用されていくためには、性能はもちろん脱硝装置全
体がより安価なものにならなければならない。その具体
的手段としては、脱硝触媒の製造プロセスの簡略化とと
もに触媒原料の低廉化、触媒必要量の低減、すなわち触
媒活性の向上がきわめて重要である。高活性な触媒が開
発され、必要触媒量が低減すれば反応装置のコンパクト
化が図られ、この点からも脱硝装置全体の経済性が向上
する。In order for the denitration catalyst to be widely used in the future, not only the performance but also the entire denitration device must be cheaper. As a concrete means, it is extremely important to simplify the manufacturing process of the denitration catalyst, reduce the cost of the catalyst raw material, reduce the required amount of the catalyst, that is, improve the catalytic activity. If a highly active catalyst is developed and the amount of required catalyst is reduced, the reactor can be made compact, which also improves the economic efficiency of the denitration apparatus as a whole.
【０００９】本発明は、上記のような背景のもとになさ
れたものであり、脱硝性能に優れ、反面低ＳＯ2 酸化性
で、かつ経済性に優れた排煙脱硝触媒の製造方法を提供
することを目的とするものである。The present invention has been made under the above-mentioned background, and provides a method for producing a flue gas denitration catalyst which is excellent in denitration performance, on the other hand, low in SO 2 oxidative property and excellent in economical efficiency. The purpose is to do.
【００１０】[0010]
【課題を解決するための手段】上記目的は、触媒活性成
分であるバナジウム、タングステンの原料のうち少なく
ともその一部を実質的に不溶性化した後、触媒原料に添
加してペーストを調製し、このペーストを用いて触媒成
形体を調製し、次いで焼成することによって達成され
る。本発明の排煙脱硝触媒の製造方法は、酸化チタン担
体またはその関連原料に、活性成分であるバナジウム、
タングステンのうちその一部または全部を実質的に不溶
性な状態で添加して触媒ペーストを調製し、このペース
トを用いて成形体とし、その後焼成するものである。[Means for Solving the Problems] The above object is to make a paste by substantially insolubilizing at least a part of vanadium and tungsten raw materials which are catalytically active components, and then to prepare a paste by adding to the catalyst raw material. This is achieved by preparing a shaped catalyst body using the paste and then calcining. The method for producing a flue gas denitration catalyst of the present invention is a titanium oxide carrier or its related raw material, vanadium as an active ingredient,
A part or all of tungsten is added in a substantially insoluble state to prepare a catalyst paste, the paste is used to form a molded body, and then fired.
【００１１】すなわち、本願で特許請求される発明は、
以下に示すとおりである。 （１）チタン、バナジウムならびにタングステンおよび
／またはモリブデンを含有する触媒原料を水の存在下で
混練して触媒ペーストを調製し、該触媒ペーストを成
形、または基材に塗布した後、焼成する排煙脱硝触媒の
製造方法において、前記バナジウムおよび／またはタン
グステンを含む触媒原料化合物の一部または全部を不溶
性の形態で、他の触媒原料と混練して触媒ペーストを調
製し、該触媒ペーストを所定の形状に成形、または基材
に塗布した後、焼成することを特徴とする排煙脱硝触媒
の製造方法。That is, the invention claimed in this application is as follows:
It is as shown below. (1) Exhaust smoke which is obtained by kneading a catalyst raw material containing titanium, vanadium, and tungsten and / or molybdenum in the presence of water to prepare a catalyst paste, molding the catalyst paste, or applying the catalyst paste to a substrate, followed by firing. In the method for producing a denitration catalyst, a part or all of the catalyst raw material compound containing vanadium and / or tungsten is mixed in an insoluble form with another catalyst raw material to prepare a catalyst paste, and the catalyst paste is formed into a predetermined shape. A method for producing a flue gas denitration catalyst, which comprises firing after being molded into or applied to a substrate.
【００１２】（２）前記バナジウムおよび／またはタン
グステンを含む触媒原料化合物を溶液化した後ゲル化
し、次いで粉砕して不溶性化することを特徴とする上記
（１）記載の排煙脱硝触媒の製造方法。 （３）前記バナジウムおよび／またはタングステンを含
む触媒原料化合物を溶融し、冷却固化し、次いで粉砕す
ることによって不溶性化することを特徴とする上記
（１）記載の排煙脱硝触媒の製造方法。 （４）触媒原料を混練する際、マンガン、鉄、クロム、
ニッケル、ニオブ、けい素およびアルミニウムのうち少
なくとも一種を含む化合物を添加することを特徴とする
上記（１）〜（３）の何れか記載の排煙脱硝触媒の製造
方法。(2) The method for producing a flue gas denitration catalyst according to the above (1), characterized in that the catalyst raw material compound containing vanadium and / or tungsten is made into a solution, gelled, and then pulverized to make it insoluble. . (3) The method for producing a flue gas denitration catalyst according to the above (1), wherein the catalyst raw material compound containing vanadium and / or tungsten is melted, solidified by cooling, and then pulverized to be insoluble. (4) Manganese, iron, chromium,
The method for producing a flue gas denitration catalyst according to any one of the above (1) to (3), characterized in that a compound containing at least one of nickel, niobium, silicon and aluminum is added.
【００１３】従来から、高活性な脱硝触媒を得るために
はＴｉＯ2 担体上に活性成分を均一に分散して担持させ
ることが重要であり、水に溶けにくい活性成分を用いた
のでは成形後も活性成分が不均一な状態で存在するため
に、高活性な触媒は得られないとされてきた。しかし、
脱硝触媒には各種排ガスに適した活性成分の形態があ
り、本発明者は各々の形態のものを調製する方法の１つ
として全活性成分の一部を不溶性として添加し、成形し
た後、焼成することにより、不溶性であった活性成分が
焼成時に溶出して高濃度の状態で存在するようになるこ
とを見出した。本発明の基本原理は、担体に担持される
活性成分を部分的に高濃度な状態で存在させることにあ
り、粒子が激しい焼結を起こさない範囲で活性成分を存
在させることによってより効果的なものとなる。It has been conventionally important to uniformly disperse and support an active ingredient on a TiO 2 carrier in order to obtain a highly active denitration catalyst. However, it has been considered that a highly active catalyst cannot be obtained because the active components exist in a non-uniform state. But,
The denitration catalyst has a form of an active ingredient suitable for various exhaust gases. As one of the methods for preparing each form of the denitration catalyst, the present inventor added a part of all the active ingredients as insoluble, molded and then calcined. It was found that, by doing so, the insoluble active ingredient was eluted at the time of baking and was present in a high concentration state. The basic principle of the present invention resides in that the active ingredient supported on the carrier is partially present in a high-concentration state, and it is more effective by allowing the active ingredient to exist in a range where particles do not undergo severe sintering. Will be things.
【００１４】本発明方法によって高活性な脱硝触媒が得
られる理由に関しては必ずしも完全には解明されていな
いが、活性成分が完全に均一分散した状態よりも、局所
的にしかるべき濃度で存在する状態の方が高活性となる
ものと推定される。本発明方法は、ＳＯ2 含有排ガスを
対象とする低バナジウム量の脱硝触媒において特に有効
である。The reason why a highly active denitration catalyst can be obtained by the method of the present invention has not been completely elucidated, but a state in which the active ingredient is locally present at an appropriate concentration rather than a state in which it is completely uniformly dispersed. Is estimated to be more active. The method of the present invention is particularly effective for a low vanadium denitration catalyst for SO 2 -containing exhaust gas.
【００１５】本発明方法を用いると、例えばタングステ
ンを不溶性（不溶性化合物）として添加することによっ
て水溶性の触媒原料化合物を用いた場合に比べて同等以
上の高脱硝活性、かつ低ＳＯ2 酸化活性の触媒を得るこ
とができる。本発明方法を用いると、より高濃度のバナ
ジウムを存在させることができ、しかも高濃度部位が触
媒中に点在するので触媒粒子の焼結が起こりにくくな
る。When the method of the present invention is used, for example, by adding tungsten as an insoluble (insoluble compound), it is possible to obtain the same or higher high denitrification activity and low SO 2 oxidation activity as compared with the case where a water-soluble catalyst raw material compound is used. A catalyst can be obtained. When the method of the present invention is used, a higher concentration of vanadium can be made to exist, and since the high concentration sites are scattered in the catalyst, sintering of the catalyst particles is less likely to occur.
【００１６】[0016]
【発明の実施の形態】次に、本発明についてさらに詳し
く説明する。図１は、不溶性Ｖを使用した、本発明の一
実施例である脱硝触媒の製造フローを示す図である。な
お以下、本明細書では触媒形状をハニカムとし、また触
媒成分をＴｉ／Ｗ／Ｖ、またはＴｉ／Ｍｏ／Ｖとして説
明する。BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail. FIG. 1 is a diagram showing a production flow of a denitration catalyst, which is an example of the present invention, using insoluble V. In the following description, the catalyst shape is honeycomb and the catalyst component is Ti / W / V or Ti / Mo / V.
【００１７】触媒担持となる酸化チタン（ＴｉＯ2 ）
は、その所定量が混練機に移し入れられ、不溶性のＶ化
合物、他の原料であるＷまたはＭｏの化合物、水、さら
には必要に応じて各種添加物とともに混練され、触媒ペ
ーストが調製される。添加剤としては強化材、溶解促進
剤、増粘剤などを使用することができる。また、これら
の原料類および水は、同時に混練機に投入されるほか、
特定の原料類をあらかじめ混合するなどの方法を採用す
ることもできるが、これらの方法の差、さらには原料の
粒径などによって本発明が制約を受けるものでない。ま
た要求される触媒性能の違いによって、例えば図３に示
したように、不溶性のＶ化合物の代わりに不溶性のＷ化
合物を添加することができる。Titanium oxide (TiO 2 ) for supporting catalyst
Is transferred to a kneading machine in a predetermined amount and kneaded with an insoluble V compound, a compound of W or Mo which is another raw material, water and, if necessary, various additives to prepare a catalyst paste. . As the additive, a reinforcing material, a dissolution accelerator, a thickener and the like can be used. Further, these raw materials and water are simultaneously charged into the kneading machine,
Although a method of previously mixing specific raw materials can be adopted, the present invention is not limited by the difference between these methods and the particle size of the raw materials. Depending on the required difference in catalyst performance, an insoluble W compound can be added instead of the insoluble V compound, as shown in FIG. 3, for example.
【００１８】本発明において不溶性の形態とは、触媒原
料化合物が、他の触媒原料と混練される際に溶解しない
状態をいい、水に対して、または各種添加剤を含んだ水
に対して不溶解性を示す形態をいう。触媒活性成分を含
む化合物を不溶性化する方法としては、例えば原料化合
物を溶液化した後ゲル化し、次いで粉砕して不溶性化す
る方法、または原料化合物を溶融し、冷却固化し、次い
で粉砕することによって不溶性化する方法等があげられ
る。In the present invention, the insoluble form means a state in which the catalyst raw material compound does not dissolve when kneaded with other catalyst raw materials, and is insoluble in water or water containing various additives. Refers to a form that exhibits solubility. Examples of the method for making the compound containing the catalytically active component insoluble include, for example, a method in which the raw material compound is made into a solution and then gelled, and then pulverized to make it insoluble, or the raw material compound is melted, solidified by cooling, and then pulverized. A method of making it insoluble can be mentioned.
【００１９】触媒原料を混練して得られた触媒ペースト
は、例えば所定の金型を取付けた押出し成形機に供給さ
れ、例えばハニカム状に成形される。ハニカム成形体
は、乾燥後５００〜６００℃の温度で焼成され、これに
より脱硝触媒が得られる。なお、本発明は高活性な触媒
基剤を得る方法を提供するものであって、他の活性成分
原料の形態、触媒の形状、乾燥および最終焼成の条件に
よって特に制限を受けるものではない。The catalyst paste obtained by kneading the catalyst raw materials is supplied to, for example, an extrusion molding machine equipped with a predetermined mold and molded into, for example, a honeycomb shape. The honeycomb formed body is dried and then fired at a temperature of 500 to 600 ° C., whereby a denitration catalyst is obtained. The present invention provides a method for obtaining a highly active catalyst base, and is not particularly limited by the form of other active ingredient materials, the shape of the catalyst, the conditions of drying and final calcination.
【００２０】本発明の基本原理は、担体上に部分的に高
濃度の活性成分を担持することである。ＴｉＯ2 系脱硝
触媒では成形性向上、活性向上、粒子の焼結防止、ＳＯ
2 酸化特性改善などを目的に、図２に示すように、あら
かじめＶ化合物、ＷやＭｏの化合物をＴｉＯ2 に添加し
た状態の原料（予備焼成粉末）を用いることがあり、こ
の場合においても本発明方法を適用することができる。
この場合、あらかじめ原料に添加されているＶ量が高濃
度（１０ａｔｍ％以上）でないことが望ましい。予備焼
成粉末を調製した後は、上述の図１の場合と同様の操作
によってハニカム触媒が製造される。The basic principle of the invention is to partially load the carrier with a high concentration of active ingredient. TiO 2 -based NOx removal catalyst improves moldability, activity, particle sintering prevention, SO
2 For the purpose of improving the oxidation characteristics, as shown in FIG. 2, a raw material (pre-baked powder) in which a V compound, a W or Mo compound is added to TiO 2 in advance may be used. The inventive method can be applied.
In this case, it is desirable that the amount of V previously added to the raw material is not a high concentration (10 atm% or more). After preparing the pre-calcined powder, the honeycomb catalyst is manufactured by the same operation as in the case of FIG. 1 described above.
【００２１】いずれの方法を用いた場合でも、ハニカム
成形体は乾燥後、焼成され、所定の活性を有するハニカ
ム触媒とされる。焼成の目的は、原料として添加した触
媒成分化合物を熱分解して所期の活性を有する形態に変
化させるとともに、部分的に存在する不溶性の活性成分
は高濃度のまま熱分解し、さらに活性を有する形態に変
化させ、触媒基剤を熱的に安定な状態にすることにあ
る。ＴｉＯ2 系脱硝触媒の場合、通常この焼成温度は５
００〜６００℃である。Whichever method is used, the honeycomb formed body is dried and then fired to obtain a honeycomb catalyst having a predetermined activity. The purpose of calcination is to thermally decompose the catalyst component compound added as a raw material to change it into a form having the desired activity, and partially insoluble active components are thermally decomposed at a high concentration to further increase the activity. It is to change the form to have and to make the catalyst base in a thermally stable state. In the case of a TiO 2 type denitration catalyst, this firing temperature is usually 5
00-600 ° C.
【００２２】不溶性の活性成分化合物の代わりに、図４
に示したように、通常用いられる水溶液の活性成分化合
物を一部を不溶化することによって上記と同等に使用す
ることができる。すなわち、メタバナジン酸アンモニウ
ム（ＮＨ4 ＶＯ3 ）、硫酸バナジル（ＶＯＳＯ4 ）、パ
ラタングステン酸アンモニウム（５（ＮＨ4 ）2 Ｏ・１
２ＷＯ3 ・５Ｈ2 Ｏ）、メタタングステン酸アンモニウ
ム（（ＮＨ4 ）2 Ｏ・４ＷＯ3 ・ｎＨ2 Ｏ）などをチタ
ニアの一部、添加物の一部（シリカ、増粘剤等）に高濃
度で低水分状態で担持しておき、ペーストの粘度が高い
段階にあるときにこれらを添加することによって、不溶
性の活性成分化合物の代わりに用いることができる。Instead of the insoluble active ingredient compound, FIG.
As shown in (1), the active ingredient compound of a commonly used aqueous solution can be used in the same manner as above by partially insolubilizing it. That is, ammonium metavanadate (NH 4 VO 3 ), vanadyl sulfate (VOSO 4 ), ammonium paratungstate (5 (NH 4 ) 2 O.1
2WO 3 · 5H 2 O), ammonium metatungstate ((NH 4 ) 2 O · 4WO 3 · nH 2 O), etc. in high concentrations in some of the titania and some of the additives (silica, thickener, etc.) It can be used in place of the insoluble active ingredient compound by supporting it in a low water content state and adding them when the paste has a high viscosity.
【００２３】上記の説明から明らかなように、本発明の
方法はＴｉＯ2 担体上に高濃度の活性成分を点在させて
脱硝触媒活性の向上を図ることに特徴を有する。したが
って、この効果が発現する限りにおいて、活性成分とし
てはＷ、Ｍｏ、Ｖに限定されるものではなく、Ｍｎ、Ｆ
ｅ、Ｃｒ、Ｎｉ、Ｎｂ、Ｓｉ、Ａｌなどを触媒ペースト
調製時に添加することができる。また、ＴｉＯ2 に対し
て添加される触媒成分の量によって本発明の方法が制限
を受けるものではないが、Ｔｉ／Ｗ／ＶおよびＴｉ／Ｍ
ｏ／Ｖ系触媒にあっては、Ｖ添加量は０．５〜１０、通
常１〜８％（原子比）とした場合に高活性な触媒が得ら
れる。Ｖ量がこの範囲以下の値になると触媒活性成分量
として不足し、一方、過剰に添加された場合には細孔を
閉塞することによって活性が低下する。As is clear from the above description, the method of the present invention is characterized in that a high-concentration active component is scattered on the TiO 2 carrier to improve the denitration catalytic activity. Therefore, as long as this effect is exhibited, the active ingredients are not limited to W, Mo and V, but Mn and F.
e, Cr, Ni, Nb, Si, Al and the like can be added when preparing the catalyst paste. Also, although the method of the present invention is not limited by the amount of the catalyst component added to TiO 2 , the Ti / W / V and Ti / M
In the case of an o / V catalyst, a highly active catalyst can be obtained when the amount of V added is 0.5 to 10, usually 1 to 8% (atomic ratio). When the amount of V is below this range, the amount of the catalytically active component is insufficient, while when it is added in excess, the activity is reduced by closing the pores.
【００２４】[0024]
【実施例】次に、具体的実施例に基づいて本発明をさら
に詳しく説明する。 実施例１〜３ 硫酸法によって製造した酸化チタン粉末（ＳＯ4 含有量
１．４ｗｔ％、平均粒径１．２μｍ、ＢＥＴ比表面積３
４０ｍ2 ／ｇ）に不溶性化合物である５酸化バナジウム
と、メタタングステン酸アンモニウム（液状）を、無機
繊維（軟化温度１１００℃）、増粘剤および水を加えて
混練し、Ｔｉ／Ｗ／Ｖ原子比が９５／４／１（実施例
１）、９４／４／２（実施例２）、９３／４／３（実施
例３）の触媒ペーストを調製した。この触媒ペーストを
用い、セルピッチ３．５mm、リブ厚さ０．６mmのハニカ
ムを押出し成形した。このハニカム成形体を温度８５
℃、湿度７０％の恒温恒湿器を用いて乾燥し、次いで温
度５５０℃で２時間焼成してハニカム触媒を得た。The present invention will be described in more detail with reference to specific examples. Examples 1 to 3 Titanium oxide powder produced by the sulfuric acid method (SO 4 content 1.4 wt%, average particle size 1.2 μm, BET specific surface area 3
40 m 2 / g), vanadium pentoxide, which is an insoluble compound, and ammonium metatungstate (liquid) were kneaded by adding inorganic fibers (softening temperature 1100 ° C.), a thickener and water, and Ti / W / V atoms A catalyst paste having a ratio of 95/4/1 (Example 1), 94/4/2 (Example 2) and 93/4/3 (Example 3) was prepared. Using this catalyst paste, a honeycomb having a cell pitch of 3.5 mm and a rib thickness of 0.6 mm was extruded. This honeycomb formed body is heated to a temperature of 85
The honeycomb catalyst was dried by using a thermo-hygrostat having a temperature of 70% and a humidity of 70%, and then fired at a temperature of 550 ° C for 2 hours to obtain a honeycomb catalyst.
【００２５】得られた触媒の脱硝活性を、供給ガスをＮ
Ｏ：２００ｐｐｍ、ＮＨ3 ：２４０ｐｐｍ、Ｏ2 ：１０
％、ＣＯ2 ：６％、Ｈ2 Ｏ：６％（残Ｎ2 ）とし、温
度：３５０℃、面積基準ガス流量ＡＶ：５１ｍ／ｈ（＝
ｍ3 ／ｈ／ｍ2 ）の条件で測定したところ、各触媒の脱
硝活性（反応速度定数比）は、後述する比較例１を基準
（１．００）とした場合、それぞれ１．６２、１．７９
および２．０８であった。The denitration activity of the obtained catalyst was determined by changing the feed gas to N 2.
O: 200ppm, NH 3: 240ppm , O 2: 10
%, CO 2: 6%, H 2 O: a 6% (residual N 2), temperature: 350 ° C., the area the reference gas flow rate AV: 51m / h (=
m 3 / h / m 2 ), the denitration activity (reaction rate constant ratio) of each catalyst was 1.62, 1 when the comparative example 1 described later was taken as the reference (1.00). .79
And 2.08.
【００２６】実施例４〜６ 実施例１における５酸化バナジウムの代わりにメタバナ
ジン酸アンモニウム（ＮＨ4 ＶＯ3 ）を用いて、実施例
１と類似の実験を行った。まずメタバナジン酸アンモニ
ウムを不溶化するために、添加物である全増粘剤のそれ
ぞれ１０、２０、３０％および全添加水のそれぞれ１
０、１５、２０％と、メタバナジン酸アンモニウムのそ
れぞれ所定量を小型混練機を用いて小塊状の硬いペース
トにして保存しておいた。次に、残りの触媒原料を混練
し、ペーストを調製した。このペーストにメタバナジン
酸アンモニウムを含んだ小塊状のペーストを添加して混
練して、Ｔｉ／Ｗ／Ｖ原子比が９５／４／１（実施例
４）、９４／４／２（実施例５）、９３／４／３（実施
例６）の触媒ペーストを調製した。以後、実施例１〜３
と同様の方法によってハニカム触媒を調製し、また同様
にして脱硝活性を測定した。その結果、調製した触媒の
脱硝活性（反応速度定数比）は、それぞれ１．４９、
１．６５および２．０１であった。Examples 4 to 6 An experiment similar to that of Example 1 was conducted using ammonium metavanadate (NH 4 VO 3 ) instead of vanadium pentoxide in Example 1. First, in order to insolubilize ammonium metavanadate, 10%, 20% and 30% of the total thickeners as additives and 1% of the total added water, respectively.
A small amount of 0, 15, 20% and a predetermined amount of ammonium metavanadate were respectively stored as small hard pastes using a small kneader. Next, the remaining catalyst raw materials were kneaded to prepare a paste. To this paste, a small paste containing ammonium metavanadate was added and kneaded so that the Ti / W / V atomic ratio was 95/4/1 (Example 4), 94/4/2 (Example 5). , 93/4/3 (Example 6) was prepared. Thereafter, Examples 1 to 3
A honeycomb catalyst was prepared by the same method as described above, and the denitration activity was measured in the same manner. As a result, the denitration activity (reaction rate constant ratio) of the prepared catalyst was 1.49,
It was 1.65 and 2.01.
【００２７】実施例７ 実施例１におけるＴｉＯ2 原料と不溶性であるタングス
テン酸カルシウムと硫酸バナジルを用いて、実施例１と
類似の実験を行った。無機繊維、増粘剤および水を加え
て混練し、Ｔｉ／Ｗ／Ｖ原子比が９５／４／１の触媒ペ
ーストを調製した。以後実施例１と同様の方法によって
ハニカム触媒を調製し、また同様にして脱硝活性を測定
した。その結果、脱硝活性（反応速度定数比）は１．９
２であった。得られた触媒のＳＯ2 酸化活性を、供給ガ
スをＳＯ2 ：５００ｐｐｍ、Ｏ2：３％（残Ｎ2 ）と
し、温度：３５０℃、面積基準ガス流量ＡＶ：６ｍ／ｈ
（＝ｍ3 ／ｈ／ｍ2 ）の条件で測定したところ、後述す
る比較例１のＳＯ2 の酸化活性を基準（１．００）とし
てＳＯ2 酸化活性（反応速度定数比）は０．５であっ
た。Example 7 An experiment similar to that of Example 1 was conducted using the TiO 2 raw material in Example 1 and insoluble calcium tungstate and vanadyl sulfate. An inorganic fiber, a thickener and water were added and kneaded to prepare a catalyst paste having a Ti / W / V atomic ratio of 95/4/1. Thereafter, a honeycomb catalyst was prepared by the same method as in Example 1, and the denitration activity was measured in the same manner. As a result, the denitration activity (reaction rate constant ratio) was 1.9.
It was 2. Regarding the SO 2 oxidation activity of the obtained catalyst, the supply gas was SO 2 : 500 ppm, O 2 : 3% (residual N 2 ), temperature: 350 ° C., area standard gas flow rate AV: 6 m / h
When measured under the condition of (= m 3 / h / m 2 ), the SO 2 oxidation activity (reaction rate constant ratio) was 0.5 based on the oxidation activity of SO 2 of Comparative Example 1 described later as a reference (1.00). Met.
【００２８】実施例８ 実施例７において、タングステン酸カルシウムの代わり
にメタタングステン酸アンモニウムを用いて、実施例７
と類似の実験を行った。まずメタバナジン酸アンモニウ
ムを不溶化するために、添加物である全増粘剤の３０％
を添加して小型混練機を用いて小塊状の硬いペーストに
して保存しておいた。次に、残りの触媒原料を混練し、
ペーストを調製した。このペーストにメタタングステン
酸アンモニウムを含んだ小塊状のペーストを添加して混
練して、Ｔｉ／Ｗ／Ｖ原子比が９５／４／１の触媒ペー
ストを調製した。以後、実施例７と同様の方法によって
ハニカム触媒を調製し、また同様にして触媒活性を測定
した。その結果、調製した触媒の脱硝活性（反応速度定
数比）は１．８１であり、ＳＯ2 酸化活性（反応速度定
数比）は０．６５であった。Example 8 In Example 7, ammonium metatungstate was used instead of calcium tungstate.
A similar experiment was performed. First, in order to insolubilize ammonium metavanadate, 30% of the total thickener as an additive is added.
Was added to a small kneading machine to make a hard paste in the form of small blocks, which was then stored. Next, knead the remaining catalyst raw material,
A paste was prepared. A small paste containing ammonium metatungstate was added to this paste and kneaded to prepare a catalyst paste having a Ti / W / V atomic ratio of 95/4/1. Thereafter, a honeycomb catalyst was prepared by the same method as in Example 7, and the catalyst activity was measured in the same manner. As a result, the denitration activity (reaction rate constant ratio) of the prepared catalyst was 1.81, and the SO 2 oxidation activity (reaction rate constant ratio) was 0.65.
【００２９】実施例９〜１１ 実施例１において、メタタングステン酸アンモニウムの
代わりにモリブデン酸アンモニウムを用いて、実施例１
と類似の実験を行った。Ｔｉ／Ｍｏ／Ｖ原子比が９５／
４／１（実施例９）、９４／４／２（実施例１０）、９
３／４／３（実施例１１）の触媒ペーストを調製した。
以後、実施例１と同様の方法によってハニカム触媒を調
製し、また同様にして脱硝活性を測定した。その結果、
脱硝活性（反応速度定数比）は、それぞれ１．４１、
１．５８および１．８８であった。Examples 9 to 11 Example 1 was repeated except that ammonium molybdate was used instead of ammonium metatungstate.
A similar experiment was performed. Ti / Mo / V atomic ratio is 95 /
4/1 (Example 9), 94/4/2 (Example 10), 9
A 3/4/3 (Example 11) catalyst paste was prepared.
Thereafter, a honeycomb catalyst was prepared by the same method as in Example 1, and the denitration activity was measured in the same manner. as a result,
Denitration activity (reaction rate constant ratio) was 1.41,
It was 1.58 and 1.88.
【００３０】比較例１〜４ 実施例１における５酸化バナジウムの代わりにメタバナ
ジン酸アンモニウム（水溶性）を用いてハニカム触媒を
調製した。Ｔｉ／Ｗ／Ｖ原子比が９５／４／１（比較例
１）、９４／４／２（比較例２）、９１／４／５（比較
例３）、８９／４／７（比較例４）の触媒ペーストを調
製した。以後、実施例１と同様の方法によってハニカム
触媒を調製し、また同様にして脱硝活性を測定した。そ
の結果、比較例２〜４で調製した触媒の脱硝活性（反応
速度定数比）は、比較例１を１．００（基準）としたと
き、それぞれ１．６５、１．９４および１．９０であっ
た。なお、Ｔｉ／Ｗ／Ｖ原子比が９５／４／１（比較例
１）の触媒のＳＯ2 酸化活性（反応速度定数比）を１．
００（基準）として各実施例または比較例と比較した。Comparative Examples 1 to 4 Honeycomb catalysts were prepared by using ammonium metavanadate (water-soluble) instead of vanadium pentoxide in Example 1. Ti / W / V atomic ratio is 95/4/1 (Comparative Example 1), 94/4/2 (Comparative Example 2), 91/4/5 (Comparative Example 3), 89/4/7 (Comparative Example 4). ) Was prepared. Thereafter, a honeycomb catalyst was prepared by the same method as in Example 1, and the denitration activity was measured in the same manner. As a result, the denitration activities (reaction rate constant ratio) of the catalysts prepared in Comparative Examples 2 to 4 were 1.65, 1.94 and 1.90, respectively, when Comparative Example 1 was set to 1.00 (reference). there were. The SO 2 oxidation activity (reaction rate constant ratio) of the catalyst having a Ti / W / V atomic ratio of 95/4/1 (Comparative Example 1) was 1.
00 (reference) was compared with each Example or Comparative Example.
【００３１】比較例５〜８ 比較例１におけるメタタングステン酸アンモニウムの代
わりにモリブデン酸アンモニウムを用いて、上記実施例
１と類似の実験を行った。Ｔｉ／Ｍｏ／Ｖ原子比が９５
／４／１（比較例５）、９４／４／２（比較例６）、９
１／４／５（比較例７）、８９／４／７（比較例８）の
触媒ペーストを調製した。以後、実施例１と同様の方法
によってハニカム触媒を調製し、また同様にして脱硝活
性を測定した。その結果、調製した触媒の脱硝活性（反
応速度定数比）は、それぞれ０．９６、１．５１、１．
８８および１．８１であった。COMPARATIVE EXAMPLES 5-8 Using ammonium molybdate in place of ammonium metatungstate in Comparative Example 1, an experiment similar to that of Example 1 was conducted. Ti / Mo / V atomic ratio is 95
/ 4/1 (Comparative Example 5), 94/4/2 (Comparative Example 6), 9
Catalyst pastes of 1/4/5 (Comparative Example 7) and 89/4/7 (Comparative Example 8) were prepared. Thereafter, a honeycomb catalyst was prepared by the same method as in Example 1, and the denitration activity was measured in the same manner. As a result, the denitration activity (reaction rate constant ratio) of the prepared catalyst was 0.96, 1.51, 1.
88 and 1.81.
【００３２】実施例１〜１１および比較例１〜８の触媒
活性成分の原子比および性能評価結果を表１に示す。Table 1 shows the atomic ratios and performance evaluation results of the catalytically active components of Examples 1-11 and Comparative Examples 1-8.
【００３３】[0033]
【表１】 本発明の方法では基本的にチタニアと１〜８％バナジウ
ムの混合物を焼成するため、多量のバナジウムを均一に
含有する物質を焼成する場合のように、焼結による活性
低下という問題は起こらない。[Table 1] In the method of the present invention, a mixture of titania and 1 to 8% vanadium is basically fired, so that there is no problem of activity reduction due to sintering as in the case of firing a substance containing a large amount of vanadium uniformly.
【００３４】また、前述のように、触媒の焼成温度を５
００〜６００℃程度で行うことができるため、強化用無
機繊維の軟化による触媒強度の低下、成形体の収縮など
といった問題を回避することができる。Further, as described above, the calcination temperature of the catalyst is set to 5
Since it can be carried out at about 00 to 600 ° C., problems such as reduction in catalyst strength due to softening of the reinforcing inorganic fibers and shrinkage of the molded body can be avoided.
【００３５】[0035]
【発明の効果】本願の請求項１記載の発明によれば、バ
ナジウムおよびタングステン原料のうち、少なくとも１
つの原料化合物の一部または全部として不溶性の形態の
ものを使用することにより、高活性な排煙脱硝触媒を製
造することができ、従来品よりも少ない触媒量で同一の
脱硝性能を達成することができる。According to the invention described in claim 1 of the present application, at least one of vanadium and tungsten raw materials is used.
A highly active flue gas denitration catalyst can be produced by using an insoluble form as a part or all of one raw material compound, and the same denitration performance can be achieved with a smaller amount of catalyst than conventional products. You can
【００３６】本願の請求項２記載の発明によれば、バナ
ジウムおよび／またはタングステン化合物を溶液化した
後ゲル化し、次いで粉砕して不溶性化原料とすることに
より、上記発明の効果に加えて水溶性のバナジウムおよ
び／またはタングステン化合物を使用することもできる
ので、汎用性が向上する。本願の請求項３記載の発明に
よれば、バナジウムおよび／またはタングステン化合物
を溶融し、冷却固化し、次いで粉砕することによって不
溶性化原料とすることにより、水溶性のバナジウムおよ
び／またはタングステン化合物を使用することもでき
る。According to the invention described in claim 2 of the present application, in addition to the effect of the invention described above, the vanadium and / or tungsten compound is made into a solution, gelled, and then pulverized to obtain an insoluble raw material. Since the vanadium and / or tungsten compound can be used, the versatility is improved. According to the invention of claim 3 of the present application, the water-soluble vanadium and / or tungsten compound is used by melting the vanadium and / or tungsten compound, cooling and solidifying it, and then pulverizing it to make it an insoluble material. You can also do it.
【００３７】本願の請求項４記載の発明によれば、触媒
原料を混練する際、マンガン、鉄、クロム、ニッケル、
ニオブ、けい素およびアルミニウムのうち少なくとも一
種を含む化合物を添加することにより、上記発明の効果
に加えて触媒活性をさらに向上させることができる。According to the invention of claim 4 of the present application, when kneading the catalyst raw material, manganese, iron, chromium, nickel,
By adding a compound containing at least one of niobium, silicon and aluminum, the catalytic activity can be further improved in addition to the effects of the above invention.
【図１】不溶性Ｖ化合物を使用した、本発明の一実施例
である脱硝触媒の製造方法を示す図。FIG. 1 is a diagram showing a method for producing a denitration catalyst, which is an example of the present invention, using an insoluble V compound.
【図２】ＴｉＯ2 にＷ化合物とＶ化合物を添加した粉末
に不溶性Ｖ化合物を使用した本発明の実施例を示す図。FIG. 2 is a diagram showing an example of the present invention in which an insoluble V compound is used in a powder obtained by adding a W compound and a V compound to TiO 2 .
【図３】不溶性Ｗ化合物を使用した本発明の実施例を示
す図。FIG. 3 is a view showing an example of the present invention using an insoluble W compound.
【図４】可溶性Ｖ化合物を不溶性状態にして使用した本
発明の実施例を示す図。FIG. 4 is a view showing an example of the present invention in which a soluble V compound is used in an insoluble state.
【図５】従来の脱硝触媒の製造方法を示す図。FIG. 5 is a diagram showing a conventional method for producing a denitration catalyst.
【図６】従来の脱硝触媒の製造方法を示す図。FIG. 6 is a diagram showing a conventional method for producing a denitration catalyst.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 37/08 Ｂ０１Ｄ 53/36 １０２Ｃ (72)発明者 溝口 忠昭 広島県呉市宝町３番36号 バブコック日立 株式会社呉研究所内─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical indication location B01J 37/08 B01D 53/36 102C (72) Inventor Tadaaki Mizoguchi No. 36 Takaracho, Kure City, Hiroshima Prefecture Babcock Hitachi Kure Research Institute
Claims (4)
ンおよび／またはモリブデンを含有する触媒原料を水の
存在下で混練して触媒ペーストを調製し、該触媒ペース
トを成形、または基材に塗布した後、焼成する排煙脱硝
触媒の製造方法において、前記バナジウムおよび／また
はタングステンを含む触媒原料化合物の一部または全部
を不溶性の形態で、他の触媒原料と混練して触媒ペース
トを調製し、該触媒ペーストを所定の形状に成形、また
は基材に塗布した後、焼成することを特徴とする排煙脱
硝触媒の製造方法。1. A catalyst raw material containing titanium, vanadium and tungsten and / or molybdenum is kneaded in the presence of water to prepare a catalyst paste, and the catalyst paste is molded or applied to a base material and then fired. In the method for producing a flue gas denitration catalyst, a part or all of the catalyst raw material compound containing vanadium and / or tungsten is kneaded with another catalyst raw material in an insoluble form to prepare a catalyst paste, and the catalyst paste is prepared according to a predetermined method. 1. A method for producing a flue gas denitration catalyst, which comprises firing after being shaped into the above shape or applied to a base material.
テンを含む触媒原料化合物を溶液化した後ゲル化し、次
いで粉砕して不溶性化することを特徴とする請求項１記
載の排煙脱硝触媒の製造方法。2. The method for producing a flue gas denitration catalyst according to claim 1, wherein the catalyst raw material compound containing vanadium and / or tungsten is made into a solution, then gelled, and then pulverized to make it insoluble.
テンを含む触媒原料化合物を溶融し、冷却固化し、次い
で粉砕することによって不溶性化することを特徴とする
請求項１記載の排煙脱硝触媒の製造方法。3. The method for producing a flue gas denitration catalyst according to claim 1, wherein the catalyst raw material compound containing vanadium and / or tungsten is melted, cooled and solidified, and then pulverized to be insoluble.
クロム、ニッケル、ニオブ、けい素およびアルミニウム
のうち少なくとも一種を含む化合物を添加することを特
徴とする請求項１〜３の何れか記載の排煙脱硝触媒の製
造方法。4. When kneading a catalyst raw material, manganese, iron,
The method for producing a flue gas denitration catalyst according to any one of claims 1 to 3, wherein a compound containing at least one of chromium, nickel, niobium, silicon and aluminum is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8001031A JPH09187652A (en) | 1996-01-08 | 1996-01-08 | Production of catalyst for stack gas denitrification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8001031A JPH09187652A (en) | 1996-01-08 | 1996-01-08 | Production of catalyst for stack gas denitrification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09187652A true JPH09187652A (en) | 1997-07-22 |
Family
ID=11490206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8001031A Pending JPH09187652A (en) | 1996-01-08 | 1996-01-08 | Production of catalyst for stack gas denitrification |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09187652A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008253955A (en) * | 2007-04-09 | 2008-10-23 | Babcock Hitachi Kk | Coating agent for denitrification catalyst, production method thereof, and denitrification catalyst |
-
1996
- 1996-01-08 JP JP8001031A patent/JPH09187652A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008253955A (en) * | 2007-04-09 | 2008-10-23 | Babcock Hitachi Kk | Coating agent for denitrification catalyst, production method thereof, and denitrification catalyst |
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